CN114843493A - One-dimensional high-entropy oxide nano material and preparation method and application thereof - Google Patents
One-dimensional high-entropy oxide nano material and preparation method and application thereof Download PDFInfo
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- 239000002184 metal Substances 0.000 claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 24
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- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
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- 235000002639 sodium chloride Nutrition 0.000 claims description 32
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- 238000003756 stirring Methods 0.000 claims description 6
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- 238000000576 coating method Methods 0.000 claims description 4
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- 239000010949 copper Substances 0.000 claims description 4
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- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004321 preservation Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
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- 230000000694 effects Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 238000004146 energy storage Methods 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
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- 229940069446 magnesium acetate Drugs 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 238000004806 packaging method and process Methods 0.000 description 2
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- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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Images
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- 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
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 relates to a one-dimensional high-entropy oxide nano material and a preparation method and application thereof, wherein at least five metal salts and conductive high polymer materials are used as precursors to prepare an electrostatic spinning solution, electrostatic spinning and high-temperature annealing are combined to obtain the one-dimensional high-entropy oxide nano material, the obtained one-dimensional high-entropy oxide nano material at least contains five transition metals, is in a mutually staggered one-dimensional structure and has a uniform diameter within the range of 300-700 nm, and the obtained one-dimensional high-entropy oxide nano material has the advantages of high length-diameter ratio, short diffusion path, sufficient ion diffusion channel, high specific capacity, high specific surface area, high conductivity, excellent structural stability and the like, and has great application prospect when being used as a lithium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of preparation of high-entropy oxide nano materials, and particularly relates to a one-dimensional high-entropy oxide nano material, and a preparation method and application thereof.
Background
Since 2015, the high-entropy oxide is reported for the first time, and becomes one of the most interesting new materials due to its unique physical and chemical properties, the high-entropy oxide is a single-phase solid solution formed by five or more metal oxides dissolved in an equimolar ratio or a nearly equimolar ratio, and is characterized by the existence of a large configuration entropy, so that the high-entropy oxide shows a unique four-core effect: high entropy effect, lattice distortion effect, delayed diffusion effect and "cocktail effect".
Researches prove that the high-entropy oxide has high ion mobility and conductivity in the field of energy storage, and simultaneously has excellent structural stability, and the high-entropy oxide is proved to have high theoretical specific capacity in a lithium ion battery at present, however, most of the reported methods of the high-entropy oxide are solid-phase methods, coating or liquid-phase methods, most of the high-entropy oxide is bulk, thin film and nano particles in appearance, the material has small specific surface area, is easy to agglomerate, has poor structural stability, and reduces the energy storage capacity and the service life of the high-entropy oxide cathode material.
The invention patent CN110190259B provides a method for synthesizing high-entropy oxide (FeTiMgZnCu) by one step by adopting a high-temperature solid phase method 3 0 4 The blocky material can be used for obtaining the nano (FeTiMgZnCu) with a flaky structure by a high-energy ball milling method 3 0 4 Powder and use of said high entropy oxide (FeTiMgZnCu) 3 0 4 Preparing the anode material of the lithium ion battery at 100mA/gThe specific capacity is stabilized at 414.4mAh/g under the charge-discharge current density.
How to prepare a high-entropy oxide negative electrode material with high specific capacity, high specific surface area, sufficient diffusion channels and high structural stability, and to make the high-entropy oxide negative electrode material fully exert potential in the field of energy storage is a problem to be solved at present, so the invention provides a one-dimensional high-entropy oxide nano material, and a preparation method and application thereof.
Disclosure of Invention
The invention aims to solve the problems and provide a one-dimensional high-entropy oxide nano material, a preparation method and application thereof.
The invention achieves the above purpose through the following technical scheme:
a one-dimensional high-entropy oxide nano material is prepared by sequentially carrying out an electrostatic spinning method and high-temperature annealing on a metal precursor solution, wherein the high-entropy oxide comprises at least 5 metal atoms, and the metal atoms are transition metals Cu, Co, Ni, Mg, Zn, Fe, Cr, Mn or Al.
As a further optimization scheme of the invention, metal atoms of the high-entropy oxide are composed of five of Cu, Co, Ni, Mg and Zn to form a one-dimensional rock salt type high-entropy oxide, or are composed of five of Fe, Co, Ni, Cr and Mn to form a one-dimensional spinel type high-entropy oxide.
As a further optimization scheme of the invention, the one-dimensional high-entropy oxide nano material has uniform diameter and is in staggered interconnection, and the diameter is within the range of 300-700 nm.
A preparation method of a one-dimensional high-entropy oxide nano material comprises the following steps:
(1) adding the conductive polymer material into an organic solvent, and stirring until the conductive polymer material is completely dissolved to form a uniform and transparent solution;
(2) adding more than five kinds of metal salt composition precursor powder into the solution in the step (1), and stirring until the powder is completely dissolved to prepare a metal precursor solution;
(3) processing the metal precursor solution in the step (2) by an electrostatic spinning method to obtain metal salt nano fibers, and drying the metal salt nano fibers;
(4) and (4) annealing the metal salt nano-fiber dried in the step (3) in the air to obtain the one-dimensional high-entropy oxide nano-material.
As a further optimized scheme of the present invention, in step (1), the conductive polymer material is one of polyacrylonitrile, polyvinylpyrrolidone or polyvinyl alcohol, preferably polyvinylpyrrolidone, and the organic solvent is N, N-dimethylformamide.
As a further optimized solution of the present invention, in step (2), the metal salt in the metal salt composition precursor powder is one of chloride, acetate or nitrate, preferably acetate and chloride, the ratio of metal atoms in the metal salt composition precursor powder is equal molar ratio, and the mass ratio of the metal salt composition precursor powder to the conductive polymer material is 1: (1-3).
As a further optimization scheme of the invention, in the step (3), the electrostatic spinning method adopts a high-voltage direct-current power supply, wherein the positive voltage is 10-20 kV, preferably 12-15 kV, the negative voltage is-1 kV, the spinning distance is 10-20 cm, preferably 15cm, and the drying treatment specifically comprises drying the metal salt nanofibers at 60-100 ℃ for 12h, preferably at 80 ℃ for 12h by a vacuum oven.
As a further optimization scheme of the invention, in the step (4), the annealing temperature is 700-1200 ℃, preferably 800-1000 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 2-6 h, preferably 2-4 h.
Application of one-dimensional high-entropy oxide nano material as lithium ion battery cathode material
A one-dimensional high-entropy oxide nano material is mixed with acetylene black and PVDF powder, NMP is added, the mixture is ground to slurry, and then the slurry is coated on the surface of copper foil and dried to obtain the lithium ion battery cathode material.
The invention has the beneficial effects that:
1) the method comprises the steps of preparing an electrostatic spinning solution by taking at least five metal salts and conductive high polymer materials as precursors, and obtaining a one-dimensional high-entropy oxide nano material by combining electrostatic spinning and high-temperature annealing, wherein the obtained one-dimensional high-entropy oxide nano material at least comprises five transition metals, is in a staggered one-dimensional structure, and has a uniform diameter within the range of 300-700 nm;
2) the one-dimensional high-entropy oxide nano material obtained by the invention has the advantages of high length-diameter ratio, short diffusion path, sufficient ion diffusion channel, high specific surface area, high conductivity, excellent structural stability and the like, and shows great application prospect when being used as a lithium ion battery cathode material.
Drawings
FIG. 1 is an XRD pattern of one-dimensional rock salt type high entropy oxide (CuCoNiMgZn) O prepared according to example 1 of the present invention;
FIG. 2 is an SEM picture of a one-dimensional high-entropy oxide nanofiber precursor prepared according to example 1 of the present invention;
FIG. 3 is an SEM picture of one-dimensional rock-salt-type high-entropy oxide (CuCoNiMgZn) O prepared according to example 1 of the present invention;
FIG. 4 is a cycle curve of a one-dimensional rock salt type high entropy oxide (CuCoNiMgZn) O negative electrode material synthesized according to example 1 of the present invention operating at a current density of 100mA/g in a lithium ion battery;
FIG. 5 is a one-dimensional spinel type high entropy oxide (FeCoNiCrMn) prepared according to example 2 of the present invention 3 O 4 An XRD pattern of (a);
FIG. 6 is an SEM picture of a one-dimensional high-entropy oxide nanofiber precursor prepared according to example 2 of the present invention;
FIG. 7 is a one-dimensional spinel type high entropy oxide (FeCoNiCrMn) prepared according to example 2 of the present invention 3 O 4 SEM picture of (a);
FIG. 8 is a one-dimensional spinel type high entropy oxide (FeCoNiCrMn) prepared according to example 2 of the present invention 3 O 4 Cycling curves of the negative electrode material in a lithium ion battery operated at a current density of 100 mA/g.
Detailed Description
The present application will now be described in further detail with reference to the drawings, it should be noted that the following detailed description is given for illustrative purposes only and is not to be construed as limiting the scope of the present application, as those skilled in the art will be able to make numerous insubstantial modifications and adaptations to the present application based on the above disclosure.
Example 1
The preparation method of the one-dimensional rock salt type high-entropy oxide (CuCoNiMgZn) O nano material comprises the following steps:
(1) 2g of polyvinylpyrrolidone (molecular weight: 1300000, Shanghai Michelin Biochemical technology Co., Ltd.) is poured into 10mLN, N-dimethylformamide solvent, and the mixture is continuously stirred for 12 hours to be fully dissolved to form transparent solution;
(2) sequentially adding 2mmol of copper acetate, 2mmol of cobalt acetate, 2mmol of nickel acetate, 2mmol of magnesium acetate and 2mmol of zinc acetate into the solution prepared in the step (1), and continuously stirring until the copper acetate, the cobalt acetate, the nickel acetate, the 2mmol of magnesium acetate and the 2mmol of zinc acetate are completely dissolved to obtain dark blue slurry, wherein the slurry is a metal precursor solution;
(3) sucking the metal precursor solution prepared in the step (2) by using a 10mL syringe, wherein the syringe is provided with a 19G type stainless steel needle, the syringe is fixed on an injection pump, an aluminum foil receiving plate is vertically placed 15cm in front of the stainless steel needle and connected with a negative electrode clamp, the front end of the needle is connected with a positive electrode clamp, positive pressure and negative pressure are respectively set to be 15kV and-1 kV, spinning is started at the flow rate of 1mL/h, after the spinning is finished, the collected metal salt nanofibers are removed and then placed in a vacuum oven, and drying is carried out at the temperature of (80 +/-5) ° C for 12 hours;
(4) tearing the metal salt nanofiber subjected to the drying treatment in the step (3) into a thin sheet, putting the thin sheet into a ceramic boat, transferring the ceramic boat into a muffle furnace, performing annealing treatment in the muffle furnace, and setting a muffle furnace program: heating from room temperature to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and then naturally cooling to finally obtain the one-dimensional rock salt type high-entropy oxide (CuCoNiMgZn) O nano material.
In step (3) of this embodiment, the positive voltage value of the positive electrode clip connected to the front end of the needle may be set to 12kV, 13kV, or 14 kV.
In step (4) of this embodiment, the muffle procedure may be further configured to:
heating from room temperature to 800 ℃ at the heating rate of 2 ℃/min, preserving heat for 4h, and then naturally cooling;
heating from room temperature to 1000 ℃ at the heating rate of 10 ℃/min, preserving heat for 3h, and then naturally cooling.
FIG. 1 is an XRD pattern of the product of example 1 measured by an X-ray diffractometer, and diffraction peaks thereof respectively correspond to (111), (200), (220), (311) and (222) crystal faces of rock salt forms, thus proving that the single-phase solid solution with the rock salt structure is successfully synthesized in example 1 of the present invention.
Fig. 2 shows the morphology of the nanofiber precursor in embodiment 1 of the present invention, which is characterized by a scanning electron microscope, and the nanofiber precursor prepared in embodiment 1 of the present invention has a smooth surface and a uniform size, a diameter of 300-500 nm, and nanofibers are interconnected in a staggered manner.
Fig. 3 is a scanning electron microscope-characterized morphology of the final one-dimensional rock salt type high-entropy oxide in embodiment 1 of the present invention, which shows a one-dimensional structure, but has a rough surface and obvious particles, and the diameter of the one-dimensional rock salt type high-entropy oxide is also slightly increased to about 500 to 700nm, but the one-dimensional structures are still staggered with each other, so as to provide sufficient one-dimensional diffusion channels.
Example 2
One-dimensional spinel type high entropy oxide (FeCoNiCrMn) 3 O 4 The preparation of the nano material comprises the following steps:
(1) 2g of polyvinylpyrrolidone (molecular weight: 1300000, manufactured by Shanghai Michelin Biochemical technology Co., Ltd.) was poured into 10ml of N-dimethylformamide solvent, and the mixture was stirred for 12 hours to dissolve it sufficiently, thereby forming a transparent solution.
(2) Sequentially adding 1mmol of ferric trichloride, 1mmol of cobalt chloride, 1mmol of nickel chloride, 1mmol of chromium chloride and 1mmol of manganese chloride into the solution prepared in the step (1), and continuously stirring until uniform electrostatic spinning slurry is formed;
(3) transferring the electrostatic spinning slurry prepared in the step (2) into a syringe with the specification of 10mL, wherein the syringe is provided with a stainless steel needle with the model of 21G, the syringe is fixed on an injection pump, an aluminum foil receiving plate is placed 15cm in front of the stainless steel needle and connected with a negative electrode clamp, the front end of the needle is connected with a positive electrode clamp, the positive pressure and the negative pressure are respectively set to be 13kV and-1 kV, electrostatic spinning is started under the condition, after the spinning is finished, the collected metal salt nanofibers are taken off and placed into a vacuum oven, and drying is carried out at the temperature of (80 +/-5) DEG C for 12 hours;
(4) tearing the metal salt nanofiber subjected to the drying treatment in the step (3) into a thin sheet, putting the thin sheet into a ceramic boat, transferring the ceramic boat into a muffle furnace, performing annealing treatment in the muffle furnace, and setting a muffle furnace program: heating from room temperature to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and naturally cooling to obtain the one-dimensional spinel type high-entropy oxide (FeCoNiCrMn) 3 O 4 And (3) nano materials.
In step (3) of this embodiment, the positive voltage value of the positive electrode clip connected to the front end of the needle may be set to 12kV, 14kV, or 15 kV.
In step (4) of this embodiment, the muffle procedure may be further configured to:
heating from room temperature to 800 ℃ at the heating rate of 4 ℃/min, preserving heat for 3h, and then naturally cooling;
heating from room temperature to 1000 ℃ at the heating rate of 7 ℃/min, preserving heat for 2h, and then naturally cooling.
FIG. 5 is an XRD pattern of the product of example 2 measured by an X-ray diffractometer, wherein diffraction peaks thereof respectively correspond to the crystal faces of spinel-type (220), (311), (222), (400), (422), (511), (440), (620), (533) and (444), and thus, it is proved that one-dimensional spinel-type high-entropy oxide (FeCoNiCrMn) is successfully prepared in example 2 of the present invention 3 O 4 。
Fig. 6 shows the morphology of the nanofiber precursor in embodiment 2 of the present invention, which is characterized by a scanning electron microscope, and the nanofiber precursor prepared in embodiment 2 of the present invention has a smooth surface and a uniform size, and has a diameter of 300-500 nm.
FIG. 7 is a scanning electron microscope representation of the final one-dimensional spinel-type high-entropy oxide of example 2 of the present invention with a rough surface but still maintaining a cross-linked one-dimensional nanostructure, the size of the one-dimensional spinel-type high-entropy oxide increasing to 500-700 nm.
Example 3
An application of a one-dimensional high-entropy oxide nano material as a lithium ion battery cathode material, in particular to a preparation method of the lithium ion battery cathode material, which comprises the following steps:
taking 40mg of (CuCoNiMgZn) O powder obtained in the step (4) in the embodiment 1, fully mixing the powder with 5mg of acetylene black and 5mg of PVDF powder, grinding the mixture into uniform powder, then dropwise adding a proper amount of N-methyl pyrrolidone (NMP) and continuously grinding the powder until uniform slurry is formed for later use, taking a 20 cm-20 cm copper foil, fixing the copper foil in a glass plate, and cleaning the copper foil with ethanol to remove surface pollutants;
secondly, pouring the slurry prepared in the step one on a copper foil, coating the copper foil by using a scraper with the thickness of 100 microns to enable the slurry to be uniformly spread on the surface of the copper foil, then putting the copper foil into a vacuum oven, and carrying out vacuum drying for 12 hours at the temperature of 80 ℃;
taking out the dried copper foil obtained in the step two, cutting the copper foil into circular electrode plates with the diameter of 12cm by using a slicing machine, weighing the mass of the electrode plates, calculating the mass of an active substance, then putting the electrode plates into a glove box (Mikanuna (China) Co., Ltd.), filling high-purity argon into the glove box, keeping the water-oxygen ratio below 0.1ppm all the time, packaging the copper foil into a lithium ion battery in the glove box, and standing for 12 hours;
and fourthly, taking out the battery after standing in the third step, connecting the battery into a Xinwei battery testing system, performing charge-discharge testing on the battery, and obtaining the lithium ion battery cathode material after the test is qualified.
FIG. 4 shows the cycle performance curve of the lithium ion battery prepared from the one-dimensional rock salt type high-entropy oxide (CuCoNiMgZn) O nanomaterial prepared in this example 1 according to example 3, when the lithium ion battery is charged and discharged at a current density of 100mA/g, after 50 cycles, the specific capacity of the lithium ion battery reaches 625mAh/g, and the lithium ion battery shows excellent cycle stability.
Example 4
An application of a one-dimensional high-entropy oxide nano material as a lithium ion battery cathode material, in particular to a preparation method of the lithium ion battery cathode material, which comprises the following steps:
first, the (FeCoNiCrMn) obtained in the step (4) of example 2 was taken 3 O 4 Fully mixing the powder, the acetylene black and the PVDF powder according to the mass ratio of 7:2:1, grinding into uniform powder, dropwise adding a proper amount of N-methylpyrrolidone (NMP), continuously grinding until uniform slurry is formed for later use, taking a copper foil with the thickness of 20cm multiplied by 20cm, fixing the copper foil in a glass plate, and cleaning with ethanol to remove surface pollutants;
secondly, pouring the slurry prepared in the step one on a copper foil, coating the copper foil by using a scraper with the thickness of 100 microns to enable the slurry to be uniformly spread on the surface of the copper foil, then putting the copper foil into a vacuum oven, and carrying out vacuum drying for 12 hours at the temperature of 80 ℃;
taking out the dried copper foil obtained in the step two, cutting the copper foil into circular electrode plates with the diameter of 12cm by using a slicing machine, weighing the mass of the electrode plates, calculating the mass of an active substance, then putting the electrode plates into a glove box (Mikanuna (China) Co., Ltd.), filling high-purity argon into the glove box, keeping the water-oxygen ratio below 0.1ppm all the time, packaging the copper foil into a lithium ion battery in the glove box, and standing for 12 hours;
and fourthly, taking out the battery after standing in the third step, connecting the battery into a Xinwei battery testing system, performing charge-discharge testing on the battery, and obtaining the lithium ion battery cathode material after the test is qualified.
FIG. 8 shows a one-dimensional spinel-type high-entropy oxide (FeCoNiCrMn) prepared in example 2 according to example 4 3 O 4 The nano material is prepared into a lithium ion battery cathode material, the cycle performance curve is obtained when the lithium ion battery is charged and discharged at the current density of 100mA/g, and the specific capacity is 410mAh/g after 100 cycles of cycle.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A one-dimensional high-entropy oxide nano-material is characterized in that: preparing the metal precursor solution into a one-dimensional high-entropy oxide nano material through an electrostatic spinning method and high-temperature annealing in sequence, wherein the high-entropy oxide contains at least 5 metal atoms, and the metal atoms are transition metals Cu, Co, Ni, Mg, Zn, Fe, Cr, Mn or Al.
2. A one-dimensional high entropy oxide nanomaterial according to claim 1, wherein: the metal atoms of the high-entropy oxide are composed of five of Cu, Co, Ni, Mg and Zn to form a one-dimensional rock salt type high-entropy oxide, or are composed of five of Fe, Co, Ni, Cr and Mn to form a one-dimensional spinel type high-entropy oxide.
3. A one-dimensional high-entropy oxide nanomaterial according to claim 1, wherein: the one-dimensional high-entropy oxide nano material is uniform in diameter and is connected in a staggered mode, and the diameter is within the range of 300-700 nm.
4. A method for preparing a one-dimensional high-entropy oxide nanomaterial according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) adding the conductive polymer material into an organic solvent, and stirring until the conductive polymer material is completely dissolved to form a uniform and transparent solution;
(2) adding more than five kinds of metal salt composition precursor powder into the solution in the step (1), and stirring until the powder is completely dissolved to prepare a metal precursor solution;
(3) processing the metal precursor solution in the step (2) by an electrostatic spinning method to obtain metal salt nano fibers, and drying the metal salt nano fibers;
(4) and (4) annealing the metal salt nano-fiber dried in the step (3) in the air to obtain the one-dimensional high-entropy oxide nano-material.
5. The preparation method of one-dimensional high-entropy oxide nano-material according to claim 4, characterized in that: in the step (1), the conductive polymer material is one of polyacrylonitrile, polyvinylpyrrolidone or polyvinyl alcohol, and the organic solvent is N, N-dimethylformamide.
6. The preparation method of one-dimensional high-entropy oxide nano-material according to claim 4, characterized in that: in the step (2), the metal salt in the metal salt composition precursor powder is one of chloride, acetate or nitrate, the proportion of metal atoms in the metal salt composition precursor powder is equal molar ratio, and the mass ratio of the metal salt composition precursor powder to the conductive polymer material is 1: (1-3).
7. The preparation method of one-dimensional high-entropy oxide nano-material according to claim 4, characterized in that: in the step (3), a high-voltage direct-current power supply is adopted in the electrostatic spinning method, wherein the positive voltage is 10-20 kV, the negative voltage is-1 kV, the spinning distance is 10-20 cm, and the drying treatment specifically comprises drying the metal salt nanofiber at 60-100 ℃ for 12 hours by a vacuum oven.
8. The preparation method of one-dimensional high-entropy oxide nano-material according to claim 4, characterized in that: in the step (4), the annealing temperature is 700-1200 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 2-6 h.
9. Use of the one-dimensional high-entropy oxide nanomaterial defined in any one of claims 1 to 3 as a negative electrode material for a lithium ion battery.
10. A lithium ion battery negative electrode material is characterized by being prepared by mixing the one-dimensional high-entropy oxide nano material as claimed in any one of claims 1 to 3, acetylene black and PVDF powder, adding NMP, grinding the mixture to slurry, coating the slurry on the surface of copper foil, and drying the copper foil.
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