CN113258050A - Five-element high-entropy alloy oxide negative electrode material and preparation method and application thereof - Google Patents
Five-element high-entropy alloy oxide negative electrode material and preparation method and application thereof Download PDFInfo
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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
- H01M4/50—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a quinary high-entropy alloy oxide cathode material and a preparation method and application thereof, belonging to the technical field of lithium ion battery cathode materials, wherein the cathode material comprises Ni, Cu, Fe, Co and Mn, and the preparation process comprises the following steps: preparing a transition metal high-entropy alloy strip by a smelting-melt spinning process according to a specific atomic ratio; forming the multi-component homogeneous phase nano-porous alloy by dealloying the five-element alloy strip; preparing alloy powder with uniform particle size from the nano porous metal by a grinding method; and (3) carrying out oxidation treatment on the alloy powder in the air atmosphere, and carrying out reduction treatment in a hydrogen/argon mixed gas to obtain the nano porous multicomponent metallic oxide negative electrode material. The invention has the advantages that: the preparation method is simple, the transition metal is low in price, and large-scale production can be realized; the multicomponent high-entropy alloy oxide prepared by the method has higher specific capacity and excellent rate capability compared with commercial graphite.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a nano-porous NiCuFeCoMn five-element high-entropy alloy oxide cathode material for a lithium ion battery, and a preparation method and application thereof.
Background
With the rapid development of science and technology, the demand of people for energy is increasing day by day. At present, the energy sources on which we rely are mainly fossil fuels, but the fossil fuels are non-renewable energy sources. As the consumption is gradually increased, the reserves all over the world are also reduced, and therefore, the development of clean energy is one of the important issues of the current research.
The technical requirements of the society on power sources are also increasing. The lithium ion battery is widely applied to daily life and production as a high-efficiency rechargeable energy storage device. Nickel cadmium batteries, which have been used previously, have already suffered from severe limitations at this stage because of the toxic side effects of cadmium batteries. Since 2005, many countries in europe have also made strict restrictions on the production and sale of lead-acid batteries, which are relatively serious in environmental pollution, as civilian use. The lithium ion battery is a high and new technology product and is a novel high-capacity environment-friendly battery. Compared with nickel-cadmium and nickel-hydrogen batteries, the lithium ion battery has the advantages of high voltage, large specific capacity, good cycle performance, less self-discharge, no memory effect, rapid charge and discharge, wide working temperature range and the like. Therefore, the development of lithium ion batteries is receiving more and more attention and is dominant. However, the specific capacity, the rapid charge and discharge performance and the cycle life of the lithium ion battery need to be further optimized, the current commercial negative electrode material is still a carbon material, and the theoretical specific capacity of the carbon material is only 372mAh/g, so that the carbon material cannot meet the increasing requirements of people.
Disclosure of Invention
The invention aims to provide a quinary high-entropy alloy oxide cathode material which is simple in preparation mode, low in price, controllable in cost, green, environment-friendly, flexible, variable and excellent in performance, and a preparation method and application of the cathode material.
In order to solve the technical problems, the invention adopts the technical scheme that: a quinary high-entropy alloy oxide cathode material comprises five metal elements of Ni, Cu, Fe, Co and Mn.
Preferably, after the five-element high-entropy alloy oxide negative electrode material is cycled for 300 circles, the specific capacity can still be maintained at 650 mAh/g.
The invention also provides a preparation method of the quinary high-entropy alloy oxide cathode material, which comprises the following steps:
(1) preparing a multi-element high-entropy alloy strip: selecting analytically pure Ni, Cu, Fe, Co and Mn metal particles with the diameter of 1-5mm, preparing alloy strips with the thickness of 20-50 mu m by smelting and spinning according to the atomic ratio of (6-10) to (50-70), wherein the rotating speed frequency of a spinning machine is 45-50Hz, and the rotating speed is 15-18 m/s; wherein the atomic proportion of Mn is 60-70 At%, and the atomic proportion of Ni, Cu, Fe and Co is 5-10At respectively;
(2) dealloying treatment: the alloy strip prepared in the step (1) is placed in ammonium sulfate solution of (0.5-2) mol/L for dealloying treatment, the temperature is 40-80 ℃, the corrosion time is 2-8h, homogeneous-phase nano porous multi-element alloy is formed, and the Mn atomic ratio after dealloying is about 10-15 At% through EDX energy spectrum analysis;
(3) oxidation treatment: placing the metal subjected to dealloying in the step (2) in an air atmosphere, wherein the specific surface area is obviously increased due to the fact that a nano porous structure is formed through dealloying, and spontaneous combustion occurs after the metal strip is contacted with air, then placing the spontaneous combustion metal strip in a muffle furnace, and preserving heat for 2-6 hours at the temperature of 300-650 ℃, wherein the heating rate is 10-30 ℃/min, so as to improve the content of oxides;
(4) reduction treatment: placing the metal strip obtained in the step (3) in a horizontal tube furnace, reducing for 1-3h in an argon/hydrogen atmosphere at a gas rate of 200-;
(5) grinding: putting the nano porous metal oxide prepared in the step (4) into a mortar for grinding uniformly, wherein the particle size is 1-5 mu m;
(6) preparing an electrode plate: fully grinding the nano porous high-entropy alloy oxide powder prepared in the step (5), polyvinylidene fluoride (PVDF) and acetylene black according to the ratio of (6-8) to (1-3) to 1, dropping N-methylpyrrolidone (NMP) to form uniform slurry, preparing an electrode slice with the thickness of 250 mu m and 100 meshes by using a coating process, placing the electrode slice in a vacuum drying box for 8-15h, and heating and drying at the temperature of 60-100 ℃;
(7) assembling the battery: and (5) placing the electrode slice prepared in the step (6) into a glove box filled with argon atmosphere to assemble the lithium ion battery.
Preferably, in the step (1), the metals Ni, Cu, Fe, Co and Mn are all selected to be particles with the diameter of 1-3mm, the frequency of the spinning speed is 45-47Hz, and the spinning speed is 16-17 m/s.
Preferably, the dealloying method in the step (2) is a chemical dealloying method, the solution is a weakly acidic ammonium sulfate solution, the concentration of the solution is 0.5-1mol/L, the temperature is 50-80 ℃, and the time is 3-8 hours.
Preferably, in the step (3), the heating temperature in the muffle furnace is 350-650 ℃, the holding time is 2-6 hours, and the heating rate is 10 ℃/min.
Preferably, the step (4) is carried out in a tubular furnace at the temperature of 200 ℃ and 400 ℃ for 2-3 h.
Preferably, the nanoporous metal strips obtained in step (5) are placed in a mortar and sufficiently ground until the strips are ground into black micron-sized powder with a particle size of 2-4 μm.
Preferably, in the step (6), the ratio of NiCuFeCoMn oxide: acetylene black: PVDF is uniformly mixed according to the proportion of 8:1:1 or 7:2:1 or 6:3:1, then a proper amount of NMP is dripped, after uniform size mixing, an electrode slice with the thickness of 100 mu m-200 mu m is prepared by a preparation device, and the electrode slice is placed in a vacuum drying oven for 12 hours at the temperature of 80-100 ℃.
The invention also provides an application of the quinary high-entropy alloy oxide cathode material prepared by the preparation method of the quinary high-entropy alloy oxide cathode material or the quinary high-entropy alloy oxide cathode material in a lithium ion battery cathode.
Compared with carbon materials, the metal oxide serving as the negative electrode material has higher theoretical specific capacity, simple preparation and lower cost. Different types of multi-element metal oxides can be obtained through different proportions of different transition metals, wherein the NiCuFeCoMn alloy oxide has high specific capacity, the nano porous structure provides more active sites, the specific capacity is nearly 3 times higher than that of the traditional graphite electrode, and the multi-element metal oxide has good specific cyclic capacity. The preparation of the multielement nano porous metal oxide negative electrode material by the dealloying method is an ideal choice for replacing graphite materials.
Compared with the prior art, the five-element alloy is prepared by smelting and strip-spinning a multi-element alloy NiCuFeCoMn metal with a certain proportion, the nano-porous metal is formed by dealloying, the nano-porous oxide is formed by spontaneous combustion and redox treatment, the oxide has a very high specific surface area, has higher specific capacity than the traditional graphite electrode material, and ensures good conductivity of metal components of the oxide, wherein the oxides of Ni, Cu, Fe, Co and Mn respectively have very high theoretical specific capacities, and Mn accounts for 60-70%, mainly because the metal Mn element has obviously different corrosion conditions compared with other four elements, the Mn element can be corroded by using an ammonium sulfate solution with weak acidity, the performance of a manufactured sample can be influenced by too much or too little Mn element, and other elements are correspondingly too little if Mn is too much, the porosity of the formed nano porous metal is too large, otherwise, the content of other elements is increased if the Mn is too small, the porosity of the formed nano porous structure is too small, and the too large or too small porosity of the porous structure is not beneficial to lithium ion deintercalation.
Compared with the prior art, the invention has the following advantages:
(1) the method directly prepares NiCuFeCoMn which is a quinary alloy by a smelting and strip-spinning mode, has a simple preparation mode, is green and environment-friendly, and forms a nano porous structure by a chemical dealloying method.
(2) The NiCuFeCoMn oxide prepared by the invention has a porous structure, is made of metal materials, has a high specific surface area, can adjust the pore diameter according to different concentrations and different temperatures of corrosive liquid, is uniformly and controllably distributed, and has more excellent performance than the conventional graphite electrode.
(3) The multi-component alloy prepared by the method has flexible variability, and the method takes the example of removing Mn metal by an alloy removing method, so that the performance of the formed multi-component alloy oxide is far higher than that of the existing traditional graphite electrode.
(4) The non-noble metal electrode material prepared by the invention has the advantages of low price, controllable cost and rich raw material content, and is a novel lithium ion battery cathode material.
Drawings
The advantages and realisation of the invention will be more apparent from the following detailed description, given by way of example, with reference to the accompanying drawings, which are given for the purpose of illustration only, and which are not to be construed in any way as limiting the invention, and in which:
FIG. 1 shows Ni of the present invention8Cu8Fe8Co8Mn68SEM comparison before and after dealloying, oxidation and reduction of quinary alloy;
FIG. 2 shows Ni of the present invention8Cu8Fe8Co8Mn68EDS element distribution diagram of the quinary alloy strip;
FIG. 3 shows Ni of the present invention8Cu8Fe8Co8Mn68XRD pattern of the quinary alloy strip;
FIG. 4 shows Ni after etching in accordance with the present invention8Cu8Fe8Co8Mn68BET plot of quinary alloy ribbon;
FIG. 5 is a constant current charge and discharge diagram of the present invention after cell assembly, cycled at a current density of 100mA/g for 300 cycles;
FIG. 6 is a graph showing the cycle rate after assembling a battery according to the present invention
Detailed Description
The invention will be further described with reference to the following examples and figures:
in the present invention, the alloy and various reagents were purchased from general chemical shops, and the battery test was performed using a battery tester known in the art.
Example 1:
a quinary high-entropy alloy oxide cathode material and a preparation method thereof comprise the following steps:
(1) preparing a multi-element alloy strip: selecting analytically pure Ni, Cu, Fe, Co and Mn metal particles with the diameter of 1-5mm, and preparing alloy strips with the thickness of 30 microns by smelting-melt spinning according to the atomic ratio of 8:8:8:8:68, wherein the rotating speed frequency of a melt spinning machine is 45Hz, and the rotating speed is 15 m/s;
(2) dealloying treatment: and (2) placing the alloy strip prepared in the step (1) in 1mol/L ammonium sulfate solution for dealloying treatment at the temperature of 50 ℃ for 8 hours to form the homogeneous nano porous multi-element alloy. EDX (electron-ray diffraction) spectrum analysis shows that the proportion of Mn atoms after dealloying is about 15 At%;
(3) oxidation treatment: and (3) placing the metal subjected to the dealloying in the step (2) in an air atmosphere, wherein the specific surface area is obviously increased due to the fact that a nano porous structure is formed through dealloying, and a spontaneous combustion phenomenon occurs after the metal is contacted with air. Then, placing the self-ignited metal strip in a muffle furnace, and preserving the heat for 4h at 350 ℃, wherein the heating rate is 10 ℃/min, so as to improve the content of oxides;
(4) reduction treatment: placing the metal strip obtained in the step (3) in a horizontal tube furnace, reducing for 1h in an argon/hydrogen atmosphere at the reduction temperature of 200 ℃ at the gas rate of 200sccm, and forming partial metal atom doping and oxygen vacancy defects on the surface of the porous structure of the oxidized alloy strip through reduction treatment, so that the conductivity of the electrode is improved;
(5) grinding: putting the nano porous metal oxide prepared in the step (4) into a mortar for grinding uniformly, wherein the particle size is 2 microns; ,
(6) preparing an electrode plate: and (3) fully grinding the nano-porous high-entropy alloy oxide powder prepared in the step (5) with polyvinylidene fluoride (PVDF), acetylene black and N-methyl pyrrolidone (NMP) according to a ratio of 8:1:1 to form uniform slurry. Preparing an electrode slice with the thickness of 100 microns by using a coating process, placing the electrode slice in a vacuum drying oven for 8 hours, and heating and drying at 60 ℃;
(7) assembling the battery: and (5) placing the electrode slice prepared in the step (6) into a glove box filled with argon atmosphere to assemble the lithium ion battery.
Various electrochemical performance tests were performed on the electrode materials prepared by the above-described methods, and the test results are shown in fig. 1 to 6.
As shown in fig. 1, the surface of the strip before alloy removal is complete and smooth and has toughness; the dealloying redox has rich nano-porous structure.
As shown in fig. 2, the prepared bands and the theoretical ratio were approximately the same, and the content of the element was determined.
As shown in fig. 3, the alloy is in the FCC phase.
As shown in figure 4, the BET multipoint analysis shows that the five-element material has a specific surface area of 23.4 square meters per gram, and the analysis shows that the pore diameter is mainly concentrated in 3-4 nm.
As shown in FIG. 5, the capacity retention rate of the material is still above 90% after 300 cycles, and the specific discharge capacity is 618mAh/g after 300 cycles.
As shown in fig. 6, the current density is 100, 200, 500, 1000 and 2000mA/g per 10 turns respectively, and in the process of gradually increasing the current, the capacity is not obviously attenuated and finally recovered to 100mA/g, so that the battery capacity is improved, and the battery has good structural stability and excellent electrochemical performance.
Example 2:
a quinary high-entropy alloy oxide cathode material and a preparation method thereof comprise the following steps:
(1) preparing a multi-element alloy strip: selecting analytically pure Ni, Cu, Fe, Co and Mn metal particles with the diameter of 1-5mm, and preparing alloy strips with the thickness of 40 microns by smelting-melt spinning according to the atomic ratio of 10:8:6:8:68, wherein the rotating speed frequency of a melt spinning machine is 50Hz, and the rotating speed is 18 m/s;
(2) dealloying treatment: and (2) placing the alloy strip prepared in the step (1) in 1.5mol/L ammonium sulfate solution for dealloying treatment at the temperature of 60 ℃ for 6 hours to form the homogeneous nano-porous multi-element alloy. EDX (electron-ray diffraction) spectrum analysis shows that the proportion of Mn atoms after dealloying is about 10 At%;
(3) oxidation treatment: and (3) placing the metal subjected to the dealloying in the step (2) in an air atmosphere, wherein the specific surface area is obviously increased due to the fact that a nano porous structure is formed through dealloying, and a spontaneous combustion phenomenon occurs after the metal is contacted with air. Then, placing the spontaneous combustion metal strip in a muffle furnace, and preserving the heat for 5h at 550 ℃, wherein the heating rate is 15 ℃/min, so as to improve the content of oxides;
(4) reduction treatment: placing the metal strip obtained in the step (3) in a horizontal tube furnace, reducing for 2h in an argon/hydrogen atmosphere at the reduction temperature of 300 ℃ at the gas rate of 300sccm, and forming partial metal atom doping and oxygen vacancy defects on the surface of the porous structure of the oxidized alloy strip through reduction treatment, so that the conductivity of the electrode is improved;
(5) grinding: putting the nano porous metal oxide prepared in the step (4) into a mortar for grinding uniformly, wherein the particle size is 5 microns under an electron microscope; ,
(6) preparing an electrode plate: and (3) fully grinding the nano-porous high-entropy alloy oxide powder prepared in the step (5) with polyvinylidene fluoride (PVDF), acetylene black and N-methyl pyrrolidone (NMP) according to a ratio of 7:2:1 to form uniform slurry. Preparing 150 μm thick electrode sheet by coating process, placing the electrode sheet in a vacuum drying oven for 10h, and heating and drying at 100 deg.C;
(7) assembling the battery: and (5) placing the electrode slice prepared in the step (6) into a glove box filled with argon atmosphere to assemble the lithium ion battery.
After 300 cycles of long cycle, the test shows that the capacity of the battery can still be kept above 85%, and the specific discharge capacity of the battery is 592mAh/g when the battery is cycled for 300 cycles. The rate performance also maintained excellent stability compared to example 1.
Example 3:
a quinary high-entropy alloy oxide cathode material and a preparation method thereof comprise the following steps:
(1) preparing a multi-element alloy strip: selecting analytically pure Ni, Cu, Fe, Co and Mn metal particles with the diameter of 1-5mm, and preparing alloy strips with the thickness of 50 microns by smelting-melt spinning according to the atomic ratio of 10:10:6:6:68, wherein the rotating speed frequency of a melt spinning machine is 47Hz, and the rotating speed is 17 m/s;
(2) dealloying treatment: and (2) placing the alloy strip prepared in the step (1) in 2mol/L ammonium sulfate solution for dealloying treatment at the temperature of 70 ℃ for 5 hours to form the homogeneous nano porous multi-element alloy. EDX (electron-ray diffraction) spectrum analysis shows that the proportion of Mn atoms after dealloying is about 10 At%;
(3) oxidation treatment: and (3) placing the metal subjected to the dealloying in the step (2) in an air atmosphere, wherein the specific surface area is obviously increased due to the fact that a nano porous structure is formed through dealloying, and a spontaneous combustion phenomenon occurs after the metal is contacted with air. Then, placing the spontaneous combustion metal strip in a muffle furnace, and preserving the heat for 5h at 600 ℃, wherein the heating rate is 20 ℃/min, so as to improve the content of oxides;
(4) reduction treatment: placing the metal strip obtained in the step (3) in a horizontal tubular furnace, reducing for 3h in an argon/hydrogen atmosphere at the reduction temperature of 400 ℃ at the gas rate of 400sccm, and forming partial metal atom doping and oxygen vacancy defects on the surface of the porous structure of the oxidized alloy strip through reduction treatment, so that the conductivity of the electrode is improved;
(5) grinding: putting the nano porous metal oxide prepared in the step (4) into a mortar for grinding uniformly, wherein the particle size is 4 mu m; ,
(6) preparing an electrode plate: and (3) fully grinding the nano-porous high-entropy alloy oxide powder prepared in the step (5) with polyvinylidene fluoride (PVDF), acetylene black and N-methyl pyrrolidone (NMP) according to the ratio of 6:3:1 to form uniform slurry. Preparing an electrode slice with the thickness of 100 microns by using a coating process, placing the electrode slice in a vacuum drying oven for 12 hours, and heating and drying at 100 ℃;
(7) assembling the battery: and (5) placing the electrode slice prepared in the step (6) into a glove box filled with argon atmosphere to assemble the lithium ion battery.
After 300 cycles of long cycle, the capacity of the battery can still be kept above 90%, the specific discharge capacity of the battery is 658mAh/g when the battery is cycled for 300 cycles, and the rate performance is still kept excellent and even improved compared with that of example 1.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. The implementation of the steps can be changed, and all equivalent changes and modifications made within the scope of the present invention should be covered by the present patent.
Claims (10)
1. A quinary high-entropy alloy oxide negative electrode material is characterized in that: comprises five metal elements of Ni, Cu, Fe, Co and Mn.
2. The five-membered high-entropy alloy oxide negative electrode material according to claim 1, characterized in that: after 300 cycles, the specific capacity is maintained at 650 mAh/g.
3. A preparation method of a quinary high-entropy alloy oxide negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a multi-element high-entropy alloy strip: selecting analytically pure Ni, Cu, Fe, Co and Mn metal particles with the diameter of 1-5mm, preparing alloy strips with the thickness of 20-50 mu m by smelting and spinning according to the atomic ratio of (6-10) to (50-70), wherein the rotating speed frequency of a spinning machine is 45-50Hz, and the rotating speed is 15-18 m/s;
(2) dealloying treatment: the alloy strip prepared in the step (1) is placed in ammonium sulfate solution of (0.5-2) mol/L for dealloying treatment, the temperature is 40-80 ℃, the corrosion time is 2-8h, homogeneous-phase nano porous multi-element alloy is formed, and the Mn atomic ratio after dealloying is about 10-15 At% through EDX energy spectrum analysis;
(3) oxidation treatment: placing the metal subjected to the alloy removal in the step (2) in an air atmosphere, enabling the metal to be in contact with air to generate a spontaneous combustion phenomenon, placing a spontaneous combustion metal strip in a muffle furnace, and preserving the heat for 2-6h at the temperature of 300-650 ℃, wherein the heating rate is 10-30 ℃/min so as to improve the content of oxides;
(4) reduction treatment: placing the metal strip obtained in the step (3) in a horizontal tube furnace, reducing for 1-3h in an argon/hydrogen atmosphere at a gas rate of 200-;
(5) grinding: putting the nano porous metal oxide prepared in the step (4) into a mortar for grinding uniformly, wherein the particle size is 1-5 mu m;
(6) preparing an electrode plate: fully grinding the nano porous high-entropy alloy oxide powder prepared in the step (5) with polyvinylidene fluoride and acetylene black according to the ratio of (6-8) to (1-3) 1, dropping N-methyl pyrrolidone to form uniform slurry, preparing an electrode slice with the thickness of 250 mu m by using a coating process, placing the electrode slice in a vacuum drying box for 8-15h, and heating and drying at the temperature of 60-100 ℃;
(7) assembling the battery: and (5) placing the electrode slice prepared in the step (6) into a glove box filled with argon atmosphere to assemble the lithium ion battery.
4. The preparation method of the five-membered high-entropy alloy oxide negative electrode material according to claim 3, characterized in that: in the step (1), the metals Ni, Cu, Fe, Co and Mn are all selected as particles with the diameter of 1-3mm, the frequency of the spinning speed is 45-47Hz, and the spinning speed is 16-17 m/s.
5. The preparation method of the five-membered high-entropy alloy oxide negative electrode material according to claim 3, characterized in that: the dealloying method in the step (2) is a chemical dealloying method, the solution is a weakly acidic ammonium sulfate solution, the concentration of the solution is 0.5-1mol/L, the temperature is 50-80 ℃, and the time is 3-8 hours.
6. The preparation method of the five-membered high-entropy alloy oxide negative electrode material according to claim 3, characterized in that: in the step (3), the heating temperature in the muffle furnace is 350-650 ℃, the heat preservation time is 2-6 hours, and the heating rate is 10 ℃/min.
7. The preparation method of the five-membered high-entropy alloy oxide negative electrode material according to claim 3, characterized in that: in the step (4), reduction treatment is carried out in a tubular furnace at the temperature of 200-400 ℃, and the reduction time is 2-3 h.
8. The preparation method of the five-membered high-entropy alloy oxide negative electrode material according to claim 3, characterized in that: and (5) fully grinding the obtained nano-porous metal strip in a mortar until micron-sized powder is formed, and observing under an electron microscope to obtain particles with the diameter of 2-4 mu m.
9. The preparation method of the five-membered high-entropy alloy oxide negative electrode material according to claim 3, characterized in that: the NiCuFeCoMn oxide in the step (6): acetylene black: PVDF is uniformly mixed according to the proportion of 8:1:1 or 7:2:1 or 6:3:1, then a proper amount of NMP is dripped, after uniform size mixing, an electrode slice with the thickness of 100 mu m-200 mu m is prepared by a preparation device, and the electrode slice is placed in a vacuum drying oven for 12 hours at the temperature of 80-100 ℃.
10. Application of the quinary high-entropy alloy oxide negative electrode material prepared by the preparation method of the quinary high-entropy alloy oxide negative electrode material according to any one of claims 1 to 2 or the quinary high-entropy alloy oxide negative electrode material according to any one of claims 3 to 9 in a lithium ion battery negative electrode.
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