CN113097478A - Double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery cathode material and preparation method thereof - Google Patents
Double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 20
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- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010406 cathode material Substances 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 15
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- 239000000835 fiber Substances 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000010041 electrostatic spinning Methods 0.000 claims description 9
- 239000002071 nanotube Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 discloses a double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery cathode material and a preparation method thereof2Two types of nanoparticles. The preparation method has the advantages of simple method, low cost, higher product yield and uniform structure, and the obtained product has larger specific surface area and better electrochemical performance.
Description
Technical Field
The invention relates to a double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery cathode material and a preparation method thereof, belonging to the field of electrochemical power sources.
Background
With the increase of global economy, energy problems have become the focus of global attention, and traditional fossil energy sources mainly comprise coal, carbon, petroleum and the like, the storage amount is limited, the utilization rate is low, so that the development of efficient and stable lithium secondary batteries becomes the current affairIt is urgent. Because the Lithium Ion Battery (LIB) has the superior performances of high energy density, long cycle life, no memory effect, environmental friendliness and the like, the lithium ion battery is widely applied to the fields of portable electronic products, power or energy storage batteries and the like. At present, the commercial lithium ion battery graphite negative electrode material has low specific capacity and poor rate capability, and the theoretical specific capacity of the commercial carbon is 372mAh g-1And the potential safety hazard is large, so that the development of a novel cathode material becomes a hotspot in the research field at present. Typically in Zn or Co based materials (e.g. ZnSe and CoSe)2) Representative lithium alloy negative electrode materials, e.g. hollow materials (ZnSe and CoSe)2Hollow spheres), and carbon-based composites (e.g., carbon-coated ZnSe and CoSe)2) Have been studied extensively. However, these anode materials undergo severe pulverization during charge and discharge, have a large volume expansion and a Solid Electrolyte Interface (SEI) layer continuously formed, and thus, generally have very limited cycle capacity.
In view of the above, it is necessary to find a simple and efficient preparation method to synthesize a nanomaterial with a specific structure and ensure that the nanomaterial has a high yield and good performance, so as to meet the application of the nanomaterial as a negative electrode material of a lithium ion battery.
Disclosure of Invention
In view of the above, the present invention is directed to providing ZnSe @ CoSe2The technical problem to be solved is to enable the preparation method to have the advantages of being simple and low in cost, and enable the obtained product to be high in yield, uniform in structure and good in electrochemical performance.
The invention solves the technical problem and adopts the following technical scheme:
a preparation method of a double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery negative electrode material comprises the following steps:
step 2, in an oven at 60-65 ℃, adding the Zn2+Soaking the polyacrylonitrile fiber film in an ethanol solution of 2-methylimidazole, taking out the polyacrylonitrile fiber film, and washing the polyacrylonitrile fiber film with absolute ethanol to obtain a polyacrylonitrile @ ZIF-8 fiber film;
step 3, in an oven at the temperature of 60-65 ℃, putting the polyacrylonitrile @ ZIF-8 fiber film into a methanol solution containing cobalt nitrate hexahydrate and 2-methylimidazole for soaking, taking out, washing with methanol, and drying in vacuum to obtain the polyacrylonitrile @ ZIF-8@ ZIF-67 fiber film;
step 4, soaking the polyacrylonitrile @ ZIF-8@ ZIF-67 fiber film in N, N-dimethylformamide to etch away polyacrylonitrile, and then carrying out centrifugal separation and freeze drying to obtain a ZIF-8@ ZIF-67 nano tube;
step 5, mixing the ZIF-8@ ZIF-67 nano tube with selenium powder, transferring the mixture into Nabo heat, and calcining the mixture in an inert atmosphere to obtain ZnSe and CoSe serving as negative electrode materials of the lithium ion battery2Double nanoparticle embedded nitrogen doped porous carbon nanotubes.
Preferably, in the step 1, the dosage ratio of the zinc acetate dihydrate, the polyacrylonitrile and the N, N-dimethylformamide solution is 0.8-0.9 g: 0.7-0.8 g: 9-10 mL.
Preferably, in the step 1, the rotation speed of the magnetic stirring is 350-450 rpm.
Preferably, in the step 1, the electrostatic spinning voltage is 10-12 KV, the flow rate is 0.1-0.5 mL/h, and the distance from the needle head to the receiving screen is 15-20 cm.
Preferably, in the step 2, the concentration of the ethanol solution of the 2-methylimidazole is 0.04-0.1 g/mL, and the soaking time is 2-4 h.
Preferably, in the step 3, the dosage ratio of the cobalt nitrate hexahydrate, the 2-methylimidazole and the methanol is 0.6-0.8 g: 1.0-1.5 g: 100mL, soaking time of 2-5 h, vacuum drying temperature of 60-65 ℃ and time of 12-24 h.
Preferably, in the step 4, the etching time is 5-10 min, and the rotation speed of centrifugal separation is 5000-8000 rpm.
Preferably, in the step 5, the inert atmosphere is Ar gas, the calcining temperature is 600-650 ℃, and the calcining time is 3-4 h.
Preferably, in step 5, the temperature increase rate during the calcination is 3 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides ZnSe @ CoSe2The preparation method of the double-nanoparticle embedded nitrogen-doped porous carbon nanotube has the advantages of simple method, low cost, high product yield and uniform structure, and compared with the traditional porous carbon nanomaterial derived from nanoparticle calcination, the product obtained by the method has larger specific surface area and better electrochemical performance.
2. The product obtained by the invention is a lithium ion battery cathode material capable of being charged and discharged, and effectively solves the problems of ZnSe and CoSe2The problems of poor stability and poor conductivity of the nano material in the charging and discharging processes of the battery are solved, and the cycle performance and the rate performance of the battery are improved.
Drawings
FIG. 1 shows Zn content obtained in step 1 of example 12+Scanning electron microscope images of the polyacrylonitrile fiber film;
FIG. 2 is a scanning electron microscope image of polyacrylonitrile @ ZIF-8 fiber film obtained in step 2 of example 1;
FIG. 3 is a scanning electron microscope image of polyacrylonitrile @ ZIF-8@ ZIF-67 fiber film obtained in step 3 of example 1;
FIG. 4 is a scanning electron micrograph of ZIF-8@ ZIF-67 nanotubes obtained in step 4 of example 1;
FIG. 5 is a TEM image of the ZIF-8@ ZIF-67 nanotubes obtained in step 4 of example 1;
FIG. 6 shows the target product ZnSe @ CoSe obtained in example 12A transmission electron microscope image of the double-nanoparticle embedded nitrogen-doped porous carbon nanotube;
FIG. 7 is a graph of the cycle performance of the target product obtained in example 1 as a negative electrode material of a lithium ion battery;
FIG. 8 is a graph of rate capability of the target product obtained in example 1 as a lithium ion battery negative electrode material.
Detailed Description
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples. The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified; the battery performance tests in the following examples all used the LAND test system.
The electrospinning direct current high voltage power source used in the following examples was provided by EST705 high precision high stability electrostatic high voltage generator (0-60KV) produced by beijing, the double injection pump used in the experiment was KI-602 injection pump produced by beijing kojiu mechanical engineering ltd, the centrifuge was Anke TGL-10B produced by shanghai pavilion scientific instruments factory, the magnetic stirrer was RT-10 multi-point magnetic stirrer produced by guangzhou instrumental laboratory technology ltd, the calciner was OTF-1200X produced by mixcrystal materials technology ltd, the scanning electron microscope was Zeiss ra sup40 produced by germany, and the transmission electron microscope was JEOL-F2010 produced by japan. The drugs used in the following examples were purchased and used without any treatment.
Example 1
This example prepares ZnSe @ CoSe as follows2Double nanoparticle embedded nitrogen doped porous carbon nanotubes:
and transferring the electrostatic spinning solution into a 10mL injector for electrostatic spinning, wherein the flow rate is set to be 0.3mL/h, the high-voltage direct current voltage is set to be 11KV, and the distance from the receiving screen to the needle head is set to be 15 cm. Can be obtained on a receiving screenZn2+The polyacrylonitrile fiber is stripped after continuous spinning for 3 hours to obtain the fiber containing Zn2+The polyacrylonitrile fiber film.
Step 2, weighing 3.25g of 2-methylimidazole, dissolving in 50mL of ethanol, and then putting the solution containing Zn in an oven at 60 DEG C2+The polyacrylonitrile fiber film is placed into an ethanol solution of 2-methylimidazole for 3 hours to be soaked, and the polyacrylonitrile fiber film is taken out and washed by absolute ethyl alcohol to obtain the polyacrylonitrile @ ZIF-8 fiber film.
And 3, weighing 0.75g of cobalt nitrate hexahydrate and 1.125g of 2-methylimidazole, dissolving in 100mL of methanol, then putting the polyacrylonitrile @ ZIF-8 fiber film into a methanol solution containing the cobalt nitrate hexahydrate and the 2-methylimidazole in a 60-DEG C oven, soaking for 5 hours, taking out, washing with the methanol, and drying in a 60-DEG C vacuum drying oven for 24 hours to obtain the polyacrylonitrile @ ZIF-8@ ZIF-67 fiber film.
And 4, soaking the polyacrylonitrile @ ZIF-8@ ZIF-67 fiber film in N, N-dimethylformamide to etch away the polyacrylonitrile, and then carrying out centrifugal separation and freeze drying at the rotating speed of 6000rpm to obtain the ZIF-8@ ZIF-67 nano tube.
Step 5, mixing the ZIF-8@ ZIF-67 nano tube and selenium powder according to the mass ratio of 1:1.5, transferring the mixture into Nabo heat, heating the mixture to 650 ℃ at the heating rate of 3 ℃/min under the Ar gas atmosphere, and carrying out heat preservation and calcination for 3h to obtain ZnSe and CoSe serving as negative electrode materials of the lithium ion battery2Double nanoparticle embedded nitrogen doped porous carbon nanotubes.
FIG. 1 shows Zn content obtained in step 1 of this example2+The scanning electron microscope image of the polyacrylonitrile fiber film shows that the fiber diameter is about 200nm, and the surface of the fiber is relatively smooth.
FIG. 2 is a scanning electron microscope image of polyacrylonitrile @ ZIF-8 fiber film obtained in step 2 of this example, which shows that ZIF-8 particles grow on the surface of the fiber.
FIG. 3 is a scanning electron microscope image of the polyacrylonitrile @ ZIF-8@ ZIF-67 fiber film obtained in step 3 of this example, which shows that ZIF-8@ ZIF-67 particles uniformly grow on the fiber surface and the fiber diameter is about 300 nm.
Fig. 4 and 5 are a scanning electron microscope image and a transmission electron microscope image of the ZIF-8@ ZIF-67 nanotube obtained in step 4 of this embodiment, respectively, and it can be seen that the etched fiber is in a tubular structure, and the structure remains good without collapse and has a good morphology.
FIG. 6 shows the target product ZnSe @ CoSe obtained in this example2The transmission electron microscope image of the nitrogen-doped porous carbon nanotube embedded with the double nanoparticles shows that the shape of the fiber after calcination is well maintained. At the same time, because of ZnSe @ CoSe2The nano particles are positioned on the surface of the carbon nano tube, so that the specific surface area of the material is greatly increased, in addition, due to the three-dimensional porous and hollow structure of the material, the internal contact area between the electrode material and the electrolyte is increased, meanwhile, the material can bear larger volume change, and the stability of the material in the circulating process is greatly increased.
The prepared ZnSe @ CoSe2The nitrogen-doped porous carbon nanotube embedded with the double nanoparticles, Keqin black and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 8: 1:1, adding N-methyl pyrrolidone (NMP), grinding into uniform slurry, uniformly coating on a copper foil, and drying in a vacuum oven at 60 ℃ to obtain the working electrode. The battery is assembled according to the sequence of the negative electrode shell, the lithium sheet, the diaphragm, the electrolyte, the negative electrode, the gasket, the elastic sheet and the positive electrode shell, the lithium battery is assembled in the glove box, and then the cycle performance test and the multiplying power performance test are carried out in the LAND test system.
FIG. 7 shows ZnSe @ CoSe obtained in this example2The cycle performance graph of the double-nanoparticle embedded nitrogen-doped porous carbon nanotube as the lithium ion battery negative electrode material shows that: at a current density of 1.0A g-1When the material is used as the negative electrode of the lithium ion battery, the first-turn specific discharge capacity is 1212mA h g-1The coulombic efficiency of the first turn is 53.58 percent, and the first turn still keeps 866mA h g after 500 cycles-1The reversible specific capacity shows that the material obtained in the embodiment has good cycle performance when being used as the negative electrode of the lithium ion battery.
FIG. 8 shows ZnSe @ CoSe obtained in this example2The multiplying power performance graph of the double-nanoparticle embedded nitrogen-doped porous carbon nanotube as the lithium ion battery cathode material shows that: when the current density is respectively 0.1, 0.5, 1.0, 2.0,3.0、5.0A g-1When the specific capacity of the battery is 849.4, 790.1, 756.8, 692.8, 626.6 and 575.7mA h g-1When the current density returns to 0.1A g-1When the specific capacity is high, the reversible specific capacity is 835.3mA h g-1And exhibits high reversibility close to the specific capacity in the initial state.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery negative electrode material is characterized by comprising the following steps:
step 1, adding zinc acetate dihydrate into N, N-dimethylformamide, magnetically stirring until the zinc acetate dihydrate is dissolved, adding polyacrylonitrile, and continuously magnetically stirring until the polyacrylonitrile is dissolved to obtain an electrostatic spinning solution; then collecting Zn by using a copper net through an electrostatic spinning technology2+Is stripped to obtain Zn-containing polyacrylonitrile fiber2+A polyacrylonitrile fiber film of (a);
step 2, in an oven at 60-65 ℃, adding the Zn2+Soaking the polyacrylonitrile fiber film in an ethanol solution of 2-methylimidazole, taking out the polyacrylonitrile fiber film, and washing the polyacrylonitrile fiber film with absolute ethanol to obtain a polyacrylonitrile @ ZIF-8 fiber film;
step 3, in an oven at the temperature of 60-65 ℃, putting the polyacrylonitrile @ ZIF-8 fiber film into a methanol solution containing cobalt nitrate hexahydrate and 2-methylimidazole for soaking, taking out, washing with methanol, and drying in vacuum to obtain the polyacrylonitrile @ ZIF-8@ ZIF-67 fiber film;
step 4, soaking the polyacrylonitrile @ ZIF-8@ ZIF-67 fiber film in N, N-dimethylformamide to etch away polyacrylonitrile, and then carrying out centrifugal separation and freeze drying to obtain a ZIF-8@ ZIF-67 nano tube;
step 5, mixing the ZIF-8@ ZIF-67 nano tube with selenium powder, transferring the mixture into a Nabo heat, and calcining the mixture in an inert atmosphere to obtain the composite materialZnSe and CoSe used as negative electrode material of lithium ion battery2Double nanoparticle embedded nitrogen doped porous carbon nanotubes.
2. The production method according to claim 1: the method is characterized in that: in the step 1, the dosage ratio of zinc acetate dihydrate, polyacrylonitrile and N, N-dimethylformamide solution is 0.8-0.9 g: 0.7-0.8 g: 9-10 mL.
3. The method of claim 1, wherein: in the step 1, the rotating speed of the magnetic stirring is 350-450 rpm.
4. The method of claim 1, wherein: in the step 1, the voltage of the electrostatic spinning is 10-12 KV, the flow rate is 0.1-0.5 mL/h, and the distance from the needle head to the receiving screen is 15-20 cm.
5. The method of claim 1, wherein: in the step 2, the concentration of the ethanol solution of the 2-methylimidazole is 0.04-0.1 g/mL, and the soaking time is 2-4 h.
6. The method of claim 1, wherein: in the step 3, the dosage ratio of the cobalt nitrate hexahydrate, the 2-methylimidazole and the methanol is 0.6-0.8 g: 1.0-1.5 g: 100mL, soaking time of 2-5 h, vacuum drying temperature of 60-65 ℃ and time of 12-24 h.
7. The method of claim 1, wherein: in the step 4, the etching time is 5-10 min, and the rotating speed of centrifugal separation is 5000-8000 rpm.
8. The method of claim 1, wherein: in the step 5, the inert atmosphere is Ar gas, the calcining temperature is 600-650 ℃, and the calcining time is 3-4 h.
9. The method of claim 8, wherein: in step 5, the temperature rise rate in the calcination process is 3 ℃/min.
10. The double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery negative electrode material obtained by the preparation method of any one of claims 1-9.
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