CN113991114A - Zn-doped Ni-based/carbon nanotube composite material and preparation method thereof - Google Patents
Zn-doped Ni-based/carbon nanotube composite 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 54
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 238000012360 testing method Methods 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000005674 electromagnetic induction Effects 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 claims 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 claims 1
- 230000037303 wrinkles Effects 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a Zn-doped Ni-based/carbon nanotube composite material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing a zinc source, a nickel source and a carbon source according to the mass ratio of zinc, nickel and carbon atoms of 1 (5-20) to (20-50), and fully grinding and dispersing to obtain a mixture A; (2) putting the mixture A into a high-temperature tube furnace, introducing inert gas, heating from room temperature to 150-; (3) and grinding the product B, then packaging the product B in a test tube filled with inert gas through a sealed glove box, placing the test tube packaged with the product B in an electromagnetic induction heater, heating to 400-700 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material. The stability and the conductivity of the interior of the carbon nano tube are improved, and the multiplying power and the cycle performance of the battery can be improved when the composite material is applied to a battery electrode material.
Description
Technical Field
The invention relates to preparation of a carbon nano tube composite material, in particular to a Zn-doped Ni-based/carbon nano tube composite material and a preparation method thereof.
Background
Carbon materials have the advantages of high conductivity, low cost, and the like, and are widely used in various energy fields including lithium batteries. The carbon nano tube is a common carbon material in carbonaceous materials, has a good graphitized structure and has excellent conductivity. More importantly, sodium and potassium ions can be intercalated into the graphite layer, and as lithium ions can have a larger specific capacity, a low operating voltage plateau and a higher initial coulombic efficiency, all of which contribute to improved battery performance. However, most carbon materials are nonpolar substances with porous carbon having an open pore structure and inactive chemical properties, which cannot effectively inhibit the loss of sodium and potassium ions in a long-term charge-discharge cycle and are easy to have a shuttle effect.
Disclosure of Invention
The invention aims to provide a Zn-doped Ni-based/carbon nanotube composite material and a preparation method thereof, wherein zinc and nickel catalyze the growth of carbon nanotubes, the stability and the conductivity in the carbon nanotubes are improved, and the composite material can improve the rate capability and the cycle performance of a battery when applied to a battery electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of Zn-doped Ni-based/carbon nanotube composite material comprises the following steps:
(1) mixing a zinc source, a nickel source and a carbon source according to the mass ratio of zinc, nickel and carbon atoms, and fully grinding and dispersing to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing inert gas, heating from room temperature to 150-;
(3) and grinding the product B, then packaging the product B in a test tube filled with inert gas through a sealed glove box, placing the test tube packaged with the product B in an electromagnetic induction heater, heating to 400-700 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material.
Further, the zinc source in the step (1) is zinc acetate or zinc sulfate.
Further, the nickel source in the step (1) is analytically pure nickel sulfate, nickel nitrate, nickel chloride, nickel sulfamate, nickel bromide or nickel hydroxide.
Further, the carbon source in the step (1) is urea, melamine or glucose.
Further, the grinding and dispersion in the step (1) adopts a high-speed centrifugal dispersion tank with the rotation speed of 1000-.
Further, the inert gas in the step (2) and the step (3) is argon or nitrogen.
A Zn-doped Ni-based/carbon nanotube composite material is a carbon nanotube structure with folds on the surface, and the diameter of a carbon tube is 200 nm.
The invention has the following beneficial effects:
by controlling the process conditions in the reaction process and matching with the transition metal zinc and nickel alloy to catalyze the growth of the carbon nano tube, the carbon nano tube has better electronic transmission path and mechanical strength, the defects of the carbon nano tube are increased, the structure is changed due to the interaction of the exposed key positions among the defects, more reaction sites are provided for the collapsed tube wall in the process of embedding sodium and potassium ions, the loss of the sodium and potassium ions is effectively inhibited in the long-range charge-discharge cycle, the shuttle effect is not easy to occur, the conductivity and internal stability of the carbon nano tube are improved, and in addition, the carbon nano tube has a highly graphitized structure, so that the problem of volume expansion in the charge-discharge reaction process can be effectively inhibited, and the battery structure is more stable. Therefore, the zinc-nickel alloy/carbon nano tube prepared by the method improves the stability and the conductivity of the carbon nano tube in the charging and discharging process, and can improve the multiplying power and the cycle performance of a battery when being applied to a battery electrode material.
Drawings
FIG. 1: an XRD (X-ray diffraction) pattern of the Zn-doped Ni-based/carbon nanotube composite material prepared in the embodiment 1;
FIG. 2: a TEM image of the Zn-doped Ni-based/carbon nanotube composite material prepared in example 1;
FIG. 3: and (3) a multiplying power performance diagram of the sodium ion battery assembled by using the electrode slice modified by the Zn-doped Ni-based/carbon nano tube composite material.
Detailed Description
The following examples are given to illustrate the present invention in further detail, but are not intended to limit the scope of the present invention.
Example 1
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 5: 20, putting zinc acetate, nickel nitrate and melamine into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 1000r/min for 20min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing argon of 200sccm, heating from room temperature to 150 ℃ at the heating rate of 10 ℃/min, preserving the heat for 2 hours, and taking out the mixture after the temperature is reduced to the room temperature to obtain a product B;
(3) and grinding the product B, then packaging the product B in a test tube filled with argon through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 700 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material.
Fig. 1 is an XRD pattern of the Zn-doped Ni-based/carbon nanotube composite material prepared in example 1, in which a diffraction peak at 26 ° is a carbon peak and diffraction peaks at 44 ° and 52 ° are zinc and nickel peaks.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the Zn-doped Ni-based/carbon nanotube composite material prepared in example 1, from which it can be seen that the carbon nanotube has a complete morphology and a size of about 200nm, and a large number of folds exist on the surface of the carbon nanotube, increasing the specific surface area, facilitating the reaction to proceed fully, and providing more active sites.
Example 2
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 6: 25 putting zinc acetate, nickel sulfate and urea into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 1500r/min for 15min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing argon of 200sccm, heating from room temperature to 200 ℃ at the heating rate of 20 ℃/min, preserving the heat for 1h, and taking out the mixture after the temperature is reduced to the room temperature to obtain a product B;
(3) and grinding the product B, then packaging the product B in a test tube filled with argon through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 500 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material.
Example 3
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 20: 50, putting zinc sulfate, nickel chloride and glucose into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 2000r/min for 5min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing nitrogen of 200sccm, heating from room temperature to 250 ℃ at the heating rate of 25 ℃/min, preserving heat for 0.5h, and taking out after the temperature is reduced to room temperature to obtain a product B;
(3) and grinding the product B, then packaging the product B in a test tube filled with nitrogen through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 600 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material.
Example 4
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 10: 30 putting zinc sulfate, nickel sulfamate and urea into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 1800r/min for 10min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing argon of 200sccm, heating to 150 ℃ at the heating rate of 15 ℃/min, preserving heat for 2 hours, and taking out when the temperature is reduced to room temperature to obtain a product B;
(3) and grinding the product B, then packaging the product B in a test tube filled with argon through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 400 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material.
Example 5
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 9: 27 putting zinc sulfate, nickel bromide and melamine into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 2000r/min for 10min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing nitrogen of 200sccm, heating from room temperature to 200 ℃ at the heating rate of 20 ℃/min, preserving heat for 1.5h, and taking out after the temperature is reduced to room temperature to obtain a product B;
(3) and grinding the product B, then packaging the product B in a test tube filled with nitrogen through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 400 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material.
Example 6
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 15: 40 putting zinc acetate, nickel hydroxide and glucose into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 1000r/min for 20min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing nitrogen of 200sccm, heating from room temperature to 150 ℃ at the heating rate of 30 ℃/min, preserving the heat for 2 hours, and taking out the mixture after the temperature is reduced to the room temperature to obtain a product B;
(3) and grinding the product B, then packaging the product B in a test tube filled with nitrogen through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 550 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material.
Assembling and testing the sodium ion battery:
the method comprises the steps of mixing and grinding ferric cyanamide (negative electrode material), Zn-doped Ni-based/carbon nanotube composite material and PVDF (adhesive) according to the mass ratio of 8:1:1 uniformly to prepare slurry, uniformly coating the slurry on copper foil by using a film coating device, drying for 12 hours in a vacuum drying oven at 80 ℃ to prepare electrode plates, assembling the electrode plates into the sodium ion battery, and adopting NaClO4+ EC ester electrolyte as electrolyte.
The binder used in the battery assembly of the invention can also be selected from hydroxymethyl cellulose (CMC), polyacrylic acid (PAA) or a mixture prepared by hydroxymethyl cellulose (CMC) and polyacrylic acid (PAA) in any proportion
FIG. 3 is a rate performance diagram of the assembled sodium-ion battery, which can respectively maintain high specific capacities of 711.8, 654.3, 546.2, 402.3, 268.1 and 146.9 under current densities of 0.1, 0.2, 0.5, 1, 2 and 5A/g, and in addition, the battery still has a high specific capacity of 644mAh/g under the condition that the test condition returns to 0.1A/g after the rate test, thereby improving the electrochemical performance of the electrode material.
Claims (7)
1. A preparation method of Zn-doped Ni-based/carbon nanotube composite material is characterized by comprising the following steps:
(1) mixing a zinc source, a nickel source and a carbon source according to the mass ratio of zinc, nickel and carbon atoms of 1 (5-20) to (20-50), and fully grinding and dispersing to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing inert gas, heating from room temperature to 150-;
(3) and grinding the product B, then packaging the product B in a test tube filled with inert gas through a sealed glove box, placing the test tube packaged with the product B in an electromagnetic induction heater, heating to 400-700 ℃, stopping heating, and collecting after natural cooling to obtain the Zn-doped Ni-based/carbon nano tube composite material.
2. The method of preparing a Zn-doped Ni-based/carbon nanotube composite material according to claim 1, wherein the zinc source of the step (1) is zinc acetate or zinc sulfate.
3. The method of claim 1, wherein the nickel source in step (1) is analytically pure nickel sulfate, nickel nitrate, nickel chloride, nickel sulfamate, nickel bromide or nickel oxyhydroxide.
4. The method for preparing Zn-doped Ni-based/carbon nanotube composite material according to claim 1, wherein the carbon source of step (1) is urea, melamine or glucose.
5. The method as claimed in claim 1, wherein the step (1) of grinding and dispersing is performed by a high-speed centrifugal dispersion tank with a rotation speed of 1000-2000r/min for 5-20 min.
6. The method of preparing a Zn-doped Ni-based/carbon nanotube composite material according to claim 1, wherein the inert gas of the step (2) and the step (3) is argon or nitrogen.
7. The Zn-doped Ni-based/carbon nanotube composite material prepared by the method of claim 1, wherein the Zn-doped Ni-based/carbon nanotube composite material is a carbon nanotube structure with wrinkles on the surface, and the diameter of the carbon nanotube is 200 nm.
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| CN115036495A (en) * | 2022-07-29 | 2022-09-09 | 赣州市瑞富特科技有限公司 | Porous nitrogen-doped carbon nanotube negative electrode material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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