CN114388764B - Bean-shaped porous nitrogen-doped carbon nanotube-coated ZnTe/Co1.11Te2Composite material, preparation method and application - Google Patents
Bean-shaped porous nitrogen-doped carbon nanotube-coated ZnTe/Co1.11Te2Composite material, preparation method and application Download PDFInfo
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- 229910007709 ZnTe Inorganic materials 0.000 title claims abstract description 104
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title description 11
- 239000002071 nanotube Substances 0.000 claims abstract description 30
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 30
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000011701 zinc Substances 0.000 claims description 41
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- 229910052723 transition metal Inorganic materials 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- -1 transition metal zinc salt Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 102000020897 Formins Human genes 0.000 claims description 2
- 108091022623 Formins Proteins 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 3
- 239000006185 dispersion Substances 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 238000001000 micrograph Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000021374 legumes Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000004771 selenides Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- 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)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a leguminous porous nitrogen-doped carbon nanotube-coated ZnTe/Co 1.11Te2 composite material, a preparation method and application thereof in a lithium ion battery. The preparation method comprises the following steps: firstly, zn and Co-ZIF are grown on tellurium nanotubes (Te NT) in situ, and then a core with a leguminous structure, znTe and Co 1.11Te2 inside and one-dimensional porous nitrogen doped carbon nanotubes (PNCNT) outside is formed through high temperature heat treatment. In the high-temperature carbonization process, zn, co-ZIF and Te NT generate active substances ZnTe and Co 1.11Te2, PNCNT beneficial to electron and ion transmission is formed at the same time, and the leguminous structure can relieve the influence caused by volume expansion in the charge and discharge process. The composite material of the invention shows good electrochemical performance in lithium ion batteries.
Description
Technical Field
The invention belongs to the field of new energy materials, relates to a lithium ion battery electrode material, a preparation method and application thereof, and in particular relates to a leguminous porous nitrogen-doped carbon nanotube-coated ZnTe/Co 1.11Te2 composite material, a preparation method and application thereof.
Background
The lithium ion battery is a representative new generation energy storage device, has the advantages of high energy density, long cycle life, low self-discharge rate and the like, and is applied to the fields of portable electronic equipment, electric automobiles and the like. Graphite is a commercially used negative electrode material for lithium ion batteries, but provides a relatively low theoretical capacity (372 mAh g -1) and cannot meet the market demand for high-performance lithium ion batteries. In recent years, transition metal compounds having higher theoretical capacities have received extensive attention from researchers as novel anode materials. However, these materials have low conductivity, and a large volume change occurs during the intercalation and deintercalation of lithium ions, resulting in poor cycle performance, which hinders their wide application in practice. The effective method for solving the problem is to combine the lithium ion battery with carbon materials, develop various carbon-based transition metal compounds, regulate the strain generated in the circulation process, improve the volume effect, accelerate the ion and electron transmission and enhance the lithium storage performance.
The Metal Organic Frameworks (MOFs) and the Zeolite Imidazole Frameworks (ZIFs) are formed by connecting metal centers and organic ligands, and are novel porous materials. The preparation method has high specific surface area, rich porous structure and a large amount of carbon-containing organic ligands, and is an effective precursor and template for preparing the carbon-based transition metal compound. In the transition metal chalcogenide, the metal telluride has weaker metal bond formed by tellurium with larger atomic radius, and has obvious advantages in electrode dynamics reaction. Compared with oxides, sulfides and selenides, the metal telluride has smaller electronegativity, higher density and electronic conductivity, and potential lithium storage performance when used in lithium ion batteries. Currently, MOFs-derived transition metal tellurides are relatively few in research as anode materials for lithium ion batteries. In addition, according to the previous documents and patents, the leguminous electrode material can effectively delay structural damage caused by volume expansion/shrinkage in the cyclic charge and discharge process, so that the service life of the lithium ion battery is greatly prolonged, and carbon-based transition metal telluride with leguminous structure derived from MOFs is not reported at present, and is still a challenge.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material and a preparation method thereof, and the leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material is applied to a lithium ion battery cathode material.
The leguminous nitrogen-doped carbon nanotube-coated ZnTe/Co 1.11Te2 electrode material is obtained by growing Zn and Co-ZIF on a tellurium nanotube in situ and then performing high-temperature heat treatment. In the high-temperature heat treatment process, the tellurium nanotubes and Zn, co-ZIF generate transition metal telluride ZnTe/Co 1.11Te2, and continuous Zn loaded on the tellurium nanotubes and Co-ZIF simultaneously form the porous nitrogen-doped carbon nanotubes. The thickness of different tubular carbon layers and the content of different ZnTe/Co 1.11Te2 in the composite electrode material are regulated and controlled by changing the total molar quantity of Zn and Co-ZIF loaded on the tellurium nanotubes and the pyrolysis temperature.
The specific technical scheme for preparing the pod nitrogen-doped carbon nano tube-coated ZnTe/Co 1.11Te2 is as follows:
step (1): preparing tellurium nanotubes;
Step (2): preparing Zn, co-ZIF@Te NT;
Step (3): znTe/Co 1.11Te2 @ PNCNT was prepared.
The following is a detailed description of the above steps:
The specific preparation method of the tellurium nanotubes comprises the following steps: mixing tellurium dioxide and polyvinylpyrrolidone in ethylene glycol according to a mass ratio of 1:1-1:2, heating to 150-200 ℃ after full stirring for reaction of 10-40 min, slowly adding sodium hydroxide, maintaining the mass ratio of the sodium hydroxide to the tellurium dioxide to be 1:1-1:2, maintaining the reaction of 20-120: 120 min, performing centrifugal separation and drying treatment on the obtained product, specifically, cleaning with 200-1000 mL deionized water, filtering, placing in a drying box, and drying at 25-80 o ℃ for 6-24 hours to obtain the tellurium nanotube.
The specific preparation method of the Zn, co-ZIF@Te NT comprises the following steps: dispersing transition metal zinc salt and cobalt salt with the molar ratio of Zn to Co of 4:1 in methanol, ethanol or mixed solution of the two, simultaneously dispersing tellurium nanotubes and 2-methylimidazole in methanol, ethanol or mixed solution of the two with the same volume respectively in an ultrasonic manner, mixing the three solutions to obtain mixed solution, stirring at room temperature to react for 3h, centrifugally separating by using 200-1000 mL methanol, ethanol or mixed solution of the two, and drying in a drying box at 25-80 o ℃ for 6-24 hours to obtain a precursor Zn, co-ZIF@Te NT.
Preferably, the transition metal zinc salt is one or more of zinc chloride, zinc nitrate or zinc acetate, and the transition metal cobalt salt is one or more of cobalt chloride, cobalt nitrate or cobalt acetate; the total molar weight of the transition metal zinc salt and the cobalt salt is 1-10 mmol, the organic solvent is methanol, ethanol or a mixed solution of the two, and the volume of the organic solvent is 20-500 ml; the ratio of the total molar quantity of the transition metal zinc salt and the cobalt salt to the molar quantity of the 2-methylimidazole is 1:2-1:32, and the concentration of the tellurium nanotubes in the mixed solution is 0.5-5 mg/ml.
The specific preparation method of ZnTe/Co 1.11Te2 @ PNCNT in the step (3) comprises the following steps: putting Zn, co-ZIF@Te NT into a quartz boat, carrying out high-temperature annealing at 500-1000 ℃ for 1-5H in a mixed atmosphere of H 2/Ar or H 2/N2 with the volume percentage of H 2 being 2-10%, and carrying out natural cooling at the temperature rising rate of 1-10 ℃ for min -1 to obtain ZnTe/Co 1.11Te2 @ PNCNT.
The leguminous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material can be directly used as a lithium ion battery anode material or mixed with other anode materials.
Preferably, the other cathode materials are carbon materials such as graphite, carbon nanotubes, graphene and the like; alloy type negative electrode materials such as Si, ge, sn, sb and the like; transition metal oxides, sulfides, phosphides, and the like.
The invention has the beneficial effects that: (1) The Zn, co-ZIF and the cobalt source form transition metal telluride ZnTe/Co 1.11Te2 with the tellurium nanotubes, and the continuous and uniform Zn is loaded on the tellurium nanotubes, and the Co-ZIF forms the porous nitrogen-doped carbon nanotubes. (2) The transition metal telluride ZnTe/Co 1.11Te2 core-shell structure is filled in the official cavity of the nitrogen-doped carbon nano tube in a segmented mode, and the pod-shaped core-shell nano structure is formed. (3) The transition metal telluride ZnTe/Co 1.11Te2 has enough gaps, so that the volume expansion of the transition metal telluride in the repeated charge and discharge process can be effectively buffered, and the high cycle stability of the composite material is ensured. (4) The tubular nitrogen doped carbon nano tube improves the conductivity and the electron transmission performance of the composite material, and can effectively improve the multiplying power performance of the material.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a leguminous nitrogen-doped carbon nanotube-coated ZnTe/Co 1.11Te2 composite material according to an embodiment of the present invention;
FIG. 2 is a scanning and transmission electron microscope image of ZnTe/Co 1.11Te2 @ PNCNT-2 provided in example 1 of the present invention;
FIG. 3 is an XRD plot of ZnTe/Co 1.11Te2 @ PNCNT-2 provided in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of ZnTe/Co 1.11Te2@PNCNT-1、ZnTe/ Co1.11Te2 @ PNCNT-3 provided in examples 2 and 3 of the present invention;
FIG. 5 is a scanning electron microscope image of ZnTe/Co 1.11Te2 @ PNCNT-2-600 and ZnTe/Co 1.11Te2 @ PNCNT-2-800 provided in examples 4 and 5 of the present invention;
FIG. 6 is a cyclic voltammogram of ZnTe/Co 1.11Te2 @ PNCNT-2 provided in example 1 of the present invention;
FIG. 7 is a charge-discharge plot of ZnTe/Co 1.11Te2 @ PNCNT-2 provided in example 1 of the present invention;
FIG. 8 is a plot of the rate capability of ZnTe/Co 1.11Te2 @ PNCNT-2 provided in example 1 of the present invention;
FIG. 9 is a plot of the rate performance of ZnTe/Co 1.11Te2 @ PNCNT-1 and ZnTe/Co 1.11Te2 @ PNCNT-3 provided in examples 2 and 3 of the present invention;
FIG. 10 is a plot of the rate performance of ZnTe/Co 1.11Te2 @ PNCNT-2-600 and ZnTe/Co 1.11Te2 @ PNCNT-2-800 provided in examples 4 and 5 of the present invention;
FIG. 11 is a graph of the cycling stability of ZnTe/Co 1.11Te2 @ PNCNT-2 provided in example 1 of the present invention;
FIG. 12 is a graph of the cycling stability of ZnTe/Co 1.11Te2 @ PNCNT-1 and ZnTe/Co 1.11Te2 @ PNCNT-3 provided in examples 2 and 3 of the present invention;
FIG. 13 is a graph of the cycling stability of ZnTe/Co 1.11Te2 @ PNCNT-2-600 and ZnTe/Co 1.11Te2 @ PNCNT-2-800 provided in examples 4 and 5 of the present invention.
Detailed Description
The invention will be better illustrated by the following examples, which are given by way of illustration of the embodiments and the specific procedures of operation, but the scope of the invention is not limited to the following examples.
Example 1
The preparation method of the leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material in the embodiment comprises the following steps:
Step one, preparing tellurium nanotubes: 150 ml ethylene glycol, 1.4 g tellurium dioxide and 1.8 g polyvinylpyrrolidone are added into a 250ml round bottom flask, the temperature is raised to 200 o C for reaction of 20 min, then 0.96 g sodium hydroxide is slowly added into the flask, the clear solution is quickly blackened, reaction 30min is maintained, after cooling down, 1000 mL deionized water is used for cleaning, filtration and drying in a drying box at 60 o C for 24 hours are carried out, and then tellurium nanotubes are obtained.
Step two, preparing Zn, co-ZIF@Te NT-2: the transition metal salt (Zn (NO 3)2·6H2 O and Co (NO 3)2·6H2 O)) with the total molar quantity of 3.75mmol and the molar ratio of Zn to Co of 4:1 is ultrasonically dispersed in 50mL methanol, simultaneously 200 mg tellurium nanotubes and 2.46 g of 2-methylimidazole are respectively ultrasonically dispersed in 50mL methanol, then the three solutions are mixed, stirred at room temperature for reaction of 3h, and the precursor Zn, co-ZIF@Te NT-2 is obtained after centrifugal separation by methanol.
Step three, preparing ZnTe/Co 1.11Te2 @ PNCNT-2: and (3) carrying out high-temperature annealing on the Zn, co-ZIF@Te NT-2 at 700 o ℃ under the condition of 5% H 2 for 3H, wherein the heating rate is 2 oC min-1, and naturally cooling to obtain ZnTe/Co 1.11Te2 @ PNCNT-2.
And (3) assembling a lithium ion battery: znTe/Co 1.11Te2 @ PNCNT-2, an acetylene black conductive agent and polyvinylidene fluoride (PVDF) are mixed according to a ratio of 8:1:1 to prepare uniform slurry, the uniform slurry is coated on a copper foil current collector, the copper foil current collector is dried in vacuum for 12: 12 h and then naturally cooled and taken out, then the composite material is used as a test electrode, a metal lithium sheet is used as a counter electrode, and the button cell is assembled in an argon glove box.
Example 2
The preparation method of the leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material in the embodiment comprises the following steps:
Step one, preparing tellurium nanotubes: as in step one of example 1.
Step two, preparing Zn, co-ZIF@Te NT-1: the transition metal salt (Zn (NO 3)2·6H2 O and Co (NO 3)2·6H2 O)) with the total molar quantity of 2.5 mmol and the molar ratio of Zn to Co of 4:1 is ultrasonically dispersed in 50mL methanol, simultaneously 200 mg tellurium nanotubes and 2.46 g of 2-methylimidazole are respectively ultrasonically dispersed in 50mL methanol, then the three solutions are mixed, stirred at room temperature for reaction of 3h, and the precursor Zn, co-ZIF@Te NT-1 is obtained after centrifugal separation by methanol.
Step three, preparing ZnTe/Co 1.11Te2 @ PNCNT-1: step three in example 1.
The method for assembling the ZnTe/Co 1.11Te2 @ PNCNT-1 lithium ion battery is the same as in example 1.
Example 3
The preparation method of the leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material in the embodiment comprises the following steps:
Step one, preparing tellurium nanotubes: as in step one of example 1.
Step two, preparing Zn, co-ZIF@Te NT-3: the transition metal salt (Zn (NO 3)2·6H2 O and Co (NO 3)2·6H2 O)) with the total molar quantity of 5 mmol and the molar ratio of Zn to Co of 4:1 is ultrasonically dispersed in 50 mL methanol, simultaneously 200 mg tellurium nanotubes and 2.46 g of 2-methylimidazole are respectively ultrasonically dispersed in 50 mL methanol, then the three solutions are mixed, stirred at room temperature for reaction of 3h, and the precursor Zn, co-ZIF@Te NT-3 is obtained after centrifugal separation by methanol.
Step three, preparing ZnTe/Co 1.11Te2 @ PNCNT-3: step three in example 1.
The method for assembling the ZnTe/Co 1.11Te2 @ PNCNT-3 lithium ion battery is the same as in example 1.
Example 4
The preparation method of the leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material in the embodiment comprises the following steps:
Step one, preparing tellurium nanotubes: as in step one of example 1.
Step two, preparing Zn, co-ZIF@Te NT-2: step two in example 1.
Step three, preparing ZnTe/Co 1.11Te2 @ PNCNT-2-600: and (3) carrying out high-temperature annealing on the Zn, co-ZIF@Te NT-2 at 600 o C under the condition of 5% H 2 for 3H, wherein the heating rate is 2 oC min-1, and naturally cooling to obtain ZnTe/Co 1.11Te2 @ PNCNT-2-600.
The method for assembling ZnTe/Co 1.11Te2 @ PNCNT-2-600 lithium ion battery is the same as in example 1.
Example 5
The preparation method of the leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material in the embodiment comprises the following steps:
Step one, preparing tellurium nanotubes: as in step one of example 1.
Step two, preparing Zn, co-ZIF@Te NT-2: step two in example 1.
Step three, preparing ZnTe/Co 1.11Te2 @ PNCNT-2-800: and (3) carrying out high-temperature annealing on the Zn, co-ZIF@Te NT-2 at 800 o C under the condition of 5% H 2 for 3H, wherein the heating rate is 2 oC min-1, and naturally cooling to obtain ZnTe/Co 1.11Te2 @ PNCNT-2-800.
The method for assembling ZnTe/Co 1.11Te2 @ PNCNT-2-800 lithium ion battery is the same as in example 1.
FIG. 1 shows a flow chart of the preparation process of ZnTe/Co 1.11Te2 @ PNCNT. Firstly, zn and Co-ZIF are grown on tellurium nanotubes in situ, and then Zn, co-ZIF@Te NT is subjected to high-temperature heat treatment, so that ZnTe/Co 1.11Te2 @ PNCNT with a leguminous structure is formed.
FIG. 2 shows a scanning and transmission electron microscope image of ZnTe/Co 1.11Te2 @ PNCNT-2. The melting point of the tellurium nanotube is 452 o C, and when the high temperature heat treatment is carried out at 700 o C, the melted tellurium nanotube reacts with Zn and Co-ZIF to generate ZnTe and Co 1.11Te2, and the one-dimensional porous nitrogen-doped carbon nanotube is filled in sections. FIG. 2 demonstrates the presence of a legume structure, and the porous structure of the one-dimensional carbon nanotubes in the material can be seen from a transmission electron microscope (FIGS. 2 c-d).
The XRD pattern of ZnTe/Co 1.11Te2 @ PNCNT-2 is shown in FIG. 3, and the diffraction peaks of the material are consistent with the standard cards of ZnTe (89-3045) and Co 1.11Te2 (89-4061), indicating that the tellurium nanotubes and Zn, co-ZIF produce ZnTe and Co 1.11Te2.
FIG. 4 shows scanning electron microscope images of ZnTe/Co 1.11Te2 @ PNCNT-1 and ZnTe/Co 1.11Te2 @ PNCNT-3. When Zn, co-ZIF@Te NT-1 and Zn, co-ZIF@Te NT-3 are subjected to high temperature heat treatment at 700 o ℃, the corresponding Zn, co-ZIF in the Co-ZIF@Te NT-1 is less, the thickness of the one-dimensional carbon nano tube in the corresponding ZnTe/Co 1.11Te2 @ PNCNT-1 is thinner, and the active material of the pod-shaped structure inside the carbon nano tube can be obviously seen from the graph of fig. 4 a-b. While Zn, co-ZIF@Te NT-3 has a relatively large amount of Zn, co-ZIF, and the one-dimensional carbon nanotubes in ZnTe/Co 1.11Te2 @ PNCNT-3 are thicker than the other two materials, although the leguminous structure is still formed, the internal active material is not clearly visible (FIG. 4 c-d).
FIG. 5 shows scanning electron microscope images of ZnTe/Co 1.11Te2 @ PNCNT-2-600 and ZnTe/Co 1.11Te2 @ PNCN T-2-800. Zn, co-ZIF@Te NT-2 was heat treated at 600, 800 o C, and it can be seen from FIG. 5 that the material had a legume-like structure at both temperatures. However, with increasing temperature, znTe/Co 1.11Te2 @ PNCNT-2-800 has a pronounced porous structure and the size of the active material is decreasing gradually, since Co catalyzes the reaction of carbon material and hydrogen in a high temperature reducing atmosphere, the higher the temperature, the more pronounced the porous structure and the limited retention of the active material.
FIG. 6 shows a cyclic voltammogram of ZnTe/Co 1.11Te2 @ PNCNT-2. The voltage interval tested was 0.01-3V and the scan rate was 0.2 mV S -1. After the first cycle, the subsequent curves almost coincide, indicating that ZnTe/Co 1.11Te2 @ PNCNT-2 has good cycling stability.
FIG. 7 shows a graph of charge and discharge performance at a current density of 0.2A g -1 for ZnTe/Co 1.11Te2 @ PNCNT-2. The specific capacities of the first discharge and charge are 965.0 and 639.8 mAh g -1 respectively, and the coulombic efficiency is 66.3%. The charge and discharge curves of 4 times tend to overlap, the coulomb efficiency is gradually increased, and the lithium removal and intercalation processes of the material are gradually stabilized.
Fig. 8 shows a graph of the rate performance of ZnTe/Co 1.11Te2 @ PNCNT-2, which shows that the specific discharge capacity of the material decreases relatively slowly with increasing current density, remains stable after several cycles at each rate, returns well when returned to low rates, and is higher than the initial capacity, indicating excellent rate performance and electrochemical reversibility.
The ZnTe/Co 1.11Te2 @ PNCNT-1 and ZnTe/Co 1.11Te2 @ PNCNT-3 are shown in FIG. 9 as rate capability test charts. The porous nitrogen-doped carbon nano tube in ZnTe/Co 1.11Te2 @ PNCNT-1 is thinnest, the sizes of ZnTe and Co 1.11Te2 are minimum, the content is minimum, the specific capacity is minimum, and the rate performance is worst. The ZnTe/Co 1.11Te2 @ PNCNT-3 has higher content of ZnTe and Co 1.11Te2, can provide more specific capacity, but the porous nitrogen-doped carbon nano tube is thickest, is unfavorable for the intercalation and deintercalation of lithium ions, and therefore, has a certain gap compared with the multiplying power performance of ZnTe/Co 1.11Te2 @ PNCNT-2.
FIG. 10 shows graphs of the rate performance tests of ZnTe/Co 1.11Te2 @ PNCNT-2-600 and ZnTe/Co 1.11Te2 @ PNCN T-2-800. Along with the rise of temperature, the more obvious the porous structure of ZnTe/Co 1.11Te2 @ PNCNT series material is, which is beneficial to the improvement of the rate performance. However, when the temperature is increased to 800 o ℃, the transition metal telluride gradually volatilizes thermally, the ZnTe and Co 1.11Te2 contents are low, the specific capacity provided under each current density is not high, and meanwhile, the continuity and stability of the one-dimensional carbon nano tube are reduced due to the obvious porous structure in the ZnTe/Co 1.11Te2 @ PNCNT-2-800, so that the active substance is lost in the charging and discharging process, and the rate performance is reduced.
FIG. 11 shows a graph of ZnTe/Co 1.11Te2 @ PNCNT-2 cycle stability, which was activated 3 cycles at a current density of 0.2A g -1, followed by a cycle of about 500 cycles at a current density of 1A g -1, and which was shown to have excellent cycle stability, with specific discharge capacity remaining at 607.6 mA h g -1.
FIG. 12 shows a graph of the cyclic stability test of ZnTe/Co 1.11Te2 @ PNCNT-1 and ZnTe/Co 1.11Te2 @ PNCNT-3. ZnTe/Co 1.11Te2 @ PNCNT-1 decays to 241.9 mA h g -1.ZnTe/Co1.11Te2 @ PNCNT-3 after 200 cycles and to 404.8 mA h g -1 after 200 cycles. This is probably due to the fact that the one-dimensional carbon nanotubes in ZnTe/Co 1.11Te2 @ PNCNT-1 are thinner, and the structure of the one-dimensional carbon nanotubes is damaged due to the intercalation and deintercalation of lithium ions in the long-time charge and discharge process, so that the active substances are lost, and the cycle performance is reduced. The one-dimensional carbon nano tube in ZnTe/Co 1.11Te2 @ PNCNT-3 is thicker, active substances cannot be fully utilized in the charge and discharge process, and the stability is gradually reduced.
FIG. 13 shows a graph of the cyclic stability test of ZnTe/Co 1.11Te2 @ PNCNT-2-600 and ZnTe/Co 1.11Te2 @ PNCN T-2-800. ZnTe/Co 1.11Te2 @ PNCNT-2-600 decays to a specific capacity of 417.2 mA h g -1.ZnTe/Co1.11Te2 @ PNCNT-2-800 after 200 cycles and to a specific capacity of 223.4 mA h g -1 after 200 cycles. In contrast, znTe/Co 1.11Te2 @ PNCNT-2 obtained by high temperature annealing at 700 o C shows optimal cycle stability, probably because the conductivity of the one-dimensional carbon nanotubes is enhanced with the increase of temperature, the more obvious the porous structure is, which is favorable for the intercalation and deintercalation of lithium ions, but when the temperature reaches 800 o C, the one-dimensional carbon nanotubes are almost broken, and active substances cannot be well protected in the long-time charge and discharge process, resulting in the reduction of stability.
According to the technical scheme and the implementation method, the leguminous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material prepared by the invention can be used as a lithium ion battery anode material to show excellent electrochemical performance.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. The preparation method of the leguminous porous nitrogen-doped carbon nanotube-coated ZnTe/Co 1.11Te2 composite material is characterized by comprising the following steps of:
Step (1): preparing Te nano tube Te NT;
Step (2): preparing a precursor Zn, co-ZIF@Te NT;
Step (3): preparing a bean-shaped porous nitrogen-doped carbon nanotube-coated ZnTe/Co 1.11Te2 composite material ZnTe/Co 1.11Te2 @ PNCNT;
The tellurium nanotubes Te NT of the step (1) are prepared by the following steps: mixing tellurium dioxide and polyvinylpyrrolidone in ethylene glycol according to the mass ratio of 1:1-1:2, heating to 150-200 ℃ for reaction for 10-40min after full stirring, adding sodium hydroxide, maintaining the mass ratio of the sodium hydroxide to the tellurium dioxide to be 1:1-1:2, maintaining the reaction for 20-120 min, and carrying out centrifugal separation and drying treatment on the obtained product to obtain tellurium nanotubes;
The precursor Zn, co-ZIF@Te NT of the step (2) is prepared by the following steps: ultrasonically dispersing a transition metal zinc salt and a cobalt salt in a molar ratio of 4:1 in an organic solvent to obtain a dispersion liquid A, respectively ultrasonically dispersing a tellurium nanotube and 2-methylimidazole in the organic solvent to obtain dispersion liquids B and C, mixing the three solutions to obtain a mixed liquid, stirring at room temperature to react for 3-12 h, centrifugally separating by using the organic solvent, and drying in an oven to obtain a precursor Zn, co-ZIF@Te NT; the ratio of the total molar quantity of the transition metal zinc salt and the cobalt salt to the molar quantity of the 2-methylimidazole is 1:8;
The leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material ZnTe/Co 1.11Te2 @ PNCNT in the step (3) is prepared by the following steps: annealing precursor Zn, co-ZIF@Te NT at 700 ℃ under a reducing atmosphere for 1-5 h, wherein the heating rate is 1-10 ℃ for min -1, and naturally cooling to obtain ZnTe/Co 1.11Te2 @ PNCNT;
The leguminous porous nitrogen-doped carbon nano tube coated ZnTe/Co 1.11Te2 composite material has the following structure: the transition metal telluride ZnTe/Co 1.11Te2 is filled in the tube cavity of the porous nitrogen-doped carbon nano tube in a segmented manner to form a bean-shaped core-shell structure; the length of the composite material is 2-20 mu m, the diameter is 50-300 nm, and the carbon layer wrapping thickness is 5-20 nm.
2. The preparation method of the leguminous porous nitrogen-doped carbon nanotube-coated ZnTe/Co 1.11Te2 composite material according to claim 1, wherein the transition metal zinc salt is one or more of zinc chloride, zinc nitrate and zinc acetate, and the transition metal cobalt salt is one or more of cobalt chloride, cobalt nitrate and cobalt acetate; the total molar weight of the transition metal zinc salt and the cobalt salt is 1-10 mmol, the organic solvent is methanol, ethanol or a mixed solution of the two, and the volume of the organic solvent is 20-500 ml; the concentration of the tellurium nanotubes in the mixed solution is 0.5-5 mg/ml.
3. The method for preparing the leguminous porous nitrogen-doped carbon nanotube-coated ZnTe/Co 1.11Te2 composite material according to claim 1, wherein the reducing atmosphere is H 2/Ar or H 2/N2, and the volume percentage of H 2 is 2-10%.
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