CN115403031B - Modified nitrogen-doped carbon nanotube and preparation method and application thereof - Google Patents
Modified nitrogen-doped carbon nanotube and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 83
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 57
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 23
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 19
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 26
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 28
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052700 potassium Inorganic materials 0.000 abstract description 12
- 239000011591 potassium Substances 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004807 desolvation Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- 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
-
- 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 modified nitrogen-doped carbon nanotube and a preparation method and application thereof, belonging to the field of potassium ion battery materials. Firstly, synthesizing a polypyrrole tube by a soft template method, preparing a nitrogen-doped carbon nano tube by high-temperature carbonization, then obtaining a nitrogen-doped carbon nano tube-molybdate/polyacrylonitrile composite material by liquid phase mixing, cross-linking and cyclizing polyacrylonitrile to be solid by low-temperature oxidation treatment, and finally preparing the modified nitrogen-doped carbon nano tube coated by a sulfur-oxidized polyacrylonitrile/molybdenum disulfide composite film by a high-temperature gas-phase vulcanization method. The method is simple to operate, high in yield, clean and environment-friendly; the outer coating layer of the modified nitrogen-doped carbon nanotube is a sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite film, plays a role in isolating electrolyte, prevents electrons from overflowing and desolvation, and greatly improves the first coulomb efficiency and the cycle performance of the battery; the inside is nitrogen doped carbon nano tube, and the hollow structure in the tube can relieve the volume expansion of potassium storage.
Description
Technical Field
The invention belongs to the field of potassium ion battery materials, and particularly relates to a modified nitrogen-doped carbon nanotube, and a preparation method and application thereof.
Background
In recent years, lithium ion batteries have been widely used in portable electronic devices due to advantages such as cleanliness, environmental protection, safety, and the like. However, because of the lack and uneven distribution of lithium resources in the crust of the earth, there is an urgent need to develop a new energy storage device. Potassium and lithium have similar electrochemical properties and potassium is abundant in the crust, which makes potassium ion batteries a potential alternative to lithium ion batteries.
Hard carbon is a promising cathode material for potassium ion batteries, and is attracting great attention from domestic researchers. Although hard carbon can exert good battery capacity, the hard carbon ratio table is generally larger, so that side reactions of the battery in the first discharging process are more, and a large amount of electrolyte is consumed, so that the first coulombic efficiency of the battery is lower. In addition, the hard carbon can generate large volume change in the potassium intercalation/deintercalation process, so that a Solid Electrolyte Interface (SEI) film is continuously destroyed and remodeled, the capacity of the battery is rapidly attenuated, and the cycle performance is poor, which prevents further industrial production of the potassium ion battery.
Strategies to improve the initial efficiency and cycling of batteries from an electrolyte standpoint are becoming accepted by more and more researchers. The interface chemical behavior is controlled by adjusting the types of solvents, salt concentration and additives in the electrolyte, so that a compact and stable SEI film is formed on the surface of the negative electrode, the generation of side reaction is greatly reduced, and the first effect and the cycle performance of the battery are improved. In Chinese patent publication No. CN112310482A, a high-concentration electrolyte of a potassium ion battery is disclosed, wherein the high-concentration electrolyte is a difluoro sulfonimide potassium salt (KFSI) electrolyte, the concentration of the electrolyte is 3-5mol/L, and the high-concentration electrolyte can form a high-efficiency SEI film in a graphite negative electrode, so that the potassium ion battery can keep a compact and stable structure of graphite in the charging/discharging process, and the potassium ion battery based on the graphite negative electrode can stably charge and discharge 1600 times. In Chinese patent publication No. CN114069050A, a high-stability potassium ion battery amide electrolyte is disclosed, the concentration of the electrolyte is 5-14mol/L, the content of an additive accounts for 0-16% of the total volume of the electrolyte, the electrolyte can buffer the volume fluctuation of graphite in the charging and discharging process, the side reaction of the electrolyte and the graphite is effectively inhibited, the SEI film after adding the additive HFE can further increase the content of KF to stabilize the interface between an electrode and the electrolyte, the local concentration of the electrolyte can be reduced, and the diffusion rate of ions in the battery can be improved. However, by adjusting the electrolyte, the composition and structure of the SEI film are not easily controlled, and the thickness and composition of the SEI film are greatly different even in the same electrolyte at different current densities, which makes it difficult to start from the electrolyte.
In addition, compared with a lithium ion battery, the potassium intercalation and deintercalation of the potassium ion battery can cause larger volume change, the damage of an SEI film is extremely easy to cause, and the effect obtained by the method for improving the SEI film from the aspect of electrolyte is not outstanding, so that a new strategy is urgently needed to be explored to improve the first effect and the cycle performance of the potassium ion battery.
Disclosure of Invention
The invention aims to provide a modified nitrogen-doped carbon nano tube and a preparation method thereof, and the modified nitrogen-doped carbon nano tube has the advantages of simple experimental process operation, controllable conditions and good structural stability.
The technical scheme is as follows: a preparation method of a modified nitrogen-doped carbon nano tube comprises the following steps:
(1) Synthesis of polypyrrole tube:
3-6g of cetyl trimethylammonium bromide (CTAB) was dispersed in 60-120mL of hydrochloric acid solution (HCl, 1 mol/L), after magnetic stirring (ice bath) for 10min, 6-12g of Ammonium Persulfate (APS) was added to the solution, and after stirring for 10min, a white reaction template precipitate was obtained. Adding 9-18g pyrrole into the prepared reaction template solution, self-assembling for 18-24h at the temperature of 0-3 ℃ to obtain black polypyrrole precipitate, filtering, washing and drying for later use.
(2) Preparation of nitrogen-doped carbon nanotubes:
transferring the polypyrrole tube prepared in the step (1) to a tube furnace, heating to 800-1000 ℃, calcining for 4-6h in a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the nitrogen-doped carbon nanotube at a gas flow rate of 50-100 mL/min.
(3) Preparation of nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material:
firstly, stirring a molybdenum source and polyacrylonitrile in an organic solvent for 2 hours to fully and uniformly mix the molybdenum source and the polyacrylonitrile and the organic solvent, wherein the mass ratio of the molybdenum source to the polyacrylonitrile to the organic solvent is 0.4:0.6:1; and mixing the slurry with the nitrogen-doped carbon nano tube, wherein the mass ratio of the nitrogen-doped carbon nano tube to the slurry is 7 (2-3), and the mixing time is 1h, so as to prepare the nitrogen-doped carbon nano tube-molybdate/polyacrylonitrile composite material.
(4) Preparation of modified nitrogen-doped carbon nanotubes coated by sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite films:
transferring the nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material prepared in the step (3) into a tube furnace, and pre-arranging a sulfur source, wherein the mass ratio of the composite material to the sulfur source is 1:4, then heating to 500-600 ℃, the heating rate is 5 ℃/min, vulcanizing for 2-3h in a nitrogen atmosphere, and the gas flow is 50-100mL/min, so as to prepare the modified nitrogen-doped carbon nanotube coated by the sulfur-oxidized polyacrylonitrile/molybdenum disulfide composite film.
Preferably, the concentration of cetyltrimethylammonium bromide in the hydrochloric acid solution described in step (1) above is 0.05g/mL. The mass ratio of the hexadecyl trimethyl ammonium bromide to the ammonium persulfate to the pyrrole is 1:2:3.
The molybdenum source in the step (3) is one or two of ammonium molybdate and sodium molybdate. The organic solvent is one or two of N, N-dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
The sulfur source in the step (4) is one or two of sulfur, thiourea and thioacetamide.
The invention also discloses the modified nitrogen-doped carbon nanotube prepared by the method, and the outer coating is a sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite film, which can serve as an artificial SEI film to isolate electrolyte and prevent electrons from overflowing and desolvation; inside is nitrogen doped carbon nano tube, the nano structure can shorten K + And the carbon nano tubes are interacted to form a three-dimensional network, which is beneficial to e - The hollow structure in the outer tube can alleviate the volume expansion of the stored potassium, and the defect sites caused by nitrogen doping can contribute additional capacity.
The invention further aims at disclosing application of the modified nitrogen-doped carbon nano tube in a cathode material of a potassium ion battery. Compared with the prior art, the invention has the following specific advantages:
(1) From the perspective of the cathode, the sulfur-coated and oxidized polyacrylonitrile/molybdenum disulfide composite film can serve as an artificial SEI film. Compared with the method for improving the SEI film from the electrolyte, the manufacturing process of the artificial SEI film is simple and controllable, the interface film is firmer, and the effect is obvious.
(2) Sulfur and oxidized polyacrylonitrile in the composite film for the first timePotassium is generated into polyacrylonitrile organic components and inorganic components such as potassium sulfide, potassium oxide, potassium carbonate and the like. The organic polyacrylonitrile has certain affinity with the organic solvent, is favorable for the infiltration of electrolyte, and in addition, the compact and insulating polyacrylonitrile film can also prevent electrons from overflowing, reduce side reaction and prevent electrolyte from being reduced to be lost. The inorganic component is not only a conductor of potassium ions, but also makes the composite membrane insoluble in organic solvents, plays a desolvation role, and avoids K + The solvent co-intercalation avoids damaging the electrode material due to large solvent molecule intercalation.
(3) The existence of molybdenum disulfide in the composite film can enhance the toughness of the composite film, can prevent the structure of the outer coating film from being damaged in the potassium embedding process, and potassium sulfide and Mo metal clusters are generated by potassium, so that not only are inorganic components of potassium sulfide in the composite film increased, but also inert Mo metal clusters penetrate through the whole composite film, and the rigidity of the composite film can be enhanced.
(4) As a cathode material of the potassium ion battery, the modified nitrogen-doped carbon nano tube provided by the invention has superior electrochemical performance. At a current density of 0.5A/g, the initial coulomb efficiency is as high as 74%, and the capacity of 280.2mAh/g remains after 100 cycles of charge and discharge, thus the potassium storage performance is excellent. The nitrogen-doped carbon nanotube without the composite film coating shows extremely low first coulombic efficiency (32.1%) and poor cycle performance, and only 208.3mAh/g of capacity remains after 100 cycles of charge and discharge at a current density of 0.5A/g.
Drawings
Fig. 1 is an XRD pattern of the modified nitrogen-doped carbon nanotube prepared in example 1 and the nitrogen-doped nanotube prepared in comparative example.
Fig. 2 is an SEM image of nitrogen-doped carbon nanotubes prepared in comparative example of the present invention.
Fig. 3 is an SEM image of the modified nitrogen-doped carbon nanotube prepared in example 1 of the present invention.
FIG. 4 shows the elemental distribution (C, N, O, S, mo) of the modified nitrogen-doped carbon nanotubes prepared in example 1 of the present invention.
FIG. 5 is a charge-discharge curve of the nitrogen-doped nanotube electrode prepared in comparative example for the first 2 turns at a current density of 0.5A/g.
FIG. 6 is a charge-discharge curve of the modified nitrogen-doped carbon nanotube electrode prepared in example 1 at a current density of 0.5A/g for the first 2 turns.
FIG. 7 is a comparison of the long cycle performance at a current density of 0.5A/g for the modified nitrogen-doped carbon nanotube electrode prepared in example 1 and the nitrogen-doped nanotube electrode prepared in comparative example.
Detailed Description
Comparative example 1
A preparation method of nitrogen-doped carbon nanotubes comprises the following steps:
(1) Synthesis of polypyrrole tube:
3g of cetyltrimethylammonium bromide was dispersed in 60mL of hydrochloric acid solution (1 mol/L), after magnetic stirring (ice bath) for 10min, 6g of ammonium persulfate was added to the solution, and after stirring for 10min, a white reaction template precipitate was obtained. Adding 9g of pyrrole into the prepared reaction template solution, self-assembling for 24 hours at the temperature of 0-3 ℃ to obtain black polypyrrole precipitate, filtering, washing and drying for later use.
(2) Preparation of nitrogen-doped carbon nanotubes:
transferring the polypyrrole tube prepared in the step (1) to a tube furnace, then heating to 800 ℃, calcining for 4 hours under a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the nitrogen-doped carbon nanotube at a gas flow rate of 50 mL/min.
The nitrogen-doped carbon nanotube prepared in comparative example 1 is adopted as an active material of a negative electrode of a potassium ion battery, the active material is mixed with a conductive agent and a binder polyvinylidene fluoride according to the mass ratio of 7:2:1, N-methyl pyrrolidone is adopted as a solvent, the mixture is uniformly coated on a copper foil after being ground, the mixture is dried in a vacuum oven at 80 ℃ for 12 hours, an electrode sheet is cut into a wafer with the diameter of about 1.2cm, a metal potassium sheet is adopted as a counter electrode, and 1.0M KPF is adopted as electrolyte 6 EC/DMC/EMC (1:1:1 vol%) was assembled into a 2032 type coin cell in an inert argon atmosphere glove box.
FIG. 2 is an SEM image of a nitrogen-doped carbon nanotube prepared according to a comparative example, showing that the morphology of the carbon nanotube remains good, and a three-dimensional interaction network is formed after carbonization, which is advantageous to e - And the nanostructure can reduce K + Is of (2)And (3) scattering distance. FIG. 5 shows the charge-discharge curve (0.5A/g) for the first 2 turns of a nitrogen-doped nanotube electrode with a first coulombic efficiency of only 32.1% and a first charge capacity of only 255.4mAh/g. The nitrogen doped pyrrole tube has a larger specific surface, a developed surface pore structure, and a great amount of side reactions occur on the surface of the carbon nanotube during the first discharge, so that electrolyte is consumed, a thick SEI film is formed on the surface of the electrode, and poor potassium storage performance is caused.
Example 1
The invention relates to a preparation method of a modified nitrogen-doped carbon nano tube, which comprises the following steps:
(1) Synthesis of polypyrrole tube:
3g of cetyltrimethylammonium bromide was dispersed in 60mL of hydrochloric acid solution (1 mol/L), after magnetic stirring (ice bath) for 10min, 6g of ammonium persulfate was added to the solution, and after stirring for 10min, a white reaction template precipitate was obtained. Adding 9g of pyrrole into the prepared reaction template solution, self-assembling for 24 hours at the temperature of 0-3 ℃ to obtain black polypyrrole precipitate, filtering, washing and drying for later use.
(2) Preparation of nitrogen-doped carbon nanotubes:
transferring the polypyrrole tube prepared in the step (1) to a tube furnace, then heating to 800 ℃, calcining for 4 hours under a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the nitrogen-doped carbon nanotube at a gas flow rate of 50 mL/min.
(3) Preparation of nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material:
firstly adding 0.1g of ammonium molybdate and 0.15g of polyacrylonitrile into 0.25g of N, N-dimethylformamide, stirring for 2 hours, fully and uniformly mixing the ammonium molybdate and the polyacrylonitrile, and then mixing the slurry with 1.75g of nitrogen-doped carbon nano tube, wherein the stirring time is 1 hour, so as to prepare the nitrogen-doped carbon nano tube-molybdate/polyacrylonitrile composite material.
(4) Preparation of modified nitrogen-doped carbon nanotubes coated by sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite films:
transferring 1.0g of the nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material prepared in the step (3) into a tube furnace, pre-placing 4.0g of sulfur, heating to 500 ℃, vulcanizing for 2 hours in a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the modified nitrogen-doped carbon nanotube coated by the sulfur-oxidized polyacrylonitrile/molybdenum disulfide composite film at a gas flow rate of 50 mL/min.
Example 2
The invention relates to a preparation method of a modified nitrogen-doped carbon nano tube, which comprises the following steps:
(1) Synthesis of polypyrrole tube:
3g of cetyltrimethylammonium bromide was dispersed in 60mL of hydrochloric acid solution (1 mol/L), after magnetic stirring (ice bath) for 10min, 6g of ammonium persulfate was added to the solution, and after stirring for 10min, a white reaction template precipitate was obtained. Adding 9g of pyrrole into the prepared reaction template solution, self-assembling for 18h at the temperature of 0-3 ℃ to obtain black polypyrrole precipitate, filtering, washing and drying for later use.
(2) Preparation of nitrogen-doped carbon nanotubes:
transferring the polypyrrole tube prepared in the step (1) to a tube furnace, then heating to 1000 ℃, wherein the heating rate is 5 ℃/min, calcining for 6 hours under the nitrogen atmosphere, and the gas flow is 100mL/min to prepare the nitrogen-doped carbon nanotube.
(3) Preparation of nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material:
firstly adding 0.1g of sodium molybdate and 0.15g of polyacrylonitrile into 0.25g of dimethyl sulfoxide, stirring for 2 hours, fully and uniformly mixing the sodium molybdate and the polyacrylonitrile, and then mixing the slurry with 1.75g of nitrogen-doped carbon nano tube for 1 hour to prepare the nitrogen-doped carbon nano tube-molybdate/polyacrylonitrile composite material.
(4) Preparation of modified nitrogen-doped carbon nanotubes coated by sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite films:
transferring 1.0g of the nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material prepared in the step (3) into a tube furnace, pre-arranging a mixture of 2.0g of sulfur and 2.0g of thiourea, heating to 600 ℃, vulcanizing for 3 hours in a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the modified nitrogen-doped carbon nanotube coated by the sulfur-oxidized polyacrylonitrile/molybdenum disulfide composite film at a gas flow rate of 100 mL/min.
Example 3
The invention relates to a preparation method of a modified nitrogen-doped carbon nano tube, which comprises the following steps:
(1) Synthesis of polypyrrole tube:
6g of cetyltrimethylammonium bromide was dispersed in 120mL of hydrochloric acid solution (1 mol/L), after magnetic stirring (ice bath) for 10min, 12g of ammonium persulfate was added to the solution, and after stirring for 10min, a white reaction template precipitate was obtained. 18g of pyrrole is added into the prepared reaction template solution, self-assembly is carried out for 24 hours at the temperature of 0-3 ℃ to obtain black polypyrrole precipitate, and the black polypyrrole precipitate is filtered, washed and dried for standby.
(2) Preparation of nitrogen-doped carbon nanotubes:
transferring the polypyrrole tube prepared in the step (1) to a tube furnace, then heating to 800 ℃, calcining for 6 hours under a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the nitrogen-doped carbon nanotube at a gas flow rate of 50 mL/min.
(3) Preparation of nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material:
adding 0.1g of ammonium molybdate, 0.1g of sodium molybdate and 0.3g of polyacrylonitrile into 0.25g of N, N-dimethylformamide and 0.25g of dimethylacetamide, stirring for 2 hours, fully and uniformly mixing the two, and then mixing the slurry with 3.0g of nitrogen-doped carbon nano tubes for 1 hour to prepare the nitrogen-doped carbon nano tube-molybdate/polyacrylonitrile composite material.
(4) Preparation of modified nitrogen-doped carbon nanotubes coated by sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite films:
transferring 1.0g of the nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material prepared in the step (3) into a tube furnace, pre-arranging 4.0g of thioacetamide, heating to 500 ℃, vulcanizing for 3 hours in a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the modified nitrogen-doped carbon nanotube coated by the sulfur-oxidized polyacrylonitrile/molybdenum disulfide composite film at a gas flow rate of 100 mL/min.
Example 4
The invention relates to a preparation method of a modified nitrogen-doped carbon nano tube, which comprises the following steps:
(1) Synthesis of polypyrrole tube
4.5g of cetyltrimethylammonium bromide was dispersed in 90mL of hydrochloric acid solution (1 mol/L), after magnetic stirring (ice bath) for 10min, 9g of ammonium persulfate was added to the solution, and after stirring for 10min, a white reaction template precipitate was obtained. 13.5g pyrrole is added into the prepared reaction template solution, self-assembly is carried out for 18 hours at the temperature of 0-3 ℃ to obtain black polypyrrole precipitate, and suction filtration, washing and drying are carried out for standby.
(2) Preparation of nitrogen-doped carbon nanotubes
Transferring the polypyrrole tube prepared in the step (1) to a tube furnace, then heating to 900 ℃, calcining for 5 hours in a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the nitrogen-doped carbon nanotube at a gas flow rate of 80 mL/min.
(3) Preparation of nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material:
firstly adding 0.12g of ammonium molybdate and 0.18g of polyacrylonitrile into 0.3g of dimethylacetamide, stirring for 2 hours, fully and uniformly mixing the ammonium molybdate and the polyacrylonitrile, and then mixing the slurry with 1.4g of nitrogen-doped carbon nano tube for 1 hour to prepare the nitrogen-doped carbon nano tube-molybdate/polyacrylonitrile composite material.
(4) Preparation of modified nitrogen-doped carbon nanotubes coated by sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite films:
transferring 1.0g of the nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material prepared in the step (3) into a tube furnace, pre-placing 4.0g of thiourea, heating to 550 ℃, vulcanizing for 3 hours in a nitrogen atmosphere at a heating rate of 2.5 ℃/min, and preparing the modified nitrogen-doped carbon nanotube coated by the sulfur-oxidized polyacrylonitrile/molybdenum disulfide composite film at a gas flow rate of 80 mL/min.
Application test:
the modified nitrogen-doped carbon nanotubes prepared in examples 1-4 were used as active materials of the negative electrode of the potassium ion battery, mixed with a conductive agent (Super-P) and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 7:2:1, ground with N-methylpyrrolidone (NMP) as a solvent, uniformly coated on a copper foil, dried at 80 ℃ for 12 hours in a vacuum oven, cut into a round piece with a diameter of about 1.2cm, and an electrolyte solution using a metallic potassium piece as a counter electrode1.0M KPF is selected 6 EC/DMC/EMC (1:1:1 vol%) was assembled into a 2032 type coin cell in an inert argon atmosphere glove box.
The test working voltage window is 0.01-3.0V, and the current density is 0.5A/g. Table 1 shows that the first coulombic efficiency and the circularity of examples 1 to 4 are significantly improved compared with the comparative examples, and this shows that the sulfur, oxidized polyacrylonitrile/molybdenum disulfide composite film serves as an artificial SEI film, plays a role in isolating electrolyte, preventing electron overflow and desolvation, and greatly improves the first coulombic efficiency and the circularity of the battery. The modified nitrogen-doped carbon nanotube coated by the sulfur-oxidized polyacrylonitrile/molybdenum disulfide composite film prepared by the preparation method provided by the invention is used as a cathode material of a potassium ion battery, and has better initial effect and cycle performance, wherein the cathode material of the potassium ion battery prepared by adopting the embodiment 1 has the best performance.
TABLE 1 comparison of the Properties of examples 1-4 and comparative examples
FIG. 1 is an XRD pattern of the modified nitrogen-doped carbon nanotube prepared in example 1 and the nitrogen-doped carbon nanotube prepared in comparative example, and it can be seen that diffraction peaks around 26℃correspond to characteristic peaks of disordered carbon, in which diffraction peaks of 14.38℃32.68℃39.54℃and 49.79℃correspond to molybdenum disulfide (MoS 2 ) This also means that the surface of the carbon nanotube has been coated with a composite film containing molybdenum disulfide.
Fig. 3 is an SEM image of the modified nitrogen-doped carbon nanotube prepared in example 1, and it can be seen that the surface of the carbon nanotube is coated with an inorganic film, and the morphology of the tube is kept good.
As can be seen from fig. 4, five elements of C, N, O, S and Mo are uniformly distributed in the composite, which also means that sulfur, oxidized polyacrylonitrile and molybdenum disulfide are interacted together in the composite film, and the composite film uniformly coats the nitrogen-doped carbon nanotubes.
FIG. 6 shows the charge and discharge curves (0.5A/g) of the modified nitrogen-doped carbon nanotube prepared in example 1 in 2 turns before the electrode, the first coulombic efficiency is as high as 74.1%, and the first charge capacity is 354.8mAh/g. Compared with the carbon nano tube which is not coated by the composite film, after being coated by the sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite film, the first coulomb efficiency and the first charge capacity of the battery are greatly improved.
FIG. 7 is a comparison of the long cycle performance of the electrodes prepared from the products of example 1 and comparative example, with the capacity remaining of example 1 and comparative example being 280.2 and 208.3mAh/g, respectively, after cycling 100 cycles at a current density of 0.5A/g. The composite film is used as an artificial SEI film, plays roles in isolating electrolyte, preventing electrons from overflowing and desolvating, and greatly improves the first coulombic efficiency and the cycle performance of the battery.
Claims (7)
1. The preparation method of the modified nitrogen-doped carbon nano tube is characterized by comprising the following steps of:
(1) Synthesis of polypyrrole tube:
dispersing 3-6g of hexadecyl trimethyl ammonium bromide in 60-120mL of hydrochloric acid solution, carrying out ice bath, magnetically stirring for 10min, adding 6-12g of ammonium persulfate into the solution, and stirring for 10min to obtain a white reaction template precipitate; adding 9-18g pyrrole into the prepared reaction template precipitate, self-assembling for 18-24h at 0-3 ℃ to obtain black polypyrrole precipitate, filtering, washing and drying for later use;
(2) Preparation of nitrogen-doped carbon nanotubes:
transferring the polypyrrole tube prepared in the step (1) to a tube furnace, heating to 800-1000 ℃, calcining for 4-6 hours in a nitrogen atmosphere at a heating rate of 5 ℃/min, and preparing the nitrogen-doped carbon nanotube at a gas flow rate of 50-100 mL/min;
(3) Preparation of nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material:
firstly, stirring a molybdenum source and polyacrylonitrile in an organic solvent for 2 hours to fully and uniformly mix the molybdenum source and the polyacrylonitrile with the organic solvent, wherein the mass ratio of the molybdenum source to the polyacrylonitrile to the organic solvent is 0.4:0.6:1, a step of; and mixing the slurry and the nitrogen-doped carbon nano tube, wherein the mass ratio of the nitrogen-doped carbon nano tube to the slurry is 7: (2-3) mixing for 1h to prepare a nitrogen-doped carbon nano tube-molybdate/polyacrylonitrile composite material;
(4) Preparation of modified nitrogen-doped carbon nanotubes coated by sulfur and oxidized polyacrylonitrile/molybdenum disulfide composite films:
transferring the nitrogen-doped carbon nanotube-molybdate/polyacrylonitrile composite material prepared in the step (3) into a tube furnace, and prepositioning a sulfur source, wherein the mass ratio of the composite material to the sulfur source is 1:4, heating to 500-600 ℃, vulcanizing for 2-3 hours in nitrogen atmosphere at the heating rate of 5 ℃/min and the gas flow rate of 50-100mL/min, and preparing the modified nitrogen-doped carbon nanotube coated by the sulfur-oxidized polyacrylonitrile/molybdenum disulfide composite film.
2. The method for preparing the modified nitrogen-doped carbon nanotube according to claim 1, wherein: the concentration of the cetyl trimethyl ammonium bromide in the hydrochloric acid in the step (1) is 0.05g/mL, and the mass ratio of the cetyl trimethyl ammonium bromide to the ammonium persulfate to the pyrrole is 1:2:3.
3. The method for preparing the modified nitrogen-doped carbon nanotube according to claim 1, wherein: the molybdenum source in the step (3) is one or two of ammonium molybdate and sodium molybdate.
4. The method for preparing the modified nitrogen-doped carbon nanotube according to claim 1, wherein: the organic solvent in the step (3) is one or two of N, N-dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
5. The method for preparing the modified nitrogen-doped carbon nanotube according to claim 1, wherein: the sulfur source in the step (4) is one or two of sulfur, thiourea and thioacetamide.
6. A modified nitrogen-doped carbon nanotube produced by the production method according to any one of claims 1 to 5.
7. The use of the modified nitrogen-doped carbon nanotube of claim 6 in a negative electrode material of a potassium ion battery.
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| CN106328387A (en) * | 2016-08-31 | 2017-01-11 | 江苏大学 | Nitrogen-doped carbon nanotube/molybdenum disulfide nanosphere composite material and preparation method thereof |
| CN106566160A (en) * | 2016-11-09 | 2017-04-19 | 嘉科（安徽）密封技术有限公司 | Preparation method of polytetrafluoroethylene sheet for automobiles |
| CN111106319A (en) * | 2018-10-27 | 2020-05-05 | 中国石油化工股份有限公司 | Nitrogen-doped molybdenum disulfide/carbon nanotube composite material |
| CN111106323A (en) * | 2018-10-27 | 2020-05-05 | 中国石油化工股份有限公司 | Nitrogen-doped molybdenum disulfide/carbon nanotube composite material |
| CN111106318A (en) * | 2018-10-27 | 2020-05-05 | 中国石油化工股份有限公司 | Nitrogen-doped molybdenum disulfide/C/carbon nanotube composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106328387A (en) * | 2016-08-31 | 2017-01-11 | 江苏大学 | Nitrogen-doped carbon nanotube/molybdenum disulfide nanosphere composite material and preparation method thereof |
| CN106566160A (en) * | 2016-11-09 | 2017-04-19 | 嘉科（安徽）密封技术有限公司 | Preparation method of polytetrafluoroethylene sheet for automobiles |
| CN111106319A (en) * | 2018-10-27 | 2020-05-05 | 中国石油化工股份有限公司 | Nitrogen-doped molybdenum disulfide/carbon nanotube composite material |
| CN111106323A (en) * | 2018-10-27 | 2020-05-05 | 中国石油化工股份有限公司 | Nitrogen-doped molybdenum disulfide/carbon nanotube composite material |
| CN111106318A (en) * | 2018-10-27 | 2020-05-05 | 中国石油化工股份有限公司 | Nitrogen-doped molybdenum disulfide/C/carbon nanotube composite material |
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