CN118162081A - Carbon-based nano reactor and preparation equipment and preparation process thereof - Google Patents
Carbon-based nano reactor and preparation equipment and preparation process thereof Download PDFInfo
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- CN118162081A CN118162081A CN202410235865.XA CN202410235865A CN118162081A CN 118162081 A CN118162081 A CN 118162081A CN 202410235865 A CN202410235865 A CN 202410235865A CN 118162081 A CN118162081 A CN 118162081A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- -1 transition metal salt Chemical class 0.000 claims abstract description 12
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 238000010926 purge Methods 0.000 claims description 27
- 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 13
- 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 13
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 2
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910001615 alkaline earth metal halide Chemical class 0.000 claims description 2
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 2
- 229910000316 alkaline earth metal phosphate Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000010924 continuous production Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- 150000003624 transition metals Chemical group 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a carbon-based nano-reactor and a preparation method and a preparation process thereof. The invention firstly provides a preparation device of a carbon-based nano reactor, which comprises a first reactor, a second reactor, a solid-liquid separator and a carbon material collector, and then the invention also provides a matched preparation process, wherein the molar ratio is 15: (1-10): (0-5): mixing the carbon source, the transition metal salt, the heteroatom source and the molten salt in the steps (1-15) to obtain a mixed material; and inputting the mixed material into a first reactor, inputting the mixed material into a second reactor after the mixed material is heated to a molten state, and finally obtaining the carbon-based nano reactor in the second reactor through high-temperature reaction. The preparation method and the process control the reaction process through the two reactors, ensure the uniformity of raw material mixing and heating, overcome the defect that the traditional process and equipment cannot prepare in a large scale, and can realize industrialized large-scale continuous production.
Description
Technical Field
The invention relates to the field of new chemical energy materials, in particular to a carbon-based nano-reactor, and a preparation device and a preparation process thereof.
Background
The carbon-based nano-reactor wraps nano-catalyst particles in the carbon nano-tubes, and the difference of flatness of the carbon nano-tubes can cause the increase of pi electron density on the convex surface, so that the electron potential difference between the inner wall and the outer wall of the carbon nano-tubes is caused, and the encapsulated nano-catalyst particles can carry out electron rearrangement with the surface of the carbon nano-tubes, so that in the case, the nano-catalyst particles are not the property of a single component on the simple composite nano-scale, but are novel materials with brand new properties.
Carbon-based nanoreactors have been used in a variety of applications due to their specific structure and composition that can be tailored to meet their respective application requirements, such as the development of different functional catalyst particles (metals, metal sulfides, metal nitrides, metal phosphides, metal carbides, etc.), due to their unique surface chemistry and high catalytic activity, carbon-based nanoreactors have been extensively studied in the fields of important electrocatalytic reaction research such as OER, ORR, HER, CO 2 RR, and have found wide application in the fields of hydrogen production by electrolysis of water, hydrogen fuel cells, new cells (lithium-oxygen cells, lithium-sulfur cells, zinc-air cells), etc. Furthermore, due to the lithium-philic nature of carbon-based nanoreactors, there is applicability in the field of energy storage, such as metal ion batteries, supercapacitors.
The current production method of the carbon-based nano-reactor mainly comprises a chemical vapor deposition method, an arc discharge method, a laser ablation method and a high-temperature calcination method; at present, the methods only realize small-scale preparation in a laboratory, often greatly limit macro preparation of the carbon-based nano reactor due to complicated preparation process, and meanwhile, the technological difficulty of continuously preparing the carbon-based nano reactor in a large scale is how to effectively ensure the mixing and heating uniformity of raw materials, thereby ensuring the single-morphology and stable-structure carbon-based nano reactor; furthermore, the above-mentioned methods also lack a device suitable for large-scale continuous production.
Disclosure of Invention
Based on the above, the present invention aims to provide a preparation device and a preparation process of a carbon-based nano-reactor, which combine with a molten salt method to realize large-scale continuous production of the carbon-based nano-reactor.
A first part:
The invention relates to a preparation device of a carbon-based nano reactor, which comprises a first reactor, a second reactor, a solid-liquid separator and a carbon material collector, wherein the first reactor is connected with the second reactor; the first reactor, the solid-liquid separator and the carbon material collector are provided with an input end and an output end, and the second reactor comprises a first input end;
a purging and collecting unit is arranged in the second reactor and comprises an air inlet pipe, an air injection assembly, a collecting funnel and a collecting pipe; the air inlet pipe is communicated with the air injection assembly, and the collecting funnel is communicated with the collecting pipe;
The output end of the first reactor is communicated with the first input end of the second reactor, the collecting pipe is communicated with the input end of the solid-liquid separator, and the output end of the solid-liquid separator is communicated with the input end of the carbon material collector.
The preparation device of the carbon-based nano reactor ensures that reactants in the reactor undergo the processes of carbon source decomposition and metal carbon dissolution-precipitation in the preparation process of the carbon-based nano reactor. The preparation raw materials of the carbon-based nano-reactor comprise a carbon source, transition metal salt and halogenated salt (the raw materials can also comprise a heteroatom source), the carbon source is pyrolyzed at high temperature in the first reactor, the halogenated salt is melted to form high-temperature molten salt, carbon atoms are combined with metal to form metal carbon-dissolved bodies (if the heteroatom source is also added, the metal carbon-dissolved bodies are doped with the heteroatom), but the excessive metal carbon combination needs higher temperature to separate out carbon, so that the high-temperature molten salt is used as a transmission medium to transfer the liquid-phase metal carbon-dissolved bodies into the second reactor for growth of carbon nano-tubes. The carbon content of the metal carbon-dissolving body transferred into the second reactor can be controlled by controlling the temperature, the raw material proportion and the like of the first reactor, so that the two reactors are arranged for effectively controlling the material morphology synthesis process. Finally, the carbon-based nano reactor is obtained through a solid-liquid separator.
The preparation device of the carbon-based nano reactor controls the reaction process through the two reactors, ensures the uniformity of raw material mixing and heating, and can realize industrialized large-scale continuous production.
As a preferred scheme, the preparation device of the carbon-based nano reactor further comprises a mixing device, wherein the mixing device is communicated to the input end of the first reactor, raw materials can be uniformly mixed through the mixing device, and continuous production is facilitated.
As a preferable scheme, the purging and collecting unit is positioned at the top of the second reactor, the air injection component is annular and fixed on the inner wall of the second reactor, the air injection component is positioned above the collecting funnel, and the collecting pipe is a negative pressure pipeline. The annular jet assembly can gather products better, and the jet assembly is located above the collecting hopper and can collect products conveniently, and the negative pressure pipeline can adjust pipeline pressure and then adjust product collecting rate.
As a preferable scheme, the preparation device of the carbon-based nano-reactor further comprises a gas separator and a gas collector; the gas separator and the gas collector are both provided with an input end and an output end, the top of the second reactor is provided with a gas output end, the gas output end is communicated to the input end of the gas separator, and the output end of the gas separator is communicated to the input end of the gas collector. The gas separator can separate the purge gas from the tail gas generated by the reaction, and collect the purge gas to the gas collector after separation so as to recycle the purge gas.
As a preferable scheme, the preparation device of the carbon-based nano-reactor further comprises a heater, wherein the heater is provided with an input end and an output end; the bottom of the second reactor is provided with a liquid output end, the side part of the second reactor is provided with a second input end, and the second input end is higher than the first input end; the liquid output end is communicated with the input end of the heater, and the output end of the heater is communicated with the second input end of the second reactor. And heating the input liquid in the heater to the same temperature as the second reactor, and flowing into the upper end of the second reactor to realize the up-and-down convection flow of reactants in the second reactor, thereby improving the growth efficiency of the carbon nano tube and controlling the carbon content of the metal carbon-dissolving body in the reaction process.
As a preferable scheme, the bottom of the solid-liquid separator is also provided with a liquid reflux end, and the liquid reflux end is communicated with the input end of the heater. In the solid-liquid separator, the separated molten salt flows back to the second reactor after passing through the heater, so that the molten salt can be reused, the production cost is reduced, and the waste is reduced.
A second part:
A preparation process of a carbon-based nano reactor is characterized in that:
The molar ratio was 15: (1-10): (0-5): mixing the carbon source, the transition metal salt, the heteroatom source and the molten salt in the steps (1-15) to obtain a mixed material;
inputting the mixed material into a first reactor of a preparation device of a first part of the carbon-based nano-reactor, wherein the temperature of the first reactor is kept at 400-600 ℃;
After the mixed materials are heated to a molten state, inputting the mixed materials into the second reactor, wherein the temperature of the second reactor is kept at 800-100 ℃, and the purging and collecting unit blows out gas through the gas injection assembly to purge and collect generated carbon materials so that the carbon materials enter a collecting funnel;
The carbon material enters the solid-liquid separator through a collecting funnel and is subjected to solid-liquid separation to obtain the carbon-based nano reactor;
Wherein the carbon source comprises at least one of dicyandiamide, melamine, dopamine, sucrose, glucose and polyvinylpyrrolidone; the heteroatom source comprises at least one of alkali metal sulfate, alkaline earth metal sulfate, alkali metal nitrate, alkaline earth metal nitrate, alkali metal phosphate, alkaline earth metal phosphate; the molten salt includes at least one of an alkali metal halide salt and an alkaline earth metal halide salt.
According to the invention, the molten salt is used as a reaction medium, a carbon source is pyrolyzed into a nano carbon material, transition metal atoms are coated in the nano carbon material, and hetero atoms are doped at the same time, so that the carbon-based nano reactor with various functions is synthesized.
In the invention, the molten salt can be used as a heat transfer agent in the reaction process, and in the melt pyrolysis process, the reaction temperature is ensured to be uniform in the whole reaction process, so that the reaction temperature, the heating rate and the reaction time are convenient to precisely control, and the shape and the size of the product nano carbon material are further controlled; meanwhile, the obvious heat capacity of the molten salt is beneficial to reducing the reaction temperature, in addition, the molten medium can also serve as a solvent or a reactant, the reaction activity of the reactant is improved, the overall reaction efficiency is further improved, and the large-scale continuous production of the carbon-based nanomaterial is realized.
As a preferable mode, the carbon source is a carbon source having a molar ratio of 1: glucose and melamine according to (1-4), wherein the molar ratio of the molten salt is 1:1, the prepared carbon material prepared by the combination has good appearance, and the production appearance of the carbon material is easy to control.
As a preferred embodiment, the transition metal salt includes at least one of manganese salt, iron salt, cobalt salt, nickel salt, and copper salt.
Third section:
The carbon-based nano reactor prepared by the preparation process in the second part is a carbon nano tube with the diameter of less than 150nm, which is coated with metal simple substance, metal sulfide, metal phosphide, metal nitride or metal carbide nano particles. The carbon-based nano reactor disclosed by the invention has the advantages that the outer layer is the carbon nano tube formed by the carbon layer, nano metal particles are coated in the carbon nano tube, the nano metal particles have better catalytic activity, the carbon nano tube ensures the electron conduction and the stability of the nano metal particles, and the carbon nano tube can be applied to the fields of energy storage and catalysis.
Drawings
FIG. 1 is a schematic structural view of a preparation apparatus of a carbon-based nano-reactor;
FIG. 2 is a cross-sectional view of a purge and collection unit in a production apparatus of a carbon-based nano-reactor;
FIG. 3 is an SEM image of Ni@NCNT prepared in example 2;
FIG. 4 is a TEM image of Ni@NCNT prepared in example 2;
FIG. 5 is an XRD pattern of Ni@NCNT prepared in example 2;
FIG. 6 is an XRD pattern of Co@NCNT prepared in example 3;
FIG. 7 is an XRD pattern of Fe@NCNT prepared in example 4;
FIG. 8 is an XRD pattern of FeP 2 @ NCNT prepared in example 5;
fig. 9 is a graph showing the cycle performance of lithium-sulfur batteries of the positive electrode materials prepared in example 6 and comparative example 1;
Wherein, 1-compounding device, 2-first reactor, 3-second reactor, 4-sweep collection unit, 41-first direction, 42-second direction, 43-intake pipe, 44-jet module, 45-collecting funnel, 46-collecting pipe, 5-solid-liquid separator, 6-gas separator, 7-heater, 8-carbon material collector, 9-gas collector.
Detailed Description
Example 1
The invention discloses a preparation device of a carbon-based nano reactor, which is shown in figures 1-2, and comprises a mixing device 1, a first reactor 2, a second reactor 3, a purging and collecting unit 4, a solid-liquid separator 5, a gas separator 6, a heater 7, a carbon material collector 8 and a gas collector 9, wherein the mixing device 1, the first reactor 2, the second reactor 3, the solid-liquid separator 5, the gas separator 6, the heater 7, the carbon material collector 8 and the gas collector 9 are provided with an input end and an output end;
The input end of the mixing device 1 is communicated with a raw material channel (not shown), the output end of the mixing device is communicated with the first reactor 2, and the output end of the first reactor 2 is connected with the second reactor 3; the second reactor 3 is provided with a plurality of output ends which are respectively communicated with the solid-liquid separator 5, the gas separator 6 and the heater 7, the second reactor 3 is also provided with a plurality of input ends, the first input end is communicated with the first reactor 2, the second input end is communicated with the output end of the heater 7, and the second input end is higher than the first input end; the output end of the solid-liquid separator 5 is connected to a carbon material collector 8, and the output end of the gas separator 6 is connected to a gas collector 9.
The raw material channel comprises a plurality of mutually independent material pipelines, each material pipeline is provided with a mass flowmeter, and each mass flowmeter is mutually independent. The measuring range of the mass flowmeter is 0-1000 ml/min, and the precision is 0.1%.
The second reactor 3 comprises a purging and collecting unit 4, and is arranged at the upper part of the reactor, wherein the purging and collecting unit 4 comprises an air inlet pipe 43, an air injection assembly 44, a collecting funnel 45 and a collecting pipe 46; wherein, jet module 44 is annular, is fixed in the inner wall of reactor, and is located and collect funnel 45 top, and collecting pipe 46 is negative pressure pipeline, evenly is provided with a plurality of fumaroles on the annular jet module 44, can gather together the product to the centre better, collects funnel 45 and is located jet module 44 below and can conveniently collect the product, and negative pressure pipeline can adjust pipeline pressure, and then adjusts the product collection rate. The product is accumulated continuously in the reaction process, slowly floats upwards due to the small density of the product, rises in the reactor along the first direction 41 (vertically upwards), is generally in a gap between the collecting funnel 45 and the inner wall of the second reactor 3, enters between the collecting funnel 45 and the annular air injection component 44, and can be blown up by an air blowing mode due to the small density of the product; the purge gas enters a jet assembly 44 through an air inlet pipe 43 along a second direction 42 (vertically downwards), the direction of the purge gas is adjusted by the jet assembly 44, and the product is sent into a collecting funnel 45 and sent into the solid-liquid separator 5 through a collecting pipe 46; in addition, the device can also be used for introducing inert gas to replace air in the device before the reaction starts to produce inert atmosphere.
In addition, the top of the second reactor 4 is provided with a gas output end which is connected to the input end of the gas separator 6, the gas separator 6 separates the purge gas from the tail gas generated in the reaction process, and the purge gas is collected to the gas collector 9 after separation so as to recycle the purge gas; the bottom of the second reactor 4 has a liquid output connected to the input of the heater 7.
The solid-liquid separator 5 has a partition plate therein to divide the space in the bottom of the separator into two, a first space and a second space. The bottom of the solid-liquid separator 5 is also provided with a fluid reflux end, the fluid reflux end is communicated with a first space and is communicated with the input end of the heater 7, the output end of the solid-liquid separator 5 is communicated with a second space, molten salt is mixed with the product collected in the separator, the product and the molten salt are separated in the first space through standing and layering, the product can be accumulated on the upper layer due to higher density of the molten salt and can overflow a baffle plate finally, the product flows into the second space, purer product can be collected in the second space, the product is finally collected into the carbon material collector 8, the molten salt flows back into the second reactor 3 after being heated by the heater 7 through the fluid reflux end, the molten salt can be recycled, the production cost is reduced, and the waste is reduced.
The heater 7 can heat the molten salt in the second reactor 3 and/or the solid-liquid separator 5 to the same temperature of the second reactor 3 and then reflux the molten salt into the second reactor 3, thereby realizing up-and-down convection flow of reactants in the second reactor, improving the growth efficiency of the carbon nano tube and controlling the carbon content of the metal carbon-dissolving body in the reaction process.
Example 2
The invention relates to a preparation process of a carbon-based nano reactor, which comprises the following steps:
with the apparatus for preparing a carbon-based nano-reactor described in example 1,
Mixing: the molar flow rate ratio was set to 5:10:5:2:6, glucose, melamine, nickel chloride hexahydrate, calcium chloride and potassium chloride enter a mixing device through a material channel at a rate of 1000ml/min to obtain a mixed material.
Preheating: the mixed material enters the first reactor from the output end of the mixing device, the preheating temperature is 600 ℃, at the preheating temperature, glucose and melamine are pyrolyzed to form a metal carbon-dissolving body with nickel chloride hexahydrate, and calcium chloride and potassium chloride are melted to form molten salt.
The reaction: after other gases in the second reactor are removed by adopting 1000ml/min nitrogen gas through a purging and collecting device, the mixture preheated to a molten state enters the second reactor from the output end of the first reactor, is calcined at 800 ℃, and after the carbon-based nano-reactor is accumulated continuously, the carbon-based nano-reactor slowly floats upwards due to smaller density and floats above molten salt, and the carbon-based nano-reactor enters a collecting funnel through purging and collecting the carbon-based nano-reactor at an air inlet rate of 500 ml/min.
Solid-liquid separation and collection: at the moment, molten salt is mixed in the carbon-based nano reactor collected from the collecting funnel, and is separated out through solid-liquid separation, heated and then returned to the second reactor; and then collecting the carbon-based nano reactor, flowing into a carbon material collector, and cooling to room temperature to obtain the carbon-based nano reactor Ni@NCNT coated with the Ni catalyst particles.
FIGS. 3 and 4 are SEM and TEM images of Ni@NCNT, respectively, and it can be seen that the synthesized Ni@NCNT has uniform morphology and stable structure; FIG. 5 is an XRD pattern of Ni@NCNT, and it can be seen that Ni@NCNT was successfully synthesized.
Example 3
The invention relates to a preparation process of a carbon-based nano reactor, which comprises the following steps:
with the apparatus for preparing a carbon-based nano-reactor described in example 1,
Mixing: the molar flow rate ratio was set to 3:12:5:3:3, glucose, urea, cobalt chloride hexahydrate, calcium chloride and sodium chloride enter a mixing device through a material channel at a rate of 1000ml/min to obtain a mixed material.
Preheating: the mixed material enters the first reactor from the output end of the mixing device, the preheating temperature is 500 ℃, at the preheating temperature, glucose and urea are pyrolyzed to form a metal carbon-dissolving body with cobalt chloride hexahydrate, and calcium chloride and sodium chloride are melted to form molten salt.
The reaction: after other gases in the second reactor are removed by adopting 1000ml/min nitrogen gas through a purging and collecting device, the mixture preheated to a molten state enters the second reactor from the output end of the first reactor, is calcined at 900 ℃, and after the carbon-based nano-reactor is accumulated continuously, the carbon-based nano-reactor slowly floats upwards due to smaller density and floats above molten salt, and the carbon-based nano-reactor enters a collecting funnel through purging and collecting the carbon-based nano-reactor at an air inlet rate of 600 ml/min.
Solid-liquid separation and collection: at the moment, molten salt is mixed in the carbon-based nano reactor collected from the collecting funnel, and is separated out through solid-liquid separation, heated and then returned to the second reactor; and then collecting the carbon-based nano reactor, flowing into a carbon material collector, and cooling to room temperature to obtain the Co@NCNT of the carbon-based nano reactor coated with the Co catalyst particles.
FIG. 6 is an XRD pattern of Co@NCNT, and it can be seen that Co@NCNT was successfully synthesized.
Example 4
The invention relates to a preparation process of a carbon-based nano reactor, which comprises the following steps:
with the apparatus for preparing a carbon-based nano-reactor described in example 1,
Mixing: the molar flow rate ratio was set to 1:14:5:1: glucose, dicyandiamide, ferric chloride hexahydrate, potassium chloride and lithium chloride of 1.5 enter a mixing device through a material channel at the speed of 1000ml/min to obtain a mixed material.
Preheating: the mixed material enters the first reactor from the output end of the mixing device, the preheating temperature is 400 ℃, at the preheating temperature, glucose and dicyandiamide are pyrolyzed to form a metal carbon-dissolving body with ferric chloride hexahydrate, and lithium chloride and potassium chloride are melted to form molten salt.
The reaction: after other gases in the second reactor are removed by adopting 1000ml/min nitrogen gas through a purging and collecting device, the mixture preheated to a molten state enters the second reactor from the output end of the first reactor, is calcined at the temperature of 1000 ℃, and after the carbon-based nano-reactor is accumulated continuously, the carbon-based nano-reactor slowly floats upwards due to smaller density and floats above molten salt, and the carbon-based nano-reactor enters a collecting funnel through purging and collecting the carbon-based nano-reactor at the air inlet rate of 800 ml/min.
Solid-liquid separation and collection: at the moment, molten salt is mixed in the carbon-based nano reactor collected from the collecting funnel, and is separated out through solid-liquid separation, heated and then returned to the second reactor; and then collecting the carbon-based nano reactor, flowing into a carbon material collector, and cooling to room temperature to obtain the carbon-based nano reactor Fe@NCNT coated with the Fe catalyst particles.
FIG. 7 is an XRD pattern of Fe@NCNT, and it can be seen that Fe@NCNT was successfully synthesized.
Example 5
The invention relates to a preparation process of a carbon-based nano reactor, which comprises the following steps:
with the apparatus for preparing a carbon-based nano-reactor described in example 1,
Mixing: the molar flow rate ratio was set to 3:12:2:5:1: glucose, dicyandiamide and sodium hypophosphite of 1.5, ferric chloride hexahydrate, potassium chloride and lithium chloride enter a mixing device through a material channel at a rate of 1000ml/min to obtain a mixed material.
Preheating: the mixed material enters the first reactor from the output end of the mixing device, the preheating temperature is 400 ℃, at the preheating temperature, glucose and dicyandiamide are pyrolyzed, and form a metal carbon-dissolving body with nickel chloride hexahydrate and sodium hypophosphite, and lithium chloride and potassium chloride are melted to form molten salt.
The reaction: after other gases in the second reactor are removed by adopting 1000ml/min nitrogen gas through a purging and collecting device, the mixture preheated to a molten state enters the second reactor from the output end of the first reactor, is calcined at the temperature of 1000 ℃, and after the carbon-based nano-reactor is accumulated continuously, the carbon-based nano-reactor slowly floats upwards due to smaller density and floats above molten salt, and the carbon-based nano-reactor is purged and collected through the air inlet rate of 1000ml/min, so that the carbon-based nano-reactor enters a collecting funnel.
Solid-liquid separation and collection: at the moment, molten salt is mixed in the carbon-based nano reactor collected from the collecting funnel, and is separated out through solid-liquid separation, heated and then returned to the second reactor; and then collecting the carbon-based nano reactor, flowing into a carbon material collector, and cooling to room temperature to obtain the FeP 2 @NCNT of the carbon-based nano reactor coated with the FeP 2 catalyst particles.
FIG. 8 is an XRD pattern for FeP 2 @ NCNT, and it can be seen that FeP 2 @ NCNT was successfully synthesized.
Example 6
The ni@ncnt obtained in example 2 was washed with 1M nitric acid followed by deionized water until the pH of the wash became neutral, followed by drying;
Sulfur melting: weighing sulfur powder and Ni@NCNT according to the mass ratio of 7:3, fully mixing, and heating to 155 ℃ to melt sulfur in a reaction kettle for 12 hours to obtain a sulfur-loaded Ni@NCNT/S anode material;
And (3) battery testing: mixing the obtained sulfur-loaded Ni@NCNT/S, carbon black conductive agent (Super P) and polyvinylidene fluoride (PVDF) binder according to a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone (NMP), grinding into paste in an agate mortar, coating on a current collector aluminum foil, drying in a vacuum drying oven at 60 ℃ for 8 hours, and cutting to prepare a pole piece. Then all the materials are transferred into a glove box filled with argon gas for assembling a button cell, the model of the button cell is CR2032, a metal lithium sheet is used as a counter electrode, a diaphragm is a polypropylene microporous membrane Celgard 2400, and electrolyte 1mol/L LiPF6/EC+DMC+EMC (V/V=1:1:1). And (3) carrying out electrochemical performance test on the assembled lithium sulfur battery on a Xinwei test system, wherein the voltage range is 1.7-2.8V.
Comparative example 1
The laboratory prepares a carbon-based nano reactor Ni@NCNT.
The molar ratio was set to 5:10:5:2:6, glucose, melamine, nickel chloride hexahydrate, calcium chloride and potassium chloride are put into a ball mill and ball-milled for 6 hours at 500 rpm. The powder was then collected and calcined in a tube furnace under nitrogen atmosphere at 600 ℃ and 800 ℃ for 4 and 2 hours, respectively. Subsequently, the resultant product was washed with 1M nitric acid followed by deionized water until the pH became neutral to remove nitric acid from the surface. And obtaining the carbon-based nano reactor Ni@NCNT coated with the Ni catalyst particles.
Sulfur melting: weighing sulfur powder and Ni@NCNT according to the mass ratio of 7:3, fully mixing, and heating to 155 ℃ to melt sulfur in a reaction kettle for 12 hours to obtain a sulfur-loaded Ni@NCNT/S anode material;
And (3) battery testing: mixing the obtained sulfur-loaded Ni@NCNT/S, carbon black conductive agent (Super P) and polyvinylidene fluoride (PVDF) binder according to a mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone (NMP), grinding into paste in an agate mortar, coating on a current collector aluminum foil, drying in a vacuum drying oven at 60 ℃ for 8 hours, and cutting to prepare a pole piece. Then all the materials are transferred into a glove box filled with argon gas for assembling a button cell, the model of the button cell is CR2032, a metal lithium sheet is used as a counter electrode, a diaphragm is a polypropylene microporous membrane Celgard 2400, and electrolyte 1mol/L LiPF6/EC+DMC+EMC (V/V=1:1:1). And (3) carrying out electrochemical performance test on the assembled lithium sulfur battery on a Xinwei test system, wherein the voltage range is 1.7-2.8V.
Fig. 9 is a graph showing the cycle performance of the positive electrode materials prepared in example 6 and the comparative example applied to a lithium sulfur battery, and it can be seen that the carbon-based nano-reactor prepared by the preparation device and the preparation process of the present invention has electrochemical performance similar to that of a carbon-based nano-reactor prepared in a small scale in a laboratory after preparing an electrode material, thereby proving that the preparation device and the preparation process of the carbon-based nano-reactor of the present invention are suitable for industrial large-scale continuous production.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (10)
1. The preparation device of the carbon-based nano reactor is characterized by comprising a first reactor, a second reactor, a solid-liquid separator and a carbon material collector; the first reactor, the solid-liquid separator and the carbon material collector are provided with an input end and an output end, and the second reactor comprises a first input end;
a purging and collecting unit is arranged in the second reactor and comprises an air inlet pipe, an air injection assembly, a collecting funnel and a collecting pipe; the air inlet pipe is communicated with the air injection assembly, and the collecting funnel is communicated with the collecting pipe;
The output end of the first reactor is communicated with the first input end of the second reactor, the collecting pipe is communicated with the input end of the solid-liquid separator, and the output end of the solid-liquid separator is communicated with the input end of the carbon material collector.
2. The apparatus for preparing a carbon-based nano-reactor according to claim 1, further comprising a mixing device, wherein the mixing device is communicated to the input end of the first reactor.
3. The device for preparing a carbon-based nano-reactor according to claim 1, wherein the purging and collecting unit is located at the top of the second reactor, the air injection assembly is annular and fixed on the inner wall of the second reactor, the air injection assembly is located above the collecting funnel, and the collecting pipe is a negative pressure pipeline.
4. The apparatus for preparing a carbon-based nano-reactor according to claim 1, further comprising a gas separator and a gas collector; the gas separator and the gas collector are both provided with an input end and an output end, the top of the second reactor is provided with a gas output end, the gas output end is communicated to the input end of the gas separator, and the output end of the gas separator is communicated to the input end of the gas collector.
5. The apparatus for preparing a carbon-based nano-reactor according to claim 1, further comprising a heater having an input end and an output end; the bottom of the second reactor is provided with a liquid output end, the side part of the second reactor is provided with a second input end, and the second input end is higher than the first input end; the liquid output end is communicated with the input end of the heater, and the output end of the heater is communicated with the second input end of the second reactor.
6. The apparatus for preparing a carbon-based nano-reactor according to claim 5, wherein the bottom of the solid-liquid separator is further provided with a liquid reflux end, and the liquid reflux end is communicated with the input end of the heater.
7. A preparation process of a carbon-based nano reactor is characterized in that:
The molar ratio was 15: (1-10): (0-5): mixing the carbon source, the transition metal salt, the heteroatom source and the molten salt in the steps (1-15) to obtain a mixed material;
Inputting the mixture into a first reactor of a preparation device of the carbon-based nano reactor according to any one of claims 1 to 6, wherein the temperature of the first reactor is kept at 400 to 600 ℃;
after the mixed materials are heated to a molten state, inputting the mixed materials into the second reactor, wherein the temperature of the second reactor is kept at 800-1000 ℃, and the purging and collecting unit blows out gas through the gas injection assembly to purge and collect generated carbon materials so that the carbon materials enter a collecting funnel;
The carbon material enters the solid-liquid separator through a collecting funnel and is subjected to solid-liquid separation to obtain the carbon-based nano reactor;
Wherein the carbon source comprises at least one of dicyandiamide, melamine, dopamine, sucrose, glucose and polyvinylpyrrolidone; the heteroatom source comprises at least one of alkali metal sulfate, alkaline earth metal sulfate, alkali metal nitrate, alkaline earth metal nitrate, alkali metal phosphate, alkaline earth metal phosphate; the molten salt includes at least one of an alkali metal halide salt and an alkaline earth metal halide salt.
8. The process for preparing a carbon-based nano-reactor according to claim 7, wherein the carbon source is a carbon source having a molar ratio of 1: glucose and melamine according to (1-4), wherein the molar ratio of the molten salt is 1:1 sodium chloride and lithium chloride.
9. The process for preparing a carbon-based nano-reactor according to claim 7, wherein the transition metal salt comprises at least one of manganese salt, iron salt, cobalt salt, nickel salt and copper salt.
10. A carbon-based nano-reactor prepared by the preparation process according to any one of claims 7 to 9, wherein the carbon-based nano-reactor is a carbon nano-tube with a diameter of less than 150nm, which is coated with metal simple substance, metal sulfide, metal phosphide, metal nitride or metal carbide nano-particles.
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