CN107792845A - A kind of preparation method of single-walled carbon nanotube - Google Patents
A kind of preparation method of single-walled carbon nanotube Download PDFInfo
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- CN107792845A CN107792845A CN201710883961.5A CN201710883961A CN107792845A CN 107792845 A CN107792845 A CN 107792845A CN 201710883961 A CN201710883961 A CN 201710883961A CN 107792845 A CN107792845 A CN 107792845A
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- carbon nanotube
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- 239000002109 single walled nanotube Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- -1 saccharide compound Chemical class 0.000 claims abstract description 8
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 241000370738 Chlorion Species 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 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 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 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 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- 235000014633 carbohydrates Nutrition 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
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- 238000003786 synthesis reaction Methods 0.000 description 13
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001423 beryllium ion Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XULDEEJZSRULEK-UHFFFAOYSA-N [Fe].CS(C)=O Chemical compound [Fe].CS(C)=O XULDEEJZSRULEK-UHFFFAOYSA-N 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of single-walled carbon nanotube, it comprises the following steps：A, at ambient temperature, a certain amount of non-metallic catalyst is added into concentrated sulfuric acid solution, is stirred, obtains mixed solution；B, a certain amount of saccharide compound powder is added in the mixed solution obtained by step A, stirring reaction, obtains the reactant mixture of carbon nanotubes；C, the reactant mixture for obtaining step B is added in hydrochloric acid solution, is stirred, and stands, upper suspension is filtrated to get into atrament, is washed with deionized, and is dried, is produced.Advantage is：Not high, succinct, easy to equipment requirement, energy consumption is low, and selectivity is good, it is easy to accomplish scale industrial production；Single-walled carbon nanotube Diameter distribution is homogeneous, and its Diameter distribution scope is between 15~20nm, and length is between 0.2~1.0 μm, and pipe range can be relatively easy to control by the adjustment in catalytic amount and reaction time.
Description
Technical field
The present invention relates to carbon nano-tube material, lithium ion battery negative material or lithium ion cell positive, negative material to add
Add the preparing technical field of agent, and in particular to a kind of preparation method of single-walled carbon nanotube.
Background technology
CNT is a kind of new carbon with tubular structure of a diameter of several nanometers to tens nanometers.Carbon
Nanotube has the advantages that high conductivity, high intensity, low-density, high-specific surface area, higher chemical stability, in energy storage, again
The fields such as condensation material, electronic device, catalysis are widely used.
The more mature technology of synthesizing carbon nanotubes synthesis at present mainly has so-called " chemical vapour deposition technique ", " laser steams
Hair method ", " Laser vaporization ", " flame synthesis ", " catalystic pyrolysis ", " arc discharge method ", " electrochemical synthesis " etc..
It is well known that the synthesis of CNT, in addition to so-called method, principle are different, one of most crucial factor is exactly catalyst,
Same principle and catalyst is different, then efficiency, the characteristic of the CNT synthesized differ widely, and catalyst is synthesis carbon nanometer
One of key factor of pipe.The catalyst of synthesizing carbon nanotubes is generally all carried noble metal, rare metal or metal oxidation
Silica, the binary metal ternary metal oxide catalytic composite material of thing, system are various.Common synthesizing carbon nanotubes
Catalyst has NiO-SiO2System, MnO-SiO2System, Fe-Mo-Al2O3、Co-Mo-Al2O3System, Ni-Co- ferrocene, two cyclopentadienyls
Iron-dimethyl sulfoxide, ferrocene catalyst, W-Fe-MgO, W-Co-MgO, Mo-Fe-MgO, Mo-Co-MgO, CeO2- Ni-MgO, two
First metal oxide system such as Ni0.5Mg1.5O, MgO-Fe bases, AByOz (wherein A=W, B=V, Cr, Mn, Fe, Co, Ni, Cu, Zn,
Rh, Ru, Pd, Pt, Au, Ag, Re, Os, Ir), Cu-Cr-O, Ho-Ni and Gd-Ni2Alloy, Er-Ni, Y-Ni catalyst etc..
The technology synthesis that the synthesis of these catalyst is typically combined using Solid phase synthesis or liquid-solid synthesis, relative skill
Difficulty is larger.Up to the present, suitable for CNT synthesis, simple non-metallic catalyst or relatively simple low cost
Liquid phase synthesis techniques document and patent it is still rare or be not disclosed, under lower temperature conditions or under room temperature condition, close
Pertinent literature or patent of invention into CNT is also rare." it is less than CNT under room temperature condition such as document report
Synthesis (Synthesis of carbon nanotubes below room temperature) " synthetic technology is 230
Electrochemically synthesizing carbon nanotubes under the conditions of~236K；In addition, Chinese invention patent CN10125493A discloses " one
The method that kind hydro-thermal method prepares CNT or rod ", but its disclosed technology is 100~240 DEG C in sulfuric acid or phosphoric acid solution
Under the conditions of hydro-thermal prepare CNT or rod, and difficulty or ease are accomplished scale production.
The technology of comprehensive existing synthesizing carbon nanotubes has the defects of notable：First, equipment requirement is high, either chemical gas
Phase sedimentation, Laser synthesizing technology or electric arc synthetic technology, it is all high to the equipment requirement of synthesizing carbon nanotubes, and condition
Control is strict；Second, technical parameter control is strict, as chemical vapour deposition technique strictly controls vacuum, the reaction of reaction system
Temperature, atmosphere oxygen content etc.；3rd, reaction time length, high energy consumption, production cost are high；Such as hydro-thermal method high energy consumption, reaction time
It is long；4th, synthesizing carbon nanotubes poor selectivity, the more walls of single wall or or nanometer rods etc., nanotube caliber or length etc. it is unsuitable easily
Control, as hydro-thermal method synthesizes possible synthesizing carbon nanotubes and nanorod hybrid；5th, energy consumption, technical conditions defect so that existing
There is technology to be all relatively difficult to efficient, scale industrial production.
The content of the invention
The present invention provides a kind of preparation method of single-walled carbon nanotube, and it has, and not high to equipment requirement, energy consumption is low, prepares
The advantages that speed is fast, it is intended to overcome the shortcomings of synthesizing carbon nanotubes technology in the prior art to a certain extent.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of preparation method of single-walled carbon nanotube, it is special
Sign is, comprises the following steps：
A, at ambient temperature, the dosage of non-metallic catalyst, non-metallic catalyst and the concentrated sulfuric acid is added into the concentrated sulfuric acid
Than for 2-12g:20-50mL, it is uniformly mixed, obtains mixed solution；
B, saccharide compound powder is added in the mixed solution obtained by step A, saccharide compound powder is molten with mixing
The amount ratio of liquid is 8-20g:20-55mL, stirring, reaction 10-55 minutes, obtain the reactant mixture of carbon nanotubes；
C, the reactant mixture for obtaining step B is added in hydrochloric acid solution, is uniformly mixed, and stands 15-45 minutes,
Upper suspension is filtrated to get atrament, nothing is washed with deionized into eluate in the atrament obtained by filtering
Sulfate radical detects without chlorion, 45-65 DEG C of dry 30-120 minute, that is, obtains described single-walled carbon nanotube.
On the basis of above-mentioned technical proposal, the present invention can also do following further specifically chosen.
Specifically, the concentration of the concentrated sulfuric acid is 75-90wt% in step A.
Specifically, saccharide compound powder is any in glucose, sucrose, maltose and water soluble starch in step B
Kind or a variety of mixing.
Specifically, the concentration of hydrochloric acid solution is 5-20wt% in step C, the dosage of hydrochloric acid solution is according to itself and B in step C
The amount ratio 100-250mL of saccharide compound powder in step:8-20g is determined.
Specifically, sulfate radical-free ion or chlorion detection refer to that sulfate concentration is less than 0.1mg/L or chlorine in eluate
Ion concentration is less than 0.05mg/L.Detection equipment used can be ion chromatograph or with saturation barium chloride solution or silver nitrate
Solution is directly quickly examined.
Specifically, the non-metallic catalyst in step A is carbon coating boron doping silicon dioxide nano material, wherein carbon silicon is former
Sub- ratio is 1.8-6.9:100, borosilicate atomic ratio is 1.2-15:100.
Above-mentioned carbon coating boron doping silicon dioxide nano material, is prepared via a method which to obtain：S1, in room temperature, stir
Under the conditions of mixing, to silicate and the mixed solution and dripping inorganic acid of tetraborate, control the pH value of reaction system for 2.5~
4.5, react 15~55 minutes, stand 15~90 minutes, obtain transparent or translucent boric acid doping silica sol, 55~
Dried 1~6 hour under the conditions of 105 DEG C, grinding, it is 6.8~7.2 to be washed to eluate pH with distillation, under the conditions of 55~105 DEG C
Dry 0.5~3 hour, that is, obtain the silicic acid gel powder of transparent or translucent boric acid doping；S2, the boron for obtaining S1 steps
The silicic acid gel powder of acid doping mixes with the aqueous solution of glucide, and wherein glucide is the silicic acid gel matter of boric acid doping
The 0.5~3% of amount, stir 15~90 minutes, the borosilicic acid for constant weight, that is, obtaining coating glucide is dried under the conditions of 85 DEG C
Gel powder mixture；S3, under room temperature, stirring condition, the mixture of powders that S2 steps obtain is added to concentrated sulfuric acid solution
In, the ratio between dosage of mixture of powders and the concentrated sulfuric acid is 105-160g:100-200mL, react 30~120 minutes, reacted
Mixture；S4, the reactant mixture obtained by S3 steps is divided into more parts and will be added gradually in 10~30 minutes
In 0.5~1.5 liter of distilled water, stir 5~30 minutes, filtering, much filtrate is washed with distilled water to eluate sulfate radical-free ion
Detection, dried 0.5~3 hour under the conditions of 55~105 DEG C, obtain powdered substance, as described carbon coating boron doping titanium dioxide
Silicon nano material.
Specifically, the concentration of silicate is 0.2~2.5mol/L in the mixed solution of S1 steps, the concentration of tetraborate is
0.003-0.01mol/L；The silicate of S1 steps is any of sodium metasilicate and potassium silicate or two kinds of mixing, tetraborate
For any of sodium tetraborate, dipotassium tetraborate and tetraboric acid ammonium or a variety of mixing；The inorganic acid of S1 steps is hydrochloric acid or sulphur
Acid, its concentration are 0.05-1.0mol/L；Specifically, the glucide of S2 steps is sucrose, glucose, maltose and water solubility
Any of starch or a variety of mixing.It is understood that in addition to the above-mentioned several soluble carbohydrate materials explicitly pointed out,
It can also be other solvable carbohydrates known in the art.Specifically, the concentration of the glucide aqueous solution of S2 steps is 5-
25wt%.Specifically, the concentration of the concentrated sulfuric acid of S3 steps is 70-90wt%.Specifically, the sulfate radical-free ion detection of S4 steps
Refer to that the concentration of sulfate radical in eluate is less than 0.05mg/L.Detection equipment used can be ion chromatograph or with saturation chlorine
Change barium solution directly quickly to examine.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, it is homogeneous using a kind of single-walled carbon nanotube Diameter distribution for synthesizing of the present invention, its Diameter distribution scope is 15~
(description of the invention accompanying drawing 1, accompanying drawing 2 are referred between 20nm)；
2nd, a kind of single length of tube synthesized using the present invention, which is grown between 0.2~1.0 μm, (refers to theory of the present invention
Bright book accompanying drawing 3, accompanying drawing 4), CNT pipe range can according to catalytic amount and reaction time adjustment it is relatively easy to control；
3rd, the fast method of a kind of single-walled carbon nanotube prepared using the present invention, can quickly, synthesize list with high selectivity
Wall carbon nano tube (SWCNTs), combined coefficient are high；
4th, synthetic technology step of the present invention is more succinct, easy, and energy consumption is low, and selectivity is good, it is easy to accomplish large-scale industrial
Production；
5th, using a kind of single tube material for preparing of the present invention, can be widely used in negative electrode of lithium ion battery and
The neck such as the materials of the energy storage such as ultracapacitor, chemical catalyst, electrochemical catalyst, organic synthesis, fine product chemical industry additive
Domain, there is good economic benefit and social benefit.
Brief description of the drawings
Fig. 1 is a kind of TEM photos for single-walled carbon nanotube that the embodiment of the present invention 1 synthesizes；
Fig. 2 be the embodiment of the present invention it is 2-in-1 into a kind of single-walled carbon nanotube TEM photos；
Fig. 3 is a kind of TEM photos for single-walled carbon nanotube that the embodiment of the present invention 3 synthesizes；
Fig. 4 is a kind of TEM photos for single-walled carbon nanotube that the embodiment of the present invention 4 synthesizes.
Embodiment
Technical scheme is described in further detail below in conjunction with drawings and the specific embodiments, example
It is served only for explaining the present invention, is not intended to limit the scope of the present invention.
Method used is then the conventional method of this area unless otherwise noted in following examples, if medicine nothing used
Special instruction is then commercially available prod.Carbon coating boron doping silicon dioxide nano material is referred to as the catalysis of carbon borosilicate in following examples
Agent.
Embodiment 1:
A kind of preparation method of single-walled carbon nanotube, it is comprised the concrete steps that：
A, at ambient temperature, 12g carbon borosilicate catalyst (C is added into 20mL, 90wt% concentrated sulfuric acid solution:Si is former
Sub- ratio about 1.8:100, B:Si atomic ratios are about 15:100), stir 15 minutes, obtain catalyst and sulfuric acid mixed solution；
B, by 8g glucose (i.e.：Carbon-source cpd, omiting below) solid powder is added to catalyst and sulphur obtained by step A
In sour mixed solution, stirring, reaction 10 minutes, the reactant mixture of carbon nanotubes is obtained；
C, the reactant mixture for obtaining step B is added to 100mL concentration in 5wt% hydrochloric acid solutions, to stir 15 minutes,
15 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized
Detected to sulfate radical-free or without chlorion, 45 DEG C of dryings 120 minutes, that is, obtain a kind of single-walled carbon nanotube；
The feature such as the pattern of synthesizing carbon nanotubes, caliber, the caliber of gained single-walled carbon nanotube with transmission electron microscope analysis
Scope is about 15~20nm, and pipe range is about 0.2~1.0 μm (referring to accompanying drawing 1).
Embodiment 2:
A kind of preparation method of single-walled carbon nanotube, it is comprised the concrete steps that：
A, at ambient temperature, 8g carbon borosilicate catalyst (C is added into 30mL, 80wt% concentrated sulfuric acid solution:Si atoms
Than being about 2.7：100, B:Si atomic ratios are about 11:100), stir 10 minutes, obtain catalyst and sulfuric acid mixed solution；
B, 12g sucrose solids powder is added in the catalyst and sulfuric acid mixed solution obtained by step A, stirring, reaction
25 minutes, obtain the reactant mixture of carbon nanotubes；
C, the reactant mixture for obtaining step B is added to 150mL concentration in 10wt% hydrochloric acid solutions, to stir 25 points
Clock, 25 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized water
Wash to sulfate radical-free or detected without chlorion, 55 DEG C of dryings 90 minutes, that is, obtain a kind of single-walled carbon nanotube；
The feature such as the pattern of synthesizing carbon nanotubes, caliber, the caliber of gained single-walled carbon nanotube with transmission electron microscope analysis
Scope is about 15~20nm, and pipe range is about 0.2~1.0 μm (referring to accompanying drawing 2).
Embodiment 3:
A kind of preparation method of single-walled carbon nanotube, it is comprised the concrete steps that：
A, at ambient temperature, 4g carbon borosilicate catalyst (C is added into 40mL, 85wt% concentrated sulfuric acid solution:Si atoms
Than being about 3.6:100, B:Si atomic ratios are about 5:100), stir 10 minutes, obtain catalyst and sulfuric acid mixed solution；
B, 16g maltose solid powders are added in the catalyst and sulfuric acid mixed solution obtained by step A, stir, be anti-
Answer 40 minutes, obtain the reactant mixture of carbon nanotubes；
C, the reactant mixture for obtaining step B is added to 200mL concentration in 15wt% hydrochloric acid solutions, to stir 35 points
Clock, 35 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized water
Wash to sulfate radical-free or detected without chlorion, 65 DEG C of dryings 30 minutes, that is, obtain a kind of single-walled carbon nanotube；
The feature such as the pattern of synthesizing carbon nanotubes, caliber, the caliber of gained single-walled carbon nanotube with transmission electron microscope analysis
Scope is about 15~20nm, and pipe range is about 0.2~1.0 μm (referring to accompanying drawing 3).
Embodiment 4:
A kind of preparation method of single-walled carbon nanotube, it is comprised the concrete steps that：
A, at ambient temperature, 2g carbon borosilicate catalyst (C is added into 50mL, 75wt% concentrated sulfuric acid solution:Si atoms
Than being about 4.2:100, B:Si atomic ratios are about 3:100), stir 15 minutes, obtain catalyst and sulfuric acid mixed solution；
B, 20g soluble starch powder is added in the catalyst and sulfuric acid mixed solution obtained by step A, stirs, be anti-
Answer 55 minutes, obtain the reactant mixture of carbon nanotubes；
C, the reactant mixture for obtaining step B is added to 250mL concentration in 20wt% hydrochloric acid solutions, to stir 45 points
Clock, 45 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized water
Wash to sulfate radical-free or detected without chlorion, 65 DEG C of dryings 45 minutes, that is, obtain a kind of single-walled carbon nanotube；
The feature such as the pattern of synthesizing carbon nanotubes, caliber, the caliber of gained single-walled carbon nanotube with transmission electron microscope analysis
Scope is about 15~20nm, and pipe range is about 0.2~1.0 μm (referring to accompanying drawing 4).
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (6)
1. a kind of preparation method of single-walled carbon nanotube, it is characterised in that comprise the following steps：
A, at ambient temperature, non-metallic catalyst is added into the concentrated sulfuric acid, the amount ratio of non-metallic catalyst and the concentrated sulfuric acid is
2-12g:20-50mL, it is uniformly mixed, obtains mixed solution；
B, saccharide compound powder is added in the mixed solution obtained by step A, saccharide compound powder and mixed solution
Amount ratio is 8-20g:20-55mL, stirring, reaction 10-55 minutes, obtain the reactant mixture of carbon nanotubes；
C, the reactant mixture for obtaining step B is added in hydrochloric acid solution, is uniformly mixed, and stands 15-45 minutes, will be upper
Layer suspension is filtrated to get atrament, and the atrament obtained by filtering is washed with deionized into eluate without sulfuric acid
Root detects without chlorion, 45-65 DEG C of dry 30-120 minute, that is, obtains described single-walled carbon nanotube.
A kind of 2. preparation method of single-walled carbon nanotube according to claim 1, it is characterised in that the non-gold in step A
Metal catalyst is carbon coating boron doping silicon dioxide nano material, and wherein carbon silicon atom ratio is 1.8-6.9:100, borosilicate atomic ratio
For 1.2-15:100.
A kind of 3. preparation method of single-walled carbon nanotube according to claim 1, it is characterised in that the concentrated sulfuric acid in step A
Concentration be 75-90wt%.
A kind of 4. preparation method of single-walled carbon nanotube according to claim 1, it is characterised in that carbohydrate in step B
Compound powder is any of glucose, sucrose, maltose and water soluble starch or a variety of mixing.
5. the preparation method of a kind of single-walled carbon nanotube according to claim 1, it is characterised in that hydrochloric acid is molten in step C
The concentration of liquid is 5-20wt%, and the dosage of hydrochloric acid solution is according to its amount ratio with saccharide compound powder in step B in step C
100-250mL:8-20g is determined.
6. the preparation method of a kind of single-walled carbon nanotube according to any one of claim 1 to 5, it is characterised in that without sulphur
Acid ion or chlorion detection refer to that sulfate concentration is less than 0.1mg/L in eluate or chlorine ion concentration is less than 0.05mg/
L。
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| CN101244817A (en) * | 2008-03-13 | 2008-08-20 | 同济大学 | Production of nano-carbon tube |
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| US20110045080A1 (en) * | 2009-03-24 | 2011-02-24 | William Marsh Rice University | Single-Walled Carbon Nanotube/Bioactive Substance Complexes and Methods Related Thereto |
| CN103303904A (en) * | 2013-06-13 | 2013-09-18 | 中国科学院金属研究所 | Method for preferentially growing metallic single-walled carbon nanotube by using non-metallic silicon oxide as catalyst |
| CN104005004A (en) * | 2014-05-16 | 2014-08-27 | 中国科学院金属研究所 | Growth method and application of minor-diameter metallic single-walled carbon nanotube |
| CN107915217A (en) * | 2016-10-10 | 2018-04-17 | 中国科学院金属研究所 | A kind of method that non-metallic catalyst SiC prepares semi-conductive single-walled carbon nanotubes |
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|---|---|---|---|---|
| CN101244817A (en) * | 2008-03-13 | 2008-08-20 | 同济大学 | Production of nano-carbon tube |
| CN101254913A (en) * | 2008-04-03 | 2008-09-03 | 天津大学 | Method for preparing carbon nano-tube or rod by hydrothermal process |
| US20110045080A1 (en) * | 2009-03-24 | 2011-02-24 | William Marsh Rice University | Single-Walled Carbon Nanotube/Bioactive Substance Complexes and Methods Related Thereto |
| CN103303904A (en) * | 2013-06-13 | 2013-09-18 | 中国科学院金属研究所 | Method for preferentially growing metallic single-walled carbon nanotube by using non-metallic silicon oxide as catalyst |
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