CN109273272A - The preparation method and its sulfur doping carbon micron tube of a kind of sulfur doping carbon micron tube and application - Google Patents
The preparation method and its sulfur doping carbon micron tube of a kind of sulfur doping carbon micron tube and application Download PDFInfo
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- CN109273272A CN109273272A CN201811019127.2A CN201811019127A CN109273272A CN 109273272 A CN109273272 A CN 109273272A CN 201811019127 A CN201811019127 A CN 201811019127A CN 109273272 A CN109273272 A CN 109273272A
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- sulfur doping
- micron tube
- doping carbon
- carbon micron
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 64
- 239000011593 sulfur Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000742 Cotton Polymers 0.000 claims abstract description 29
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 4
- 241000241602 Gossypianthus Species 0.000 claims description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 10
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 230000005518 electrochemistry Effects 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of preparation method of sulfur doping carbon micron tube and its sulfur doping carbon micron tube and applications, and this method is by single step reaction by cotton directly in H2It is carbonized and vulcanizes under S/Ar atmosphere, obtain sulfur doping carbon micron tube.The present invention prepares the method for sulfur doping carbon micron tube using cotton as raw material, is pyrolyzed to obtain a kind of sulfur doping carbon micron tube material by a step.This method simple process, the raw material used is environmentally protective, it is suitable for producing in batches, it is repeatable strong, and it is at low cost, sulfur doping and carbonization can be realized by single step reaction, and adulterated by hydrogen sulfide gas under high temperature so that sulfur doping more evenly, natural cotton can be used without by any purification process.Sulfur doping carbon micron tube produced by the present invention surface produces a large amount of nano-pore, and specific surface area is larger, and has excellent chemical property, can be used as ideal anode material of lithium-ion battery.
Description
Technical field
The invention belongs to electrode material technical fields, and in particular to a kind of preparation method of sulfur doping carbon micron tube and its institute
Sulfur doping carbon micron tube obtained and application.
Background technique
In extensive energy storage field, one of the sodium-ion battery substitute most potential as lithium ion battery is by more next
The advantages that more concern, this is primarily due to its resourceful and environment friendly.However, due to sodium ion radiusGreater than lithium ion radiusCause the kinetics of diffusion of sodium ion more blunt.Currently, reported one
A little sodium-ion battery host materials include carbon-based material, titanium base material, alloy-type material and metal oxide/sulfide material
Material etc., these materials all show preferable storage sodium performance, but their cyclical stability and unsatisfactory.
In recent years, by construct it is porous it is carbon nano-structured achieved in terms of sodium-ion battery cyclical stability it is very big
Progress.In addition, the Heteroatom dopings such as nitrogen, boron, sulphur and phosphorus are also received as the effective measures for improving carbon-based material storage sodium performance
Greatly concern.Sulphur is a kind of high electrochemical activity element, can reversibly be reacted with sodium.Therefore, sulphur is introduced into carbon material
Additional storage sodium site can be increased, lead to the increase of reversible capacity.
Summary of the invention
Goal of the invention: in view of the problems of the existing technology, the present invention provides a kind of preparation side of sulfur doping carbon micron tube
Method, this method is environmentally protective, simple process, can be obtained by a kind of sulfur doping carbon micron tube material by step pyrolysis.
The present invention also provides a kind of sulfur doping carbon micron tube material and its applications.
Technical solution: to achieve the goals above, a kind of preparation method of sulfur doping carbon micron tube as described herein, packet
Include following steps: by single step reaction by cotton directly in H2S/Ar atmosphere is carbonized in next step and vulcanization, and it is micro- to obtain sulfur doping carbon
Mitron.
Preferably, the H2In S/Ar atmosphere, H2The percent by volume of S gas is 5%~10%.
Wherein, the carbonization and vulcanization are that cotton is placed in tube furnace, make tube furnace with the rate liter of 2~10 DEG C/min
Temperature is to keeping 2~3h after 600~800 DEG C.
Preferably, under 600~800 DEG C of high temperature hydrogen sulfide gas adulterate so that sulfur doping more evenly.
Wherein, the cotton needs not move through any purification process for natural cotton and can be used.
Further, the cotton dosage is 1-2g.
The preparation-obtained sulfur doping carbon micron tube of the preparation method of sulfur doping carbon micron tube of the present invention.
Wherein, the sulfur doping carbon micron tube is by the way that after sulfur doping, the derivative carbon micron tube surface of cotton is produced largely
Nano-pore, and specific surface area is larger.
The preparation-obtained sulfur doping carbon micron tube of the preparation method of sulfur doping carbon micron tube of the present invention is as sodium
The application of ion battery cathode material.
Invention is using cotton as presoma, in H2Under S/Ar or Ar atmosphere, several carbon micron tube materials are prepared, and study
They store up sodium performance.Being found through experiments that sulfur doping carbon micron tube is with higher when as anode material of lithium-ion battery can
Inverse specific capacity, is a kind of high performance anode material of lithium-ion battery.
The cotton that preparation method of the invention is widely present using nature is raw material, by cotton in H2Vulcanize under S/Ar atmosphere
And it is carbonized and obtains sulfur doping carbon micron tube and be carbonized under an ar atmosphere to obtain carbon micron tube.Using X-ray diffractometer (XRD) and red
The ingredient of external spectrum (FT-IR) test gained sulfur doping carbon micron tube；It is aobvious using scanning electron microscope (SEM), transmitted electron
Size, pattern and the micro- knot of micro mirror (TEM) and high resolution transmission electron microscopy (HRTEM) observation gained sulfur doping carbon micron tube
Structure etc..The result shows that the sulfur doping carbon micron tube rough surface and size is larger.
The present invention uses H2S/Ar directly vulcanizes cotton, and carries out carbonization treatment simultaneously, raw materials cotton
Any purification process is needed not move through, method is simple, and the specific surface area of products therefrom is larger, is 307.6m2g-1, and exist
A large amount of micropore；And the specific surface area of biomass derived carbon material in the prior art is smaller.
Therefore, present invention gained sulfur doping carbon material specific surface area is larger, table when as anode material of lithium-ion battery
Reveal excellent high rate performance, discharge curve can be divided into two regions, and high voltage part (0.83-2V) is the strong bonding of sodium and sulphur
Effect storage sodium；Low-voltage part (being lower than 0.83V) includes inserting for the graphene film interlayer of unordered nanocrystal surface defect storage sodium sum
Layer storage sodium.Compared with undoped carbon micron tube, even if in low-voltage land regions, the specific capacity of the carbon micron tube of sulfur doping
It is still higher than undoped carbon micron tube, this is because sulfur doping introduces a large amount of micropore, is conducive to store up sodium.In addition, of the invention
The presoma of resulting materials is biomass cotton and sulphur source is hydrogen sulfide gas；And similar sulfur doping carbon material in the prior art
It is to use glucose or carbonaceous organic material for carbon matrix precursor, is vulcanized using sulphur powder as sulphur source, the predecessor of the two and choosing
The sulphur source or vulcanization taken is also entirely different.
The utility model has the advantages that compared with prior art, the invention has the following advantages that
(1) method that the present invention prepares sulfur doping carbon micron tube is pyrolyzed to obtain a kind of sulphur by a step using cotton as raw material
Doped carbon micron tube material.This method simple process, the raw material used is environmentally protective, is suitable for producing in batches, and repeatability is strong,
And it is at low cost, sulfur doping and carbonization can be realized by single step reaction, and by hydrogen sulfide gas doping under high temperature so that sulphur is mixed
It is miscellaneous more evenly, and natural cotton need not move through any purification process i.e. can be used.
(2) sulfur doping carbon micron tube produced by the present invention surface produces a large amount of nano-pore, and specific surface area is larger, and
With excellent chemical property, ideal anode material of lithium-ion battery can be used as.
Detailed description of the invention
Fig. 1 is that the SEM of sulfur doping carbon micron tube schemes, it can be observed that the average-size of sulfur doping carbon micron tube is about 8-14
μm；
Fig. 2 is that the HRTEM of sulfur doping carbon micron tube schemes, which shows that gained carbon material contains a large amount of nano-pore and micron
The surface of pipe is relatively rough；
Fig. 3 be sulfur doping carbon micron tube (S-CMTs) XRD diagram, the figure show the characteristic peak of carbon appear in 23.8 ° and
43.7 °, corresponding with (002) and (101) crystal face respectively, this is consistent with the result that HRTEM is observed, and does not have sulphur simple substance
With the diffraction maximum of pure cotton flower；
The FT-IR that Fig. 4 is S-CMTs schemes, in~1344 and~881cm-1The absorption peak that place observes can belong to C-S key
With the stretching vibration of S -- S, show that sulfur doping enters carbon structure；In 1167cm-1Absorption peak be C-O key stretching vibration,
Show that the surface S-CMTs forms the aromatic ring structure of many defects.
Fig. 5 is the charge/discharge curve figure of S-CMTs.The figure shows that first circle charge/discharge capacity is respectively 532 and 850mAh g-1, coulombic efficiency is 62.6% or so；First circle irreversible capacity loss (37.4%) is due to electrolyte decomposition and in carbon micron tube
Caused by surface forms solid electrolyte film；
Fig. 6 is S-CMTs high rate performance figure.Even if high rate performance figure shows S-CMTs at higher current densities, such as 5 Hes
10Ag-1, specific capacity can still be kept at 199 and 140mAh g-1；
Fig. 7 is S-CMTs and cotton 700 DEG C of obtained undoped carbon micron tubes (CMTs) of carbonization under an argon atmosphere
Cycle performance figure.It specifically, is 0.01-3V in voltage range, current density is 1A g-1Under conditions of, S-CMTs and
CMTs reversible capacity after the circle of circulation 1000 is respectively 281mAh g-1With 59.6mAh g-1, the results showed that the specific volume of S-CMTs
Amount will be significantly larger than the specific capacity of CMTs.
Specific embodiment
Below in conjunction with drawings and examples, the invention will be further described.
Embodiment 1
(1) preparation of sulfur doping carbon micron tube (S-CMTs)
It weighs 2g cotton to be placed in porcelain boat and be transferred in tube furnace, in H2Under S/Ar atmosphere, H2The volume basis of S gas
Than being 10%, 700 DEG C are warming up to the heating rate of 5 DEG C/min, 3h is kept, obtains the S-CMTs of black.
(2) characterization of S-CMTs
Utilize size, pattern and the micro-structure of S-CMTs obtained by SEM, XRD and HRTEM map analysis.Fig. 1 is S-CMTs's
SEM figure, the figure show that the diameter of sulfur doping carbon micron tube is about 8-14 μm；The HRTEM that Fig. 2 is S-CMTs schemes, which shows S-
The surface CMTs is rougher and there are a large amount of nano-pores.
The ingredient of gained S-CMTs is tested using XRD.Fig. 3 is the XRD diagram of S-CMTs, be can be observed in the figure
23.8 ° and 43.7 ° there are two apparent broad peaks, corresponding with (002) of S-CMTs and (101) crystal face, it was demonstrated that obtained by pyrolysis
Carbon material be amorphous structure, and do not observe in the XRD diagram of S-CMTs the peak of sulphur simple substance and pure cotton flower, show that sulphur is complete
Full doping enters carbon structure.Fig. 4 is that the FT-IR of sulfur doping carbon micron tube schemes, in 1344 and 881cm in the figure-1Place can observe
To the stretching vibration of C-S key and S -- S, in 1167cm-1Place is observed that the stretching vibration of C-O key, further demonstrates that sulphur is mixed
It is miscellaneous to enter in carbon structure.
(3) electrochemical property test
Using water as solvent, by S-CMTs obtained by the present embodiment and Super-P carbon black, sodium carboxymethylcellulose
(CMC) more uniform than ground and mixed with the quality of 70:15:15, resulting even slurry is applied on Cu foil and by it at 40 DEG C
Lower vacuum drying 12h, obtained load capacity are about 1.0mg cm-2Electrode slice.Use 1mol L-1NaClO4Propene carbonate/
Fluoro carbon ethylene carbonate (volume ratio 1:0.05) solution is as sodium-ion battery electrolyte, glass fibre and pure sodium metal foil
Respectively as sodium-ion battery diaphragm and to electrode.Electrochemical property test uses CR2032 battery.All behaviour in relation to battery
Make all to carry out in the glove box full of argon atmosphere.
The constant current charge-discharge test of battery carries out at room temperature, with blue electricity CT2001A multi-channel battery test system,
It is carried out within the scope of 0.01-3V fixed voltage.Cyclic voltammetric (CV) and electrochemical impedance spectroscopy (EIS) 4000 electrochemistry of PARSTAT
Work station is tested.CV is in 0.1mV s-1Sweep and carried out under speed, EIS is then 100kHz-10mHz in frequency range, and amplitude is
It is carried out under the sine wave of 10.0mV.
Specific chemical property is shown in Fig. 5-7.Fig. 5 is the first circle charge/discharge curve figure of S-CMTs, which shows, S-CMTs
First circle charge/discharge capacity be respectively 532 and 850mAh g-1, coulombic efficiency is 62.6% or so；First circle irreversible capacity loss
It (37.4%) is as electrolyte decomposition and caused by the surface S-CMTs forms solid electrolyte film.Fig. 6 is S-CMTs not
With the high rate performance figure under current density, even if the figure shows S-CMTs at higher current densities, such as in 5 and 10A g-1, can
Inverse capacity can still maintain 199 and 140mAh g respectively-1.Fig. 7 is the cycle performance figure of S-CMTs, S-CMTs first circle charging capacity
For 312mAhg-1, reversible capacity is 281mAh g after circulation 1000 is enclosed-1.The result of Fig. 5-7 illustrates manufactured in the present embodiment
Sulfur doping carbon micron tube has excellent chemical property, can be used as ideal anode material of lithium-ion battery.
Comparative example 1
(1) preparation of CMTs
It weighs 2g cotton to be transferred in porcelain boat and be transferred in tube furnace, under an argon atmosphere with the heating rate of 5 DEG C/min
700 DEG C are warming up to, then keeps 3h at 700 DEG C, obtains the carbon micron tube (CMTs) of black.
(2) electrochemical property test
Using water as solvent, by CMTs obtained by the present embodiment and Super-P carbon black, CMC sodium with the matter of 70:15:15
Amount is more uniform than ground and mixed, and resulting even slurry is applied on Cu foil and it is dried in vacuo 12h at 40 DEG C, is made negative
Carrying capacity is about 1.0mg cm-2Electrode slice.Use 1mol L-1NaClO4Propene carbonate/fluoro carbon ethylene carbonate (volume
Than for 1:0.05) solution as sodium-ion battery electrolyte, glass fibre and pure sodium metal foil respectively as sodium-ion battery every
Film and to electrode.The test of chemical property uses CR2032 battery.All operations in relation to battery are all being full of argon atmosphere
Glove box in carry out.
Sodium-ion battery performance test is carried out to CMTs, detailed process and conditional parameter are same as Example 1, specific to survey
Test result is shown in Fig. 5-7.As illustrated in figs. 5-7, first circle charge/discharge curve figure (Fig. 5) shows that the first circle charge/discharge capacity of CMTs is
146/270mAh g-1, charge/discharge capacity is down to 59.6/59.7mAh g after cycle performance figure (Fig. 7) shows 1000 circle of circulation-1, hence it is evident that the cycle performance lower than S-CMTs.
Comparative example 1 illustrates obviously to be not so good as the embodiment of the present invention 1 without containing its chemical property of the carbon micron tube of sulfur doping
The sulfur doping carbon micron tube of preparation.
Embodiment 2
It weighs 1g cotton to be placed in porcelain boat and be transferred in tube furnace, in H2Under S/Ar atmosphere, H2The percent by volume of S is
5%, 700 DEG C are warming up to the heating rate of 2 DEG C/min, 3h is kept, obtains the S-CMTs-2 of black.
Structural characterization and electrochemistry are carried out to obtained S-CMTs-2 compound in the same manner as shown in Example 1
It can test, it is as a result substantially the same manner as Example 1.
Embodiment 3
It weighs 2g cotton to be placed in porcelain boat and be transferred in tube furnace, in H2Under S/Ar atmosphere, H2The percent by volume of S is
10%, 800 DEG C are warming up to the heating rate of 10 DEG C/min, 3h is kept, obtains the S-CMTs-3 of black.
Structural characterization and electrochemistry are carried out to obtained S-CMTs-3 compound in the same manner as shown in Example 1
It can test, it is as a result substantially the same manner as Example 1.
Embodiment 4
It weighs 2g cotton to be placed in porcelain boat and be transferred in tube furnace, in H2Under S/Ar atmosphere, H2The percent by volume of S is
8%, 600 DEG C are warming up to the heating rate of 5 DEG C/min, 2h is kept, obtains the S-CMTs-4 of black.
Structural characterization and electrochemistry are carried out to obtained S-CMTs-4 compound in the same manner as shown in Example 1
It can test, it is as a result substantially the same manner as Example 1.
Embodiment 5
It weighs 2g cotton to be placed in porcelain boat and be transferred in tube furnace, in H2Under S/Ar atmosphere, H2The percent by volume of S is
6%, 750 DEG C are warming up to the heating rate of 8 DEG C/min, 2h is kept, obtains the S-CMTs-5 of black.
Structural characterization and electrochemistry are carried out to obtained S-CMTs-5 compound in the same manner as shown in Example 1
It can test, it is as a result substantially the same manner as Example 1.
Claims (9)
1. a kind of preparation method of sulfur doping carbon micron tube, which comprises the steps of: by single step reaction by cotton
Directly in H2It is carbonized and vulcanizes simultaneously under S/Ar atmosphere, obtain sulfur doping carbon micron tube.
2. the preparation method of sulfur doping carbon micron tube according to claim 1, which is characterized in that the H2In S/Ar atmosphere,
H2The percent by volume of S gas is 5%~10%.
3. the preparation method of sulfur doping carbon micron tube according to claim 1, which is characterized in that the carbonization and vulcanization are
Cotton is placed in tube furnace, 2~3h is kept after so that tube furnace is warming up to 600~800 DEG C with the rate of 2~10 DEG C/min.
4. the preparation method of sulfur doping carbon micron tube according to claim 3, which is characterized in that 600~800 DEG C of height
Temperature is lower adulterated using hydrogen sulfide gas so that sulfur doping more evenly.
5. the preparation method of sulfur doping carbon micron tube according to claim 1, which is characterized in that the cotton is natural cotton
Flower needs not move through any purification process and can be used.
6. the preparation method of sulfur doping carbon micron tube according to claim 1, which is characterized in that the cotton dosage is preferred
For 1-2g.
7. it is micro- to obtain sulfur doping carbon prepared by a kind of preparation method of any sulfur doping carbon micron tube of claim 1-6
Mitron.
8. sulfur doping carbon micron tube according to claim 7, which is characterized in that the sulfur doping carbon micron tube is mixed by sulphur
After miscellaneous, the derivative carbon micron tube surface of cotton produces a large amount of nano-pore, and specific surface area is larger.
9. a kind of preparation-obtained sulfur doping carbon of preparation method of any sulfur doping carbon micron tube of claim 1-6 is micro-
Application of the mitron as anode material of lithium-ion battery.
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