CN103395767A - Preparation method of sulfur-containing carbon material as well as sulfur-containing carbon material prepared by using same - Google Patents
Preparation method of sulfur-containing carbon material as well as sulfur-containing carbon material prepared by using same Download PDFInfo
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Abstract
The invention relates to a preparation method of a sulfur-containing carbon material as well as the sulfur-containing carbon material prepared by using the preparation method. The preparation method comprises the following steps of: with sulfate, sulfite or a calcined product of the sulfate or the sulfite as a template agent, and reacting with a carbon source through a gas phase chemical deposition method or a groove liquid phase impregnation method so as to prepare sulfur-containing graphene or porous carbon. The sulfur content of the prepared sulfur-containing graphene or porous carbon is 0.1-30% in percentage by mass. By using the gas phase chemical deposition method or the groove liquid phase impregnation method, sulfur-containing graphene or porous carbon can be prepared in batch. The operation condition of the method is easy to control and the operation cost is low.
Description
Technical field
The invention belongs to the new carbon preparing technical field, relate to specifically a kind of preparation method of sulfur-bearing carbon material and the sulfur-bearing carbon material of preparation thereof.
Background technology
In recent years, increasing scientific worker had carried out deep research to the doping of carbon material.For example, the major reason that Graphene can be applicable to microelectronic device is exactly the adjustability of its carrier concentration and carrier polarity, and chemical doping is realized the important way of this regulation and control exactly.The people such as Wei adopt CH
4And NH
3Grown on the copper film surface under 800 ℃ of conditions for the prepared using chemical Vapor deposition process minority layer graphene of nitrogen doping, electrical measurement shows that the Graphene of N doping shows the behavior of n-N-type semiconductorN.The people such as Dai Hongjie utilize adulterate on graphene nano band boundaries N atom and realize the n-type doping of Graphene and successfully prepare n-type field-effect transistor of electrothermal reaction method.Therefore doped graphene has potential using value in microelectronics industry.Except nitrogen atom doping, the doping of boron and sulphur atom also has report, and for example, the carbon material of mixing sulphur has good electrode capacity (Chemical Communications48 (86): 10663-10665) and catalytic activity (Acs Nano2012; 6 (1): 205-211).
With respect to nitrogen-doping, the doping of S element research report is relatively less.The people such as Yang (Acs Nano2012; 6 (1): 205-211) reported a kind of method that adopts chemical process preparation to mix sulfur graphite alkene, they adopt graphene oxide is mixed with benzyl disulfide the method for calcining afterwards obtained sulphur content 1.5% in argon gas mix sulfur graphite alkene.This research shows: after mixing sulphur, Graphene has higher catalytic performance in fuel cell.But they obtain, and to mix the sulphur sulfur-bearing also lower, also has a lot of work to remain further investigation at aspects such as preparation method and product performance.And proposition of the present invention, further enriched the preparation method of sulfur-bearing carbon material, utilize the sulfur-bearing template can obtain the controlled sulfur-bearing carbon material of pattern, and the more important thing is: adopt the art of this patent can realize the low-cost preparation in batches of sulfur-bearing Graphene or porous carbon, this lays a good foundation for the widespread use of this material.
Summary of the invention
One object of the present invention is to provide a kind of preparation method of sulfur-bearing carbon material, and method running cost of the present invention is low and technique simple, can realize that suitability for industrialized production is to prepare in batches the sulfur-bearing carbon material.
Another object of the present invention is to provide the sulfur-bearing carbon material of the method for the invention preparation.
Sulfur-bearing carbon material in the present invention refers to, in the skeleton structure of carbon material C atomic building, the S element is replaced or added to the C atom.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of preparation method of sulfur-bearing carbon material, described method comprises uses vitriol, sulphite or its calcinate to react and prepare the sulfur-bearing carbon material with carbon source by chemical vapor deposition method or liquid impregnation method as template.
Wherein preferred described carbon material is Graphene or porous carbon.
The defined vitriol of the present invention and sulphite also comprise vitriol and the corresponding hydrate of sulphite.
The present invention can also be further preferably use under carrier gas exists vitriol, sulphite or its calcinate as template by chemical vapor deposition method or the standby sulfur-bearing carbon material that obtains of liquid impregnation legal system.
According to method of the present invention, the sulfur-bearing carbon material sulphur content for preparing is mass percent 0.1%-30%.
Wherein further be preferably 1～30%.
According to method of the present invention, described vitriol comprises the one or more kinds of mixtures among ferric sulfate, ferrous sulfate, rose vitriol, single nickel salt, manganous sulfate, Tai-Ace S 150, zinc sulfate, titanium sulfate, sal epsom, alkali magnesium sulfate, copper sulfate, Basic Chrome Sulphate, lead sulfate, sublimed lead, calcium sulfate, vitriolate of tartar, sulfate of ammoniac, monoammonium sulfate, dihydrogen sulfate ammonium; Sulphite comprises the one or more kinds of mixtures in S-WAT, potassium sulfite, sodium bisulfite, Potassium hydrogen sulfite, calcium sulfite.
Any above-mentioned method according to the present invention, in described chemical vapor deposition method, carbon-source gas can adopt carbon-source gas used in carbon material in prior art (Graphene) preparation, yet in order with of the present invention, with vitriol, sulphite or its calcinate preparation method as template, to match, further to improve the sulfur-bearing carbon material quality of preparation, the preferred carbon-source gas of the present invention is the one or more kinds of mixtures among methane, ethane, ethene, acetylene, propane, propylene, butane, liquefied petroleum gas (LPG) and carbon monoxide;
Wherein be more preferably methane, ethene or acetylene;
Any above-mentioned method according to the present invention, carrier gas in described chemical vapor deposition method can be adopted carrier gas used in carbon material in prior art (Graphene) preparation, yet in order with of the present invention, with vitriol, sulphite or its calcinate preparation method as template, to match, further to improve the sulfur-bearing carbon material quality of preparation, the preferred carrier gas of the present invention is the one or more kinds of mixtures in nitrogen, argon gas, helium and ammonia;
Any above-mentioned method according to the present invention, described carrier gas and carbon-source gas amount ratio can be with reference to the amount ratios of prior art carbon material (Graphene), yet in order with of the present invention, with vitriol, sulphite or its calcinate preparation method as template, to match, further to improve the sulfur-bearing carbon material quality of preparation, and the preferred carrier gas of the present invention and carbon-source gas mol ratio are 0.1-10:1;
0.5-2:1 more preferably wherein.
The consumption of the further preferred carbon-source gas of the present invention is every gram template 0.001-0.5mol.
According to method of the present invention, the concrete operations of described chemical vapor deposition method can be with reference to prior art carbon material (Graphene) preparation manipulation, and the present invention preferably comprises the steps:
1) make simultaneously reactor be warming up to temperature of reaction to passing into carrier gas in reactor, template is added in reactor, then pass into carbon-source gas, react;
2) the question response device naturally cools to room temperature, takes out reaction product;
3) pickling purifying, then be washed to neutrality, obtain the sulfur-bearing carbon material after drying.
Wherein preferred described carbon material is Graphene.
Wherein the reactor of step 1) can prepare for this area the reactor of any suitable prior art of carbon material (Graphene) such as vertical fluidized bed bioreactor.
Wherein the preferred carrier gas of step 1) and carbon-source gas gas speed are 0.001-1m/s; 0.005-0.1m/s more preferably.
Wherein the actual conditions of the described reaction of step 1) can be with reference to the preparation feedback condition of prior art carbon material (Graphene) or other doping carbon materials (Graphene), yet in order with of the present invention, with vitriol, sulphite or its calcinate preparation method as template, to match, further to improve sulfur-bearing carbon material (Graphene) quality of preparation, the reaction times preferred for this invention is 5-200 minute;
More preferably the reaction times is 10-30min; Be preferably again 10-20min.
Wherein further preferred temperature of reaction is 300-1000 ℃;
Wherein preferred temperature of reaction is 350-900 ℃.
Can also preferred reaction pressure be wherein 0.1-0.15Mpa;
Wherein more preferably reaction pressure is normal pressure.
Naturally cooling after wherein the step 1) reaction finishes.
Any above-mentioned method according to the present invention, solvent in described liquid impregnation method (or claiming dispersion agent) can adopt solvent used in carbon material in prior art (porous carbon) preparation, yet in order with of the present invention, with vitriol, sulphite or its calcinate preparation method as template, to match, further to improve the sulfur-bearing carbon material quality of preparation, the preferred solvent of the present invention is selected from the one or more kinds of mixtures among water, ethanol, acetone, n-formyl sarcolysine base pyrrolidone, benzene, toluene, p-Xylol and m-xylene;
Wherein more preferably water or toluene.
Any above-mentioned method according to the present invention, solute in described liquid impregnation method (or claiming dispersate) can adopt solute used in carbon material in prior art (porous carbon) preparation, yet in order with of the present invention, with vitriol, sulphite or its calcinate preparation method as template, to match, further to improve the sulfur-bearing carbon material quality of preparation, the preferred solute of the present invention is selected from sucrose, vacuum residuum, pitch, wax oil, catalytic cracking product higher than the slurry oil of 500 ℃ of cuts and the one or more kinds of mixtures among coal tar;
Be this area higher than the slurry oil of 500 ℃ of cuts and coal tar in vacuum residuum of the present invention, pitch, wax oil, catalytic cracking product and commonly use, those skilled in the art can select above-mentioned substance in the scope of this area.
The present invention further the recovered temperature in the underpressure distillation that is petrochemical iy produced (such as crude production) of preferred wax oil the component of 350-500 ℃.
Any above-mentioned method according to the present invention, carrier gas in described chemical vapor deposition method can be adopted carrier gas used in carbon material in prior art (porous carbon) preparation, yet in order with of the present invention, with vitriol, sulphite or its calcinate preparation method as template, to match, further to improve the sulfur-bearing carbon material quality of preparation, the preferred carrier gas of the present invention is selected from the one or more kinds of mixtures among nitrogen, argon gas, helium, ammonia.
According to method of the present invention, described liquid impregnation method comprises the steps:
1) template is immersed in the solution of solvent and solute preparation, stirs and obtain mixed solution;
2) this mixed solution is carried out drying and processing, the template that obtains drying;
3) with step 2) template of the oven dry that obtains puts into reactor, and pass into carrier gas and reactor is heated up react;
4) the question response device naturally cools to room temperature, takes out reaction product;
5) pickling purifying, then be washed to neutrality, obtain the sulfur-bearing carbon material after drying.
Wherein further preferred described carbon material is porous carbon.
Further preferred steps 1 wherein) in the solution of described solvent and solute preparation, solute concentration is 0.01-10g/mL.
The present invention is preferably 0.01-5:1 as the solute of carbon source and the mass ratio of template;
As the solute of carbon source and the mass ratio of template, be more preferably wherein 0.01-2:1.
In order to obtain superior in quality sulfur-bearing carbon material (porous carbon) product, the solution of step 1) preparation needs evenly, when the present invention preferably is immersed in template in step 1) in the solution of solvent and solute preparation, and ultra-sonic dispersion 1-40min;
Wherein the actual conditions of the described reaction of step 3) can be with reference to the preparation feedback condition of prior art carbon material (porous carbon) or other doping carbon materials (porous carbon), yet in order with of the present invention, with vitriol, sulphite or its calcinate preparation method as template, to match, further to improve sulfur-bearing carbon material (porous carbon) quality of preparation, preferable reaction temperature of the present invention is 300-1000 ℃;
400-900 ℃ more preferably;
Wherein further the preferred reaction time is 5-600 minute;
Wherein more preferably the reaction times is 10-30 minute.
Wherein further preferred reaction pressure is 0.1-0.5Mpa;
Wherein more preferably reaction pressure is 0.1-0.15Mpa.
Naturally cooling after wherein the step 3) reaction finishes.
Template of the present invention can be any form of above-mentioned template in prior art, and the present invention is a kind of among particulate state, sheet, cylindric, block, tubulose, porous flake, Round Porous column and porous block pattern or more than one preferably.
The present invention further specific surface area of preferred described template is 1-500m
2/ g.
The present invention is in order further to improve prepared sulfur-bearing carbon material performance, preferably in any above-mentioned method of the present invention, first vitriol, sulphite or its calcinate are prepared whisker, then with the whisker of vitriol, sulphite or its calcinate as template by the standby sulfur-bearing carbon material that obtains of chemical vapor deposition method or liquid impregnation legal system.
The present invention finds, uses whisker structure better in the performance of electrochemical energy storage aspect of performance as the sulfur-bearing carbon material of template preparation.
In the preparation of sulfur-bearing carbon material of the present invention, the first step is exactly the template that preparation has the specific morphology feature.
Take alkali magnesium sulfate crystal whisker as template as example, at first adopt document Journal of Inorganic Materials2004,19, the method of introducing in 784 prepares alkali magnesium sulfate crystal whisker, whisker used is for take sal epsom and ammoniacal liquor as raw material, and reaction 5-10h is prepared under the hydrothermal condition of 160 ℃.
Then at 700 ℃ to 1000 ℃ temperature lower calcinations, thereby obtain to have the porous crystal whisker-shaped template (as shown in Figure 1) of porous circular cylinder shape.And other vitriol, sulphite or its calcinate also can even carry out the suitable adjustment of those skilled in the art's reasonably foreseeable with reference to the method to the concrete operations parameter, to prepare the whisker structure of various vitriol, sulphite or its calcinate.
The present invention further specific surface area of preferred prepared whisker is 20～60m
2/ g, its pore size distribution be 1-100nm(as shown in Figure 2).
The also further preferred described whisker length of the present invention is 5-200 μ m, and the width of whisker is 0.1-1 μ m, and the length-to-diameter ratio of whisker is at 10-550.
Wherein further preferred whisker length is 10-200 μ m; 10-100 μ m more preferably.
Wherein further preferred whisker width is 0.2-1 μ m.
Wherein further preferred whisker length-to-diameter ratio is at 40-550.
The present invention first is prepared as whisker with template, has following advantage: can prepare the sulfur-bearing porous carbon materials with tubulose or cage structure, length-to-diameter ratio is higher, and specific surface area is larger.
The present invention preferably uses sal epsom and calcium sulfate to prepare whisker, then the whisker that will prepare as template by the standby sulfur-bearing carbon material that obtains of chemical vapor deposition method or liquid impregnation legal system.
According to method of the present invention, the described pickling purifying of step (5) is this area routine operation, select the conventional acid solution in this area to wash and get final product, for example utilize hydrochloric acid soln (deionized water of the concentrated hydrochloric acid of 60% volume+40% volume) pickling reaction product to remove the metal oxide that generates in template and reaction process.
On the other hand, the present invention also provides the sulfur-bearing carbon material of described method preparation, and its specific surface area is 100-2200m
2/ g, sulphur content is the 0.1%-30%(mass percent).
Wherein preferred specific surface area is 300-1200m
2/ g;
Wherein further preferred described sulfur-bearing carbon material pore size distribution is 1-100nm, and the number of plies of this sulfur-bearing carbon material is the 1-20 layer;
Wherein preferably the number of plies of this carbon material is the 1-10 layer.
The preferred described carbon material of the present invention is Graphene or porous carbon.
In sum, the invention provides a kind of preparation method of sulfur-bearing carbon material and the sulfur-bearing carbon material of preparation thereof.Of the present invention have a following advantage: the method adopts chemical vapor deposition method or liquid impregnation method can prepare in batches the sulfur-bearing carbon material.The method operational condition is easy to control, and process cost is lower.Can control shape characteristic and the specific surface area of gained sulfur-bearing carbon material by the template of selecting different-shape, can access the higher sulfur-bearing carbon material of sulphur content, and the sulphur content that can regulate easily product by changing processing parameter; The products obtained therefrom specific surface area is higher, can reach 2200m
2/ g; , by the chemical vapor deposition method, can obtain the sulfur-bearing carbon material that is formed by 1-20 layer graphite linings.
Description of drawings
Fig. 1 is the scanning electron microscope picture of the alkali magnesium sulfate crystal whisker template after calcining 1h under 750 ℃ of conditions in embodiment 1, and wherein b is the partial enlarged drawing of a.
Fig. 2 is the pore size distribution curve of the alkali magnesium sulfate crystal whisker template after calcining 1h under 750 ℃ of conditions in embodiment 1.
Fig. 3 is the thermogravimetric analysis curve of gained sulfur-bearing Graphene in embodiment 1.
Fig. 4 is the X-ray photoelectron spectroscopic analysis of gained sulfur-bearing Graphene in embodiment 1.
Fig. 5 is adsorption/desorption curve and the pore distribution curve of gained sulfur-bearing Graphene in embodiment 1.
Fig. 6 is the Raman spectrogram of gained sulfur-bearing Graphene in embodiment 1.
Fig. 7 a is the transmission electron microscope picture of gained sulfur-bearing Graphene in embodiment 1.
Fig. 7 b is the transmission electron microscope picture of gained sulfur-bearing Graphene in embodiment 3.
Fig. 8 a, Fig. 8 b are the scanning electron microscope picture of gained sulfur-bearing Graphene in embodiment 1.
Fig. 8 c, Fig. 8 d be in embodiment 3 take ethene as carbon source, the alkali magnesium sulfate crystal whisker after calcining is the scanning electron microscope picture of the sulfur-bearing Graphene prepared of template.
Fig. 9 is that in embodiment 2, the sulfur-bearing Graphene is applied to high rate performance in ion cathode material lithium.
Figure 10 is that in embodiment 11, the sulfur-bearing porous carbon is applied to high rate performance in ion cathode material lithium.
Figure 11 is without the X ray diffracting spectrum of the reaction product of pickling purifying in embodiment 14.
Figure 12 is that in Comparative Examples 1, Graphene is applied to high rate performance in ion cathode material lithium.
Figure 13 is that in Comparative Examples 2, porous carbon is applied to high rate performance in ion cathode material lithium.
Embodiment
Below describe the beneficial effect of implementation process of the present invention and generation in detail by specific embodiment, be intended to help the reader to understand better essence of the present invention and characteristics, but not as the restriction to this case practical range.
Adopt alkali magnesium sulfate crystal whisker to prepare the sulfur-bearing Graphene as template, chemical Vapor deposition process.
Adopt document Journal of Inorganic Materials2004,19, the method of introducing in 784 prepares alkali magnesium sulfate crystal whisker, take 13.00g under 750 ℃ of conditions the calcining 1h after alkali magnesium sulfate crystal whisker as template, pass into the 0.4L/min argon gas and with the speed of 15 ℃/min, be warming up to 900 ℃ to the vertical fluidized bed bioreactor of 50mm diameter, reactor operates under condition of normal pressure, add template in the vertical fluidized bed bioreactor, then passed into the 0.4L/min methane gas stream 10 minutes, the mol ratio of argon gas and methane is 1:1.Take out reaction product after naturally cooling to room temperature, under 50-100 ℃, utilize hydrochloric acid soln (deionized water of the concentrated hydrochloric acid of 60% volume+40% volume) pickling reaction product to remove the metal oxide that generates in template and reaction process, be washed till neutrality and in 80 ℃ of oven dry, obtained the finished product 0.06g in 24 hours with deionized water finally.
Fig. 1 is that alkali magnesium sulfate crystal whisker is being calcined the electromicroscopic photograph of the template that obtains after 1h under 750 ℃ of conditions, and this template has three-dimensional porous structure.Fig. 2 is adsorption/desorption curve and the pore distribution curve of this template, has peak value at the 2-5nm place in pore distribution curve, and pore size distribution is between 1-100nm, and the whisker specific surface area is 35.8m
2/ g, the length of whisker is 40-80 μ m, and the width of whisker is 0.3-0.8 μ m, and the length-to-diameter ratio of whisker is at 50-260.The sulfur-bearing Graphene thermogravimetric analysis curve of Fig. 3 for take methane as carbon source, preparing, the sample purity of this Graphene can be up to 99.95%.According to X-ray photoelectron spectroscopic analysis (XPS sees Fig. 4), in the sulfur-bearing Graphene that this kind processing condition make, the sulfur-bearing molar percentage is 3.35%, and mass percent is 8.20%.Fig. 5 is adsorption/desorption curve and the pore distribution curve of the sulfur-bearing Graphene prepared take methane as carbon source, and the specific surface area of this Graphene is 927m
2/ g, this adsorption/desorption isothermal curve belong to H2 type lag loop (according to the classification of the IUPAC of IUPAC).There is peak value at the 3.8nm place in pore distribution curve, between pore size distribution 1-100nm.Fig. 6 is the Raman spectrum of this sulfur-bearing Graphene, and the D peak is higher, shows in Graphene and has more defective bit, and the 2D peak is the characteristic peak of graphene sheet layer, and the Graphene that electron microscopic observation shows the present embodiment preparation is the 3-10 layer approximately.
Adopt the alkali magnesium sulfate crystal whisker after calcining to prepare the sulfur-bearing Graphene as template, chemical Vapor deposition process.
Adopt document Journal of Inorganic Materials2004, the method for introducing in 19,784 prepares alkali magnesium sulfate crystal whisker, then alkali magnesium sulfate crystal whisker is calcined 1h under 750 ℃ of conditions.Pore size distribution is between 1-100nm, and the whisker specific surface area is 58.2m
2/ g, the length of whisker is 30-90 μ m, and the width of whisker is 0.2-1.0 μ m, and the length-to-diameter ratio of whisker is at 30-450.Take the alkali magnesium sulfate crystal whisker template after 10.0g calcines, pass into the 0.4L/min argon gas and with the speed of 15 ℃/min, be warming up to 900 ℃ to the vertical fluidized bed bioreactor of 50mm diameter, reactor operates under condition of normal pressure, add template in the vertical fluidized bed bioreactor, then pass into the 0.4L/min methane gas stream 10 minutes, then 900 ℃ of constant temperature 30 minutes, take out reaction product after then naturally cooling to room temperature, the pickling purification step is same as Example 1, obtains the finished product 0.05g after drying.
It is carbon source that Fig. 7 a, Fig. 8 a and Fig. 8 b have provided employing methane, the scanning of the sulfur-bearing Graphene of making and transmission electron microscope picture, and this Graphene presents sheet as can be seen from FIG., and larger with the exterior appearance difference of original template agent.
The sulfur-bearing Graphene specific surface area of the present embodiment preparation is 1200m
2/ g, pore size distribution are 1-100nm, and sulphur content is 7.96%, and the number of plies of this Graphene is the 1-4 layer.Fig. 9 is for being applied to this sulfur-bearing Graphene the high rate performance in ion cathode material lithium, and under the current density under 1000mA/g, electrical capacity is up to 720mAh/g.
Embodiment 3
Employing ethene is that carbon-source gas, chemical Vapor deposition process prepare the sulfur-bearing Graphene.
Adopt the alkali magnesium sulfate template after the process preparation described in embodiment 2 is calcined, take the 10.00g template, pass into the 0.8L/min argon gas and with the speed of 15 ℃/min, be warming up to 650 ℃ to the vertical fluidized bed bioreactor of 50mm diameter, reactor operates under condition of normal pressure, add template in the vertical fluidized bed bioreactor, then pass into 0.4L/min ethene air-flow reaction 10 minutes, take out reaction product after then naturally cooling to room temperature, the pickling purification step is same as Example 1, obtains the finished product 0.09g after drying.
It is carbon source that Fig. 7 b, Fig. 8 c and Fig. 8 d have provided employing ethene, the scanning of the sulfur-bearing Graphene of making and transmission electron microscope picture, the number of plies of this Graphene is the 3-8 layer as can be seen from FIG., and its to have similar pattern to the original template agent be porous cage shape.Because graphite flake layer is more, so its structure is comparatively stable, and reaction product still can keep original template agent pattern after the pickling purifying.
The sulfur-bearing Graphene specific surface area of the present embodiment preparation is 450m
2/ g, pore size distribution are 1-100nm, and sulphur content is 4.52%.
Embodiment 4
Employing acetylene is that carbon-source gas, chemical Vapor deposition process prepare the sulfur-bearing Graphene.
Adopt the flow process identical with embodiment 2, just adopt acetylene as carbon-source gas, temperature of reaction is 350 ℃, can prepare the sulfur-bearing Graphene.The sulfur-bearing Graphene of the present embodiment preparation has 3-10 layer graphite linings, and specific surface area is 320m
2/ g, pore size distribution are 1-100nm, sulphur content 2.36%.
Adopt MgSO
4Powder prepares the sulfur-bearing Graphene as template, chemical Vapor deposition process.
Take 30.00g MgSO
4Powder, pass into the 0.4L/min argon gas and with the speed of 15 ℃/min, be warming up to 900 ℃ to the vertical fluidized bed bioreactor of 50mm diameter, reactor operates under condition of normal pressure, add template in the vertical fluidized bed bioreactor, then pass into 0.4L/min methane gas stream reaction 20 minutes, pickling purification step and last drying step are same as Example 1, obtain the finished product 0.29g after drying.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 10.22%(massfraction in the sulfur-bearing Graphene that makes in the present embodiment).The sulfur-bearing Graphene specific surface area of the present embodiment preparation is 1136m
2/ g, pore size distribution are 1-100nm, and the number of plies of this Graphene is the 1-5 layer.
Embodiment 6
Adopt FeSO
47H
2The O crystal prepares the sulfur-bearing Graphene as template.
Take the FeSO after calcining 30min under 25.00g300 ℃ of condition
47H
2The O crystal, pass into the 0.4L/min argon gas and with the speed of 15 ℃/min, be warming up to 900 ℃ to the vertical fluidized bed bioreactor of 50mm diameter, and reactions steps, pickling purification step and last drying step are same as Example 1, obtain the finished product 0.24g after drying.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 12.55%(massfraction in the sulfur-bearing Graphene that this kind processing condition make).The sulfur-bearing Graphene specific surface area of the present embodiment preparation is 963m
2/ g, pore size distribution are 1-100nm, and the number of plies of this Graphene is the 2-6 layer.
Embodiment 7
Adopt ZnSO
47H
2The O crystal prepares the sulfur-bearing Graphene as template.
Take the 30.00g300 ℃ of ZnSO after calcining 30min
47H
2The O crystal, pass into the 0.4L/min argon gas and with the speed of 15 ℃/min, be warming up to 350 ℃ to the vertical fluidized bed bioreactor of 50mm diameter, and reactions steps, pickling purification step and last drying step are same as Example 2, obtain the finished product 0.30g after drying.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 13.85%(massfraction in the sulfur-bearing Graphene that this kind processing condition make).The sulfur-bearing Graphene specific surface area of the present embodiment preparation is 987m
2/ g, pore size distribution are 1-100nm, and the number of plies of this Graphene is the 3-8 layer.
Embodiment 8
Employing sucrose is the standby sulfur-bearing porous carbon of carbon source, liquid impregnation legal system.
take 10.00g sucrose, add the 20ml deionized water to be mixed with sucrose solution, take the alkali magnesium sulfate crystal whisker template (preparation method is identical with embodiment 2) of calcining 1h under 5.00g750 ℃ of condition, template is placed in sucrose solution normal temperature ultra-sonic dispersion 30-60min, obtain template suspension, this suspension is placed in 80 ℃ of dry 48h of baking oven, gray mixture is placed in porcelain boat, put into the argon gas that the backward stove of horizontal pipe furnace passes into 200mL/min, horizontal stove rises to 600 ℃ with 15 ℃/min temperature rise rate simultaneously, and maintenance 30min hour, normal pressure, after naturally cooling to room temperature, furnace temperature takes out the black product.The pickling purification step is same as Example 1, obtains the finished product 1.57g after drying.
The sulfur-bearing Graphene specific surface area of the present embodiment preparation is 620m
2/ g, the number of plies of this Graphene is the 3-20 layer.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 15.40%(massfraction in the sulfur-bearing Graphene that this kind processing condition make).
Embodiment 9
Employing sucrose is the standby sulfur-bearing porous carbon of carbon source, liquid impregnation legal system.
take 0.20g sucrose, add the 20ml deionized water to be mixed with sucrose solution, take the alkali magnesium sulfate crystal whisker template (preparation method is identical with embodiment 2) of calcining 1h under 5.00g750 ℃ of condition, template is placed in sucrose solution normal temperature ultra-sonic dispersion 30-60min, obtain template suspension, this suspension is placed in 80 ℃ of dry 48h of baking oven, gray mixture is placed in porcelain boat, put into the argon gas that the backward stove of horizontal pipe furnace passes into 200mL/min, horizontal stove rises to 600 ℃ with 15 ℃/min temperature rise rate simultaneously, and maintenance 30min hour, pressure is normal pressure, after naturally cooling to room temperature, furnace temperature takes out the black product.The pickling purification step is same as Example 1, obtains the finished product 0.045g after drying.
The sulfur-bearing porous carbon specific surface area of the present embodiment preparation is 920m
2/ g, the number of plies of this Graphene is the 1-5 layer.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 29.40%(massfraction in the sulfur-bearing porous carbon that this kind processing condition make).
Adopt the S-WAT particle as template, Liquid preparation methods sulfur-bearing porous carbon.
Take 4.00g sucrose, add the 20ml deionized water to be mixed with sucrose solution, take 8.00g Na
2SO
3The powder template, template dipping sucrose step, reactions steps and pickling purification step are same as Example 8, obtain the finished product 0.86g after drying.
The sulfur-bearing Graphene specific surface area of the present embodiment preparation is 420m
2/ g, the number of plies of this Graphene is the 3-8 layer.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 21.95%(massfraction in the sulfur-bearing porous carbon that this kind processing condition make).
Embodiment 11
Employing pitch is the standby sulfur-bearing porous carbon of carbon source, liquid impregnation legal system.
Take 2.00g pitch, add the ultrasonic 20min of 40ml toluene to be mixed with bituminous solution, take under 10.00g750 ℃ of condition calcining 1h alkali magnesium sulfate crystal whisker template (preparation method is identical with embodiment 2), template is placed in bituminous solution normal temperature ultra-sonic dispersion 30-60min, obtain template suspension, this suspension is placed in 80 ℃ of dry 48h of baking oven, and remaining reaction step and pickling purification step are same as Example 8, obtain the finished product 0.99g after drying.
According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 19.42%(massfraction in the sulfur-bearing porous carbon that this kind processing condition make), the sample specific surface area is 365m
2/ g.
Figure 11 is for being applied to this sulfur-bearing porous carbon the high rate performance in ion cathode material lithium, and under the current density under 1000mA/g, electrical capacity is up to 650mAh/g.
Embodiment 12
Adopt calcium sulfate crystal whiskers as template, utilize the standby sulfur-bearing porous carbon of liquid impregnation legal system.
The employing document (inorganic chemicals industry, 2010, v.42; No.25401:44-47) method of introducing in prepares calcium sulfate crystal whiskers as template, and the whisker pore size distribution is between 1-60nm, and the whisker specific surface area is 23m
2/ g, the length of whisker is 9-50 μ m, and the width of whisker is 0.1-0.9 μ m, and the length-to-diameter ratio of whisker is at 10-500.Take 3.00g pitch, add the ultrasonic 20min of 40ml toluene to be mixed with bituminous solution, take the 10.00g template, the template impregnation steps is same as Example 7, and dip compound is placed in porcelain boat, puts into the backward stove of horizontal stove and passes into the 200mL/min argon gas, horizontal stove is warming up to 700 ℃, and keeping 30min, reaction pressure 0.1-0.15Mpa, take out the black product after furnace temperature naturally cools to room temperature.The pickling purification step is same as Example 1, obtains the finished product 0.75g after drying.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 21.32%(massfraction in the sulfur-bearing porous carbon that this kind processing condition make) the sample specific surface area is 342m
2/ g.
Embodiment 13
Utilize NiSO
46H
2The O crystal has obtained sulfur-bearing porous carbon-NiO matrix material as template.
Take 1.00g pitch, add the ultrasonic 20min of 40ml toluene to be mixed with bituminous solution, take the 10.00g200 ℃ of NiSO after calcining 30min
46H
2O crystal template, template is flooded the sucrose step, reactions steps is same as Example 7, uses hydrochloric acid in shortage in the pickling purge process, only has like this part NiO to be removed, therefore obtain sulfur-bearing Graphene-NiO matrix material, obtained the finished product 0.6g after drying.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 14.36%(mass percent in the matrix material that this kind processing condition make), nickeliferous 20%(mass percent) and, the sample specific surface area is 530m
2/ g.
Embodiment 14
Liquid preparation methods sulfur-bearing porous carbon when temperature of reaction is 700 ℃.
Under the pitch that takes equal in quality with example 12 and 750 ℃ of conditions of the toluene that measures equal volume and equal in quality calcining 1h the alkali magnesium sulfate crystal whisker template, template impregnating pitch step is same as Example 9, dip compound is placed in porcelain boat, put into the backward stove of horizontal stove and pass into argon gas, pass into speed 150mL/min), the horizontal stove temperature of reaction is 700 ℃, and constant temperature 30 minutes, reaction pressure 0.1-0.15Mpa, the pickling purification step is same as Example 1, obtains the finished product 0.70g after drying.
According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 28.96%(massfraction in the sulfur-bearing porous carbon that this kind processing condition make).Analyze the not reaction product of pickling purifying according to X ray diffracting spectrum (Figure 13), contain characteristic peak and the MgSO of MgO in collection of illustrative plates
4Characteristic peak, illustrate under these processing condition, and pitch and segment template agent reaction have generated sulfur-bearing porous carbon and MgO, and the sample specific surface area is 650m
2/ g.
Liquid preparation methods sulfur-bearing porous carbon when temperature of reaction is 800 ℃.
Under the pitch that takes equal in quality with example 12 and 750 ℃ of conditions of the toluene that measures equal volume and equal in quality calcining 1h the alkali magnesium sulfate crystal whisker template, template impregnating pitch step is identical with example 12, dip compound is placed in porcelain boat, put into the backward stove of horizontal stove and pass into nitrogen, pass into speed 200ml/min), the horizontal stove temperature of reaction is 800 ℃, and constant temperature 30 minutes, reaction pressure 0.1-0.15Mpa, the pickling purification step is same as Example 1, obtains the finished product 0.53g after drying.
According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 28.04%(massfraction in the sulfur-bearing porous carbon that this kind processing condition make).Adopt the not reaction product of pickling purifying of X-ray diffraction analysis, only contain the characteristic peak of MgO in collection of illustrative plates, illustrate under these processing condition, reaction has occurred in pitch and whole template, has generated sulfur-bearing Graphene and MgO.The sulfur-bearing porous carbon specific surface area of the present embodiment preparation is 680m
2/ g, the number of plies of this Graphene is the 2-10 layer.
Embodiment 16
Liquid preparation methods sulfur-bearing porous carbon when temperature of reaction is 900 ℃.
Under the pitch that takes equal in quality with example 12 and 750 ℃ of conditions of the toluene that measures equal volume and equal in quality calcining 1h the alkali magnesium sulfate crystal whisker template, template impregnating pitch step is identical with example 12, dip compound is placed in porcelain boat, put into the backward stove of horizontal stove and pass into 100mL/min nitrogen, the horizontal stove temperature of reaction is 900 ℃, and constant temperature 30 minutes, reaction pressure 0.1-0.15Mpa, the pickling purification step is same as Example 1, obtains the finished product 0.45g after drying.
According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 23.59%(massfraction in the sulfur-bearing porous carbon that this kind processing condition make).Adopt the not reaction product of pickling purifying of X-ray diffractogram spectrum analysis, only contain the characteristic peak of MgO in collection of illustrative plates, and peak intensity is higher, explanation is under these processing condition, reaction has occurred in pitch and whole template, has generated sulfur-bearing Graphene and MgO, and the sample specific surface area is 730m
2/ g.
Embodiment 17
Liquid preparation methods sulfur-bearing porous carbon when temperature of reaction is 1000 ℃.
Under the pitch that takes equal in quality with example 12 and 750 ℃ of conditions of the toluene that measures equal volume and equal in quality calcining 1h the alkali magnesium sulfate crystal whisker template, template impregnating pitch step is identical with example 12, dip compound is placed in porcelain boat, put into the backward stove of horizontal stove and pass into the 500mL/min argon gas, the horizontal stove temperature of reaction is 1000 ℃, and constant temperature 30 minutes, reaction pressure 0.1-0.2Mpa, the pickling purification step is same as Example 1, obtains the finished product 0.37g after drying.
According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 12.75%(massfraction in the sulfur-bearing Graphene that this kind processing condition make), gained sulfur-bearing Graphene specific surface area is 921m
2/ g, the number of plies of this Graphene is the 3-8 layer.
Embodiment 18
Adopt the mixture of nitrogen and krypton as carrier gas Liquid preparation methods sulfur-bearing porous carbon.
Under the pitch that takes equal in quality with example 12 and 750 ℃ of conditions of the toluene that measures equal volume and equal in quality calcining 1h the alkali magnesium sulfate crystal whisker template, template impregnating pitch step is identical with example 12, dip compound is placed in porcelain boat, put into the mixture that the backward stove of horizontal stove passes into nitrogen and krypton and pass into speed 200ml/min, the horizontal stove temperature of reaction is 700 ℃, and constant temperature 30 minutes, reaction pressure 0.1-0.2Mpa, the pickling purification step is same as Example 1, obtains the finished product 0.70g after drying.
According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 23.36%(massfraction in the sulfur-bearing Graphene that this kind processing condition make), specific surface area is 685m
2/ g.
Comparative Examples 1
Magnesia crystal whisker after the employing calcining is as template, process for preparing graphenes by chemical vapour deposition.
Alkali magnesium sulfate crystal whisker is calcined 1h under 1200 ℃ of conditions and obtained the not magnesia crystal whisker of sulfur-bearing.Take the magnesia crystal whisker template after 10.0g calcines, pass into the 0.4L/min argon gas and with the speed of 15 ℃/min, be warming up to 900 ℃ to the vertical fluidized bed bioreactor of 50mm diameter, reactor operates under condition of normal pressure, add template in the vertical fluidized bed bioreactor, then pass into the 0.4L/min methane gas stream 10 minutes, then 900 ℃ of constant temperature 30 minutes, take out reaction product after then naturally cooling to room temperature, the pickling purification step is same as Example 1, obtains the finished product 0.12g after drying.
Figure 10 is for being applied to this Graphene the high rate performance in ion cathode material lithium, and under the current density under 1000mA/g, electrical capacity is 300mAh/g, lower than the electrical capacity of sulfur-bearing Graphene in example 3.
Comparative Examples 2
Employing pitch is the standby porous carbon of carbon source, liquid impregnation legal system.
Take 2.00g pitch, add the ultrasonic 20min of 40ml toluene to be mixed with bituminous solution, take under 10.00g1200 ℃ of condition calcining 1h the magnesia crystal whisker template, template is placed in bituminous solution normal temperature ultra-sonic dispersion 30-60min, obtain template suspension, this suspension is placed in 80 ℃ of dry 48h of baking oven, and remaining reaction step and pickling purification step are same as Example 7, obtain the finished product 0.13g after drying.
Figure 12 is for being applied to this Graphene the high rate performance in ion cathode material lithium, and under the current density under 1000mA/g, electrical capacity is 320mAh/g, lower than the electrical capacity of sulfur-bearing Graphene in example 11.
Claims (10)
1. the preparation method of a sulfur-bearing carbon material, it is characterized in that, described method comprises uses vitriol, sulphite or its calcinate to react and prepare the sulfur-bearing carbon material with carbon source by chemical vapor deposition method or liquid impregnation method as template, and preferred described carbon material is Graphene or porous carbon.
2. method according to claim 1, is characterized in that, the sulfur-bearing carbon material sulphur content for preparing is mass percent 0.1%-30%.
3. method according to claim 1, it is characterized in that, described vitriol comprises the one or more kinds of mixtures among ferric sulfate, ferrous sulfate, rose vitriol, single nickel salt, manganous sulfate, Tai-Ace S 150, zinc sulfate, titanium sulfate, sal epsom, alkali magnesium sulfate, copper sulfate, Basic Chrome Sulphate, lead sulfate, sublimed lead, calcium sulfate, vitriolate of tartar, sulfate of ammoniac, monoammonium sulfate, dihydrogen sulfate ammonium; Sulphite comprises the one or more kinds of mixtures in S-WAT, potassium sulfite, sodium bisulfite, Potassium hydrogen sulfite, calcium sulfite.
4. according to claim 1-3 described methods of any one, it is characterized in that, described chemical vapor deposition method selects one or more kinds of mixtures among methane, ethane, ethene, acetylene, propane, propylene, butane, liquefied petroleum gas (LPG) and carbon monoxide as carbon-source gas; Select one or more kinds of mixtures in nitrogen, argon gas, ammonia and helium as carrier gas; Preferred carrier gas and carbon-source gas mol ratio are 0.1-10:1, more preferably 0.5-2:1.
5. method according to claim 4, is characterized in that, described chemical vapor deposition method comprises the steps:
1) make simultaneously reactor be warming up to temperature of reaction to passing into carrier gas in reactor, template is added in reactor, then pass into carbon-source gas, react; Preferred carrier gas and carbon-source gas gas speed are 0.001-1m/s; The preferred reaction time is 5-200 minute; Preferable reaction temperature is 300-1000 ℃, and more preferably temperature of reaction is 350-900 ℃; Preferred reaction pressure is 0.1-0.15Mpa;
2) the question response device naturally cools to room temperature, takes out reaction product;
3) pickling purifying, then be washed to neutrality, obtain the sulfur-bearing carbon material after drying; Preferred described carbon material is Graphene.
6. according to claim 1-3 described methods of any one, it is characterized in that, solvent in described liquid impregnation method is selected from the one or more kinds of mixtures among water, ethanol, acetone, n-formyl sarcolysine base pyrrolidone, benzene, toluene, p-Xylol and m-xylene, is preferably water or toluene; Solute as carbon source is selected from sucrose, vacuum residuum, pitch, wax oil, catalytic cracking product higher than the slurry oil of 500 ℃ of cuts and the one or more kinds of mixtures among coal tar; Carrier gas is selected from the one or more kinds of mixtures among nitrogen, argon gas, helium, ammonia.
7. method according to claim 6, is characterized in that, described liquid impregnation method comprises the steps:
1) template is immersed in the solution of solvent and solute preparation, stirs and obtain mixed solution; In the solution of preferred described solvent and solute preparation, solute concentration is 0.01-10g/mL;
2) this mixed solution is carried out drying and processing, the template that obtains drying;
3) with step 2) template of the oven dry that obtains puts into reactor, passes into carrier gas and reactor heated up react, and preferred temperature is 300-1000 ℃, more preferably 400-900 ℃; The preferred reaction time is 5-600 minute; Preferred reaction pressure 0.1-0.5Mpa;
4) the question response device naturally cools to room temperature, takes out reaction product;
5) pickling purifying, then be washed to neutrality, obtaining the sulfur-bearing carbon material after drying is porous carbon.
8. according to claim 1-7 described methods of any one, it is characterized in that, described method first prepares whisker with vitriol, sulphite or its calcinate, then with the whisker of vitriol, sulphite or its calcinate as template by the standby sulfur-bearing carbon material that obtains of chemical vapor deposition method or liquid impregnation legal system.
9. method according to claim 8, is characterized in that, the length of described whisker is 5-200 μ m, and the width of whisker is 0.1-1 μ m, and the length-to-diameter ratio of whisker is at 10-550.
10. the sulfur-bearing carbon material of the described method of claim 1-9 any one preparation; Preferred its specific surface area is 100-2200m
2/ g, sulphur content is 0.1%-30%; Described carbon material is Graphene or porous carbon.
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