CN103395767B - A kind of preparation method of sulfur-bearing carbon material and the sulfur-bearing carbon material of preparation thereof - Google Patents
A kind of preparation method of sulfur-bearing carbon material and the sulfur-bearing carbon material of preparation thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of sulfur-bearing carbon material and the sulfur-bearing carbon material of preparation thereof, described method is comprised and uses vitriol, sulphite or its calcinate to be reacted by chemical vapor deposition method or liquid-phase impregnation process and carbon source as template to prepare sulfur-bearing Graphene or porous carbon.The sulfur-bearing Graphene prepared or porous carbon sulphur content are mass percent 0.1%-30%.The method adopts chemical vapor deposition method or liquid-phase impregnation process can prepare sulfur-bearing Graphene or porous carbon in batches.The method operational condition is easy to control, and process cost is lower.
Description
Technical field
The invention belongs to new carbon preparing technical field, relate to a kind of preparation method of sulfur-bearing carbon material and the sulfur-bearing carbon material of preparation thereof specifically.
Background technology
In recent years, increasing scientific worker had carried out deep research to the doping of carbon material.Such as, 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 realizes the important way of this regulation and control exactly.The people such as Wei adopt CH
4and NH
3for prepared using chemical Vapor deposition process under 800 DEG C of conditions in Copper thin film surface-borne the minority layer graphene of N doping, electrical measurement shows that the Graphene that N adulterates shows the behavior of n-type semi-conductor.The people such as Dai Hongjie utilize electrothermal reaction method adulterate in graphene nano band boundaries atom N and realize Graphene n-type doping and successfully prepare n-type field-effect transistor.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 such as, the carbon material mixing sulphur has good electrode capacity (ChemicalCommunications48 (86): 10663-10665) and catalytic activity (AcsNano2012; 6 (1): 205-211).
Relative to nitrogen-doping, the doping research report of S element is relatively less.The people such as Yang (AcsNano2012; 6 (1): 205-211) report and a kind ofly adopt chemical process to prepare to mix the method for sulfur graphite alkene, what the method that they calcine after adopting and being mixed with benzyl disulfide by graphene oxide in argon gas obtained sulphur content 1.5% mixes sulfur graphite alkene.This research shows: after mixing sulphur, and Graphene has higher catalytic performance in a fuel cell.It is also lower that what but they obtained mix sulphur sulfur-bearing, also has a lot of work to need to be studied in preparation method and product performance etc.And proposition of the present invention, enrich the preparation method of sulfur-bearing carbon material further, utilize sulfur-bearing template can obtain the sulfur-bearing carbon material of morphology controllable, and the more important thing is: adopt the art of this patent can realize the low cost batch preparation of sulfur-bearing Graphene or porous carbon, this is that the widespread use of this material is laid a good foundation.
Summary of the invention
One object of the present invention is the preparation method providing a kind of sulfur-bearing carbon material, and method running cost of the present invention is low and technique simple, can realize suitability for industrialized production prepares sulfur-bearing carbon material with batch.
Another object of the present invention is to the sulfur-bearing carbon material providing the method for the invention to prepare.
Sulfur-bearing carbon material in the present invention refer in the skeleton structure of carbon material C atomic building by C atom replace or add S element.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of preparation method of sulfur-bearing carbon material, described method is comprised and uses vitriol, sulphite or its calcinate to be reacted by chemical vapor deposition method or liquid-phase impregnation process and carbon source as template to prepare sulfur-bearing carbon material.
Wherein preferred described carbon material is Graphene or porous carbon.
The vitriol that the present invention defines and sulphite also comprise vitriol and the corresponding hydrate of sulphite.
The present invention can also preferably further use vitriol, sulphite or its calcinate to prepare sulfur-bearing carbon material as template by chemical vapor deposition method or liquid-phase impregnation process under carrier gas exists.
According to method of the present invention, the sulfur-bearing carbon material sulphur content prepared 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, magnesium sulfate, alkali magnesium sulfate, copper sulfate, Basic Chrome Sulphate, lead sulfate, sublimed lead, calcium sulfate, potassium sulfate, 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.
The method above-mentioned arbitrarily according to the present invention, the carbon-source gas that in described chemical vapor deposition method, carbon-source gas is used during carbon material in prior art (Graphene) can be adopted to prepare, but in order to match with vitriol of the present invention, sulphite or its calcinate preparation method as template, 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;
The method above-mentioned arbitrarily according to the present invention, the carrier gas that carrier gas in described chemical vapor deposition method is used during carbon material in prior art (Graphene) can be adopted to prepare, but in order to match with vitriol of the present invention, sulphite or its calcinate preparation method as template, 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;
The method above-mentioned arbitrarily according to the present invention, described carrier gas and carbon-source gas amount ratio can with reference to the amount ratios of prior art carbon material (Graphene), but in order to match with vitriol of the present invention, sulphite or its calcinate preparation method as template, 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;
Wherein be more preferably 0.5-2:1.
The consumption of the further preferably carbon-source gas of the present invention is every gram of template 0.001-0.5mol.
According to method of the present invention, the concrete operations of described chemical vapor deposition method can with reference to prior art carbon material (Graphene) preparation manipulation, and the present invention preferably comprises the steps:
1) in reactor, pass into carrier gas makes reactor be warming up to temperature of reaction simultaneously, template is added in reactor, then passes into carbon-source gas, react;
2) question response device naturally cools to room temperature, takes out reaction product;
3) pickling purifying, then be washed to neutrality, obtain sulfur-bearing carbon material after drying.
Wherein preferred described carbon material is Graphene.
Wherein the reactor of step 1) can prepare the reactor of any suitable prior art of carbon material (Graphene) for this area, 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; Be more preferably 0.005-0.1m/s.
The actual conditions wherein reacted described in step 1) can with reference to the preparation feedback condition of prior art carbon material (Graphene) or other doping carbon materials (Graphene), but in order to match with vitriol of the present invention, sulphite or its calcinate preparation method as template, 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 10-20min again.
Wherein preferred temperature of reaction is 300-1000 DEG C further;
Wherein preferred temperature of reaction is 350-900 DEG C.
Can also preferred reaction pressure be wherein 0.1-0.15Mpa;
Wherein more preferably reaction pressure is normal pressure.
Wherein step 1) reaction terminates rear naturally cooling.
The method above-mentioned arbitrarily according to the present invention, solvent used during solvent (or claiming dispersion agent) can adopt carbon material in prior art (porous carbon) to prepare in described liquid-phase impregnation process, but in order to match with vitriol of the present invention, sulphite or its calcinate preparation method as template, 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, nitrogen methyl-2-pyrrolidone, benzene, toluene, p-Xylol and m-xylene;
Wherein more preferably water or toluene.
The method above-mentioned arbitrarily according to the present invention, solute used during solute (or claiming dispersate) can adopt carbon material in prior art (porous carbon) to prepare in described liquid-phase impregnation process, but in order to match with vitriol of the present invention, sulphite or its calcinate preparation method as template, 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 one or more kinds of mixtures among the slurry oil of 500 DEG C of cuts and coal tar;
In vacuum residuum of the present invention, pitch, wax oil, catalytic cracking product higher than the slurry oil of 500 DEG C of cuts and coal tar be this area commonly use, those skilled in the art can select above-mentioned substance within the scope of this area.
The present invention further preferred wax oil is the recovered temperature in the underpressure distillation of petrochemical iy produced (such as crude production) the component of 350-500 DEG C.
The method above-mentioned arbitrarily according to the present invention, the carrier gas that carrier gas in described chemical vapor deposition method is used during carbon material in prior art (porous carbon) can be adopted to prepare, but in order to match with vitriol of the present invention, sulphite or its calcinate preparation method as template, 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-phase impregnation process 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, obtain the template of drying;
3) by step 2) template of oven dry that obtains puts into reactor, and pass into carrier gas and make reactor heat up to react simultaneously;
4) question response device naturally cools to room temperature, takes out reaction product;
5) pickling purifying, then be washed to neutrality, obtain sulfur-bearing carbon material after drying.
Wherein further preferred described carbon material is porous carbon.
Wherein further preferred steps 1) described in solvent and solute preparation solution in solute concentration be 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;
Be more preferably wherein 0.01-2:1 as the solute of carbon source and the mass ratio of template.
In order to obtain superior in quality sulfur-bearing carbon material (porous carbon) product, the solution of step 1) preparation needs evenly, the present invention preferably when template to be immersed in the solution of solvent and solute preparation by step 1), ultrasonic disperse 1-40min;
Wherein step 2) described in oven dry be the oven dry that this area is understood usually, namely dry to solvent be the degree that this area accepts usually.
The actual conditions wherein reacted described in step 3) can with reference to the preparation feedback condition of prior art carbon material (porous carbon) or other doping carbon materials (porous carbon), but in order to match with vitriol of the present invention, sulphite or its calcinate preparation method as template, further to improve sulfur-bearing carbon material (porous carbon) quality of preparation, preferable reaction temperature of the present invention is 300-1000 DEG C;
Be more preferably 400-900 DEG C;
Wherein the preferred reaction time is 5-600 minute further;
Wherein more preferably the reaction times is 10-30 minute.
Can also preferred reaction pressure be wherein 0.1-0.5Mpa further;
Wherein more preferably reaction pressure is 0.1-0.15Mpa.
Wherein step 3) reaction terminates rear naturally cooling.
Template of the present invention can be any form of above-mentioned template in prior art, the one or more than one of the present invention preferably among particulate state, sheet, cylindric, block, tubulose, porous flake, Round Porous column and porous block pattern.
The specific surface area of the further preferred described template of the present invention is 1-500m
2/ g.
The present invention is in order to improve prepared sulfur-bearing carbon material performance further, preferably in the method that the present invention is above-mentioned arbitrarily, first vitriol, sulphite or its calcinate are prepared whisker, then the whisker of vitriol, sulphite or its calcinate is prepared sulfur-bearing carbon material as template by chemical vapor deposition method or liquid-phase impregnation process.
The present invention finds, the sulfur-bearing carbon material using whisker structure to prepare as template is better in the performance of electrochemical energy storage aspect of performance.
In the preparation of sulfur-bearing carbon material of the present invention, the first step is exactly the template that preparation has specific morphology feature.
For alkali magnesium sulfate crystal whisker as template, first adopt document JournalofInorganicMaterials2004,19, the method introduced in 784 prepares alkali magnesium sulfate crystal whisker, whisker used be with magnesium sulfate and ammoniacal liquor for raw material, under the hydrothermal condition of 160 DEG C, react 5-10h be prepared from.
Then at 700 DEG C to 1000 DEG C temperature lower calcinations, thus the porous crystal whisker-shaped template (as shown in Figure 1) with porous circular cylinder shape is obtained.And other vitriol, sulphite or its calcinate also can refer to the method, even concrete operations parameter is carried out to the suitable adjustment of those skilled in the art's reasonably foreseeable, to prepare the whisker structure of various vitriol, sulphite or its calcinate.
The specific surface area of the whisker that the present invention is preferably prepared is further 20 ~ 60m
2/ g, its pore size distribution be 1-100nm(as shown in Figure 2).
The present invention also further preferred described whisker length is 5-200 μm, and the width of whisker is 0.1-1 μm, and the length-to-diameter ratio of whisker is at 10-550.
Wherein preferably whisker length is 10-200 μm further; Be more preferably 10-100 μm.
Wherein preferably whisker width is 0.2-1 μm further.
Wherein further preferably whisker length-to-diameter ratio is at 40-550.
Template is first prepared as whisker by the present invention, and tool has the following advantages: 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 magnesium sulfate and calcium sulfate to prepare whisker, then the whisker of preparation is prepared sulfur-bearing carbon material as template by chemical vapor deposition method or liquid-phase impregnation process.
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 carry out washing, such as utilize hydrochloric acid soln (deionized water of concentrated hydrochloric acid+40% volume of 60% volume) pickling reaction product to remove the metal oxide generated in template and reaction process.
On the other hand, present invention also offers sulfur-bearing carbon material prepared by described method, its specific surface area is 100-2200m
2/ g, sulphur content is 0.1%-30%(mass percent).
Wherein preferably specific surface area is 300-1200m
2/ g;
Can also further preferred described sulfur-bearing carbon material pore size distribution be wherein 1-100nm, the number of plies of this sulfur-bearing carbon material be 1-20 layer;
Can also the number of plies of preferred this carbon material be wherein 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.Tool of the present invention has the following advantages: the method adopts chemical vapor deposition method or liquid-phase impregnation process can prepare sulfur-bearing carbon material in batches.The method operational condition is easy to control, and process cost is lower.By shape characteristic and the specific surface area selecting the template of different-shape to control gained sulfur-bearing carbon material, can obtain the sulfur-bearing carbon material that sulphur content is higher, and the sulphur content of product can be regulated easily by changing processing parameter; Products obtained therefrom specific surface area is higher, can reach 2200m
2/ g; By chemical vapor deposition method, the sulfur-bearing carbon material be made up of 1-20 layer graphite linings can be obtained.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of the alkali magnesium sulfate crystal whisker template after calcining 1h in embodiment 1 under 750 DEG C of conditions, 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 in embodiment 1 under 750 DEG C of conditions.
Fig. 3 is the thermal gravimetric 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 microscopic picture of gained sulfur-bearing Graphene in embodiment 1.
Fig. 8 c, Fig. 8 d are in embodiment 3 be carbon source with ethene, and the alkali magnesium sulfate crystal whisker after calcining is the scanning electron microscopic picture of the sulfur-bearing Graphene that template is prepared.
Fig. 9 is that in embodiment 2, sulfur-bearing Graphene is applied to the high rate performance in ion cathode material lithium.
Figure 10 is that in embodiment 11, sulfur-bearing porous carbon is applied to the high rate performance in ion cathode material lithium.
Figure 11 is the X ray diffracting spectrum without the reaction product of pickling purifying in embodiment 14.
Figure 12 is that in comparative example 1, Graphene is applied to the high rate performance in ion cathode material lithium.
Figure 13 is that in comparative example 2, porous carbon is applied to the high rate performance in ion cathode material lithium.
Embodiment
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
Embodiment 1
Alkali magnesium sulfate crystal whisker is adopted to prepare sulfur-bearing Graphene as template, chemical Vapor deposition process.
Adopt document JournalofInorganicMaterials2004,19, the method introduced in 784 prepares alkali magnesium sulfate crystal whisker, take 13.00g under 750 DEG C of conditions, calcine 1h after alkali magnesium sulfate crystal whisker as template, vertical fluidized bed bioreactor to 50mm diameter passes into 0.4L/min argon gas and with the ramp to 900 DEG C of 15 DEG C/min, reactor operates in atmospheric conditions, template is added in vertical fluidized bed bioreactor, then pass into 0.4L/min methane gas stream 10 minutes, the mol ratio of argon gas and methane is 1:1.Reaction product is taken out after naturally cooling to room temperature, at 50-100 DEG C, utilize hydrochloric acid soln (deionized water of concentrated hydrochloric acid+40% volume of 60% volume) pickling reaction product to remove the metal oxide generated in template and reaction process, be finally washed till neutrality with deionized water and within 24 hours, obtain the finished product 0.06g in 80 DEG C of oven dry.
Fig. 1 is the electromicroscopic photograph of the template obtained after alkali magnesium sulfate crystal whisker calcines 1h under 750 DEG C of conditions, and this template has three-dimensional porous structure.Fig. 2 is adsorption/desorption curve and the pore distribution curve of this template, there is peak value in pore distribution curve at 2-5nm place, and pore size distribution is between 1-100nm, and whisker specific surface area is 35.8m
2/ g, the length of whisker is 40-80 μm, and the width of whisker is 0.3-0.8 μm, and the length-to-diameter ratio of whisker is at 50-260.Fig. 3 is take methane as the sulfur-bearing Graphene thermal gravimetric analysis curve that carbon source is prepared, and the sample purity of this Graphene can up to 99.95%.According to X-ray photoelectron spectroscopic analysis (XPS is shown in Fig. 4), in the sulfur-bearing Graphene that this kind of processing condition are obtained, sulfur-bearing molar percentage is 3.35%, and mass percent is 8.20%.Fig. 5 is take methane as adsorption/desorption curve and the pore distribution curve of the sulfur-bearing Graphene that carbon source is prepared, and the specific surface area of this Graphene is 927m
2/ g, this adsorption/desorption isothermal curve belongs to H2 type lag loop (classification according to IUPAC IUPAC).Peak value is there is at 3.8nm place, between pore size distribution 1-100nm in pore distribution curve.Fig. 6 is the Raman spectrum of this sulfur-bearing Graphene, and D peak is higher, shows to have more defective bit in Graphene, and 2D peak is then the characteristic peak of graphene sheet layer, and electron microscopic observation shows that Graphene prepared by the present embodiment is about 3-10 layer.
Embodiment 2
The alkali magnesium sulfate crystal whisker after calcining is adopted to prepare sulfur-bearing Graphene as template, chemical Vapor deposition process.
Adopt document JournalofInorganicMaterials2004,19, the method introduced in 784 prepares alkali magnesium sulfate crystal whisker, then alkali magnesium sulfate crystal whisker is calcined 1h under 750 DEG C of conditions.Pore size distribution is between 1-100nm, and whisker specific surface area is 58.2m
2/ g, the length of whisker is 30-90 μm, and the width of whisker is 0.2-1.0 μm, and the length-to-diameter ratio of whisker is at 30-450.Take the alkali magnesium sulfate crystal whisker template after 10.0g calcining, vertical fluidized bed bioreactor to 50mm diameter passes into 0.4L/min argon gas and with the ramp to 900 DEG C of 15 DEG C/min, reactor operates in atmospheric conditions, template is added in vertical fluidized bed bioreactor, then 0.4L/min methane gas stream is passed into 10 minutes, then 900 DEG C of constant temperature 30 minutes, take out reaction product after then naturally cooling to room temperature, pickling purification step is same as Example 1, obtains the finished product 0.05g after drying.
Fig. 7 a, Fig. 8 a and Fig. 8 b give and adopt methane to be carbon source, and the scanning nuclear microprobe picture of the sulfur-bearing Graphene made, this Graphene presents sheet as can be seen from FIG., and larger with the exterior appearance difference of original template agent.
Sulfur-bearing Graphene specific surface area prepared by the present embodiment is 1200m
2/ g, pore size distribution is 1-100nm, and sulphur content is 7.96%, and the number of plies of this Graphene is 1-4 layer.Fig. 9 is the high rate performance be applied to by this sulfur-bearing Graphene 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 carbon-source gas, chemical Vapor deposition process prepares sulfur-bearing Graphene.
Adopt the alkali magnesium sulfate template after the process preparation calcining described in embodiment 2, take 10.00g template, vertical fluidized bed bioreactor to 50mm diameter passes into 0.8L/min argon gas and with the ramp to 650 DEG C of 15 DEG C/min, reactor operates in atmospheric conditions, template is added in vertical fluidized bed bioreactor, then pass into 0.4L/min ethene air-flow and react 10 minutes, reaction product is taken out after then naturally cooling to room temperature, pickling purification step is same as Example 1, obtains the finished product 0.09g after drying.
Fig. 7 b, Fig. 8 c and Fig. 8 d give and adopt ethene to be carbon source, and the scanning nuclear microprobe picture of the sulfur-bearing Graphene made, the number of plies of this Graphene is 3-8 layer as can be seen from FIG., and itself and original template agent have similar pattern and porous caged.Because graphite flake layer is more, therefore its structure is comparatively stable, and reaction product still can keep original template agent pattern after pickling purifying.
Sulfur-bearing Graphene specific surface area prepared by the present embodiment is 450m
2/ g, pore size distribution is 1-100nm, and sulphur content is 4.52%.
Embodiment 4
Employing acetylene is carbon-source gas, chemical Vapor deposition process prepares sulfur-bearing Graphene.
Adopt the flow process identical with embodiment 2, just adopt acetylene as carbon-source gas, temperature of reaction is 350 DEG C, can prepare sulfur-bearing Graphene.Sulfur-bearing Graphene prepared by the present embodiment has 3-10 layer graphite linings, and specific surface area is 320m
2/ g, pore size distribution is 1-100nm, sulphur content 2.36%.
Embodiment 5
Adopt MgSO
4powder prepares sulfur-bearing Graphene as template, chemical Vapor deposition process.
Take 30.00gMgSO
4powder, vertical fluidized bed bioreactor to 50mm diameter passes into 0.4L/min argon gas and with the ramp to 900 DEG C of 15 DEG C/min, reactor operates in atmospheric conditions, template is added in vertical fluidized bed bioreactor, then pass into 0.4L/min methane gas stream and react 20 minutes, pickling purification step and last drying step 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 sulfur-bearing Graphene obtained in the present embodiment).Sulfur-bearing Graphene specific surface area prepared by the present embodiment is 1136m
2/ g, pore size distribution is 1-100nm, and the number of plies of this Graphene is 1-5 layer.
Embodiment 6
Adopt FeSO
47H
2o crystal prepares sulfur-bearing Graphene as template.
The FeSO after 30min is calcined under taking 25.00g300 DEG C of condition
47H
2o crystal, the vertical fluidized bed bioreactor to 50mm diameter passes into 0.4L/min argon gas and with the ramp to 900 DEG C of 15 DEG C/min, 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 of processing condition are obtained).Sulfur-bearing Graphene specific surface area prepared by the present embodiment is 963m
2/ g, pore size distribution is 1-100nm, and the number of plies of this Graphene is 2-6 layer.
Embodiment 7
Adopt ZnSO
47H
2o crystal prepares sulfur-bearing Graphene as template.
Take the ZnSO after 30.00g300 DEG C of calcining 30min
47H
2o crystal, the vertical fluidized bed bioreactor to 50mm diameter passes into 0.4L/min argon gas and with the ramp to 350 DEG C of 15 DEG C/min, 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 of processing condition are obtained).Sulfur-bearing Graphene specific surface area prepared by the present embodiment is 987m
2/ g, pore size distribution is 1-100nm, and the number of plies of this Graphene is 3-8 layer.
Embodiment 8
Employing sucrose is carbon source, liquid-phase impregnation process prepares sulfur-bearing porous carbon.
Take 10.00g sucrose, add 20ml deionized water and be mixed with sucrose solution, the alkali magnesium sulfate crystal whisker template (preparation method is identical with embodiment 2) of 1h is calcined under taking 5.00g750 DEG C of condition, template is placed in sucrose solution normal temperature ultrasonic disperse 30-60min, obtain template suspension, this suspension is placed in 80 DEG C of dry 48h of baking oven, gray mixture is placed in porcelain boat, pass into the argon gas of 200mL/min to stove after putting into horizontal pipe furnace, horizontal stove rises to 600 DEG C with 15 DEG C/min temperature rise rate simultaneously, and keep 30min hour, normal pressure, naturally cool to after room temperature until furnace temperature and take out black product.Pickling purification step is same as Example 1, obtains the finished product 1.57g after drying.
Sulfur-bearing Graphene specific surface area prepared by the present embodiment is 620m
2/ g, the number of plies of this Graphene is 3-20 layer.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 15.40%(massfraction in the sulfur-bearing Graphene that this kind of processing condition are obtained).
Embodiment 9
Employing sucrose is carbon source, liquid-phase impregnation process prepares sulfur-bearing porous carbon.
Take 0.20g sucrose, add 20ml deionized water and be mixed with sucrose solution, the alkali magnesium sulfate crystal whisker template (preparation method is identical with embodiment 2) of 1h is calcined under taking 5.00g750 DEG C of condition, template is placed in sucrose solution normal temperature ultrasonic disperse 30-60min, obtain template suspension, this suspension is placed in 80 DEG C of dry 48h of baking oven, gray mixture is placed in porcelain boat, pass into the argon gas of 200mL/min to stove after putting into horizontal pipe furnace, horizontal stove rises to 600 DEG C with 15 DEG C/min temperature rise rate simultaneously, and keep 30min hour, pressure is normal pressure, naturally cool to after room temperature until furnace temperature and take out black product.Pickling purification step is same as Example 1, obtains the finished product 0.045g after drying.
Sulfur-bearing porous carbon specific surface area prepared by the present embodiment is 920m
2/ g, the number of plies of this Graphene is 1-5 layer.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 29.40%(massfraction in the sulfur-bearing porous carbon that this kind of processing condition are obtained).
Embodiment 10
Adopt S-WAT particle as template, Liquid preparation methods sulfur-bearing porous carbon.
Take 4.00g sucrose, add 20ml deionized water and be mixed with sucrose solution, take 8.00gNa
2sO
3powder template, template dipping sucrose step, reactions steps and pickling purification step are same as Example 8, obtain the finished product 0.86g after drying.
Sulfur-bearing Graphene specific surface area prepared by the present embodiment is 420m
2/ g, the number of plies of this Graphene is 3-8 layer.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 21.95%(massfraction in the sulfur-bearing porous carbon that this kind of processing condition are obtained).
Embodiment 11
Employing pitch is carbon source, liquid-phase impregnation process prepares sulfur-bearing porous carbon.
Take 2.00g pitch, add the ultrasonic 20min of 40ml toluene and be mixed with bituminous solution, calcine under taking 10.00g750 DEG C of condition 1h alkali magnesium sulfate crystal whisker template (preparation method is identical with embodiment 2), template is placed in bituminous solution normal temperature ultrasonic disperse 30-60min, obtain template suspension, this suspension is placed in 80 DEG C of dry 48h of baking oven, remaining reaction step and pickling purification step 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 of processing condition are obtained), sample specific surface area is 365m
2/ g.
Figure 11 is the high rate performance be applied to by this sulfur-bearing porous carbon 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 liquid-phase impregnation process to prepare sulfur-bearing porous carbon.
Employing document (inorganic chemicals industry, 2010, v.42; No.25401:44-47) method introduced in prepares calcium sulfate crystal whiskers as template, and whisker pore size distribution is between 1-60nm, and whisker specific surface area is 23m
2/ g, the length of whisker is 9-50 μm, and the width of whisker is 0.1-0.9 μm, and the length-to-diameter ratio of whisker is at 10-500.Take 3.00g pitch, add the ultrasonic 20min of 40ml toluene and be mixed with bituminous solution, take 10.00g template, template impregnation steps is same as Example 7, and dip compound is placed in porcelain boat, passes into 200mL/min argon gas after putting into horizontal stove to stove, horizontal stove is warming up to 700 DEG C, and keep 30min, reaction pressure 0.1-0.15Mpa, naturally cool to after room temperature until furnace temperature and take out black product.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 of processing condition are obtained) sample specific surface area is 342m
2/ g.
Embodiment 13
Utilize NiSO
46H
2o crystal obtains sulfur-bearing porous carbon-NiO matrix material as template.
Take 1.00g pitch, add the ultrasonic 20min of 40ml toluene and be mixed with bituminous solution, take the NiSO after 10.00g200 DEG C of calcining 30min
46H
2the agent of O crystal template, template dipping sucrose step, reactions steps are same as Example 7, use hydrochloric acid in shortage, only have part NiO to be removed like this in pickling purge process, therefore obtain sulfur-bearing Graphene-NiO matrix material, after drying, obtain the finished product 0.6g.According to X-ray photoelectron spectroscopic analysis, sulfur-bearing 14.36%(mass percent in the matrix material that this kind of processing condition are obtained), nickeliferous 20%(mass percent) and, sample specific surface area is 530m
2/ g.
Embodiment 14
Liquid preparation methods sulfur-bearing porous carbon when temperature of reaction is 700 DEG C.
The pitch taking equal in quality with example 12 with measure the toluene of same volume and 750 DEG C of conditions of equal in quality under calcine 1h alkali magnesium sulfate crystal whisker template, template impregnating pitch step is same as Example 9, dip compound is placed in porcelain boat, argon gas is passed into stove after putting into horizontal stove, pass into speed 150mL/min), horizontal stove temperature of reaction is 700 DEG C, and constant temperature 30 minutes, reaction pressure 0.1-0.15Mpa, 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 of processing condition are obtained).The reaction product of non-pickling purifying is analyzed, the characteristic peak containing MgO in collection of illustrative plates and MgSO according to X ray diffracting spectrum (Figure 13)
4characteristic peak, illustrates under these processing condition, and pitch and segment template agent are reacted and generated sulfur-bearing porous carbon and MgO, and sample specific surface area is 650m
2/ g.
Embodiment 15
Liquid preparation methods sulfur-bearing porous carbon when temperature of reaction is 800 DEG C.
The pitch taking equal in quality with example 12 with measure the toluene of same volume and 750 DEG C of conditions of equal in quality under calcine 1h alkali magnesium sulfate crystal whisker template, template impregnating pitch step is identical with example 12, dip compound is placed in porcelain boat, nitrogen is passed into stove after putting into horizontal stove, pass into speed 200ml/min), horizontal stove temperature of reaction is 800 DEG C, and constant temperature 30 minutes, reaction pressure 0.1-0.15Mpa, 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 of processing condition are obtained).Adopt the reaction product of the non-pickling purifying of X-ray diffraction analysis, the characteristic peak only containing MgO in collection of illustrative plates, illustrate under these processing condition, pitch and whole template there occurs reaction, generate sulfur-bearing Graphene and MgO.Sulfur-bearing porous carbon specific surface area prepared by the present embodiment is 680m
2/ g, the number of plies of this Graphene is 2-10 layer.
Embodiment 16
Liquid preparation methods sulfur-bearing porous carbon when temperature of reaction is 900 DEG C.
The pitch taking equal in quality with example 12 with measure the toluene of same volume and 750 DEG C of conditions of equal in quality under calcine 1h alkali magnesium sulfate crystal whisker template, template impregnating pitch step is identical with example 12, dip compound is placed in porcelain boat, 100mL/min nitrogen is passed into stove after putting into horizontal stove, horizontal stove temperature of reaction is 900 DEG C, and constant temperature 30 minutes, reaction pressure 0.1-0.15Mpa, 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 of processing condition are obtained).Adopt the reaction product of the non-pickling purifying of X-ray diffractogram spectrum analysis, the characteristic peak only containing MgO in collection of illustrative plates, and peak intensity is higher, illustrate under these processing condition, pitch and whole template there occurs reaction, generate sulfur-bearing Graphene and MgO, and sample specific surface area is 730m
2/ g.
Embodiment 17
Liquid preparation methods sulfur-bearing porous carbon when temperature of reaction is 1000 DEG C.
The pitch taking equal in quality with example 12 with measure the toluene of same volume and 750 DEG C of conditions of equal in quality under calcine 1h alkali magnesium sulfate crystal whisker template, template impregnating pitch step is identical with example 12, dip compound is placed in porcelain boat, 500mL/min argon gas is passed into stove after putting into horizontal stove, horizontal stove temperature of reaction is 1000 DEG C, and constant temperature 30 minutes, reaction pressure 0.1-0.2Mpa, 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 of processing condition are obtained), gained sulfur-bearing Graphene specific surface area is 921m
2/ g, the number of plies of this Graphene is 3-8 layer.
Embodiment 18
Adopt the mixture of nitrogen and krypton as carrier gas Liquid preparation methods sulfur-bearing porous carbon.
The pitch taking equal in quality with example 12 with measure the toluene of same volume and 750 DEG C of conditions of equal in quality under calcine 1h alkali magnesium sulfate crystal whisker template, template impregnating pitch step is identical with example 12, dip compound is placed in porcelain boat, the mixture passing into nitrogen and krypton to stove after putting into horizontal stove passes into speed 200ml/min, horizontal stove temperature of reaction is 700 DEG C, and constant temperature 30 minutes, reaction pressure 0.1-0.2Mpa, 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 of processing condition are obtained), specific surface area is 685m
2/ g.
Comparative example 1
Adopt the magnesia crystal whisker after calcining as template, process for preparing graphenes by chemical vapour deposition.
Alkali magnesium sulfate crystal whisker is calcined the magnesia crystal whisker that 1h obtains not sulfur-bearing under 1200 DEG C of conditions.Take the magnesia crystal whisker template after 10.0g calcining, vertical fluidized bed bioreactor to 50mm diameter passes into 0.4L/min argon gas and with the ramp to 900 DEG C of 15 DEG C/min, reactor operates in atmospheric conditions, template is added in vertical fluidized bed bioreactor, then 0.4L/min methane gas stream is passed into 10 minutes, then 900 DEG C of constant temperature 30 minutes, take out reaction product after then naturally cooling to room temperature, pickling purification step is same as Example 1, obtains the finished product 0.12g after drying.
Figure 10 is the high rate performance be applied to by this Graphene 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 example 2
Employing pitch is carbon source, liquid-phase impregnation process prepares porous carbon.
Take 2.00g pitch, add the ultrasonic 20min of 40ml toluene and be mixed with bituminous solution, calcine under taking 10.00g1200 DEG C of condition 1h magnesia crystal whisker template, template is placed in bituminous solution normal temperature ultrasonic disperse 30-60min, obtain template suspension, this suspension is placed in 80 DEG C of dry 48h of baking oven, remaining reaction step and pickling purification step same as Example 7, obtain the finished product 0.13g after drying.
Figure 12 is the high rate performance be applied to by this Graphene 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 (28)
1. the preparation method of a sulfur-bearing carbon material, it is characterized in that, described method is comprised and uses vitriol, sulphite or its calcinate to be reacted by chemical vapor deposition method or liquid-phase impregnation process and carbon source as template to prepare sulfur-bearing carbon material, and the sulfur-bearing carbon material sulphur content prepared is mass percent 0.1%-30%.
2. method according to claim 1, is characterized in that, described carbon material is Graphene or porous carbon.
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, magnesium sulfate, alkali magnesium sulfate, copper sulfate, Basic Chrome Sulphate, lead sulfate, sublimed lead, calcium sulfate, potassium sulfate, 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. the method according to claim 1-3 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.
5. method according to claim 4, is characterized in that, carrier gas and carbon-source gas mol ratio are 0.1-10:1.
6. method according to claim 5, is characterized in that, carrier gas and carbon-source gas mol ratio are 0.5-2:1.
7. method according to claim 4, is characterized in that, described chemical vapor deposition method comprises the steps:
1) in reactor, pass into carrier gas makes reactor be warming up to temperature of reaction simultaneously, template is added in reactor, then passes into carbon-source gas, react;
2) question response device naturally cools to room temperature, takes out reaction product;
3) pickling purifying, then be washed to neutrality, obtain sulfur-bearing carbon material after drying.
8. method according to claim 7, is characterized in that, carrier gas and carbon-source gas gas speed are 0.001-1m/s.
9. method according to claim 7, is characterized in that, the described reaction times is 5-200 minute.
10. method according to claim 7, is characterized in that, described temperature of reaction is 300-1000 DEG C.
11. methods according to claim 10, is characterized in that, described temperature of reaction is 350-900 DEG C.
12. methods according to claim 7, is characterized in that, described reaction pressure is 0.1-0.15Mpa.
13. methods according to claim 7, is characterized in that, described carbon material is Graphene.
14. methods according to claim 1-3 any one, it is characterized in that, the solvent in described liquid-phase impregnation process is selected from the one or more kinds of mixtures among water, ethanol, acetone, nitrogen methyl-2-pyrrolidone, benzene, toluene, p-Xylol and m-xylene; Solute as carbon source is selected from sucrose, vacuum residuum, pitch, wax oil, catalytic cracking product higher than the one or more kinds of mixtures among the slurry oil of 500 DEG C of cuts and coal tar; Carrier gas is selected from the one or more kinds of mixtures among nitrogen, argon gas, helium, ammonia.
15. methods according to claim 14, is characterized in that, the solvent in described liquid-phase impregnation process is selected from water or toluene.
16. methods according to claim 14, is characterized in that, described liquid-phase impregnation process 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, obtain the template of drying;
3) by step 2) template of oven dry that obtains puts into reactor, and pass into carrier gas and make reactor heat up to react simultaneously;
4) question response device naturally cools to room temperature, takes out reaction product;
5) pickling purifying, then be washed to neutrality, obtaining sulfur-bearing carbon material after drying is porous carbon.
17. methods according to claim 16, is characterized in that, step 1) described solvent and solute preparation solution in solute concentration be 0.01-10g/mL.
18. method according to claim 16, is characterized in that, step 3) temperature is 300-1000 DEG C.
19. method according to claim 18, is characterized in that, step 3) temperature is 400-900 DEG C.
20. method according to claim 16, is characterized in that, step 3) reaction times is 5-600 minute.
21. methods according to claim 16, is characterized in that, step 3) reaction pressure 0.1-0.5Mpa.
22. according to the method in claim 1-3,5-13 and 15-21 described in any one, it is characterized in that, vitriol, sulphite or its calcinate are first prepared whisker by described method, then the whisker of vitriol, sulphite or its calcinate is prepared sulfur-bearing carbon material as template by chemical vapor deposition method or liquid-phase impregnation process.
23. methods according to claim 4, it is characterized in that, vitriol, sulphite or its calcinate are first prepared whisker by described method, then the whisker of vitriol, sulphite or its calcinate is prepared sulfur-bearing carbon material as template by chemical vapor deposition method or liquid-phase impregnation process.
24. methods according to claim 14, it is characterized in that, vitriol, sulphite or its calcinate are first prepared whisker by described method, then the whisker of vitriol, sulphite or its calcinate is prepared sulfur-bearing carbon material as template by chemical vapor deposition method or liquid-phase impregnation process.
25. methods according to claim 22, is characterized in that, the length of described whisker is 5-200 μm, and the width of whisker is 0.1-1 μm, and the length-to-diameter ratio of whisker is at 10-550.
26. methods according to claim 23 or 24, it is characterized in that, the length of described whisker is 5-200 μm, and the width of whisker is 0.1-1 μm, and the length-to-diameter ratio of whisker is at 10-550.
The sulfur-bearing carbon material that described in 27. claim 1-26 any one prepared by method.
28. sulfur-bearing carbon materials according to claim 27, 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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| CN106450230A (en) * | 2016-11-28 | 2017-02-22 | 中国石油大学(北京) | Lithium removal method by sulfur-doped modulation carbon materials on voltage platform |
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| CN107892288B (en) * | 2017-11-22 | 2020-08-28 | 黑龙江省能源环境研究院 | Method for preparing catalytic slurry oil based solid carbon spheres and novel chemical deposition system |
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| KR20230125175A (en) * | 2020-12-22 | 2023-08-29 | 디킨슨 코포레이션 | Oxygen anion template for surface replication |
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