CN109071236A - The method for preparing nitrogen-doped porous carbon material as raw material using coal - Google Patents
The method for preparing nitrogen-doped porous carbon material as raw material using coal Download PDFInfo
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Abstract
There is provided a kind of preparation method of nitrogen-doped porous carbon material, comprising: (1) refine: coal raw material is refined, obtain refinement coal dust；(2) be carbonized: coal dust and nitrogen source are mixed to get Temperature fall after homogeneous mixture is carbonized under inert gas or ammonia and inert gas mixed atmosphere, obtain carbonized product；(3) it cleans: carbonized product acid elution, then be washed with deionized；(4) dry: drying process obtains the porous carbon materials of N doping.This method has many advantages, such as that raw material reserves are big, at low cost, preparation process is simple, easily batch production and application, has direct application value in the fields such as gas absorption separation and electrochemical energy storage.
Description
It is the present invention relates to the preparation method of nitrogen-doped carbon material, in particular to a kind of using coal as the nitrogen-doped porous carbon material one-step method for synthesizing of carbon source.
Heteroatom doping carbon material, especially nitrogen atom doping carbon material, the electronics due to that can improve carbon material skeleton is distributed and surface polarity, to significantly improve absorption and the energy storage characteristic of porous carbon.The preparation method of nitrogen-doped carbon material mainly includes polymer with nitrogen high temperature cabonization method, nitrogen substance post-processing etching method and self-assembling method etc. at present.However the complexity of the high cost of raw material and preparation process is the critical bottleneck of current N doping porous carbon large-scale promotion application.
In addition, graphene (GraPhene), i.e., by sp2Carbon atom assembles the two-dimension single layer carbon nano-structured material of formation from bottom to top, due to its excellent conductive, thermally conductive, mechanical performance and chemical stability, it is widely applied in fields such as high-performance nanometer electronic device, sensor, nanocomposite, electrochemical energy storages.Be mainly obtained by the methods of mechanical stripping method, chemical vapour deposition technique, graphene oxide reduction method and liquid phase stripping method of graphene obtain [Nat.Mater., 14,271-279 (2015)] at present.Wherein mechanical stripping method and chemical vapour deposition technique can obtain the single-layer graphene structure that regularity is high, impurity content is few, however the shortcomings that high cost, low-yield will they be limited in the synthesis of laboratory scope；Compared to first two method, liquid phase removing and the reduction of graphene oxide can improve the generation scale of graphene to a certain extent, however graphene charge stripping efficiency is low, low structural integrity is still problem urgently to be resolved.The production technology of current graphene is made a general survey of, it is still the core bottleneck for hindering its large-scale application that High-performance graphene, which moves towards the industrialization from the synthesis of laboratory scale and produces,.
Based on above-mentioned analysis, the nitrogen-doped graphene and porous carbon preparation method for material that research and development are inexpensive, are produced on a large scale are of great significance, and the especially simplified preparation process of the raw material of inexpensive, the big reserves of searching and operation is particularly important.The internal structure of coal includes to be considered as one of porous carbon materials scale, the important source material of low cost preparation all the time largely using aromatic hydrocarbon, polyaromatic hydrocarbon as the natural class graphite laminate structure of basic unit.It is at present raw material production porous carbon materials mainly using the higher bituminous coal of degree of coalification, anthracite as raw material using coal, prepares coal based activated carbon material by being carbonized and activating (physically activated or chemical activation) processing.Wherein, coal characteristic, activator species and activation condition are the key influence factors for influencing porous carbon pore structure.Lignite has biggish reserves in China, cheap compared to other coals, and especially this year in the low-rank coal resource (quasi- east lignite) of the quasi- east the Ge Er discovery rich reserves of Xinjiang, China, predicts resource reserve up to 390,000,000,000 tons.On the one hand, lignite is led due to lower degree of coalification, higher alkali metal and moisture content in coal fired power generation
Domain large-scale application has larger technical bottleneck.However on the other hand, lignite but has significant advantage as raw material prepared by porous carbon materials: (1) lignite volatile matter content is high, is conducive to form more flourishing pore structure in high temperature pyrolysis process；(2) degree of coalification of lignite is low, includes a large amount of oxygen-containing groups in internal aromatic structure, makes it have high reaction activity, it is easier to carbon structure differentiation and pore generation process are adjusted in preparing porous carbon materials.
The present invention is intended to provide a kind of low cost, can large-scale industrial production nitrogen-doped graphene and porous carbon preparation method for material.Specifically, nitrogen-doped graphene and nitrogen-doped porous carbon material is prepared by nitrogen source and activator mixing, high temperature one step carbonization using low order lignite as raw material.Nitrogen-doped graphene and porous carbon preparation method for material simple process of the present invention, it is low in cost, be easy to extensive, mass production；The N doping porous carbon prepared in this way has many advantages, such as that micro-structure is flourishing, specific surface area is controllable, nitrogen content is controllable, in electrochemical energy storage (electric double layer capacitance electrode material, the outlet of sodium-ion battery cathode) and gas (SO2、CO2) adsorbing domain have important application potentiality.
Summary of the invention
The invention solves costs of material existing for existing nitrogen-doped graphene and the more technologies of preparing of porous carbon materials it is high, preparation process is many and diverse the problems such as, utilize the porous carbon or grapheme material that simple one step carbonization preparation pore structure is controllable, N doping amount is controllable.The following steps are included:
Refinement step: coal raw material is refined, and obtains refinement coal dust；
Carburising step: the refinement coal dust is mixed with nitrogen source, is carbonized under inert gas or ammonia and inert gas mixed atmosphere, Temperature fall obtains carbonized product；
Cleaning step: by the carbonized product pickling, washing process；
Drying steps: the carbonized product after cleaning is dried to get nitrogen-doped porous carbon material is arrived.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, the coal raw material is lignite.
Preferably, above-mentioned to be prepared in the method for nitrogen-doped porous carbon material by raw material of coal, it is prepared in the method for nitrogen-doped porous carbon material by raw material of coal, the nitrogen source is one of ammonia, melamine, Lauxite, urea and itrogenous organic substance or a variety of.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, the inert gas is the nitrogen or argon gas of purity > 99.99%.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, coal dust and nitrogen source mass ratio are 1: 0.1~1: 10.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, when the nitrogen source is ammonia, ammonia and inert atmosphere volume ratio are 1: 0.1~1: 100 in carburizing atmosphere.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, carburizing temperature is 700 DEG C~1200 DEG C, and the carbonization dwell time is 0~10h.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, the heating rate of carbonisation is 0.1~15 DEG C/min.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, the pickling solution that pickling processes use is dilute hydrochloric acid or nitric acid, and the concentration of pickling solution is 0.5mol/L~2mol/L.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, the temperature of drying process is 60~200 DEG C.
Preferably, above-mentioned to be prepared in the method for nitrogen-doped porous carbon material by raw material of coal, in carburising step, the refinement coal dust is mixed with nitrogen source and activator, the nitrogen-doped porous carbon material of preparation is N doping porous graphene.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, the activator is alkali metal hydroxide, the solution of the hydroxide of alkaline-earth metal or their mixture.
Preferably, above-mentioned to prepare in the method for nitrogen-doped porous carbon material by raw material of coal, the mass ratio of the refinement coal dust and the activator is 1: 0.1~1: 10.
Another aspect of the present invention also provides a kind of nitrogen-doped porous carbon material by being prepared using coal as the method that raw material prepares nitrogen-doped porous carbon material.
Compared with prior art, present invention has an advantage that
(1) present invention can be mixed with nitrogen source by activator using big reserves, inexpensive lignite as carbon source and a step carbonisation prepares N doping porous graphene material；
(2) in the porous carbon materials prepared by the present invention, the control of pore structure and N doping amount can be realized by introducing the adjusting of atmosphere type, coal dust and activator and nitrogen source ratio, carburizing temperature when carbonization；
(3) it is analyzed by x-ray photoelectron spectroscopy (XPS), shows porous carbon materials N doping amount that method of the invention obtains controllably between 0%~10%；
(4) it is analyzed by N2 adsorption, the porous carbon materials pore structure for showing that method of the invention obtains is controllable, and specific surface area is in 500~1300m2 g-1Between；
(5) traditional coal based activated carbon preparation process usually requires pre- carbonization treatment to obtain the carbonized stock with preliminary hole framework, then carbonized stock is mixed with activator and passes through high-temperature activation process and obtains active carbon material.The young brown coal that the present invention is low by using degree of metamorphism, carbon skeleton plasticity is strong is not necessarily to pre- carbonisation, nitrogen-doped graphene and porous carbon materials only can be obtained by a step carbonisation, enormously simplify preparation process, reduce preparation cost；
(6) compared to porous carbon activation method under simple inert atmosphere conditions, the present invention provides introduce NH in activation process3Technical solution, NH3Play the role of pore creating material and nitrogen dopant simultaneously, to realize the coordinated regulation of pore structure and N doping.
Fig. 1 (a), (b), (c), the SEM and TEM image that (d) is the different multiplying of N doping porous carbon that embodiment 1 is prepared.
Fig. 2 (a), (b), (c), the characterization result that (d) is the aqueous super capacitive property of N doping porous carbon that embodiment 1 is prepared.
Fig. 3 is the CO for the N doping porous carbon that embodiment 1 obtains2Adsorption isotherm.
Fig. 4 be the obtained N doping porous carbon of embodiment 1 as anode material of lithium-ion battery in 200mAh g-1Under cycle characteristics curve；
Fig. 5 is the SO for the N doping porous carbon that embodiment 1 obtains2Curve of adsorption kinetics.
Fig. 6 is the N doping porous carbon Nitrogen adsorption isotherm that embodiment 1 obtains.
Fig. 7 is the N doping porous carbon Nitrogen adsorption isotherm that embodiment 2 obtains.
Fig. 8 is the N doping porous carbon Nitrogen adsorption isotherm that embodiment 3 obtains.
Fig. 9 is the N doping porous carbon Nitrogen adsorption isotherm that embodiment 4 obtains.
With reference to the accompanying drawing and specific embodiment, advantage of the invention is elaborated.
Embodiment 1:
Present embodiment porous graphene preparation method follows these steps to realize:
(1) the lignite coal dust that partial size after 3g ball milling sieves is 80-100 mesh is weighed；
(2) coal dust that step (1) obtains is put into tube furnace and carries out heating carbonization: rising to 900 DEG C from room temperature, control heating rate is 5 DEG C/min, under NH3 and N2 the mixed gas atmosphere that the volume ratio shared by NH3 is 50%, at a temperature of 900 DEG C, Temperature fall obtains carbonized product after constant temperature carbonization 3h；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dilute hydrochloric acid, then be washed with deionized 2~3 times, it is finally dry at 80 DEG C, obtain target product nitrogen doped micropore carbon (number NMC-0.5).
The structure and method for analyzing performance of embodiment 1:
Using transmission electron microscope, N2The means such as absorption join 1 gained nitrogen doped micropore carbon microscopic appearance of embodiment and pore structure
Number carries out detailed characterizations.
Using 1 gained nitrogen doped micropore carbon of embodiment as aqueous super capacitor material, it uses following experimental test performances: nitrogen doped micropore carbon, carbon black and PTFE emulsion being added to grinding in dehydrated alcohol with 8: 1: 1 ratios and form self-supporting film, it is about 1cm that the two panels film for cutting quality identical (1~2mg effect) rolls into area in mortar2Sheet pole piece, be pressed on nickel foam collector as capacitive property test electrode slice.It is spare that electrode slice dries 12h under 120 DEG C, vacuum environment.It is reference by electrolyte, saturated calomel electrode of 6M KOH, Pt piece is to test Cyclic voltamogram curve and permanent capacitor constant current charge-discharge curve under three-electrode system to electrode.Wherein, nitrogen doped micropore carbon ratio capacity C calculation method is as follows:I is discharge current density in formula；Δ t is a discharge time；M is active material quality contained by anode pole piece；Δ V is to deduct voltage drop IRdropDischarge voltage section afterwards.
Using 1 gained nitrogen doped micropore carbon of embodiment as adsorbent, it is tested to CO using volumetric adsorption method2Adsorption isotherm, obtain its CO2Storge quality.
Using 1 gained nitrogen doped micropore carbon of embodiment as anode material of lithium-ion battery, its performance test methods are as follows: with sodium piece for electrode, nitrogen doped micropore carbon is working electrode active material, and assembling CR2032 button cell tests it as anode material of lithium-ion battery performance.Wherein working electrode is the preparation method comprises the following steps: being dissolved in NMP for nitrogen doped micropore carbon, carbon black and PVDF with 7: 1.5: 1.5 mass ratio and being ground into uniform slurry, later by slurry coated in vacuum drying 12h obtains working electrode pole piece on copper foil and at 80 DEG C.The pole piece of drying is cut to round sheet and keeps active material density be 0.5~1mg cm-2, button cell is assembled into glove box with fresh lithium piece, electrolyte is 1M NaClO4(solvent is ethylene carbonate and diethyl carbonate 1: 1), Whatman glass fibre membrane is diaphragm.Battery is tested in 0.01~3.0V vs.Li/Li+Cyclic voltamogram curve and permanent capacitor constant current charge-discharge curve in voltage range.
Using 1 gained nitrogen doped micropore carbon of embodiment as gaseous pollutant molecule SO2Adsorbent passes through its SO of following experimental tests2Adsorption dynamics adsorption kinetics performance: homemade fixed bed reaction system is used, is made of air distribution system, fixed bed reaction system, heating and heat-insulation system, five subsystems of measuring system etc..Wherein fixed bed reactors are that glass tube and sand core are fired, bore 20mm.The control of reaction temperature is realized that temperature fluctuation is ± 1 DEG C by vertical tubular furnace.Glass reactor equipped with 1g doped micropore carbon is placed in tube furnace and carries out pipeline sealing；Simulated flue gas (N is introduced at room temperature2And SO2；Specific proportion is SO22000ppm, remaining is N2)；Reactor imports and exports SO2Concentration is detected by the portable FTIR (Gasmet company, Finland, DX-4000) produced, works as SO2Import and export SO2Concentration is unchanged to reach adsorbing and removing saturation or SO2Conversion ratio stops experiment when being lower than a certain setting value, and the gas after measurement is discharged into atmosphere after sufficiently cleaned up through drexel bottle (built-in NaOH solution).
Nitrogen doped micropore the carbon SEM and TEM that Fig. 1 (a), (b), (c), (d) obtain for specific embodiment/embodiment 1
Image.It can be seen that being class graphite microcrystal packing structure inside nitrogen doped micropore carbon, TEM image interior surface includes a large amount of graphene sheet layer packed structures.
The nitrogen doped micropore carbon aqueous super capacitive property characterization result that Fig. 2 (a), (b), (c), (d) obtain for specific embodiment/embodiment 1.It can be found that present invention gained nitrogen doped micropore carbon has high specific capacitance, high rate performance and cyclical stability in 6M KOH system: Cyclic voltamogram curve shows still to maintain preferable rectangular capacitive behavior in the case where height sweeps fast 200mV/s in Fig. 2 (a)；Specific capacitance is up to 205F/g under 0.5A/g current density, and specific capacitance still has nearly 129F/g under high 50A/g current density；Capacity is almost undamped after 5A/g cyclical stability curve shows 10000 circulations in Fig. 2 (d).
Fig. 3 is the nitrogen doped micropore carbon CO that specific embodiment/embodiment 1 obtains2Adsorption isotherm, CO under 0 degree Celsius of lower 1 atmospheric pressure2Adsorption capacity is up to 3.71mmol g-1。
Fig. 4 is the nitrogen doped micropore carbon Nitrogen adsorption isotherm that specific embodiment/embodiment 1 obtains, specific surface area 1235m2g-1, Kong Rongwei 0.58cm3g-1。
Fig. 5 is the obtained nitrogen doped micropore carbon of embodiment 1 in 0.2A g-1Stable circulation linearity curve under current density.During 500 circulations, nitrogen doped micropore carbon sodium ion cathode still possesses 190mAh g-1Capacity.
The nitrogen doped micropore carbon that Fig. 6 embodiment 1 obtains is at room temperature to the accumulation adsorption capacity curve of SO2, SO in (25 DEG C) 30 minutes2Adsorption capacity is accumulated up to 53mg g-1。
And nitrogen doped micropore carbon nitrogen content obtained by the present embodiment is 5.93wt-% as known from Table 1.
Specific embodiment/embodiment 2:
(1) the lignite coal dust that partial size after 3g ball milling sieves is 80-100 mesh is weighed；
(2) heating carbonization will be carried out in coal dust tube furnace that step (1) obtains: rising to 900 DEG C from room temperature, control heating rate is 10 DEG C/min, under NH3 and N2 the mixed gas atmosphere that the volume ratio shared by NH3 is 10%, at a temperature of 900 DEG C, Temperature fall obtains carbonized product after constant temperature carbonization 2h；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dilute hydrochloric acid, then be washed with deionized 2~3 times, it is finally dry at 100 DEG C, obtain target product nitrogen doped micropore carbon (number NMC-0.1).
It is characterized using the microporous carbon that structure described in embodiment 1 and performance test methods obtain the present embodiment.Can obtain the micropore graphene specific surface area that the present embodiment obtains from Fig. 5 adsorption isotherm and table 1 is 48m2/ g, Kong Rongwei 0.02cm3/ g, nitrogen content 2.09%.
Specific embodiment/embodiment 3:
(1) the lignite coal dust that partial size after 3g ball milling sieves is 120 mesh is weighed；
(2) heating carbonization will be carried out in coal dust tube furnace that step (1) obtains: rising to 900 DEG C from room temperature, control heating rate is 15 DEG C/min, under NH3 and N2 the mixed gas atmosphere that the volume ratio shared by NH3 is 75%, Temperature fall obtains carbonized product after constant temperature activation 1h at a temperature of 900 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dust technology, then be washed with deionized 2~3 times, it is finally dry at 100 DEG C, obtain target product nitrogen doped micropore carbon (number NMC-0.75).
It is characterized using the microporous carbon that structure described in embodiment 1 and performance test methods obtain the present embodiment.Can obtain the micropore graphene specific surface area that the present embodiment obtains from Fig. 5 adsorption isotherm and table 1 is 721m2/ g, Kong Rongwei 0.35cm3/ g, nitrogen content 6.80%.
Specific embodiment/embodiment 4:
(1) the lignite coal dust that partial size after 3g ball milling sieves is 120 mesh is weighed；
(2) heating carbonization will be carried out in coal dust tube furnace that step (1) obtains: rising to 800 DEG C from room temperature, control heating rate is 8 DEG C/min, under pure NH3 atmosphere, Temperature fall obtains carbonized product after constant temperature activation 3h at a temperature of 800 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dust technology, then be washed with deionized 2~3 times, it is finally dry at 100 DEG C, obtain target product nitrogen doped micropore carbon (number NMC-1).
It is characterized using the microporous carbon that structure described in embodiment 1 and performance test methods obtain the present embodiment.Can obtain the micropore graphene specific surface area that the present embodiment obtains from Fig. 5 adsorption isotherm and table 1 is 437m2/ g, Kong Rongwei 0.21cm3/ g, nitrogen content 5.97%.
Specific embodiment/embodiment 5:
(1) partial size is the lignite coal dust of 120 mesh after weighing the screening of 3g ball milling, forms mixed material with 1g melamine ball milling mixing；
(2) mixed material that step (1) obtains is subjected in tube furnace heating carbonization: rises to 900 DEG C from room temperature, control heating rate is 5 DEG C/min, under pure N2 atmosphere, Temperature fall obtains carbonized product after constant temperature carbonization 3h at a temperature of 900 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 1mol//L dust technology, then be washed with deionized 2~3 times, it is finally dry at 120 DEG C, obtain target product N doping porous carbon.
Using the microporous carbon that structure described in embodiment 1 and performance test methods obtain the present embodiment characterized known to this
The porous carbon specific surface area that embodiment obtains is 157m2/ g, Kong Rongwei 0.08cm3/ g, nitrogen content 6.97%.
Specific embodiment/embodiment 6:
(1) partial size is the lignite coal dust of 120 mesh, the addition 6M KOH solution high speed mixing of 1g melamine after weighing the screening of 3g ball milling, and coal dust and KOH mass ratio are controlled 1: 2；
(2) mixed solution that step (1) obtains is dried at 100 DEG C and removes moisture removal, the mixed material of acquisition carries out heating activation in tube furnace: rising to 950 DEG C from room temperature, control heating rate is 8 DEG C/min, in pure Ar atmosphere, Temperature fall obtains activation products after constant temperature activation 3h at a temperature of 950 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dust technology, then be washed with deionized 2~3 times, it is finally dry at 150 DEG C, obtain target product N doping porous graphene material；
Known to being characterized using structure described in embodiment 1 and performance test methods to the N doping porous graphene material that the present embodiment obtains: it is internal containing 1 layer or multi-layer graphene lamellar structure, specific surface area 1635m2/ g, Kong Rongwei 0.8cm3/ g, nitrogen content 4.25%.
Specific embodiment/embodiment 7:
(1) partial size is the lignite coal dust addition 6M KOH solution high speed mixing of 120 mesh after weighing the screening of 3g ball milling, and coal dust and KOH mass ratio are controlled 1: 3；
(2) mixed solution that step (1) obtains is dried at 120 DEG C and removes moisture removal, the mixed material of acquisition carries out heating activation in tube furnace: rising to 900 DEG C from room temperature, control heating rate is 5 DEG C/min, under NH3 and N2 the mixed gas atmosphere that the volume ratio shared by NH3 is 25%, Temperature fall obtains activation products after constant temperature activation 1h at a temperature of 900 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 4mol//L dilute hydrochloric acid, then be washed with deionized 2~3 times, it is finally dry at 120 DEG C, obtain target product N doping porous graphene.
Known to being characterized using structure described in embodiment 1 and performance test methods to the N doping porous graphene material that the present embodiment obtains: it is internal containing 1 layer or multi-layer graphene lamellar structure, specific surface area 2015m2/ g, Kong Rongwei 0.95cm3/ g, nitrogen content 3.05%.
Specific embodiment/embodiment 8:
(1) partial size is the lignite coal dust of 120 mesh, the addition 2M NaOH solution high speed mixing of 0.5g urea after taking 3g ball milling to sieve, and coal dust and NaOH mass ratio are controlled 1: 2；
(2) mixed solution that step (1) obtains is dried at 120 DEG C and removes moisture removal, the mixed material of acquisition is in tube furnace
In carry out heating activation: rise to 900 DEG C from room temperature, control heating rate is 10 DEG C/min, and under pure Ar atmosphere, Temperature fall obtains activation products after constant temperature activation 2h at a temperature of 900 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dust technology, then be washed with deionized 2~3 times, it is finally dry at 150 DEG C, obtain target product N doping porous carbon.
Use structure described in embodiment 1 and performance test methods to the N doping porous carbon that the present embodiment obtains characterized known to its specific surface area for 1015m2/ g, Kong Rongwei 0.55cm3/ g, nitrogen content 1.93%.
Specific embodiment/embodiment 9:
(1) partial size is the lignite coal dust of 120 mesh after weighing the screening of 3g ball milling, is mixed to form mixed material with 1g urea ball milling；
(2) mixed material that step (1) obtains is subjected in tube furnace heating carbonization: rises to 900 DEG C from room temperature, control heating rate is 10 DEG C/min, in NH3The NH that shared volume ratio is 50%3Under Ar mixed gas atmosphere, Temperature fall obtains carbonized product after constant temperature carbonization 3h at a temperature of 900 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dilute hydrochloric acid, then be washed with deionized 2~3 times, it is finally dry at 120 DEG C, obtain target product N doping porous carbon.
Use structure described in embodiment 1 and performance test methods to the N doping porous carbon that the present embodiment obtains characterized known to its specific surface area for 895m2/ g, Kong Rongwei 0.45cm3/ g, nitrogen content 8.52%.
Specific embodiment/embodiment 10:
(1) partial size is lignite coal dust, 0.5g urea, the 0.5g melamine of 120 mesh after taking 3g ball milling to sieve, and the mixing of 6M KOH solution high speed is added, and coal dust and KOH mass ratio are controlled 1: 2；
(2) mixed solution that step (1) obtains is dried at 150 DEG C and removes moisture removal, the mixed material of acquisition carries out heating activation in tube furnace: rising to 1000 DEG C from room temperature, control heating rate is 5 DEG C/min, in pure N2Under atmosphere, Temperature fall obtains activation products after constant temperature activation 1h at a temperature of 1000 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dilute hydrochloric acid, then be washed with deionized 2~3 times, it is finally dry at 150 DEG C, obtain target product N doping porous graphene material.
Known to being characterized using structure described in embodiment 1 and performance test methods to the N doping porous graphene material that the present embodiment obtains: it is internal containing 1 layer or multi-layer graphene lamellar structure, specific surface area 1830m2/ g, Kong Rongwei 0.74cm3/ g, nitrogen content 5.52%.
Specific embodiment/embodiment 11:
(1) partial size is lignite coal dust, the 0.3g urea of 120 mesh after taking 3g ball milling to sieve, and the mixing of 6M KOH solution high speed is added, and coal dust and KOH mass ratio are controlled 1: 10；
(2) mixed solution that step (1) obtains is dried at 200 DEG C and removes moisture removal, the mixed material of acquisition carries out heating activation in tube furnace: rising to 1200 DEG C from room temperature, control heating rate is 8 DEG C/min, in pure N2Under atmosphere, Temperature fall obtains activation products after constant temperature activation 3h at a temperature of 1200 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dilute hydrochloric acid, then be washed with deionized 2~3 times, it is finally dry at 150 DEG C, obtain target product N doping porous graphene material.
Known to being characterized using structure described in embodiment 1 and performance test methods to the N doping porous graphene material that the present embodiment obtains: it is internal containing 1 layer or multi-layer graphene lamellar structure, specific surface area 1140m2/ g, Kong Rongwei 1.55cm3/ g, nitrogen content 0.73%.
Specific embodiment/embodiment 12:
(1) partial size is lignite coal dust, the 30g melamine of 80-100 mesh after taking 3g ball milling to sieve, and the mixing of 6M KOH solution high speed is added, and coal dust and KOH mass ratio are controlled 1: 0.1；
(2) mixed solution that step (1) obtains is dried at 200 DEG C and removes moisture removal, the mixed material of acquisition carries out heating activation in tube furnace: rising to 700 DEG C from room temperature, control heating rate is 10 DEG C/min, under pure Ar atmosphere, Temperature fall obtains activation products after constant temperature carbonization 3h at a temperature of 700 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 0.5mol//L dilute hydrochloric acid, then be washed with deionized 2~3 times, it is finally dry at 200 DEG C, obtain target product nitrogen-doped porous carbon material.
Known to being characterized using the nitrogen-doped porous carbon material that structure described in embodiment 1 and performance test methods obtain the present embodiment: it is internal to contain 1 layer or multi-layer graphene lamellar structure, specific surface area 98m2/ g, Kong Rongwei 0.05m3/ g, nitrogen content 2.55%.
Specific embodiment/embodiment 13:
(1) partial size is lignite coal dust, 0.15g melamine, the 0.15g urea of 120 mesh after taking 3g ball milling to sieve, and the mixing of 6M KOH solution high speed is added, and coal dust and KOH mass ratio are controlled 1: 0.1；
(2) mixed solution that step (1) obtains is dried at 150 DEG C and removes moisture removal, the mixed material of acquisition carries out heating activation in tube furnace: rising to 900 DEG C from room temperature, control heating rate is 15 DEG C/min, in NH3The NH that shared volume ratio is 99%3Under Ar mixed gas atmosphere, Temperature fall obtains carbonized product after constant temperature carbonization 3h at a temperature of 900 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 0.5mol//L dilute hydrochloric acid, then be washed with deionized
It is 2~3 times, finally dry at 60 DEG C, obtain target product nitrogen-doped porous carbon material.
Known to being characterized using the nitrogen-doped porous carbon material that structure described in embodiment 1 and performance test methods obtain the present embodiment: it is internal to contain 1 layer or multi-layer graphene lamellar structure, specific surface area 490m2/ g, Kong Rongwei 0.28m3/ g, nitrogen content 7.85%.
Specific embodiment/embodiment 14:
(1) partial size is lignite coal dust, 15g melamine, the 15g urea of 120 mesh after taking 3g ball milling to sieve, and the mixing of 6M KOH solution high speed is added, and coal dust and KOH mass ratio are controlled 1: 10；
(2) mixed solution that step (1) obtains is dried at 200 DEG C and removes moisture removal, the mixed material of acquisition carries out heating activation in tube furnace: rising to 700 DEG C from room temperature, control heating rate is 10 DEG C/min, in NH3The NH that shared volume ratio is 10%3Under Ar mixed gas atmosphere, Temperature fall obtains carbonized product under pure Ar atmosphere after constant temperature carbonization 3h at a temperature of 700 DEG C, and Temperature fall obtains activation products after constant temperature activation 1h at a temperature of 950 DEG C；
(3) step (2) resulting carbonized product is washed 2~3 times with 2mol//L dilute hydrochloric acid, then be washed with deionized 2~3 times, it is finally dry at 200 DEG C, obtain target product N doping porous graphene material.
Known to being characterized using structure described in embodiment 1 and performance test methods to the N doping porous graphene material that the present embodiment obtains: it is internal containing 1 layer or multi-layer graphene lamellar structure, specific surface area 1030m2/ g, Kong Rongwei 0.68m3/ g, nitrogen content 8.65%.
N doping stone porous carbon or graphene pore structure parameter and N doping amount obtained by the different embodiments of table 1
The explanation of above section embodiment is merely used to help understand method and its core concept of the invention.It should be pointed out that for those skilled in the art, it without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (14)
- The method for preparing nitrogen-doped porous carbon material as raw material using coal, comprising the following steps:Refinement step: coal raw material is refined, and obtains refinement coal dust；Carburising step: the refinement coal dust is mixed with nitrogen source, is carbonized under inert gas or ammonia and inert gas mixed atmosphere, Temperature fall obtains carbonized product；Cleaning step: by the carbonized product pickling, washing process；Drying steps: the carbonized product after cleaning is dried to get nitrogen-doped porous carbon material is arrived.
- The method according to claim 1, wherein the coal raw material is lignite.
- The method according to claim 1, wherein the nitrogen source is one of ammonia, melamine, Lauxite, urea and itrogenous organic substance or a variety of.
- The method according to claim 1, wherein the inert gas is the nitrogen or argon gas of purity > 99.99%.
- The method according to claim 1, wherein coal dust and nitrogen source mass ratio are 1: 0.1~1: 10.
- The method according to claim 1, wherein ammonia and inert atmosphere volume ratio are 1: 0.1~1: 100 in carburizing atmosphere when the nitrogen source is ammonia.
- The method according to claim 1, wherein carburizing temperature is 700 DEG C~1200 DEG C, the carbonization dwell time is 0~10h.
- The method according to claim 1, wherein the heating rate of carbonisation is 0.1~15 DEG C/min.
- The method according to claim 1, wherein the pickling solution that pickling processes use is dilute hydrochloric acid or nitric acid, and the concentration of pickling solution is 0.5mol/L~2mol/L.
- The method according to claim 1, wherein the temperature being dried is 60~200 DEG C.
- - 10 any method according to claim 1, which is characterized in that in carburising step, the refinement coal dust is mixed with nitrogen source and activator, the nitrogen-doped porous carbon material of preparation is N doping porous graphene.
- According to the method for claim 11, which is characterized in that the activator is alkali metal hydroxide, the solution of the hydroxide of alkaline-earth metal or their mixture.
- According to the method for claim 11, which is characterized in that the mass ratio of the refinement coal dust and the activator is 1: 0.1~1: 10.
- A kind of nitrogen-doped porous carbon material that the synthetic method as described in claim 1 to 13 obtains.
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