WO2018099173A1 - 以煤为原料制备氮掺杂多孔碳材料的方法 - Google Patents

以煤为原料制备氮掺杂多孔碳材料的方法 Download PDF

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WO2018099173A1
WO2018099173A1 PCT/CN2017/103496 CN2017103496W WO2018099173A1 WO 2018099173 A1 WO2018099173 A1 WO 2018099173A1 CN 2017103496 W CN2017103496 W CN 2017103496W WO 2018099173 A1 WO2018099173 A1 WO 2018099173A1
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nitrogen
coal
porous carbon
doped porous
doped
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PCT/CN2017/103496
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French (fr)
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张雨虹
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建添企业有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge

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  • the invention relates to a preparation method of a nitrogen-doped carbon material, in particular to a one-step synthesis method of a nitrogen-doped porous carbon material using coal as a carbon source.
  • the heteroatom-doped carbon material can improve the electron distribution and surface polarity of the carbon material skeleton, thereby significantly improving the adsorption and energy storage characteristics of the porous carbon.
  • the preparation methods of nitrogen-doped carbon materials mainly include a high-temperature carbonization method of a nitrogen-containing polymer, a post-treatment etching method of a nitrogen-containing substance, and a self-assembly method.
  • the high cost of raw materials and the complexity of the preparation process are the key bottlenecks for the large-scale popularization and application of nitrogen-doped porous carbon.
  • the graphene i.e. a two-dimensional single-walled carbon nanostructured material by the bottom-up assembly of sp 2 carbon atoms is formed, because of its excellent electrical conductivity, thermal conductivity, mechanical properties and chemical stability, so that high-performance Nanoelectronic devices, sensors, nanocomposites, electrochemical energy storage and other fields have been widely used.
  • the obtained graphene is mainly obtained by a mechanical stripping method, a chemical vapor deposition method, a graphene oxide reduction method, and a liquid phase stripping method [Nat. Mater., 14, 271-279 (2015)].
  • the mechanical stripping method and the chemical vapor deposition method can obtain a single-layer graphene structure with high regularity and low impurity content, but the disadvantages of high cost and low yield still limit them to the laboratory-scale synthesis; compared with the first two
  • the liquid phase stripping and the reduction of graphene oxide can increase the scale of graphene formation to some extent.
  • the low graphene stripping efficiency and low structural regularity are still difficult problems to be solved.
  • the development of high-performance graphene from laboratory scale to industrial production is still the core bottleneck that hinders its large-scale application.
  • the internal structure of coal contains a large number of natural graphite layered structures with aromatic hydrocarbons and polyaromatic hydrocarbons as basic units, and has been regarded as one of the important raw materials for large-scale and low-cost preparation of porous carbon materials.
  • the production of porous carbon materials from coal as raw materials is mainly based on the use of bituminous coal and anthracite coal with higher degree of coalification as raw materials, and carbon-based activated carbon materials are obtained by carbonization and activation (physical activation or chemical activation).
  • coal characteristics, activator type and activation conditions are the key influencing factors affecting the pore structure of porous carbon.
  • Lignite has a large reserve in China, and it is cheaper than other coal types. In particular, this year, we found abundant reserves of low-grade coal resources (Jiandong brown coal) in the eastern part of Zhungeer, Xinjiang, China, with a predicted resource reserve of 390 billion tons. .
  • lignite is in the coal-fired power generation due to the lower degree of coalification, higher alkali metal and moisture content. Large-scale application of the domain has a large technical bottleneck.
  • lignite has significant advantages as a raw material for the preparation of porous carbon materials: (1) high volatile matter content of lignite is beneficial to the formation of more developed pore structure during pyrolysis in high temperature; (2) low degree of coalification of lignite, internal The aromatic structure contains a large number of oxygen-containing groups, which makes it highly reactive, and it is easier to adjust the carbon structure evolution and pore formation process in the preparation of porous carbon materials.
  • the present invention aims to provide a low-cost, large-scale industrial production of nitrogen-doped graphene and a method for preparing a porous carbon material.
  • a nitrogen-doped graphene and a nitrogen-doped porous carbon material are prepared by using a low-order lignite as a raw material, a nitrogen source and an activator, and a high-temperature one-step carbonization method.
  • the method for preparing nitrogen-doped graphene and porous carbon material according to the invention is simple in process, low in cost, and easy to be mass-produced and mass-produced; the nitrogen-doped porous carbon prepared by the method has developed microstructure, controlled specific surface area, and nitrogen.
  • the content is controllable and has the important application potential in the field of electrochemical energy storage (electric double layer capacitor electrode material, sodium ion battery anode outlet) and gas (SO 2 , CO 2 ) adsorption.
  • the invention solves the problems of high raw material cost and complicated preparation process of the existing nitrogen-doped graphene and porous carbon material multi-preparation technology, and adopts a simple one-step carbonization method to prepare a porous structure with controlled pore structure and controlled nitrogen doping amount.
  • Carbon or graphene material Includes the following steps:
  • Refinement step refining the coal raw material to obtain refined coal powder
  • Carbonization step mixing the refined pulverized coal powder with a nitrogen source, carbonizing in an inert gas or an atmosphere mixed with an inert gas, and naturally cooling to obtain a carbonized product;
  • a washing step pickling and washing the carbonized product
  • Drying step drying the washed carbonized product to obtain a nitrogen-doped porous carbon material.
  • the coal raw material is lignite.
  • the nitrogen source is ammonia gas, melamine, urea-formaldehyde resin, urea, and One or more of nitrogen organics.
  • the inert gas is nitrogen or argon having a purity of >99.99%.
  • the mass ratio of the coal powder to the nitrogen source is 1:0.1 to 1:10.
  • a volume ratio of ammonia gas to an inert atmosphere in the carbonization atmosphere is 1:0.1 to 1:100.
  • the carbonization temperature is 700 ° C to 1200 ° C
  • the carbonization residence time is 0 to 10 h.
  • the heating rate of the carbonization process is 0.1 to 15 ° C/min.
  • the pickling liquid used for the pickling treatment is dilute hydrochloric acid or nitric acid, and the concentration of the pickling liquid is 0.5 mol/L to 2 mol/L.
  • the drying treatment temperature is 60 to 200 °C.
  • the refined coal powder is mixed with a nitrogen source and an activator, and the prepared nitrogen-doped porous carbon material is nitrogen-doped.
  • Heteroporous graphene is a nitrogen-doped graphene
  • the activator is a solution of an alkali metal hydroxide, an alkaline earth metal hydroxide or a mixture thereof.
  • the mass ratio of the refined coal powder to the activator is 1:0.1 to 1:10.
  • a nitrogen-doped porous carbon material prepared by a method for preparing a nitrogen-doped porous carbon material from coal.
  • the invention can prepare a nitrogen-doped porous graphene material by using a large reserve and low-cost lignite as a carbon source, mixing an activator with a nitrogen source, and a one-step carbonization process;
  • the pore structure and the nitrogen doping amount can be controlled by introducing the type of atmosphere during carbonization, the ratio of the coal powder to the activator and the nitrogen source, and the carbonization temperature;
  • the nitrogen adsorption analysis shows that the pore structure of the porous carbon material obtained by the method of the invention is controllable, and the specific surface area is between 500 and 1300 m 2 g -1 ;
  • the conventional coal-based activated carbon preparation process usually requires pre-carbonization treatment to obtain a carbonized material having a preliminary pore framework, and then the carbonized material is mixed with an activator and subjected to a high-temperature activation process to obtain an activated carbon material.
  • the invention can obtain nitrogen-doped graphene and porous carbon material only by one-step carbonization process without using a pre-carbonization process, which greatly simplifies the preparation process and reduces the preparation cost;
  • the present invention provides a technical scheme for introducing NH 3 in the activation process, and NH 3 functions as both a pore former and a nitrogen dopant, thereby realizing the pores. Synergistic regulation of structure and nitrogen doping.
  • Example 3 is a CO 2 adsorption isotherm of the nitrogen-doped porous carbon obtained in Example 1.
  • Example 4 is a cycle characteristic curve of the nitrogen-doped porous carbon obtained in Example 1 as a negative electrode material of a sodium ion battery at 200 mAh g -1 ;
  • Example 5 is a SO 2 adsorption kinetics curve of the nitrogen-doped porous carbon obtained in Example 1.
  • Fig. 6 is a nitrogen-doped porous carbon-nitrogen adsorption isotherm obtained in Example 1.
  • Example 7 is a nitrogen-doped porous carbon-nitrogen adsorption isotherm obtained in Example 2.
  • Example 8 is a nitrogen-doped porous carbon-nitrogen adsorption isotherm obtained in Example 3.
  • Figure 9 is a nitrogen-doped porous carbon-nitrogen adsorption isotherm obtained in Example 4.
  • the pulverized coal obtained in the step (1) is placed in a tube furnace for temperature-increasing carbonization: from room temperature to 900 ° C, the temperature rising rate is controlled to 5 ° C / min, and the NH 3 in the volume ratio of NH 3 is 50%. Under the atmosphere of N2 mixed gas, at a temperature of 900 ° C, the carbonization product is naturally cooled after constant carbonization for 3 hours;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 2 mol//L of dilute hydrochloric acid, washed 2 to 3 times with deionized water, and finally dried at 80 ° C to obtain a target product nitrogen-doped micro Hole carbon (numbered NMC-0.5).
  • microstructure and pore structure parameters of the nitrogen-doped microporous carbon obtained in Example 1 were characterized by transmission electron microscopy and N 2 adsorption.
  • the nitrogen-doped microporous carbon obtained in Example 1 was used as the water-based supercapacitor material, and the performance was tested by the following test: nitrogen-doped microporous carbon, carbon black, and PTFE emulsion were added to absolute ethanol at a ratio of 8:1:1. Medium-grinding forms a self-supporting film, and the two films with the same cutting quality (1 ⁇ 2mg effect) are formed into a sheet-like pole piece with an area of about 1cm 2 in a mortar, which is pressed on the nickel foam current collector as a capacitance performance test. Electrode sheet. The electrode sheets were dried at 120 ° C for 12 hours under vacuum.
  • the nitrogen-doped microporous carbon specific capacity C is calculated as follows: Where I is the discharge current density; ⁇ t is the primary discharge time; m is the mass of the active material contained in the positive electrode tab; ⁇ V is the discharge voltage interval after subtracting the voltage drop IR drop .
  • Example 1 The nitrogen-doped microporous carbon obtained in Example 1 was used as an adsorbent, and its adsorption isotherm for CO 2 was measured by volume adsorption method to obtain its CO 2 storage performance.
  • the nitrogen-doped microporous carbon obtained in the first embodiment is a negative electrode material of a sodium ion battery, and the performance test method is as follows: using a sodium sheet as a counter electrode and a nitrogen-doped microporous carbon as a working electrode active material, and assembling a CR2032 button battery to test the same Sodium ion battery anode material properties.
  • the working electrode is prepared by dissolving nitrogen-doped microporous carbon, carbon black, and PVDF in a mass ratio of 7:1.5:1.5 in NMP and grinding into a uniform slurry, and then coating the slurry on the copper foil.
  • the working electrode pole piece was obtained by vacuum drying at 80 ° C for 12 h.
  • the dried pole piece is cut into a circular sheet shape and the active material density is 0.5-1 mg cm-2.
  • the fresh lithium piece is assembled into a button battery in a glove box, and the electrolyte is 1 M NaClO 4 (the solvent is ethylene carbonate). And diethyl carbonate 1:1), Whatman glass fiber membrane is a membrane.
  • the cyclic volt-ampere characteristic curve and the constant capacitance constant current charge and discharge curve of the test battery in the range of 0.01 to 3.0 V vs. Li/Li + were measured.
  • the nitrogen-doped microporous carbon obtained in Example 1 was used as a gaseous pollutant molecular SO 2 adsorbent, and its SO 2 adsorption kinetic performance was tested by the following test: a self-made fixed bed reaction system was used, and a gas distribution system and a fixed bed reaction were used. The system, heating and insulation system, and five subsystems of the measurement system are composed.
  • the fixed bed reactor is made of glass tube and sand core, and the inner diameter of the tube is 20 mm.
  • the reaction temperature is controlled by a vertical tube furnace with a temperature fluctuation of ⁇ 1 °C.
  • Example 1(a), (b), (c), and (d) are nitrogen-doped microporous carbon SEM and TEM obtained in the specific embodiment/Example 1. image. It can be seen that the interior of the nitrogen-doped microporous carbon is a graphite-like microcrystalline stacking structure, and the surface of the TEM image contains a large amount of graphene layer stacking structure.
  • the nitrogen-doped microporous carbon obtained by the present invention has high specific capacitance, rate performance and cycle stability in the 6M KOH system: the cyclic voltammetric characteristic curve in Fig. 2(a) indicates that it remains at a high sweep speed of 200 mV/s.
  • CO 2 adsorption isotherm obtained in the specific embodiment/Example 1, and the CO 2 adsorption capacity can reach 3.71 mmol g -1 at 0 ° C at 1 atmosphere.
  • Example 4 is a nitrogen-doped microporous carbon-nitrogen adsorption isotherm obtained in the specific embodiment/Example 1, having a specific surface area of 1235 m 2 g -1 and a pore volume of 0.58 cm 3 g -1 .
  • Example 5 is a cycle stability curve of the nitrogen-doped microporous carbon obtained in Example 1 at a current density of 0.2 A g -1 .
  • the nitrogen-doped microporous sodium carbonate ion anode still retained a capacity of 190 mAh g -1 .
  • Fig. 6 shows the cumulative adsorption capacity curve of SO2 in the nitrogen-doped microporous carbon obtained in Example 1 at room temperature (25 ° C) for 30 minutes, and the cumulative adsorption capacity of SO 2 can reach 53 mg g -1 .
  • the carbon powder tube furnace obtained in the step (1) is subjected to temperature-increasing carbonization: from room temperature to 900 ° C, the temperature rising rate is controlled to 10 ° C / min, and the NH 3 and N 2 in the volume ratio of NH 3 are 10%.
  • temperature-increasing carbonization from room temperature to 900 ° C, the temperature rising rate is controlled to 10 ° C / min, and the NH 3 and N 2 in the volume ratio of NH 3 are 10%.
  • a mixed gas atmosphere at a temperature of 900 ° C, the carbonization product is naturally cooled after constant temperature carbonization for 2 hours;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 2 mol//L of dilute hydrochloric acid, and then washed 2 to 3 times with deionized water, and finally dried at 100 ° C to obtain a target product nitrogen-doped micro Hole carbon (numbered NMC-0.1).
  • Example microporous carbon obtained in this example was characterized by the structure and performance test methods described in Example 1.
  • Example microporous graphene obtained from an adsorption isotherm of FIG. 5 and Table 1 of the present embodiment can be obtained specific surface area of 48m 2 / g, a pore volume of 0.02cm 3 / g, a nitrogen content of 2.09%.
  • the carbon powder tube furnace obtained in the step (1) is subjected to temperature-increasing carbonization: from room temperature to 900 ° C, the controlled heating rate is 15 ° C / min, and the NH 3 and N 2 in the volume ratio of NH 3 are 75%.
  • temperature-increasing carbonization from room temperature to 900 ° C, the controlled heating rate is 15 ° C / min, and the NH 3 and N 2 in the volume ratio of NH 3 are 75%.
  • a mixed gas atmosphere after being heated at a constant temperature of 900 ° C for 1 h, it is naturally cooled to obtain a carbonized product;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 2 mol//L of dilute nitric acid, washed 2 to 3 times with deionized water, and finally dried at 100 ° C to obtain a target product nitrogen-doped micro Porous carbon (numbered NMC-0.75).
  • microporous carbon obtained in this example was characterized by the structure and performance test methods described in Example 1. From the adsorption isotherm of Fig. 5 and Table 1, the microporous graphene obtained in this example had a specific surface area of 721 m 2 /g, a pore volume of 0.35 cm 3 /g, and a nitrogen content of 6.80%.
  • the carbon powder tube furnace obtained in the step (1) is subjected to temperature-increasing carbonization: from room temperature to 800 ° C, the controlled heating rate is 8 ° C / min, and the temperature is constant at 800 ° C in a pure NH 3 atmosphere. After 3 hours of activation, the product is naturally cooled to obtain a carbonized product;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 2 mol//L of dilute nitric acid, washed 2 to 3 times with deionized water, and finally dried at 100 ° C to obtain a target product nitrogen-doped micro Hole carbon (numbered NMC-1).
  • microporous carbon obtained in this example was characterized by the structure and performance test methods described in Example 1. From the adsorption isotherm of Figure 5 and Table 1, the microporous graphene obtained in this example had a specific surface area of 437 m 2 /g, a pore volume of 0.21 cm 3 /g, and a nitrogen content of 5.97%.
  • step (2) The mixture obtained in the step (1) is subjected to temperature-raising carbonization in a tube furnace: from room temperature to 900 ° C, the controlled heating rate is 5 ° C / min, in a pure N 2 gas atmosphere at 900 ° C temperature After constant temperature carbonization for 3h, the natural cooling is carried out to obtain a carbonized product;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 1 mol//L of dilute nitric acid, washed 2 to 3 times with deionized water, and finally dried at 120 ° C to obtain a target product nitrogen-doped porous. carbon.
  • microporous carbon obtained in the present example was characterized by the structure and performance test method described in Example 1. It was found that the porous carbon had a specific surface area of 157 m 2 /g, a pore volume of 0.08 cm 3 /g, and a nitrogen content. It is 6.97%.
  • the mixed solution obtained in the step (1) is dried at 100 ° C to remove water, and the obtained mixture is heated and activated in a tube furnace: from room temperature to 950 ° C, and the controlled heating rate is 8 ° C / min, In a pure Ar atmosphere, after a constant temperature activation at 950 ° C for 3 h, the temperature is naturally cooled to obtain an activated product;
  • the nitrogen-doped porous graphene material obtained in the present embodiment was characterized by the structure and performance test method described in Example 1. It was found that the inside thereof contained one or more layers of graphene sheet structure, and the specific surface area was 1635 m 2 /g. The pore volume was 0.8 cm 3 /g, and the nitrogen content was 4.25%.
  • the mixed solution obtained in the step (1) is dried at 120 ° C to remove water, and the obtained mixture is heated and activated in a tube furnace: from room temperature to 900 ° C, and the controlled heating rate is 5 ° C / min, Under the atmosphere of NH3 and N2 with a volume ratio of NH2 of 25%, the product is naturally cooled down at a temperature of 900 °C for 1 h to obtain an activated product;
  • the nitrogen-doped porous graphene material obtained in the present example was characterized by the structure and performance test method described in Example 1. It was found that the inside thereof contained one or more layers of graphene sheet structure, and the specific surface area was 2015 m 2 /g. The pore volume was 0.95 cm 3 /g, and the nitrogen content was 3.05%.
  • the mixed solution obtained in the step (1) is dried at 120 ° C to remove moisture, and the obtained mixture is in a tube furnace.
  • the temperature is activated and activated: from room temperature to 900 ° C, the controlled heating rate is 10 ° C / min, in a pure Ar atmosphere, at a constant temperature of 900 ° C for 2 h after the natural cooling to obtain an activated product;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 2 mol//L of dilute nitric acid, washed 2 to 3 times with deionized water, and finally dried at 150 ° C to obtain a target product nitrogen-doped porous. carbon.
  • the nitrogen-doped porous carbon obtained in the present example was characterized by the structure and performance test method described in Example 1.
  • the specific surface area was 1015 m 2 /g, the pore volume was 0.55 cm 3 /g, and the nitrogen content was 1.93%.
  • step (2) The mixture obtained in the step (1) is subjected to temperature-raising carbonization in a tube furnace: from room temperature to 900 ° C, the temperature rise rate is controlled to 10 ° C / min, and the NH 3 volume ratio is 50% NH. 3 and Ar mixed gas atmosphere, carbonization at a constant temperature of 900 ° C for 3h, then naturally cooled to obtain carbonized products;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 2 mol//L of dilute hydrochloric acid, and then washed 2 to 3 times with deionized water, and finally dried at 120 ° C to obtain a target product nitrogen-doped porous. carbon.
  • the nitrogen-doped porous carbon obtained in the present example was characterized by the structure and performance test method described in Example 1.
  • the specific surface area was 895 m 2 /g, the pore volume was 0.45 cm 3 /g, and the nitrogen content was 8.52%.
  • the mixed solution obtained in the step (1) is dried at 150 ° C to remove water, and the obtained mixture is heated and activated in a tube furnace: from room temperature to 1000 ° C, and the controlled heating rate is 5 ° C / min, In a pure N 2 atmosphere, after a constant temperature activation at 1000 ° C for 1 h, the temperature is naturally cooled to obtain an activated product;
  • the nitrogen-doped porous graphene material obtained in the present embodiment was characterized by the structure and performance test method described in Example 1. It was found that the inside thereof contained one or more layers of graphene sheets, and the specific surface area was 1830 m 2 /g. The pore volume was 0.74 cm 3 /g, and the nitrogen content was 5.52%.
  • the mixed solution obtained in the step (1) is dried at 200 ° C to remove water, and the obtained mixture is heated and activated in a tube furnace: from room temperature to 1200 ° C, and the controlled heating rate is 8 ° C / min, In a pure N 2 atmosphere, after a constant temperature activation at 1200 ° C for 3 h, the temperature is naturally cooled to obtain an activated product;
  • the nitrogen-doped porous graphene material obtained in the present embodiment was characterized by the structure and performance test method described in Example 1. It was found that the inside thereof contained one or more layers of graphene sheet structure, and the specific surface area was 1140 m 2 /g. The pore volume was 1.55 cm 3 /g, and the nitrogen content was 0.73%.
  • the mixed solution obtained in the step (1) is dried at 200 ° C to remove water, and the obtained mixture is heated and activated in a tube furnace: from room temperature to 700 ° C, and the controlled heating rate is 10 ° C / min, In a pure Ar atmosphere, the temperature is naturally reduced at 700 ° C for 3 h and then naturally cooled to obtain an activated product;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 0.5 mol/L of dilute hydrochloric acid, washed 2 to 3 times with deionized water, and finally dried at 200 ° C to obtain target product nitrogen doping. Porous carbon material.
  • the nitrogen-doped porous carbon material obtained in the present embodiment was characterized by the structure and performance test method described in Example 1, and the inside thereof contained one or more layers of graphene sheets having a specific surface area of 98 m 2 /g.
  • the pore volume was 0.05 m 3 /g and the nitrogen content was 2.55%.
  • the particle size is 120 mesh lignite coal powder, 0.15g melamine, 0.15g urea, added to 6M KOH solution for high-speed mixing, the mass ratio of pulverized coal to KOH is controlled at 1:0.1;
  • the mixed solution obtained in the step (1) is dried at 150 ° C to remove water, and the obtained mixture is heated and activated in a tube furnace: from room temperature to 900 ° C, and the controlled heating rate is 15 ° C / min, in the occupied volume ratio of NH 3 99% and an NH 3 mixed gas atmosphere of Ar, at a temperature of 900 deg.] C after the natural cooling temperature carbonization 3h obtained carbonized product;
  • the carbonized product obtained in the step (2) is washed 2 to 3 times with 0.5 mol//L of dilute hydrochloric acid, and then washed with deionized water. 2 to 3 times, and finally dried at 60 ° C to obtain a target product nitrogen-doped porous carbon material.
  • the nitrogen-doped porous carbon material obtained in the present embodiment was characterized by the structure and performance test method described in Example 1, and the inside thereof contained one or more layers of graphene sheets having a specific surface area of 490 m 2 /g.
  • the pore volume was 0.28 m 3 /g and the nitrogen content was 7.85%.
  • the mixed solution obtained in the step (1) is dried at 200 ° C to remove water, and the obtained mixture is heated and activated in a tube furnace: from room temperature to 700 ° C, and the controlled heating rate is 10 ° C / min, Under the atmosphere of NH 3 and Ar mixed with NH 3 in a volume ratio of 10%, the carbonization product was naturally cooled at a temperature of 700 ° C for 3 h, and the carbonized product was naturally activated at 950 ° C for 1 h. Cooling to obtain an activated product;
  • the nitrogen-doped porous graphene material obtained in the present embodiment was characterized by the structure and performance test method described in Example 1. It was found that the inside thereof contained one or more layers of graphene sheet structure, and the specific surface area was 1030 m 2 /g. The pore volume was 0.68 m 3 /g, and the nitrogen content was 8.65%.

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Abstract

提供一种氮掺杂多孔碳材料的制备方法，包括：（1）细化：将煤原料进行细化，得到细化煤粉；（2）碳化：煤粉与氮源混合得到均匀混合物在惰性气体或氨气与惰性气体混合气氛下碳化后自然降温，得到碳化产物；（3）清洗：碳化产物用酸洗涤，再用去离子水洗涤；（4）干燥：干燥处理得到氮掺杂的多孔碳材料。该方法具有原料储量大、成本低、制备过程简单等优点，易批量生产及应用，在气体吸附分离及电化学储能等领域有直接的应用价值。

Description

以煤为原料制备氮掺杂多孔碳材料的方法 技术领域
本发明涉及氮掺杂碳材料的制备方法，特别涉及一种以煤为碳源的氮掺杂多孔碳材料一步合成方法。
背景技术
杂原子掺杂碳材料，特别是氮原子掺杂碳材料，由于能够改善碳材料骨架的电子分布及表面极性，从而显著提高多孔碳的吸附及储能特性。目前氮掺杂碳材料的制备方法主要包括含氮聚合物高温碳化法、含氮物质后处理刻蚀法及自组装方法等。然而原材料的高成本及制备过程的复杂性是目前氮掺杂多孔碳大规模推广应用的关键瓶颈。
此外，石墨烯(GraPhene)，即由sp2碳原子自下而上组装形成的二维单层碳纳米结构材料，由于其优异的导电、导热、机械性能以及化学稳定性，使其在高性能纳电子器件、传感器、纳米复合材料、电化学储能等领域获得广泛应用。目前石墨烯的获得主要是通过机械剥离法、化学气相沉积法、氧化石墨烯还原法以及液相剥离法等方法获得[Nat.Mater.，14，271-279(2015)]。其中机械剥离法及化学气相沉积法能够获得规整度高、杂质含量少的单层石墨烯结构，然而高成本、低产率的缺点仍将它们限制在了实验室范围的合成；相比于前两种方法，液相剥离及氧化石墨烯的还原能够一定程度上提高石墨烯的生成规模，然而石墨烯剥离效率低、结构规整度低仍是亟待解决的难题。纵观目前石墨烯的生产工艺，高性能石墨烯从实验室规模的合成走向工业化生产仍是阻碍其大规模应用的核心瓶颈。
基于上述分析，研发低成本、可规模化生产的氮掺杂石墨烯及多孔碳材料制备方法具有重要意义，特别是寻找低成本、大储量的原料以及操作简化的制备工艺尤为重要。煤炭的内部结构包含大量以芳香烃、聚芳香烃为基本单元的天然类石墨层状结构，一直以来被视为多孔碳材料规模化、低成本制备的重要原料之一。目前以煤炭为原料生产多孔碳材料主要是以煤化程度较高的烟煤、无烟煤为原料，通过碳化及活化(物理活化或化学活化)处理制备获得煤基活性碳材料。其中，煤种特性、活化剂种类及活化条件是影响多孔碳孔隙结构的关键影响因素。褐煤在我国具有较大的储量，相比于其他煤种，价格便宜，特别是今年在中国新疆准格尔东部发现储量丰富的低阶煤炭资源(准东褐煤)，预测资源储量达3900亿吨。一方面，褐煤由于较低的煤化程度、较高的碱金属及水分含量，在燃煤发电领 域大规模应用具有较大技术瓶颈。然而另一方面，褐煤作为多孔碳材料制备的原料却具有显著优势：(1)褐煤挥发分含量高，有利于在高温热解过程形成更发达孔隙结构；(2)褐煤的煤化程度低，内部芳香结构内包含大量含氧基团，使其具有高反应活性，更容易在制备多孔碳材料中调节碳结构演变及孔隙生成过程。
本发明旨在提供了一种低成本、可大规模工业生产的氮掺杂石墨烯及多孔碳材料制备方法。具体地说，以低阶褐煤为原料，通过氮源及活化剂混合、高温一步碳化法制备得到氮掺杂石墨烯及氮掺杂多孔碳材料。本发明涉及的氮掺杂石墨烯及多孔碳材料制备方法工艺简单、成本低廉、易于大规模、批量化生产；以该方法制备的氮掺杂多孔碳具有微结构发达、比表面积可控、氮含量可控等优点，在电化学储能(双电层电容电极材料、钠离子电池负极出口)和气体(SO2、CO2)吸附领域具有重要应用潜力。
发明内容
本发明要解决现有氮掺杂石墨烯及多孔碳材料多制备技术存在的原料成本高、制备工艺繁杂等问题，利用简单的一步碳化法制备孔结构可控、氮掺杂量可控的多孔碳或石墨烯材料。包括以下步骤：
细化步骤：将煤原料进行细化，得到细化煤粉；
碳化步骤：将所述细化煤粉与氮源混合，在惰性气体或氨气与惰性气体混合气氛下碳化，自然降温，得到碳化产物；
清洗步骤：将所述碳化产物酸洗、水洗处理；
干燥步骤：将清洗后的碳化产物干燥处理，即得到氮掺杂多孔碳材料。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，所述煤原料为褐煤。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，以煤炭为原料制备氮掺杂多孔碳材料的方法中，所述氮源为氨气、三聚氰胺、脲醛树脂、尿素及含氮有机物中的一种或多种。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，所述惰性气体为纯度＞99.99％的氮气或氩气。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，煤粉与氮源质量比为1∶0.1～1∶10。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，所述氮源为氨气时，碳化气氛中氨气与惰性气氛体积比为1∶0.1～1∶100。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，碳化温度为700℃～1200℃，碳化停留时间为0～10h。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，碳化过程的升温速率为0.1～15℃/min。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，酸洗处理采用的酸洗液为稀盐酸或硝酸，且酸洗液的浓度为0.5mol/L～2mol/L。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，干燥处理的温度为60～200℃。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，在碳化步骤中，将所述细化煤粉与氮源及活化剂混合，制备的氮掺杂多孔碳材料为氮掺杂多孔石墨烯。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，所述活化剂为碱金属氢氧化物，碱土金属的氢氧化物或他们的混合物的溶液。
优选地，上述以煤炭为原料制备氮掺杂多孔碳材料的方法中，所述细化煤粉与所述活化剂的质量比为1∶0.1～1∶10。
本发明的另一方面，还提供一种由以煤炭为原料制备氮掺杂多孔碳材料的方法制备得到的氮掺杂多孔碳材料。
与现有技术相比较，本发明的优势在于：
(1)本发明可以以大储量、低成本褐煤为碳源，通过活化剂与氮源混合以及一步碳化过程制备氮掺杂多孔石墨烯材料；
(2)本发明所制备的多孔碳材料中，孔结构和氮掺杂量的控制可通过碳化时引入气氛种类、煤粉与活化剂及氮源比例、碳化温度的调节来实现；
(3)通过X射线光电子能谱(XPS)分析，表明本发明的方法获得的多孔碳材料氮掺杂量可控在0％～10％之间；
(4)通过氮吸附分析，表明本发明的方法获得的多孔碳材料孔结构可控，比表面积在500～1300m2 g-1之间；
(5)传统的煤基活性碳制备过程通常需要预碳化处理以得到具有初步孔隙构架的碳化料，再将碳化料与活化剂混合并经过高温活化过程得到活性碳材料。本发明通过采用变质程度低、碳骨架可塑性强的年轻褐煤，无需预碳化过程，仅通过一步碳化过程即可得到氮掺杂石墨烯及多孔碳材料，大大简化了制备工艺、降低了制备成本；
(6)相比于单纯惰性气氛条件下多孔碳活化方法，本发明提供了在活化过程引入NH3的技术方案，NH3同时起到造孔剂和氮掺杂剂的作用，从而实现了孔结构和氮掺杂的协同调控。
附图说明
图1(a)、(b)、(c)、(d)为实施例1制备得到的氮掺杂多孔碳的不同倍率的SEM及TEM图像。
图2(a)、(b)、(c)、(d)为实施例1制备得到的氮掺杂多孔碳的水系超级电容性能的表征结果。
图3为实施例1得到的氮掺杂多孔碳的CO2吸附等温线。
图4为实施例1得到的氮掺杂多孔碳作为钠离子电池负极材料在200mAh g-1下的循环特性曲线；
图5为实施例1得到的氮掺杂多孔碳的SO2吸附动力学曲线。
图6为实施例1得到的氮掺杂多孔碳氮吸附等温线。
图7为实施例2得到的氮掺杂多孔碳氮吸附等温线。
图8为实施例3得到的氮掺杂多孔碳氮吸附等温线。
图9为实施例4得到的氮掺杂多孔碳氮吸附等温线。
具体实施方式
下面结合附图及具体实施例，详细阐述本发明的优势。
实施例1：
本实施方式多孔石墨烯制备方法按下列步骤实现：
(1)称取3g球磨筛分后粒径为80-100目的褐煤煤粉；
(2)将步骤(1)得到的煤粉放入管式炉中进行升温碳化：从室温升至900℃，控制升温速率为5℃/min，在NH3所占体积比为50％的NH3与N2混合气体氛围下，900℃温度下，恒温碳化3h后自然降温得到碳化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀盐酸洗涤2～3次，再用去离子水洗涤2～3次，最后在80℃下干燥，得到目标产物氮掺杂微孔碳(编号为NMC-0.5)。
实施例1的结构及性能分析方法：
采用透射电镜、N2吸附等手段对实施例1所得氮掺杂微孔碳微观形貌以及孔隙结构参 数进行详细表征。
以实施例1所得氮掺杂微孔碳为水系超级电容器材料，采用下述试验测试性能：将氮掺杂微孔碳、炭黑、和PTFE乳液以8∶1∶1比例加到无水乙醇中研磨形成自支撑薄膜，裁剪质量完全相同(1～2mg作用)的两片薄膜在研钵中擀成面积约为1cm2的片状极片，压在镍泡沫集流体上作为电容性能测试的电极片。电极片在120℃、真空环境下烘干12h备用。以6M KOH为电解液、饱和甘汞电极为参比，Pt片为对电极，测试三电极体系下循环伏安特性曲线及恒电容恒电流充放电曲线。其中，氮掺杂微孔碳比容量C计算方法如下：
Figure PCTCN2017103496-appb-000001
式中I为放电电流密度；Δt为一次放电时间；m为正极极片所含的活性材料质量；ΔV为扣除电压降IRdrop后的放电电压区间。
以实施例1所得氮掺杂微孔碳为吸附剂，采用体积吸附法测试其对CO2的吸附等温线，获得其CO2储存性能。
以实施例1所得氮掺杂微孔碳为钠离子电池负极材料，其性能测试方法为：以钠片为对电极，氮掺杂微孔碳为工作电极活性物质，组装CR2032纽扣电池测试其作为钠离子电池负极材料性能。其中工作电极制备方法为：将氮掺杂微孔碳、炭黑、和PVDF以7∶1.5∶1.5的质量比溶于NMP并研磨成均一浆料，之后将浆料涂覆在铜箔上并在80℃下真空烘干12h得到工作电极极片。烘干的极片裁剪为圆形片状并保持活性物质密度为0.5～1mg cm-2，与新鲜锂片在手套箱内组装为纽扣电池，电解液为1M NaClO4(溶剂为碳酸亚乙酯和碳酸二乙酯1∶1)，Whatman玻璃纤维膜为隔膜。测试电池在0.01～3.0V vs.Li/Li+电压范围内的循环伏安特性曲线及恒电容恒电流充放电曲线。
以实施例1所得氮掺杂微孔碳为气态污染物分子SO2吸附剂，通过下述试验测试其SO2吸附动力学性能：采用自制的固定床反应系统，由配气系统、固定床反应系统、加热与保温系统、测量系统五个子系统等组成。其中固定床反应器为玻璃管和砂芯烧制而成，管内径20mm。反应温度的控制由立式管式炉实现，温度波动为±1℃。装有1g掺杂微孔碳的玻璃反应器放置在管式炉内并进行管路密封；在室温条件下引入模拟烟气(N2和SO2；具体配比为SO2 2000ppm，其余为N2)；反应器进出口SO2浓度由生产的便携式FTIR(芬兰Gasmet公司，DX-4000)检测，当SO2进出口SO2浓度无变化即达到吸附脱除饱和或SO2转化率低于某一设定值时停止实验，测量后的气体经洗气瓶(内装NaOH溶液)，充分净化后排入大气。
图1(a)、(b)、(c)、(d)为具体实施方式/实施例1得到的氮掺杂微孔碳SEM及TEM 图像。可以看出氮掺杂微孔碳内部为类石墨微晶堆砌结构，TEM图像表面内部包含大量石墨烯片层堆积结构。
图2(a)、(b)、(c)、(d)为具体实施方式/实施例1得到的氮掺杂微孔碳水系超级电容性能表征结果。能够发现本发明所得氮掺杂微孔碳在6M KOH体系中具有高比电容、倍率性能及循环稳定性：图2(a)中循环伏安特性曲线表明在高扫速200mV/s下仍保持了较好的矩形电容行为；0.5A/g电流密度下比电容可达205F/g，在极高的50A/g电流密度下比电容仍有近129F/g；图2(d)中5A/g循环稳定性曲线表明10000次循环后容量几乎无衰减。
图3为具体实施方式/实施例1得到的氮掺杂微孔碳CO2吸附等温线，0摄氏度下1个大气压下CO2吸附容量可达3.71mmol g-1。
图4为具体实施方式/实施例1得到的氮掺杂微孔碳氮吸附等温线，比表面积为1235m2g-1，孔容为0.58cm3g-1。
图5为实施例1得到的氮掺杂微孔碳在0.2A g-1电流密度下的循环稳定性曲线。500次循环期间，氮掺杂微孔碳钠离子负极仍保有190mAh g-1的容量。
图6实施例1得到的氮掺杂微孔碳在室温条件下(25℃)30分钟内对SO2的累积吸附容量曲线，SO2累积吸附容量可达53mg g-1。
而，从表1可知本实施例所得氮掺杂微孔碳氮含量为5.93wt-％。
具体实施方式/实施例2：
(1)称取3g球磨筛分后粒径为80-100目的褐煤煤粉；
(2)将步骤(1)得到的煤粉管式炉中进行升温碳化：从室温升至900℃，控制升温速率为10℃/min，在NH3所占体积比为10％的NH3与N2混合气体氛围下，在900℃温度下，恒温碳化2h后自然降温得到碳化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀盐酸洗涤2～3次，再用去离子水洗涤2～3次，最后在100℃下干燥，得到目标产物氮掺杂微孔碳(编号为NMC-0.1)。
采用实施例1中所述的结构及性能测试方法对本实施例获得的微孔碳进行表征。从图5吸附等温线及表1能够得到本实施例得到的微孔石墨烯比表面积为48m2/g，孔容为0.02cm3/g，氮含量为2.09％。
具体实施方式/实施例3：
(1)称取3g球磨筛分后粒径为120目的褐煤煤粉；
(2)将步骤(1)得到的煤粉管式炉中进行升温碳化：从室温升至900℃，控制升温速率为15℃/min，在NH3所占体积比为75％的NH3与N2混合气体氛围下，在900℃温度下恒温活化1h后自然降温得到碳化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀硝酸洗涤2～3次，再用去离子水洗涤2～3次，最后在100℃下干燥，得到目标产物氮掺杂微孔碳(编号为NMC-0.75)。
采用实施例1中所述的结构及性能测试方法对本实施例获得的微孔碳进行表征。从图5吸附等温线及表1能够得到本实施例得到的微孔石墨烯比表面积为721m2/g，孔容为0.35cm3/g，氮含量为6.80％。
具体实施方式/实施例4：
(1)称取3g球磨筛分后粒径为120目的褐煤煤粉；
(2)将步骤(1)得到的煤粉管式炉中进行升温碳化：从室温升至800℃，控制升温速率为8℃/min，在纯NH3气体氛围下，在800℃温度下恒温活化3h后自然降温得到碳化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀硝酸洗涤2～3次，再用去离子水洗涤2～3次，最后在100℃下干燥，得到目标产物氮掺杂微孔碳(编号为NMC-1)。
采用实施例1中所述的结构及性能测试方法对本实施例获得的微孔碳进行表征。从图5吸附等温线及表1能够得到本实施例得到的微孔石墨烯比表面积为437m2/g，孔容为0.21cm3/g，氮含量为5.97％。
具体实施方式/实施例5：
(1)称取3g球磨筛分后粒径为120目的褐煤煤粉，与1g三聚氰胺球磨混合形成混合物料；
(2)将步骤(1)得到的混合物料在管式炉中进行升温碳化：从室温升至900℃，控制升温速率为5℃/min，在纯N2气体氛围下，在900℃温度下恒温碳化3h后自然降温得到碳化产物；
(3)将步骤(2)所得的碳化产物用1mol//L稀硝酸洗涤2～3次，再用去离子水洗涤2～3次，最后在120℃下干燥，得到目标产物氮掺杂多孔碳。
采用实施例1中所述的结构及性能测试方法对本实施例获得的微孔碳进行表征可知本 实施例得到的多孔碳比表面积为157m2/g，孔容为0.08cm3/g，氮含量为6.97％。
具体实施方式/实施例6：
(1)称取3g球磨筛分后粒径为120目的褐煤煤粉、1g三聚氰胺加入6M KOH溶液中高速混合，煤粉与KOH质量比控制在1∶2；
(2)将步骤(1)得到的混合溶液在100℃下干燥去除水分，获得的混合物料在管式炉中进行升温活化：从室温升至950℃，控制升温速率为8℃/min，在纯Ar气氛，在950℃温度下恒温活化3h后自然降温得到活化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀硝酸洗涤2～3次，再用去离子水洗涤2～3次，最后在150℃下干燥，得到目标产物氮掺杂多孔石墨烯材料；
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔石墨烯材料进行表征可知：其内部含有1层或多层石墨烯片层结构，比表面积为1635m2/g，孔容为0.8cm3/g，氮含量为4.25％。
具体实施方式/实施例7：
(1)称取3g球磨筛分后粒径为120目的褐煤煤粉加入6M KOH溶液中高速混合，煤粉与KOH质量比控制在1∶3；
(2)将步骤(1)得到的混合溶液在120℃下干燥去除水分，获得的混合物料在管式炉中进行升温活化：从室温升至900℃，控制升温速率为5℃/min，在NH3所占体积比为25％的NH3与N2混合气体氛围下，在900℃温度下恒温活化1h后自然降温得到活化产物；
(3)将步骤(2)所得的碳化产物用4mol//L稀盐酸洗涤2～3次，再用去离子水洗涤2～3次，最后在120℃下干燥，得到目标产物氮掺杂多孔石墨烯。
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔石墨烯材料进行表征可知：其内部含有1层或多层石墨烯片层结构，比表面积为2015m2/g，孔容为0.95cm3/g，氮含量为3.05％。
具体实施方式/实施例8：
(1)取3g球磨筛分后粒径为120目的褐煤煤粉、0.5g尿素加入2M NaOH溶液中高速混合，煤粉与NaOH质量比控制在1∶2；
(2)将步骤(1)得到的混合溶液在120℃下干燥去除水分，获得的混合物料在管式炉 中进行升温活化：从室温升至900℃，控制升温速率为10℃/min，在纯Ar气氛下，在900℃温度下恒温活化2h后自然降温得到活化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀硝酸洗涤2～3次，再用去离子水洗涤2～3次，最后在150℃下干燥，得到目标产物氮掺杂多孔碳。
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔碳进行表征可知其比表面积为1015m2/g，孔容为0.55cm3/g，氮含量为1.93％。
具体实施方式/实施例9：
(1)称取3g球磨筛分后粒径为120目的褐煤煤粉，与1g尿素球磨混合形成混合物料；
(2)将步骤(1)得到的混合物料在管式炉中进行升温碳化：从室温升至900℃，控制升温速率为10℃/min，在NH3所占体积比为50％的NH3与Ar混合气体氛围下，在900℃温度下恒温碳化3h后自然降温得到碳化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀盐酸洗涤2～3次，再用去离子水洗涤2～3次，最后在120℃下干燥，得到目标产物氮掺杂多孔碳。
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔碳进行表征可知其比表面积为895m2/g，孔容为0.45cm3/g，氮含量为8.52％。
具体实施方式/实施例10：
(1)取3g球磨筛分后粒径为120目的褐煤煤粉、0.5g尿素、0.5g三聚氰胺，加入6M KOH溶液中高速混合，煤粉与KOH质量比控制在1∶2；
(2)将步骤(1)得到的混合溶液在150℃下干燥去除水分，获得的混合物料在管式炉中进行升温活化：从室温升至1000℃，控制升温速率为5℃/min，在纯N2气氛下，在1000℃温度下恒温活化1h后自然降温得到活化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀盐酸洗涤2～3次，再用去离子水洗涤2～3次，最后在150℃下干燥，得到目标产物氮掺杂多孔石墨烯材料。
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔石墨烯材料进行表征可知：其内部含有1层或多层石墨烯片层结构，比表面积为1830m2/g，孔容为0.74cm3/g，氮含量为5.52％。
具体实施方式/实施例11：
(1)取3g球磨筛分后粒径为120目的褐煤煤粉、0.3g尿素，加入6M KOH溶液中高速混合，煤粉与KOH质量比控制在1∶10；
(2)将步骤(1)得到的混合溶液在200℃下干燥去除水分，获得的混合物料在管式炉中进行升温活化：从室温升至1200℃，控制升温速率为8℃/min，在纯N2气氛下，在1200℃温度下恒温活化3h后自然降温得到活化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀盐酸洗涤2～3次，再用去离子水洗涤2～3次，最后在150℃下干燥，得到目标产物氮掺杂多孔石墨烯材料。
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔石墨烯材料进行表征可知：其内部含有1层或多层石墨烯片层结构，比表面积为1140m2/g，孔容为1.55cm3/g，氮含量为0.73％。
具体实施方式/实施例12：
(1)取3g球磨筛分后粒径为80-100目的褐煤煤粉、30g三聚氰胺，加入6M KOH溶液中高速混合，煤粉与KOH质量比控制在1∶0.1；
(2)将步骤(1)得到的混合溶液在200℃下干燥去除水分，获得的混合物料在管式炉中进行升温活化：从室温升至700℃，控制升温速率为10℃/min，在纯Ar气氛下，在700℃温度下恒温碳化3h后自然降温得到活化产物；
(3)将步骤(2)所得的碳化产物用0.5mol//L稀盐酸洗涤2～3次，再用去离子水洗涤2～3次，最后在200℃下干燥，得到目标产物氮掺杂多孔碳材料。
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔碳材料进行表征可知：其内部含有1层或多层石墨烯片层结构，比表面积为98m2/g，孔容为0.05m3/g，氮含量为2.55％。
具体实施方式/实施例13：
(1)取3g球磨筛分后粒径为120目的褐煤煤粉、0.15g三聚氰胺、0.15g尿素，加入6M KOH溶液中高速混合，煤粉与KOH质量比控制在1∶0.1；
(2)将步骤(1)得到的混合溶液在150℃下干燥去除水分，获得的混合物料在管式炉中进行升温活化：从室温升至900℃，控制升温速率为15℃/min，在NH3所占体积比为99％的NH3与Ar混合气体氛围下，在900℃温度下恒温碳化3h后自然降温得到碳化产物；
(3)将步骤(2)所得的碳化产物用0.5mol//L稀盐酸洗涤2～3次，再用去离子水洗涤 2～3次，最后在60℃下干燥，得到目标产物氮掺杂多孔碳材料。
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔碳材料进行表征可知：其内部含有1层或多层石墨烯片层结构，比表面积为490m2/g，孔容为0.28m3/g，氮含量为7.85％。
具体实施方式/实施例14：
(1)取3g球磨筛分后粒径为120目的褐煤煤粉、15g三聚氰胺、15g尿素，加入6M KOH溶液中高速混合，煤粉与KOH质量比控制在1∶10；
(2)将步骤(1)得到的混合溶液在200℃下干燥去除水分，获得的混合物料在管式炉中进行升温活化：从室温升至700℃，控制升温速率为10℃/min，在NH3所占体积比为10％的NH3与Ar混合气体氛围下，在700℃温度下恒温碳化3h后自然降温得到碳化产物在纯Ar气氛下，在950℃温度下恒温活化1h后自然降温得到活化产物；
(3)将步骤(2)所得的碳化产物用2mol//L稀盐酸洗涤2～3次，再用去离子水洗涤2～3次，最后在200℃下干燥，得到目标产物氮掺杂多孔石墨烯材料。
采用实施例1中所述的结构及性能测试方法对本实施例获得的氮掺杂多孔石墨烯材料进行表征可知：其内部含有1层或多层石墨烯片层结构，比表面积为1030m2/g，孔容为0.68m3/g，氮含量为8.65％。
表1不同实施例所得氮掺杂石多孔碳或石墨烯孔结构参数及氮掺杂量
Figure PCTCN2017103496-appb-000002
Figure PCTCN2017103496-appb-000003
以上部分实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (14)

  1. 以煤为原料制备氮掺杂多孔碳材料的方法，包括以下步骤：
    细化步骤：将煤原料进行细化，得到细化煤粉；
    碳化步骤：将所述细化煤粉与氮源混合，在惰性气体或氨气与惰性气体混合气氛下碳化，自然降温，得到碳化产物；
    清洗步骤：将所述碳化产物酸洗、水洗处理；
    干燥步骤：将清洗后的碳化产物干燥处理，即得到氮掺杂多孔碳材料。
  2. 根据权利要求1所述的方法，其特征在于，所述煤原料为褐煤。
  3. 根据权利要求1所述的方法，其特征在于，所述氮源为氨气、三聚氰胺、脲醛树脂、尿素及含氮有机物中的一种或多种。
  4. 根据权利要求1所述的方法，其特征在于，所述惰性气体为纯度＞99.99％的氮气或氩气。
  5. 根据权利要求1所述的方法，其特征在于，煤粉与氮源质量比为1∶0.1～1∶10。
  6. 根据权利要求1所述的方法，其特征在于，所述氮源为氨气时，碳化气氛中氨气与惰性气氛体积比为1∶0.1～1∶100。
  7. 根据权利要求1所述的方法，其特征在于，碳化温度为700℃～1200℃，碳化停留时间为0～10h。
  8. 根据权利要求1所述的方法，其特征在于，碳化过程的升温速率为0.1～15℃/min。
  9. 根据权利要求1所述的方法，其特征在于，酸洗处理采用的酸洗液为稀盐酸或硝酸，且酸洗液的浓度为0.5mol/L～2mol/L。
  10. 根据权利要求1所述的方法，其特征在于，干燥处理的温度为60～200℃。
  11. 根据权利要求1-10任一所述的方法，其特征在于，在碳化步骤中，将所述细化煤粉与氮源及活化剂混合，制备的氮掺杂多孔碳材料为氮掺杂多孔石墨烯。
  12. 根据权利要求11所述的方法，其特征在于，所述活化剂为碱金属氢氧化物，碱土金属的氢氧化物或他们的混合物的溶液。
  13. 根据权利要求11所述的方法，其特征在于，所述细化煤粉与所述活化剂的质量比为1∶0.1～1∶10。
  14. 一种由权利要求1至13所述的合成方法得到的氮掺杂多孔碳材料。
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