CN101531357A - Method for preparing nitrogen-doped porous carbon material by two-step method and application thereof - Google Patents
Method for preparing nitrogen-doped porous carbon material by two-step method and application thereof Download PDFInfo
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- CN101531357A CN101531357A CN200810208054A CN200810208054A CN101531357A CN 101531357 A CN101531357 A CN 101531357A CN 200810208054 A CN200810208054 A CN 200810208054A CN 200810208054 A CN200810208054 A CN 200810208054A CN 101531357 A CN101531357 A CN 101531357A
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Abstract
The invention relates to a method for preparing a nitrogen-doped porous carbon material by a two-step method and application thereof, and belongs to the field of hydrogen storage materials and new energy materials. The nitrogen-doped porous carbon material is prepared by adopting a template carbonization method, which comprises that: firstly, a microporous molecular sieve such as ZSM-5, 3A, 5A, 13X, Y, beta and the like is used as a template, and then nitrogen-doped porous carbon material is prepared by adopting the two-step method combining liquid-phase impregnation and chemical precipitation. The liquid-phase impregnation uses sucrose, furfuryl alcohol, polyacrylonitrile and the like as a carbon or carbon-nitrogen precursor which is impregnated in the template, and the chemical precipitation comprises that propylene, acetonitrile, phenyl ethylene, methylbenzene and the like are precipitated on the template by a CVD method in turn. And then, nitrogen-doped porous carbon is further obtained through the process steps such as high temperature carbonization, template removal and the like. The nitrogen-doped porous carbon material with different structures can be obtained by controlling process conditions. The nitrogen-doped porous carbon material prepared by the method has the advantages of high specific surface area, large pore volume, narrow aperture distribution and adjustable pore structure, and can be used for the hydrogen storage materials and super-capacitor electrode materials.
Description
Technical field
The invention belongs to hydrogen storage material and new energy materials field, provide the method for a class method for preparing nitrogen-doped porous carbon material by two-step and in the application of hydrogen storage material and electrode material for super capacitor.
Background technology
Porous carbon material is because its low density, high specific surface area, good chemical stability, good electrical conductivity, pore structure can regulate and control and not harsh advantages such as application conditions have obtained numerous concerns, becomes one of important object of hydrogen storage material and electrode material for super capacitor research.
In the hydrogen storage material field, because the memory by using of porous material is the physical adsorption of hydrogen molecule, therefore this porous material can be realized the big quality storage of small volume.In theory, the specific surface area of carbon material is high more, and corresponding hydrogen-storage amount also should be big more.Studies show that, for the ideal porous carbon materials, for obtaining bigger hydrogen, need higher specific surface area so that more absorption position to be provided on the one hand, also need the micro pore volume of larger proportion to improve ratio [Y Gogotsi et al, Adv.Funct.Mater., 2006 of active adsorption position in addition, 16,2288.].Recently, utilize template to prepare the common concern that porous carbon or carbon-nitrogen material have obtained people, but adopt porous material that single stage method synthesizes separately when containing a certain amount of micropore, exist a large amount of bigger mesoporous equally.
In the ultracapacitor field, electrode materials is the core integral part of ultracapacitor, and its composition, structure and character play decisive influence to the performance of electrical condenser.Studies show that reasonably the matched well of pore size distribution and aperture and electrolyte ion adds higher specific surface area, can access higher capacitance.Reasonably pore size distribution is in order to help transporting of electrolyte ion, and the matched well of aperture and electrolyte ion is in order to obtain electrostatic double layer absorption preferably, and higher specific surface area is the prerequisite of acquisition higher capacitance value.In addition, porous carbon materials is carried out impurity atoms mix, can obtain a certain amount of fake capacitance, further improve the capacitance of porous carbon materials.
In order further to improve the performance of carbon back porous material, can prepare the porous material that contains a large amount of micropores by two step method, be very suitable for hydrogen storage material.The micropore that contains in this material helps the accumulation of electric charge simultaneously, and smaller mesoporous (about 2nm) help ionic and transport, and therefore helps improving the capacitive property of material.
Summary of the invention
The objective of the invention is in order to obtain high-specific surface area, to have a nitrogen-doped porous carbon material of high hydrogen storage, high capacity simultaneously, a kind of method of method for preparing nitrogen-doped porous carbon material by two-step is provided, this nitrogen-doped porous carbon material specific surface area height, pore volume are big, but pore size modulation and narrow distribution, micro pore volume obviously improve, it has good low temperature hydrogen storage property as hydrogen storage material, has good electrochemical capacitor performance as electrode material for super capacitor, and whole preparation process simple controllable, mild condition, cost are cheap relatively.
The technical scheme that technical solution problem of the present invention is taked is: at first adopting micro porous molecular sieve is template, adopts liquid impregnation and electroless plating two one step process to be prepared from.The exsiccant micro porous molecular sieve is immersed in the solution of carbon such as containing sucrose, furfuryl alcohol, polyacrylonitrile or carbon nitrogen precursor, fully is immersed in the duct of template up to the carbon precursor; The mixture that obtains is placed tube furnace, in carbonization, precursors such as propylene, acetonitrile, vinylbenzene, toluene are deposited in the duct of not filling by vapour deposition; Carbon nitrogen/the molecular screen composite that obtains after the carbonization is joined in hydrofluoric acid solution and the hydrochloric acid soln, and repetitive scrubbing repeatedly separates, washing, drying obtain removing the nitrogen-doped porous carbon material after the template then after filtration.
Performance evaluation as hydrogen storage material of the present invention adopts weighting method to measure the adsorptive capacity of hydrogen on nitrogen-doped porous carbon material.Earlier with sample pre-treatment under vacuum, hot conditions, remove the gas of absorption and residual moisture before the test.Treat that temperature reduces to after the room temperature, the helium atmosphere that charges into different pressures is carried out the buoyancy test, obtains the volume of sample with this.By liquid nitrogen adsorption system is reduced to temperature requiredly again, feed hydrogen gas and carry out transformation absorption test.At last, obtain the adsorptive capacity of hydrogen under a certain pressure by the result of system ensemble changes in weight and buoyancy test.Under the 1bar condition, the result that this weight test macro and volumetric method (BET method) provide matches, and the height of accuracy as a result that this weighting method test macro provides is described.
The evaluation of electrode of super capacitor performance of the present invention is carried out with method well-known in the art, and the nitrogen porous material that mixes is pressed into electrode slice, adopts the method for cyclic voltammetric to test.
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) to select orderly micro porous molecular sieve in earlier stage for use be template, adopt two step method to prepare nitrogen doping porous carbon in the present invention, make nitrogen-doped porous carbon material have open pore passage structure and a large amount of micropores, the micro-porous adsorption characteristic that has kept molecular sieve, the absorption that this helps hydrogen is the prerequisite that obtains excellent hydrogen storage property.
(2) to select orderly micro porous molecular sieve in earlier stage for use be template, adopt two step method to prepare nitrogen doping porous carbon in the present invention, make nitrogen-doped porous carbon material have open pore passage structure and a large amount of micropores, also contain smaller mesoporous simultaneously, this helps the accumulation of electric charge and the transmission of electrolytic solution, is the prerequisite that obtains excellent electrochemical performance.
(3) its low temperature hydrogen-storage amount of hydrogen storage material of the inventive method acquisition obviously increases, and has extraordinary reversible adsorption performance.
(3) contain nitrogen-atoms in the precursor that the present invention adopts, the introducing of nitrogen-atoms helps improving its capacitive property, make its specific capacitance of electrode materials obviously increase, and its stability is kept preferably.
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Embodiment
Below in the mode of specific embodiment the present invention is described, but be not limited only to embodiment.
Embodiment 1
With molecular sieve 13X is template, introduces carbon or carbon nitrogen precursor by two step method, is respectively liquid impregnation and sedimentary carbon of gas phase or carbon nitrogen precursor with furfuryl alcohol and acetonitrile, by template Carbonization Preparation nitrogen doping porous carbon.The specific surface area of used 13X is 674m
2/ g, pore volume are 0.32cm
3/ g.At first taking by weighing 4g 13X is immersed in the solution of being made up of 1.5ml furfuryl alcohol, 10ml dehydrated alcohol and 0.01g oxalic acid, stir 4h under the room temperature and make its abundant mixing, then under 60 ℃ and 80 ℃, respectively heat 16h respectively, the yellowish brown pressed powder that obtains is put into tube furnace, then at 150 ℃, N
2Heating 3h finishes the prepolymerization of furfuryl alcohol under the atmosphere, temperature is elevated to 700 ℃ subsequently, and then with 70cm
3The N of/min
2For carrier gas feeds acetonitrile gas, heating 4h finishes the carbonization of furfuryl alcohol and the deposition of acetonitrile.Continue to be warming up to 900 ℃ then, nitrogen atmosphere is insulation 3h down.HF solution and 3M HCl solution with 10wt% washs 12h, repetitive scrubbing twice respectively at last, to remove the molecular sieve template, after filtration, washing, 100 ℃ of dryings obtain nitrogen doping porous carbon.
Adopt weighting method to test the low temperature hydrogen storage property of this nitrogen-doped porous carbon material.Fig. 2 is the variation of this nitrogen doping porous material hydrogen under different pressures, can see the raising along with pressure, and hydrogen increases, and hydrogen-storage amount does not reach capacity yet under 20bar pressure, is indicating under higher pressure and can realize higher hydrogen-storage amount.Listed the concrete test result of this nitrogen doping porous hydrogen storage material in the table 1.Fig. 4 has showed the variation of this electrode materials specific capacitance under different scanning rates, can see the raising along with scanning speed, and specific capacitance reduces gradually.Listed the concrete test result of this electrode materials in the table 2.
Embodiment 2
The method of present embodiment is substantially the same manner as Example 1, different only be: after temperature was elevated to 700 ℃, heating 8h finished the carbonization of furfuryl alcohol and the deposition of acetonitrile under acetonitrile atmosphere.Fig. 1 has showed the transmission electron microscope picture of this nitrogen-doped porous carbon material, orderly as can be seen micropore canals structure.Fig. 2 is the variation of this nitrogen doping porous material hydrogen under different pressures, can see the raising along with pressure, and hydrogen increases.Fig. 3 is that this nitrogen doping porous material is inhaled hydrogen under different pressures and dehydrogenation changes, and whole as can be seen adsorption process is a reversible, can reach absorption and desorption balance fast.Fig. 4 has showed the variation of this electrode materials specific capacitance under different scanning rates.Listed the concrete test result of this nitrogen doping porous hydrogen storage material in the table 1.Listed the concrete test result of this electrode materials in the table 2.
Embodiment 3
The method of present embodiment is substantially the same manner as Example 1, different only be: 4g 13X is immersed in the solution of being made up of 3.0ml furfuryl alcohol, 10ml dehydrated alcohol and 0.02g oxalic acid.The concrete test result of this electrode materials can obtain from Fig. 4 and table 2.
Embodiment 4
The method of present embodiment is substantially the same manner as Example 1, different only be: after temperature was elevated to 800 ℃, heating 4h finished the carbonization of furfuryl alcohol and the deposition of acetonitrile under acetonitrile atmosphere.Showed the concrete test result of this electrode materials among Fig. 4 and the table 2.
In table 1, hydrogen-storage amount is the hydrogen adsorption amount under 77K, the 20bar condition, and this numerical value is high more, shows that the hydrogen storage property of nitrogen doping porous material is good more.Can find out obviously that from table 1 with respect to the porous material of Comparative Examples 1, nitrogen doping porous material specific surface area of the present invention, pore volume, micro pore volume all are improved significantly, pore structure has obtained regulation and control.The micropore occupation rate all remains on more than 75%.On hydrogen storage property, hydrogen-storage amount is greatly improved.Among the embodiment 1, hydrogen-storage amount has been brought up to 4.81wt%, and among the embodiment 2, hydrogen-storage amount has been brought up to 6.16wt%.
Table 1
In table 2, specific capacitance is that cyclic voltammetry curve under the 2mV/s calculates by scanning speed; The electric capacity conservation rate be ratio electric capacity under the 50mV/s scanning speed with respect to per-cent more shared under the 2mV/s than electric capacity, this numerical value is high more, shows that electrode materials is subjected to the influence of scanning speed more little, corresponding electrochemical capacitor performance is good more.As can be seen, the nitrogen doping porous material of the present invention's preparation is a kind of more satisfactory electrode material for super capacitor, and it all remains on more than the 240F/g than capacitance.
Table 2
Claims (4)
1, the method for method for preparing nitrogen-doped porous carbon material by two-step is characterized in that comprising the steps:
(1) the exsiccant micro porous molecular sieve is immersed in the solution of carbon such as containing sucrose, furfuryl alcohol, polyacrylonitrile or carbon nitrogen precursor, the quality consumption proportion of micro porous molecular sieve and carbon or carbon nitrogen precursor is 1:0.1～1:2, stirring at room 1～6 hour, fully be immersed in the duct of template up to the carbon precursor, handled 6～36 hours down at 40～100 ℃ then;
(2) mixture that obtains is previously placed tube furnace, carbonization under inert atmosphere, carbonization temperature is 600～1200 ℃, in carbonization, precursors such as propylene, acetonitrile, vinylbenzene, toluene are deposited in the duct of not filling by vapour deposition, inert gas flow is 20～300 ml/min, and constant temperature time is 2～10 hours;
(3) after vapour deposition finishes, continue under inert atmosphere 600～1200 ℃ of insulation 0～6h;
(4) the carbon nitrogen/molecular screen composite that obtains after the carbonization being joined mass ratio is in 2～20% the hydrofluoric acid solution, stirring at room 6～24 hours, and then adopt the hydrochloric acid soln of 1～6M, stirred 2～24 hours down at 20～100 ℃, repetitive scrubbing repeatedly separates, washing, drying obtain removing the nitrogen-doped porous carbon material after the template then after filtration.
2, according to the method for the described method for preparing nitrogen-doped porous carbon material by two-step of claim 1, it is characterized in that introducing carbon or carbon nitrogen precursor in template by two step method, the template of use adopts micro porous molecular sieve.
3, according to the method for claim 1 or 2 described method for preparing nitrogen-doped porous carbon material by two-step, it is characterized in that this material is to be made of nitrogen-doped porous carbon material, this class nitrogen-doped porous carbon material specific surface area height, pore volume is big, pore size distribution is narrow, pore structure can be regulated and control.
4,, it is characterized in that this material can be applied to hydrogen storage material and electrode material for super capacitor according to the method for claim 1 or 2 described method for preparing nitrogen-doped porous carbon material by two-step.
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| CN103170308A (en) * | 2013-04-02 | 2013-06-26 | 南京理工大学 | Preparation of magnetic mesoporous carbon nitride adsorbent and method for removing perfluorooctane compound in water |
| CN107265433A (en) * | 2017-05-12 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | Three-dimensional porous nitrating carbon material and its preparation method and application |
| CN109292749A (en) * | 2018-10-16 | 2019-02-01 | 辽宁科技大学 | A kind of porous carbon and preparation method thereof of complex ordered pore structure |
| CN110482523A (en) * | 2019-08-16 | 2019-11-22 | 中山大学 | A kind of application in the classifying porous carbon material of N doping and its supercapacitor preparation |
| CN111097367A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Adsorbent for adsorbing normal alkane and preparation method and application thereof |
| CN112299388A (en) * | 2020-09-21 | 2021-02-02 | 中国科学院金属研究所 | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor |
| CN113800499A (en) * | 2021-11-09 | 2021-12-17 | 中国石油大学(华东) | Mesoporous microporous hierarchical structure carbon and preparation method thereof |
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| CN103170308B (en) * | 2013-04-02 | 2015-08-26 | 南京理工大学 | The preparation of magnetic mesoporous carbon nitride adsorbent and for removing PFO compound in water |
| CN103170308A (en) * | 2013-04-02 | 2013-06-26 | 南京理工大学 | Preparation of magnetic mesoporous carbon nitride adsorbent and method for removing perfluorooctane compound in water |
| CN107265433A (en) * | 2017-05-12 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | Three-dimensional porous nitrating carbon material and its preparation method and application |
| CN109292749A (en) * | 2018-10-16 | 2019-02-01 | 辽宁科技大学 | A kind of porous carbon and preparation method thereof of complex ordered pore structure |
| CN111097367A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Adsorbent for adsorbing normal alkane and preparation method and application thereof |
| CN110482523B (en) * | 2019-08-16 | 2021-09-10 | 中山大学 | Nitrogen-doped hierarchical porous carbon material and application thereof in preparation of supercapacitor |
| CN110482523A (en) * | 2019-08-16 | 2019-11-22 | 中山大学 | A kind of application in the classifying porous carbon material of N doping and its supercapacitor preparation |
| CN112299388A (en) * | 2020-09-21 | 2021-02-02 | 中国科学院金属研究所 | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor |
| CN113800499A (en) * | 2021-11-09 | 2021-12-17 | 中国石油大学(华东) | Mesoporous microporous hierarchical structure carbon and preparation method thereof |
| CN113800499B (en) * | 2021-11-09 | 2023-02-21 | 中国石油大学(华东) | Mesoporous microporous hierarchical structure carbon and preparation method thereof |
| CN114409010A (en) * | 2022-02-09 | 2022-04-29 | 河北科技大学 | Catalytic reactor for brine purification and application thereof |
| CN116613299A (en) * | 2023-07-17 | 2023-08-18 | 浙江锂宸新材料科技有限公司 | Preparation method of novel silicon-carbon anode material and product thereof |
| CN116613299B (en) * | 2023-07-17 | 2023-11-24 | 浙江锂宸新材料科技有限公司 | Preparation method of silicon-carbon anode material and product thereof |
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