CN104192819A - Clubbed phosphor-doped mesoporous carbon as well as preparation method and application thereof - Google Patents
Clubbed phosphor-doped mesoporous carbon as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses clubbed phosphor-doped mesoporous carbon as well as a preparation method and an application thereof. The clubbed phosphor-doped mesoporous carbon is of a mesoporous structure; in terms of atomic percent, the clubbed phosphor-doped mesoporous carbon comprises 0.51-0.66% of phosphor element and the balance of carbon; and the aperture distribution of the clubbed phosphor-doped mesoporous carbon is 1.57-2.04nm, the specific surface area is 942-1513m<2>/g and the pore volume is 0.85-1.18cm<3>/g. The preparation method comprises the following steps: mixing clubbed mesoporous silicon dioxide, an organic high-molecular polymer, a phosphor-containing precursor and ethyl alcohol; stirring to ensure that the carbon source and the phosphor source are sufficiently dipped into the pore passage of the mesoporous silicon dioxide; after the ethyl alcohol fully volatilizes, drying to obtain a phosphor source/carbon source/silicon dioxide compound; carrying out high-temperature carbonization to obtain a clubbed phosphor-doped mesoporous carbon/silicon dioxide compound; putting the clubbed phosphor-doped mesoporous carbon/silicon dioxide compound in a hydrofluoric acid water solution to remove the silicon dioxide; and drying to obtain the clubbed phosphor-doped mesoporous carbon which is used for preparing electrode materials for super capacitors.
Description
Technical field
The present invention relates to a kind of bar-shaped phosphorus doping meso-porous carbon material and preparation method thereof with it for making the application of ultracapacitor electrode materials used, belong to inorganic nano material and electrochemical field.
Background technology
According to the difference of electron energy Storage mechanism, ultracapacitor is divided into double layer capacitor and fake capacitance electrical condenser, compares and has higher power density, fast charging and discharging process and longer cycle life with secondary cell with traditional electrical condenser.The core of ultracapacitor is exactly electrode materials, and what be applied at present electrode of super capacitor is mainly carbon back porous material, requires material to have larger specific surface area and suitable hole dimension.In order to improve the performance of carbon-based material, people concentrate the change of research at the pore passage structure producing by topographical transition, have prepared the carbon material with different structure.But except the design to structure, people produce keen interest to the fake capacitance of Heteroatom doping.The doping of carbon material being carried out to nitrogen, sulphur, boron or phosphorus can improve fake capacitance and the electron conduction of material, thereby improves its chemical property.
The people such as Meng Li utilize melamine resin and resol respectively as nitrogenous source and carbon source, F127 is cross-linked in conjunction with the ordered mesoporous carbon material that has obtained nitrogen doping by hydro-thermal reaction as structure directing agent, and further with two-dimentional graphite olefinic carbon framework as the compound nitrogen-doped carbon/grapheme material that obtains of conductive substrates as electrode, at 0.2 Ag
-1specific capacitance under current density can reach 289 Fg
-1, the grapheme material of nitrogen doping and modification shows good chemical property (Meng Li, Junmin Xue. J. Phys. Chem. C 2014,118,2,507 2517).
The people such as Liu Ziwu utilize triphenylphosphine and toluene respectively as phosphorus source and carbon source, at solid catalyst FeMo/Al
2o
3under the katalysis of gas phase catalyst ferrocene, obtain the carbon nano-tube material of phosphorus doping through vapour deposition process (CVD method).This patent has just reported that a kind of CVD of use method prepares the method for phosphorus doped multi-walled carbon nano tube, the doping of phosphoric may cause the variation of the appearance structure of carbon material etc., but in patent not the variation of the performance to material etc. make further research (Liu Ziwu; Peng Feng. a kind of preparation method of phosphorus doped multi-walled carbon nano tube: China, 102020264A[P], 2011-04-20).
The people such as Gou Xinglong mix graphene oxide with phosphorous presoma, make active phosphorus element or doping or be attached to the Graphene oxygen reduction electro-catalyst that obtains phosphorus doping on graphene oxide base carbon skeleton.Through the doping of phosphoric, the catalytic activity of this catalyzer is good, good stability both can be applied to the eelctro-catalyst of fuel cell and metal-air battery, also can be applied to the field such as lithium ion battery and ultracapacitor (Gou Xinglong, Li Rong. a kind of phosphorus doping Graphene oxygen reduction electro-catalyst and its preparation method and application: China, 103495430A[P], 2014-01-08).
At present for the Heteroatom doping of carbon material and prepare the focus that carbon back mixture is electric chemical super capacitor research, can improve specific capacitance by the method for Heteroatom doping.Wherein, the material of nitrogen-doping is applied to electrode material for super capacitor, and chemical property is better; But the ultracapacitor performance study of the carbon complex to phosphorus doping obtains fewer.
At present, also there is not having special appearance as the report of bar-shaped phosphorus doping mesoporous carbon.
Summary of the invention
One of object of the present invention is to provide a kind of bar-shaped phosphorus doping meso-porous carbon material.
Two of object of the present invention is to provide the preparation method of above-mentioned a kind of bar-shaped phosphorus doping meso-porous carbon material.
Three of object of the present invention is to provide the preparation method of a kind of above-mentioned bar-shaped phosphorus doping meso-porous carbon material as ultracapacitor electrode materials used.
Technical scheme of the present invention
A bar-shaped phosphorus doping meso-porous carbon material, calculates by atomic percent, and the doping content of phosphoric is 0.51-0.66%, and surplus is carbon, and pore size distribution is at 1.57-2.04nm, the about 942-1513m of specific surface area
2/ g, pore volume is 0.85-1.18cm
3/ g.
The preparation method of above-mentioned bar-shaped phosphorus doping meso-porous carbon material, specifically comprises the steps:
(1), taking bar-shaped mesoporous silicon oxide as hard template, organic high molecular polymer makees solvent as carbon source, phosphorous presoma as phosphorus source, ethanol;
Mesoporous silicon oxide, organic high molecular polymer, phosphorous presoma and ethanol are mixed, stirring is fully immersed in the duct of bar-shaped mesoporous silicon oxide organic high molecular polymer, phosphorous presoma, after etoh solvent is evaporated completely, control temperature is 40-100 DEG C and is dried, obtains phosphorus source/carbon source/silica composite;
Above-mentioned bar-shaped mesoporous silicon oxide used, organic high molecular polymer, the amount of phosphorous presoma and ethanol, the mesoporous silicon oxide by bar-shaped: organic high molecular polymer: phosphorous presoma: the mass ratio of ethanol is that 1:1.11～1.25:0.11～1.0:20 calculates;
Described bar-shaped mesoporous silicon oxide, its pore volume is 1.0-1.5cm
3/ g, preferably its major axis is 2.80 μ m, and minor axis is approximately 0.55 μ m, and axial ratio is 5.1;
Described organic high molecular polymer is resol, furfuryl alcohol resin or sucrose;
Described phosphorous presoma is triphenylphosphine or dipotassium hydrogen phosphate;
(2), under nitrogen atmosphere, be that 1 DEG C/min is warmed up to 600 DEG C of roasting 2h by phosphorus source/carbon source/silica composite control temperature rise rate of step (1) gained, and then be warmed up to 700-1000 DEG C of roasting 2h with 2 DEG C/min, obtain bar-shaped phosphorus doping mesoporous carbon/silica composite;
(3) in the hydrofluoric acid aqueous solution that the bar-shaped phosphorus doping mesoporous carbon/silica composite, step (2) being obtained is 5-10% at mass percent concentration, stir 2h, to remove template silicon-dioxide, then centrifugal, the precipitate with deionized water washing of gained is until the pH of elutant is neutral, control temperature is 100 DEG C and is dried, obtains bar-shaped phosphorus doping mesoporous carbon;
The usage quantity of the hydrofluoric acid aqueous solution that above-mentioned bar-shaped phosphorus doping mesoporous carbon/silica composite and mass percent concentration are 5-10%, the phosphorus doping mesoporous carbon/silica composite in bar-shaped: the ratio that the hydrofluoric acid aqueous solution that mass percent concentration is 5-10% is 1g:16-17ml is calculated.
Above-mentioned preparation method is also applicable to the preparation of the phosphorus doping mesoporous carbon of other shapes, just by bar-shaped mesoporous silicon oxide used with the mesoporous silicon oxide of other special shapes as spherical, fibrous etc. alternative, finally obtain the shape phosphorus doping mesoporous carbon corresponding with meso-porous titanium dioxide silicon shape.
Above-mentioned a kind of bar-shaped phosphorus doping mesoporous carbon is for making ultracapacitor electrode materials used, and its making method step is as follows:
By bar-shaped phosphorus doping meso-porous carbon material and polyfluortetraethylene of binding element emulsion, electrically conductive graphite calculates in mass ratio, be bar-shaped phosphorus doping meso-porous carbon material: ptfe emulsion: the ratio that electrically conductive graphite is 8:1:1 is mixed and is milled into sheet, and drip several 1-Methyl-2-Pyrrolidone solvents and be as the criterion to form mud shape mixture, then mud shape mixture is evenly applied in the nickel foam of 1cm*1cm, after 10MPa pressure lower sheeting is processed, at 120 DEG C, carry out vacuum-drying 10h, make ultracapacitor electrode materials used.
The ultracapacitor electrode materials used of above-mentioned gained, under the scanning speed of 10mV/s, its specific capacitance is 202-261F/g.
Beneficial effect of the present invention
The preparation method of a kind of bar-shaped phosphorus doping meso-porous carbon material of the present invention, combine control to material pattern and doping two aspects of assorted element phosphor, improve the performance of meso-porous carbon material, the bar-shaped phosphorus doping meso-porous carbon material of final gained, press atomic percent and calculate, the doping content of phosphoric is 0.51-0.66%, and surplus is carbon, pore size distribution is at 1.57-2.04nm, the about 942-1513m of specific surface area
2/ g, pore volume is 0.85-1.18cm
3/ g.
The preparation method of a kind of bar-shaped phosphorus doping meso-porous carbon material of the present invention, because the mesoporous silicon oxide by taking bar-shaped is template, organic high molecular polymer is carbon source, phosphorous presoma is phosphorus source, under 700-1000 DEG C of high temperature, carbonizing treatment obtains the mixture of bar-shaped phosphorus doping mesoporous carbon/silicon-dioxide, obtain by using acid treatment to remove silica template pattern and the structure that bar-shaped phosphorus doping meso-porous carbon material has kept template silicon-dioxide, therefore, preparation method of the present invention is easy to the pattern of carbon material to control, and the good thermal stability of the bar-shaped phosphorus doping mesoporous carbon of final gained, duct is difficult for caving in, be easy to copy.
Further, the bar-shaped phosphorus doping mesoporous carbon that the preparation method of bar-shaped phosphorus doping mesoporous carbon of the present invention obtains has good meso-hole structure, and has accomplished the control to carbon material pattern, and this is not have in the preparation of other phosphorus doping carbon materials.
Further, the preparation method of a kind of bar-shaped phosphorus doping mesoporous carbon of the present invention, due to the control of pattern of mesoporous carbon and the control of the doping of phosphoric of passing through phosphorus doping to form in preparation process, prepared bar-shaped phosphorus doping meso-porous carbon material has good chemical property, can be for ultracapacitor electrode materials used.
Brief description of the drawings
The SEM of bar-shaped mesoporous silicon oxide used figure in Fig. 1, embodiment 1;
The SEM figure of the bar-shaped phosphorus doping meso-porous carbon material of Fig. 2, embodiment 1 gained;
The little angle XRD figure spectrum of the bar-shaped phosphorus doping meso-porous carbon material of Fig. 3, embodiment 1 gained;
Fig. 4, the bar-shaped phosphorus doping meso-porous carbon material of embodiment 1 gained are made into the cyclic voltammetry curve of ultracapacitor electrode materials used.
Embodiment
Below by specific embodiment, also the invention will be further described by reference to the accompanying drawings, but the present invention is not limited to following examples.
Described in various embodiments of the present invention, method if no special instructions, is ordinary method.The various starting material that adopt if no special instructions, all can be bought and obtain from open commercial sources.
The information of the instrument that various embodiments of the present invention are used or the model of equipment and manufacturer is as follows:
Air dry oven, model DHG-9920A, manufacturer Shanghai one perseverance;
Tube furnace, model SL1700 II type, Shanghai Sheng Li testing tool company limited of manufacturer;
Retort furnace, model DC-B8/11 type, Beijing original creation Science and Technology Ltd. of manufacturer;
The X'pert Pro MRD type X-ray diffractometer of the Dutch PANalytical of x ray diffraction (XRD) test use company;
Scanning electronic microscope (SEM) test is used the S-3400 type scanning electronic microscope of HIT.
The electrochemical property test of ultracapacitor of the present invention electrode materials used adopts cyclic voltammetry.Instrument is the CHI660C electrochemical workstation of Shanghai Chen Hua Instrument Ltd., uses three-electrode method, and platinum electrode is as to electrode, and mercurous chloride electrode is reference electrode, uses 6M KOH solution as ionogen.
Bar-shaped mesoporous silicon oxide used in various embodiments of the present invention is prepared by the following method:
By 1.5g P123(polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer) join and contain 28g 2M HCl solution, in the mixture of 6.8g KCl and 1.5g ethanol, stirring 1.5h to P123 dissolves completely, and then add 3.12g tetraethyl silicate resin, continue to stir 5-10min, after covering watch-glass, leave standstill 24h, then global transfer is in tetrafluoroethylene reactor, control temperature is 120 DEG C and carries out hydro-thermal reaction 24h, the reaction solution suction filtration of gained, the filter cake of gained is not with till containing KCl in deionized water wash elutant, the filter cake of gained being controlled in retort furnace to temperature again and be 500 DEG C of calcining 300min, to obtain pore volume be 1.0-1.5cm
3the bar-shaped mesoporous silicon oxide of/g, its major axis is 2.80 μ m, and minor axis is approximately 0.55 μ m, and axial ratio is 5.1.
embodiment 1
A preparation method for bar-shaped phosphorus doping meso-porous carbon material, specifically comprises the steps:
(1), phosphorous 0.11g presoma is dissolved in 20g ethanol, add the bar-shaped mesoporous silicon oxide of 1.0g, and then add the organic high molecular polymer of 1.13g, stirring fully mixes it, then place it in room temperature after ethanol volatilization completely, be dried 24h in 40 DEG C, obtain carbon source/phosphorus source/silica composite;
The consumption of above-mentioned bar-shaped mesoporous silicon oxide used, organic high molecular polymer, phosphorous presoma and ethanol, the mesoporous silicon oxide according to bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that the mass ratio of ethanol is 1:1.13:0.11:20 is calculated;
Described bar-shaped mesoporous silicon oxide pore volume is 1.0-1.5cm
3/ g, its major axis is 2.80 μ m, and minor axis is approximately 0.55 μ m, and axial ratio is 5.1;
Described organic high molecular polymer is resol;
Described phosphorous presoma is triphenylphosphine;
Above-mentioned bar-shaped mesoporous silicon oxide used is observed by scanning electron microscope, and its SEM schemes as shown in Figure 1, and as can be seen from Figure 1 silicon-dioxide is Rod-like shape, and major axis is approximately 2.80 μ m, and minor axis is approximately 0.55 μ m;
(2) carbon source/phosphorus source/silica composite, step (1) being obtained is transferred in magnetic boat and is placed in tube furnace, under nitrogen atmosphere, be warmed up to 600 DEG C of roasting 2h with the speed of 1 DEG C/min, and then be warmed up to 700 DEG C of roasting 2h with the speed of 2 DEG C/min, naturally cool to room temperature and obtain bar-shaped phosphorus doping mesoporous carbon/silica composite;
(3), 1.2g step (2) is obtained in hydrofluoric acid aqueous solution that mass percent that bar-shaped phosphorus doping mesoporous carbon/silica composite joins 20ml is 5%, stir 2h, to remove template silicon-dioxide, then centrifugal, gained precipitate with deionized water washing is until after the pH value of elutant is neutrality, control temperature is 100 DEG C and is dried 24h, finally obtains bar-shaped phosphorus doping meso-porous carbon material.
The pattern of above-mentioned obtained bar-shaped phosphorus doping meso-porous carbon material is observed by scanning electron microscope, the results are shown in Figure 2, and material has the Rod-like shape of homogeneous as shown in Figure 2.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is composed by its little angle XRD figure of x-ray diffractometer (XRD) structural analysis, result as shown in Figure 3, as can be seen from Figure 3 be that 1 degree left and right has an obvious diffraction peak at 2 θ, there are two diffraction peaks 2 degree left and right.Illustrated that thus sample has orderly meso-hole structure, high-temperature calcination does not destroy meso-hole structure.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is analyzed to the chemical element composition of bar-shaped phosphorus doping meso-porous carbon material by energy dispersion x-ray spectrometer (EDS), pressing atomic percent calculates, wherein the doping content of phosphoric is 0.51%, and surplus is carbon.
Adopt Micromeritics ASAP 2020 to measure the phosphorus doping meso-porous carbon material of above-mentioned gained, its specific surface area is 1513m
2/ g, pore volume is 1.18cm
3/ g, aperture is 1.57nm.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is made to ultracapacitor electrode materials used, and its preparation method comprises the steps:
By bar-shaped phosphorus doping meso-porous carbon material and ptfe emulsion obtained above, electrically conductive graphite calculates in mass ratio, be bar-shaped phosphorus doping meso-porous carbon material: ptfe emulsion: the mass ratio that electrically conductive graphite is 8:1:1 is fully milled after mixing, and drip several 1-Methyl-2-Pyrrolidone solvents and obtain mud shape mixture, then mud shape mixture is evenly applied in nickel foam (1cm*1cm), after 10MPa pressure lower sheeting is processed, at 120 DEG C, carry out vacuum-drying 10h, make ultracapacitor electrode materials used.
The ultracapacitor electrode materials used of above-mentioned gained adopts cyclic voltammetry by Shanghai occasion China CHI660C electrochemical workstation, respectively at 10mVs
-1, 20mV/s, 50mV/s, 100mV/s, 200mV/s scanning speed under measure, measurement result is shown in Fig. 4, as can be seen from Figure 4, curve becomes similar rectangular configuration, its specific capacitance is respectively 253F/g, 240F/g, 220F/g, 196F/g, 157F/g, and sample has obvious electrochemical behavior.
embodiment 2
A preparation method for bar-shaped phosphorus doping meso-porous carbon material, specifically comprises the steps:
(1), the phosphorous presoma of 0.33g is dissolved in 20g ethanol, then add the bar-shaped mesoporous silicon oxide of 1.0g, add again 1.11g organic high molecular polymer and, stirring is fully immersed in the duct of bar-shaped mesoporous silicon oxide organic high molecular polymer and phosphorous presoma, then after placing it in room temperature and being evaporated completely down to alcohol solvent, be dried 24h in 60 DEG C, obtain carbon source/phosphorus source/silica composite;
The amount of above-mentioned bar-shaped mesoporous silicon oxide used, organic high molecular polymer, phosphorous presoma and ethanol, the mesoporous silicon oxide in bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that the mass ratio of ethanol is 1:1.11:0.33:20 is calculated;
Described bar-shaped mesoporous silicon oxide pore volume is 1.0-1.5cm
3/ g, its major axis is 2.80 μ m, and minor axis is approximately 0.55 μ m, and axial ratio is 5.1;
Described organic high molecular polymer is resol;
Described phosphorous presoma is dipotassium hydrogen phosphate;
(2) carbon source/phosphorus source/silica composite, step (1) being obtained is transferred in magnetic boat and is positioned in tube furnace, under nitrogen atmosphere, controlling temperature rise rate is that 1 DEG C/min is warmed up to 600 DEG C of roasting 2h, and then be warmed up to 800 DEG C of roasting 2h with 2 DEG C/min, naturally cool to room temperature, obtain bar-shaped phosphorus doping mesoporous carbon/silica composite;
(3) mass percent concentration that the bar-shaped phosphorus doping mesoporous carbon/silica composite, 1.2g step (2) being obtained joins 20ml is to stir 2h in 5% hydrofluoric acid aqueous solution, to remove template silicon-dioxide, then centrifugal, gained precipitate with deionized water washing is until after the pH value of elutant is neutrality, control temperature is 100 DEG C and is dried, obtains bar-shaped phosphorus doping meso-porous carbon material.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is analyzed to the chemical element composition of bar-shaped phosphorus doping meso-porous carbon material by energy dispersion x-ray spectrometer (EDS), pressing atomic percent calculates, wherein phosphoric doping content is 0.66%, and surplus is carbon.
Adopt Micromeritics ASAP 2020 to measure the phosphorus doping meso-porous carbon material of above-mentioned gained, its specific surface area is 1065m
2/ g, pore volume is 1.16cm
3/ g, aperture is 2.04nm.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is made to ultracapacitor electrode materials used, its production method is with embodiment 1, the ultracapacitor electrode materials used of final gained uses Shanghai occasion China CHI660C electrochemical workstation to adopt cyclic voltammetry to measure, under the scanning speed of 10mV/s, its specific capacitance is 261F/g.
embodiment 3
A preparation method for bar-shaped phosphorus doping meso-porous carbon material, specifically comprises the steps:
(1), phosphorous 0.58g presoma is dissolved in 20g ethanol, add the bar-shaped mesoporous silicon oxide of 1.0g, and then add the organic high molecular polymer of 1.16g, stirring is fully immersed in the duct of bar-shaped mesoporous silicon oxide organic high molecular polymer and phosphorous presoma, then place it in room temperature after ethanol volatilization completely, be dried 24h in 80 DEG C, obtain phosphorus source/carbon source/silica composite;
The consumption of above-mentioned bar-shaped mesoporous silicon oxide used, organic high molecular polymer, phosphorous presoma and ethanol, the mesoporous silicon oxide according to bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that the mass ratio of ethanol is 1:1.16:0.58:20 is calculated;
Described bar-shaped mesoporous silicon oxide pore volume is 1.0-1.5cm
3/ g, its major axis is 2.80 μ m, and minor axis is approximately 0.55 μ m, and axial ratio is 5.1;
Described organic high molecular polymer is furfuryl alcohol resin;
Described phosphorous presoma is triphenylphosphine;
(2) carbon source/phosphorus source/silica composite, step (1) being obtained is transferred in magnetic boat and is placed in tube furnace, under nitrogen atmosphere, be warmed up to 600 DEG C of roasting 2h with the speed of 1 DEG C/min, and then be warmed up to 900 DEG C of roasting 2h with the speed of 2 DEG C/min, naturally cool to room temperature and obtain bar-shaped phosphorus doping mesoporous carbon/silica composite;
(3), 1.2g step (2) is obtained in hydrofluoric acid aqueous solution that mass percent that bar-shaped phosphorus doping mesoporous carbon/silica composite joins 20ml is 10%, stir 2h, to remove template silicon-dioxide, then centrifugal, gained precipitate with deionized water washing is until after the pH value of elutant is neutrality, control temperature is 100 DEG C and is dried 24h, finally obtains bar-shaped phosphorus doping meso-porous carbon material.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is analyzed to the chemical element composition of bar-shaped phosphorus doping meso-porous carbon material by energy dispersion x-ray spectrometer (EDS), pressing atomic percent calculates, wherein phosphoric doping content is 0.52%, and surplus is carbon.
Adopt Micromeritics ASAP 2020 instruments to measure the bar-shaped phosphorus doping meso-porous carbon material of above-mentioned gained, its specific surface area is 942m
2/ g, pore volume is 0.85cm
3/ g, aperture is 1.94nm.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is made to ultracapacitor electrode materials used, its production method is with embodiment 1, the ultracapacitor electrode materials used of final gained uses Shanghai occasion China CHI660C electrochemical workstation to adopt cyclic voltammetry to measure, under the scanning speed of 10mV/s, its specific capacitance is 240F/g.
embodiment 4
A preparation method for bar-shaped phosphorus doping meso-porous carbon material, specifically comprises the steps:
(1), the phosphorous presoma of 1.0g is dissolved in 20g ethanol, then add the bar-shaped mesoporous silicon oxide of 1.0g, add again 1.25g organic high molecular polymer and, stirring is fully immersed in the duct of bar-shaped mesoporous silicon oxide organic high molecular polymer and phosphorous presoma, then place it in room temperature down to after alcohol solvent is evaporated completely, be dried in 100 DEG C, obtain carbon source/phosphorus source/silica composite;
Above-mentioned bar-shaped mesoporous silicon oxide used, organic high molecular polymer, the amount of phosphorous presoma and ethanol, the mesoporous silicon oxide in bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that ethanol mass ratio is 1:1.25:1.0:20 is calculated;
Described bar-shaped mesoporous silicon oxide pore volume is 1.0-1.5cm
3/ g, its major axis is 2.80 μ m, and minor axis is approximately 0.55 μ m, and axial ratio is 5.1;
Described organic high molecular polymer is furfuryl alcohol resin;
Described phosphorous presoma is dipotassium hydrogen phosphate;
(2) carbon source/phosphorus source/silica composite, step (1) being obtained is transferred in magnetic boat and is positioned in tube furnace, under nitrogen atmosphere, controlling temperature rise rate is that 1 DEG C/min is warmed up to 600 DEG C of roasting 2h, and then be warmed up to 1000 DEG C of roasting 2h with 2 DEG C/min, naturally cool to room temperature, obtain bar-shaped phosphorus doping mesoporous carbon/silica composite;
(3) mass percent concentration that the bar-shaped phosphorus doping mesoporous carbon/silica composite, 1.2g step (2) being obtained joins 20ml is to stir 2h in 10% hydrofluoric acid aqueous solution, to remove template silicon-dioxide, then centrifugal, gained precipitate with deionized water washing is until after the pH value of elutant is neutrality, control temperature is 100 DEG C and is dried, obtains bar-shaped phosphorus doping meso-porous carbon material.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is analyzed to the chemical element composition of bar-shaped phosphorus doping meso-porous carbon material by energy dispersion x-ray spectrometer (EDS), pressing atomic percent calculates, wherein the doping content of phosphoric is 0.62%, and surplus is carbon.
Adopt Micromeritics ASAP 2020 instruments to measure the bar-shaped phosphorus doping meso-porous carbon material of above-mentioned gained, its specific surface area is 958m
2/ g, pore volume is 0.97cm
3/ g, aperture is 1.92nm.
Bar-shaped phosphorus doping meso-porous carbon material obtained above is made to ultracapacitor electrode materials used, its production method is with embodiment 1, the ultracapacitor electrode materials used of final gained uses Shanghai occasion China CHI660C electrochemical workstation to adopt cyclic voltammetry to measure, under the scanning speed of 10mV/s, its specific capacitance is 202F/g.
In sum, a kind of phosphorus doping meso-porous carbon material of the present invention, has typical Rod-like shape, calculates by atomic percent, and the content of phosphoric is 0.51-0.66%, and surplus is carbon.Pore size distribution is at 1.57-2.04nm, the about 942-1513m of specific surface area
2/ g, pore volume is 0.85-1.18cm
3/ g.
The above is only giving an example of embodiments of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the technology of the present invention principle; can also make some improvement and modification, these improve and modification all should be considered as protection scope of the present invention.
Claims (9)
1. a bar-shaped phosphorus doping meso-porous carbon material, is characterized in that described bar-shaped phosphorus doping meso-porous carbon material is meso-hole structure, calculates by atomic percent, the doping content of phosphoric is 0.51-0.66%, surplus is carbon, and pore size distribution is at 1.57-2.04nm, the about 942-1513m of specific surface area
2/ g, pore volume is 0.85-1.18cm
3/ g.
2. the preparation method of bar-shaped phosphorus doping meso-porous carbon material as claimed in claim 1, is characterized in that specifically comprising the steps:
(1), taking bar-shaped mesoporous silicon oxide as hard template, organic high molecular polymer makees solvent as carbon source, phosphorous presoma as phosphorus source, ethanol;
Mesoporous silicon oxide, organic high molecular polymer, phosphorous presoma and ethanol are mixed, stirring is fully immersed in the duct of bar-shaped mesoporous silicon oxide organic high molecular polymer, phosphorous presoma, after etoh solvent is evaporated completely, control temperature is 40-100 DEG C and is dried, obtains phosphorus source/carbon source/silica composite;
The amount of above-mentioned bar-shaped mesoporous silicon oxide used, organic high molecular polymer, phosphorous presoma and ethanol, the mesoporous silicon oxide in bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that the mass ratio of ethanol is 1:1.11～1.25:0.11～1.0:20 is calculated;
Described bar-shaped mesoporous silicon oxide, its pore volume is 1.0-1.5cm
3/ g;
Described organic high molecular polymer is resol, furfuryl alcohol resin or sucrose;
Described phosphorous presoma is triphenylphosphine or dipotassium hydrogen phosphate;
(2), under nitrogen atmosphere, be that 1 DEG C/min is warmed up to 600 DEG C of roasting 2h by phosphorus source/carbon source/silica composite control temperature rise rate of step (1) gained, and then be warmed up to 700-1000 DEG C of roasting 2h with 2 DEG C/min, obtain bar-shaped phosphorus doping mesoporous carbon/silica composite;
(3) in the hydrofluoric acid aqueous solution that the bar-shaped phosphorus doping mesoporous carbon/silica composite, step (2) being obtained is 5-10% at mass percent concentration, stir 2h, to remove template silicon-dioxide, then centrifugal, the precipitate with deionized water washing of gained is until after the pH of elutant is neutrality, control temperature is 100 DEG C and is dried, obtains bar-shaped phosphorus doping mesoporous carbon;
The usage quantity of the hydrofluoric acid aqueous solution that above-mentioned bar-shaped phosphorus doping mesoporous carbon/silica composite and mass percent concentration are 5-10%, the phosphorus doping mesoporous carbon/silica composite in bar-shaped: the ratio that the hydrofluoric acid aqueous solution that mass percent concentration is 5-10% is 1g:16-17ml is calculated.
3. the preparation method of a kind of bar-shaped phosphorus doping mesoporous carbon as claimed in claim 2, it is characterized in that the consumption of bar-shaped mesoporous silicon oxide used in step (1), organic high molecular polymer, phosphorous presoma and ethanol, the mesoporous silicon oxide in bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that the mass ratio of ethanol is 1:1.13:0.11:20 is calculated;
Described organic high molecular polymer is resol;
Described phosphorous presoma is triphenylphosphine.
4. the preparation method of a kind of bar-shaped phosphorus doping mesoporous carbon as claimed in claim 2, it is characterized in that the consumption of bar-shaped mesoporous silicon oxide used in step (1), organic high molecular polymer, phosphorous presoma and ethanol, the mesoporous silicon oxide according to bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that the mass ratio of ethanol is 1:1.11:0.33:20 is calculated;
Described organic high molecular polymer is resol;
Described phosphorous presoma is dipotassium hydrogen phosphate.
5. the preparation method of a kind of bar-shaped phosphorus doping mesoporous carbon as claimed in claim 2, it is characterized in that the consumption of bar-shaped mesoporous silicon oxide used in step (1), organic high molecular polymer, phosphorous presoma and ethanol, the mesoporous silicon oxide according to bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that the mass ratio of ethanol is 1:1.16:0.58:20 is calculated;
Described organic high molecular polymer is furfuryl alcohol resin;
Described phosphorous presoma is triphenylphosphine.
6. the preparation method of a kind of bar-shaped phosphorus doping mesoporous carbon as claimed in claim 2, it is characterized in that the consumption of bar-shaped mesoporous silicon oxide used in step (1), organic high molecular polymer, phosphorous presoma and ethanol, the mesoporous silicon oxide according to bar-shaped: organic high molecular polymer: phosphorous presoma: the ratio that the mass ratio of ethanol is 1:1.25:1.0:20 is calculated;
Described organic high molecular polymer is furfuryl alcohol resin;
Described phosphorous presoma is dipotassium hydrogen phosphate.
7. the preparation method of the bar-shaped phosphorus doping meso-porous carbon material as described in as arbitrary in claim 2-6, the major axis that it is characterized in that bar-shaped mesoporous silicon oxide used in step (1) is 2.80 μ m, and minor axis is approximately 0.55 μ m, and axial ratio is 5.1.
8. a kind of bar-shaped phosphorus doping mesoporous carbon as claimed in claim 1 is for making ultracapacitor electrode materials used.
9. the making method of bar-shaped phosphorus doping mesoporous carbon as claimed in claim 8 for making ultracapacitor electrode materials used, is characterized in that step is as follows:
By bar-shaped phosphorus doping meso-porous carbon material and polyfluortetraethylene of binding element emulsion, electrically conductive graphite calculates in mass ratio, be bar-shaped phosphorus doping meso-porous carbon material: ptfe emulsion: the ratio that electrically conductive graphite is 8:1:1 is mixed and is milled into sheet, and drip 1-Methyl-2-Pyrrolidone solvent and be as the criterion to form mud shape mixture, then mud shape mixture is evenly applied in the nickel foam of 1cm*1cm, after 10MPa pressure lower sheeting is processed, at 120 DEG C, carry out vacuum-drying 10h, make ultracapacitor electrode materials used.
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