CN108288547A - The preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material - Google Patents
The preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material Download PDFInfo
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- CN108288547A CN108288547A CN201810032994.3A CN201810032994A CN108288547A CN 108288547 A CN108288547 A CN 108288547A CN 201810032994 A CN201810032994 A CN 201810032994A CN 108288547 A CN108288547 A CN 108288547A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material, the present invention relates to a kind of preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material, it improves to solve the problems, such as existing single Heteroatom doping to meso-porous carbon material capacitive property limited.Ordered mesoporous silica dioxide template (KIT 6) is prepared first；Sucrose, phosphoric acid and thiosemicarbazides mixed solution and 6 dispersion liquids of KIT are stirred to ageing 10 h~14 h by nanometer perfusion at 40 DEG C~60 DEG C.Obtained paste compound is positioned in baking oven at 70 DEG C~90 DEG C the dry h of 10 h~14, (nitrogen flow rate is 50 mL/s) is finally placed in tube furnace under high pure nitrogen and is pyrolyzed 1~3 h in 700 DEG C~900 DEG C, the rate of heat addition is 2 DEG C/min.Composite material after carbonization is immersed in HF solution and stirs to remove silica template, filters, is respectively washed with ultra-pure water and ethyl alcohol, and obtains nitrogen phosphorus sulphur codope ordered mesoporous carbon material after drying（NPS‑OMC）.The present invention prepares nitrogen phosphorus sulphur codope ordered mesoporous carbon material by template using nanometer perfusion, and the specific capacitance of the material electrodes can reach 343 F/g.
Description
Technical field
The present invention relates to a kind of preparation methods of nitrogen phosphorus sulphur codope ordered mesoporous carbon material.
Background technology
With the fast development of global economy, environmental problem and energy crisis worsening have seriously threatened the life of the mankind
It deposits and social progress.Therefore, environmental pollution and energy supply have become the big most urgent problem in the world today two.Environment
There is close contact in pollution and the two fields of energy supply, renewable by sustainable, environmental-friendly technological development
New energy to carry out substitute fossil fuels be a completely new solution.
In order to obtain the reproducible new energy of safety and reduce the discharge of greenhouse gases, scientists have developed storage energy
New material and new method.Ultracapacitor and advanced battery system have been considered to very promising energy storage dress
It sets, they can store regenerative resource also and can reduce the demand to fossil fuel.Especially ultracapacitor, quickly with it
Charge and discharge process, high specific capacity, the cycle life of length, simple principle, high power density and energy density etc. at
For efficient, practical and environmentally friendly energy storage device.Currently, ultracapacitor is mainly used in portable electronic device, hybrid power
The fields such as automobile, terminal, aerospace.It is well known that the electrode material of ultracapacitor plays its capacitive property
Conclusive effect includes mainly three classes：Transistion metal compound, conducting polymer and porous carbon materials.Wherein, porous carbon
Expect using cycle life, high power density, wide work potential window and the low cost of its length as advanced electrode material
It is widely used in the super capacitor of business.But the specific capacitance of pure Carbon-based supercapacitor is relatively low, generally less than 150 F/
G, it is difficult to meet the needs of mankind are to energy density.Therefore, synthesize that have both high-energy density, high power density, long circulating steady
Qualitative, economic and environment-friendly electrode material is still a project being of great significance.
Carbon-based electrode material is to generate based on electric double layer capacitance.The carbon-based postclimax material of most study mainly has work at present
Property charcoal (ACs), graphene (Graphene), carbon nanotube (CNTs), carbon nano-fiber (CNFs) and ordered mesopore carbon (OMC)
Deng.In various carbon materials, ordered mesopore carbon because with uniform aperture and due to special duct with high power density and
A kind of good cyclical stability, it is considered to be electrode material for super capacitor extremely having application potential.Many researchs are
It proves：The pore-size distribution of porous carbon plays an important role in chemical property.If the aperture of carbon material be less than solvation from
Son, then carbon material is just difficult to be infiltrated by electrolyte, and then will limiting capacitance value.Ordered mesopore carbon is because with uniform and suitable
Aperture (2-50 nm) and the orderly channel in electron-transport path can be shortened, therefore result in excellent chemical property,
It is considered as very promising super electric material.However, due to simple ordered mesopore carbon have higher chemical reaction inertia with
The shortcomings of poor surface wettability, in the electrode material as ultracapacitor, only seldom active site can be used for electricity
Lotus stores, and causes electrochemical capacitor performance undesirable, this seriously constrains its practical application.So to order mesoporous carbon materials
Material, which carries out physical and chemical modified, becomes the Hot Contents of ordered mesopore carbon research field.
Recently, the doped meso-porous carbon material of nonmetallic heteroatoms has caused great concern in terms of energy stores.Example
Such as, research finds that nitrogen is mixed in carbon skeleton is remarkably improved specific capacitance.This is because the incorporation of nitrogen can：1. leading to
It crosses faraday's redox reaction and improves total fake capacitance.2. increase carbon electrode material electric conductivity, and then improve double layer capacity and
The capacity retention of pseudo-capacitance.3. improving surface wettability of the carbon electrode material to electrolyte.Therefore, N doping may insure pair
Storage charge exposed surface makes full use of.The carbon material of various forms is handled with N doping, and shows excellent electricity
Chemical capacitive property.Nonmetallic heteroatoms currently used for doping include nitrogen (N), phosphorus (P), sulphur (S) and boron (B) etc..These are miscellaneous
Atom is mutually connected in carbon material by covalent bond with carbon atom and introduces functional group, changes carbon materials by electron or sucting electronic effect
The physicochemical properties of material.Since faraday's reaction can be generated between these functional groups and electrolyte, counterfeit electricity can be passed through
Holding effect enhances total specific capacitance.Wherein, N doping is enhancing specific capacitance while keeping most having for the good rate capacity of carbon material
The method of effect.Nitrogen-atoms has In frared spectra relative to carbon atom, it is thus possible to the physicochemical properties for improving carbon material, than
Such as surface polarity, electric conductivity and wetability.Therefore, N doping ordered mesoporous carbon material has received prodigious concern.
Invention content
The invention aims to work out a kind of method preparing nitrogen phosphorus sulphur codope ordered mesoporous carbon material.From
And it is limited to solve the problems, such as that single Heteroatom doping improves meso-porous carbon material capacitive property.
The preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material of the present invention follows these steps to realize：
One, using hydrothermal synthesis method synthesizing ordered mesoporous silica dioxide template (KIT-6)；
Two,（1）Dry KIT-6 is ultrasonically treated to obtain uniform dispersion in deionized water；Simultaneously by sucrose, phosphoric acid and
Thiosemicarbazides, which is add to deionized water, stirs to get uniform solution.(2) the latter is transferred in the former and in draught cupboard
Continue to stir the h of 10 h~14 at 40 DEG C~60 DEG C.(3) obtained paste compound is positioned in baking oven in 70 DEG C~90
The dry h of 10 h~14 at DEG C, then remaining solid abrasive at powder.(4) composite powder is placed in tube furnace
In under high pure nitrogen in 700 DEG C~900 DEG C be pyrolyzed 1~3 h, the rate of heat addition be 2 DEG C/min.(5) compound after carbonization
Material is immersed in HF solution and stirs to remove silica template.(6) it filters, is respectively washed with ultra-pure water and ethyl alcohol, and do
Nitrogen phosphorus sulphur codope ordered mesopore carbon is obtained after dry（NPS-OMC）.
The present invention is mixed by nitrogen phosphorus sulphur codope ordered mesoporous carbon material powder and polytetrafluoroethylene (PTFE) (PTFE) solution
It closes, stirs into slurries, be then uniformly applied in nickel foam, it is tabletted, obtain nitrogen phosphorus sulphur codope ordered mesopore carbon
Material electrode of super capacitor.
The present invention is using polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and ethyl orthosilicate water
Thermosetting ordered mesoporous silica dioxide film version（KIT-6）, the good nitrogen phosphorus sulphur of order three has been synthesized by nanometer method for filling
First codope ordered mesopore carbon.The effect of silicon dioxide film version and sucrose, phosphoric acid and thiosemicarbazides includes mainly：
1, silica template is mainly that synthesizing ordered mesoporous carbon material provides pore passage structure, makes the carbon material being perfused by template
Ordered mesopore structure can be maintained；2, sucrose can be with as the carbon source of synthetic nitrogen phosphorus sulphur codope ordered mesopore carbon
Hard template KIT-6 forms good compatibility, keeps perfusion degree more complete；3, phosphoric acid is as synthetic nitrogen phosphorus sulphur codope
The phosphorus source of ordered mesopore carbon can be that material itself provides Faraday pseudo-capacitance, and the capacitive property of material is made to improve；4, amino sulphur
Nitrogen source and sulphur source of the urea as synthetic nitrogen phosphorus sulphur codope ordered mesopore carbon, can promote the wetting of material itself and raising
The Faraday pseudo-capacitance of material.
Nitrogen phosphorus sulphur codope ordered mesopore carbon has higher specific surface area simultaneously, can be provided more for capacitance reaction
More reactivity sites further increases the capacitance of material, and its orderly meso-hole structure can shorten conducting particles transport
Path, to improve the chemical property of material.
In the case where concentration of electrolyte is the KOH solution of 6 mol/L, which is orderly situated between the present invention
The specific capacitance of hole carbon can reach 343 F/g.
Description of the drawings
Fig. 1 is the XRD diagram for the ordered mesoporous silica dioxide KIT-6 that one step 1 of embodiment obtains；
The TEM figures that Fig. 2 is the ordered mesoporous silica dioxide KIT-6 that one step 1 of embodiment obtains；
Fig. 3 is the XRD diagram for the nitrogen phosphorus sulphur codope ordered mesoporous carbon material that embodiment one obtains；
Fig. 4 is physical absorption-desorption and the aperture point for the nitrogen phosphorus sulphur codope ordered mesoporous carbon material that embodiment one obtains
Butut；
Fig. 5 is the TEM figures for the nitrogen phosphorus sulphur codope ordered mesoporous carbon material that embodiment one obtains；
Fig. 6 is the SEM figures for the nitrogen phosphorus sulphur codope ordered mesoporous carbon material that embodiment one obtains；
Fig. 7 is the EDS figures for the nitrogen phosphorus sulphur codope ordered mesoporous carbon material that embodiment one obtains；
Fig. 8 is the XPS figures for the nitrogen phosphorus sulphur codope ordered mesoporous carbon material that embodiment one obtains；
Fig. 9 is the cyclic voltammetry curve figure of nitrogen phosphorus sulphur codope ordered mesoporous carbon material in example one, two, three；
Figure 10 is the constant current charge-discharge curve graph of nitrogen phosphorus sulphur codope ordered mesoporous carbon material in example one, two, three.
Specific implementation mode
Specific implementation mode one：The preparation method of present embodiment nitrogen phosphorus sulphur codope ordered mesoporous carbon material is pressed
Row step is implemented：
One, using hydrothermal synthesis method synthesizing ordered mesoporous silica dioxide template (KIT-6)；
Two,（1）Dry KIT-6 is ultrasonically treated to obtain uniform dispersion in deionized water；Simultaneously by sucrose, phosphoric acid and
Thiosemicarbazides, which is add to deionized water, stirs to get uniform solution, and mass ratio, m (KIT-6)：M (sucrose)：M (phosphoric acid)：
M (thiosemicarbazides)=8: 8:(2~1):(2~1).(2) the latter is transferred in the former and is continued at 40 DEG C in draught cupboard
Stir 12h.(3) obtained paste compound is positioned in baking oven at 80 DEG C dry 12h, then the solid after drying
Grind into powder.(4) composite powder is placed in tube furnace under high pure nitrogen (50 ml/s) and is pyrolyzed 2 in 800 DEG C
H, the rate of heat addition are 2 DEG C/min.(5) composite material after carbonization is immersed in the HF solution that 100 mL mass fractions are 5%
In and stir 24 h remove silica template.(6) it filters, is respectively washed to pH=7 with ultra-pure water and ethyl alcohol, and nitrogen is obtained after drying
Phosphorus sulphur codope ordered mesopore carbon（NPS-OMC）.
Carbon source, nitrogen source, phosphorus source, sulphur source are filled into order mesoporous dioxy by present embodiment respectively by nanometer method for filling
SiClx template（KIT-6）, silicon template is removed again after carbonization, obtains nitrogen phosphorus sulphur codope ordered mesopore carbon nano material.
Specific implementation mode two：Step 2 pyrolysis temperature unlike one of present embodiment and specific implementation mode one to four
Degree is 700 DEG C, and other steps and parameter are identical as one of specific implementation mode one to four.
Specific implementation mode three：Step 2 pyrolysis temperature unlike one of present embodiment and specific implementation mode one to five
Degree is 900 DEG C, and other steps and parameter are identical as one of specific implementation mode one to five.
Specific implementation mode four：Step 2 unlike one of present embodiment and specific implementation mode one to six is being divulged information
12 h are stirred in cupboard at 60 DEG C, other steps and parameter are identical as one of specific implementation mode one to six.
Specific implementation mode five：Step 2 unlike one of present embodiment and specific implementation mode one to seven is being divulged information
12 h are stirred in cupboard at 70 DEG C, other steps and parameter are identical as one of specific implementation mode one to seven.
Specific implementation mode six：Step 2 is 800 unlike one of present embodiment and specific implementation mode one to eight
3 h of calcination process at DEG C.Other steps and parameter are identical as one of specific implementation mode one to eight.
Embodiment one：
One, using hydrothermal synthesis method synthesizing ordered mesoporous silica dioxide template (KIT-6)；
Two,（1）Dry KIT-6 (1.0 g) is ultrasonically treated 1 h in 15 mL DI water and obtains uniform dispersion；Simultaneously will
1.0 g sucrose, 0.25 g phosphoric acid and 0.25 g thiosemicarbazides, which are added to, to be stirred 1 h in 15 mL DI water and obtains uniform solution.
(2) the latter is transferred in the former and continues to stir 12 h at 50 DEG C in draught cupboard.(3) the paste compound that will be obtained
Dry 12 hs are positioned in baking oven at 80 DEG C, then remaining solid abrasive at powder.(4) the composite powder
It is placed in tube furnace under high pure nitrogen (50 mL/s) and is pyrolyzed 2 h in 800 DEG C, the rate of heat addition is 2 DEG C/min.(5) carbon
Composite material after change is immersed in the HF solution that 100 mL mass fractions are 5% and stirs 24 h to remove silica mould
Plate.(6) it filters, is respectively washed 3 times with ultra-pure water and ethyl alcohol, and obtain nitrogen phosphorus sulphur after dry 12 h at 100 DEG C and be co-doped with
Sequence mesoporous carbon（NPS-OMC）.
Embodiment two：
One, using hydrothermal synthesis method synthesizing ordered mesoporous silica dioxide template (KIT-6)；
Two,（1）Dry KIT-6 (1.0 g) is ultrasonically treated 1 h in 15 mL DI water and obtains uniform dispersion；Simultaneously will
1.0 g sucrose, 0.33 g phosphoric acid and 0.33 g thiosemicarbazides, which are added to, to be stirred 1 h in 15 mL DI water and obtains uniform solution.
(2) the latter is transferred in the former and continues to stir 12 h at 50 DEG C in draught cupboard.(3) the paste compound that will be obtained
Dry 12 hs are positioned in baking oven at 80 DEG C, then remaining solid abrasive at powder.(4) the composite powder
It is placed in tube furnace under high pure nitrogen (50 mL/s) and is pyrolyzed 2 h in 800 DEG C, the rate of heat addition is 2 DEG C/min.(5) carbon
Composite material after change is immersed in the HF solution that 100 mL mass fractions are 5% and stirs 24 h to remove silica mould
Plate.(6) it filters, is respectively washed 3 times with ultra-pure water and ethyl alcohol, and obtain nitrogen phosphorus sulphur after dry 12 h at 100 DEG C and be co-doped with
Sequence mesoporous carbon（NPS-OMC）.
Embodiment three：
One, using hydrothermal synthesis method synthesizing ordered mesoporous silica dioxide template (KIT-6)；
Two,（1）Dry KIT-6 (1.0 g) is ultrasonically treated 1 h in 15 mL DI water and obtains uniform dispersion；Simultaneously will
1.0 g sucrose, 0.17 g phosphoric acid and 0.17 g thiosemicarbazides, which are added to, to be stirred 1 h in 15 mL DI water and obtains uniform solution.
(2) the latter is transferred in the former and continues to stir 12 h at 50 DEG C in draught cupboard.(3) the paste compound that will be obtained
Dry 12 hs are positioned in baking oven at 80 DEG C, then remaining solid abrasive at powder.(4) the composite powder
It being placed in tube furnace under high pure nitrogen (nitrogen flow rate be 50 mL/s) and is pyrolyzed 2 h in 800 DEG C, the rate of heat addition is 2 DEG C/
min.(5) composite material after carbonization is immersed in the HF solution that 100 mL mass fractions are 5% and stirs 24 h to remove
Silica template.(6) it filters, is respectively washed 3 times with ultra-pure water and ethyl alcohol, and nitrogen phosphorus sulphur three is obtained after dry 12 h at 100 DEG C
First codope ordered mesopore carbon（NPS-OMC）.
The present embodiment step 1 hydrothermal method prepares ordered mesoporous silica dioxide template（KIT-6）Process it is as follows：
6.0 g polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymers (P123) are taken to be dissolved in 217.0 g
Deionized water and 11.8 g hydrochloric acid（HCl）In, it is slowly added to 6.0 g n-butanols under being stirred at 35 DEG C（BuOH）And ethyl orthosilicate
（TEOS）And TEOS: P-123 : HCl : H2O:BuOH = 1 : 0.017 : 1.83 : 195 : 1.31.It mixes molten
Liquid stirs 24 h at 35 DEG C, is transferred in reaction kettle later, and 24 h are reacted at 100 DEG C.Sample obtains white powder after filtering
End is transferred to after dry 12 h in Muffle furnace at 80 DEG C, through 550 DEG C of 6 h of roasting.Obtain ordered mesoporous silica dioxide template
（KIT-6）.
The crystal form of the nitrogen phosphorus sulphur codope ordered mesoporous carbon material obtained in embodiment by X-ray diffractometer (XRD,
RigakuD/max- II) it is characterized；Pattern and microstructure be using scanning electron microscope analysis (SEM, S-3400) and
Transmitted electron shows mirror (TEM, H-7650) and is characterized；Material element distribution is characterized by energy disperse spectroscopy (EDS, S-3400)；
Material surface valence state information is characterized by X-ray photoelectron spectroscopic analysis (XPS, 250Xi)；The ducts such as material specific surface area
Information is characterized by Physisorption Analyzer (BET, AUTOSORB-1).
Fig. 1 is the XRD diagram for implementing the ordered mesoporous silica dioxide template (KIT-6) that one obtains, can be clearly from figure
Finding out at 2 θ=0.8 ° and 1.2 ° two has apparent characteristic diffraction peak to occur, and corresponds to respectively（211）With（220）Crystal face.This says
Obtained KIT-6 has the pore passage structure of high-sequential after bright high temperature pyrolysis removal surfactant P123.Fig. 2 is to implement
The TEM figures of ordered mesoporous silica dioxide template (KIT-6) in example one.It is apparent that KIT-6 silicon templates have from figure
The 3D pore passage structures of high-sequential, this is consistent with the characterization result of XRD in Fig. 1.
Fig. 3 is the XRD diagram of nitrogen phosphorus sulphur codope ordered mesoporous carbon material in embodiment one, can be clearly from figure
Finding out at 2 θ=0.8 ° and 1.2 ° two has apparent characteristic diffraction peak to occur, and corresponds to respectively（211）With（220）Crystal face.But with
KIT-6 silicon templates in Fig. 1（220）The characteristic peak of crystal face compares, nitrogen phosphorus sulphur codope ordered mesopore carbon（220）
The characteristic diffraction peak of crystal face is smooth-out, shows that high-temperature heat treatment can cause the skeleton of material to shrink in one section of degree.
Fig. 4 is nitrogen adsorption-desorption isothermal curve of nitrogen phosphorus sulphur codope ordered mesoporous carbon material in embodiment one
Figure and the embedded BJH pore size distribution curves obtained by desorption branch.Nitrogen suction-desorption isotherm of material is IV type adsorption curves
And in middle pressure area (P/P0=0.4-0.8) there is the H1 types hysteresis loop caused by capillary condensation phenomenon, corresponding synthesis carbon material
Meso-hole structure.Specific surface area by nitrogen phosphorus sulphur codope ordered mesoporous carbon material is calculated is 637 m2/ g, average hole
Diameter is 1.9 nm.The larger specific surface area of material can provide more active sites for electrochemical reaction, improve the ratio of material
Capacitance.
Fig. 5 is the TEM figures of nitrogen phosphorus sulphur codope ordered mesoporous carbon material in embodiment one.Fig. 5 is clearly showed that
The orderly striped of presentation illustrates that material has the higher degree of order, is typical 3D meso-hole structures.It can also be clear from image
Ground is observed has largely open uniform duct in carbon material, is that the reverse phase of KIT-6 template 3D mesoscopic structures replicates.With
Fig. 4 nitrogen adsorptions-desorption is consistent with the result that the TEM of Fig. 2 KIT-6 is characterized.
Fig. 6 is the SEM figures of nitrogen phosphorus sulphur codope ordered mesoporous carbon material in embodiment one.Therefrom show nitrogen phosphorus sulphur
It is relatively independent between ternary codope ordered mesopore carbon particle, even particle distribution.
Fig. 7 is the EDS of carbon, nitrogen phosphate and sulfur element in nitrogen phosphorus sulphur codope ordered mesoporous carbon material in embodiment one
Figure.Carbon can be clearly observed from figure, uniform distribution is presented in nitrogen phosphate and sulfur element.This illustrates nitrogen phosphate and sulfur element
It equably adulterates among entering ordered mesoporous carbon material.
Fig. 8 is the full spectrograms of XPS of nitrogen phosphorus sulphur codope ordered mesoporous carbon material in embodiment one, can be seen from figure
Observe carbon, nitrogen phosphate and sulfur, oxygen peak type exist, this illustrate nitrogen phosphate and sulfur element really doping enter ordered mesoporous carbon material it
In.This with Fig. 7 EDS result it is consistent.
Application Example：By the polytetrafluoroethylene (PTFE) of 5mg nitrogen phosphorus sulphur codope ordered mesoporous carbon material powder and 5 wt%
（PTFE）Solution mixes, and stirs into slurries, is then uniformly applied in the nickel foam of 1 × 10 cm, tabletted, obtains nitrogen phosphorus
Sulphur codope ordered mesoporous carbon material electrode of super capacitor.
For the Application Example using mercuric oxide electrode as reference electrode, platinum electrode is auxiliary electrode, with CHI660E electrochemistry works
It stands（Shanghai Chen Hua）Cyclic voltamogram curve, permanent electricity have been carried out to nitrogen phosphorus sulphur codope ordered mesoporous carbon material electrode
Flow the electric performance tests such as charge and discharge and AC impedance.
Fig. 9 is that the nitrogen phosphorus sulphur codope ordered mesoporous carbon material electrode in embodiment one, two, three is scanned in 1 mV/s
Cyclic voltammetry curve under rate and 6 mol/LKOH electrolytic solutions., it is evident that nitrogen phosphorus sulphur codope is orderly from figure
The CV curves of meso-porous carbon material electrode illustrate that prepared nitrogen phosphorus sulphur is co-doped with closest to the rectangular shape of ideal capacitor
There is very small resistance, symmetry, invertibity are good, therefore can when miscellaneous ordered mesoporous carbon material is as electrode of super capacitor
To be considered as the ideal electrode material of ultracapacitor；Increase the doping of nitrogen phosphate and sulfur in example two, specific capacitance becomes instead
It is small, it can be seen that be not nitrogen phosphate and sulfur doping it is The more the better；The doping of nitrogen phosphate and sulfur, ratio are reduced in example three
Capacitance becomes smaller, it can be seen that less nitrogen phosphate and sulfur doping can not significantly increase the Faraday pseudo-capacitance of material.
Figure 10 is the constant current charge-discharge curve of nitrogen phosphorus sulphur codope ordered mesopore carbon in embodiment one, two, three.From
It can be seen from the figure that constant current charge-discharge curve charging time section and discharge time section substantially close to, this illustrate it is compound after electricity
Pole material recycles row with good.And constant current charge-discharge curve has certain symmetry, shows the electrode material
Invertibity it is preferable.It is consistent with the chemical property that cyclic voltammetry curve figure is showed in Fig. 9：Excessive or very few nitrogen phosphate and sulfur
Doping can influence the Faraday pseudo-capacitance of material.As we can clearly see from the figure in electrolyte（KOH electrolyte）A concentration of 6
When mol/L, the specific capacitance of the nitrogen phosphorus sulphur codope ordered mesoporous carbon material in embodiment one has reached 343 F/g.
Claims (7)
1. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material, it is characterised in that be to follow these steps to realize：
One, using hydrothermal synthesis method synthesizing ordered mesoporous silica dioxide template (KIT-6)；
Two,（1）Dry KIT-6 is ultrasonically treated to obtain uniform dispersion in deionized water；Simultaneously by sucrose, phosphoric acid and
Thiosemicarbazides, which is add to deionized water, stirs to get uniform solution；(2) mixing of sucrose, phosphoric acid and thiosemicarbazides is molten
Liquid is added in KIT-6 dispersion liquids and stirring is aged 10~14h at 40~60 DEG C in draught cupboard；(3) paste that will be obtained
Compound is positioned in baking oven at 70~90 DEG C dry 10~14 h, grind into powder；(4) composite powder is set
(nitrogen flow rate is 50 mL/s) is pyrolyzed 1~3 h, the rate of heat addition 2 in 700~900 DEG C under high pure nitrogen in tube furnace
℃/min；(5) composite material after carbonization is immersed in a certain amount of 5% HF solution and is stirred to remove silica template；
(6) it filters, is respectively washed with ultra-pure water and ethyl alcohol, and nitrogen phosphorus sulphur codope ordered mesopore carbon is obtained after drying（NPS-OMC）.
2. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that step
Each material mass ratio is m (KIT-6) in rapid two：M (sucrose)：M (phosphoric acid)：M (thiosemicarbazides)=8: 8:(2~1):(2~1).
3. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that step
Mixture Aging Temperature is 40~60 DEG C in rapid two.
4. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that step
Mixture digestion time is 10~14h in rapid two.
5. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that
Step 2 paste compound drying temperature is 70~90 DEG C, and drying time is 10~14 h.
6. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that
Step 2 pyrolysis temperature is 700 DEG C~900 DEG C.
7. the preparation method of nitrogen phosphorus sulphur codope ordered mesoporous carbon material according to claim 1, it is characterised in that
It is 2 DEG C/min that step 2, which is pyrolyzed heating rate,..
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