CN106744898A - A kind of modifies three-dimensional grapheme powder of nitrogen plasma and its preparation and application - Google Patents
A kind of modifies three-dimensional grapheme powder of nitrogen plasma and its preparation and application Download PDFInfo
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- CN106744898A CN106744898A CN201611110475.1A CN201611110475A CN106744898A CN 106744898 A CN106744898 A CN 106744898A CN 201611110475 A CN201611110475 A CN 201611110475A CN 106744898 A CN106744898 A CN 106744898A
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Abstract
The present invention provides a kind of modifies three-dimensional grapheme powder of nitrogen plasma and its preparation and application, and it is comprised the following steps：(1), on the bottom electrode that the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity, adjustment top electrodes cause to keep a suitable spacing between bottom electrode and top electrodes, chamber air is removed, then to being passed through nitrogen in chamber；(2), after after pressure stability in plasma apparatus cavity, open high-voltage DC power supply and nitrogen gas plasma atmosphere is produced with stabilization, and the nitrogen gas plasma modification of three-dimensional grapheme powder is carried out under the atmosphere, after treatment terminates, the modifies three-dimensional grapheme powder of the nitrogen plasma is obtained.The modifies three-dimensional grapheme powder of the nitrogen plasma that is prepared using the present invention replaces conventional electrode materials Pt as assembling DSSC to electrode material, can be obviously improved cell photovoltaic efficiency, reduces battery production cost.
Description
Technical field
The present invention relates to a kind of modifies three-dimensional grapheme powder of nitrogen plasma and its preparation and application, belong to graphite
Alkene material and its preparation and application technical field.
Background technology
Three-dimensional grapheme powder has good electric conductivity, big specific surface area, low cost and to a certain extent
Electro catalytic activity, its be considered as preferable DSSC to electrode material, but itself if it is desired to provide compared with
Good catalysis activity, it is required larger to thickness of electrode, and follow-up encapsulation that this is unfavorable for battery and practical application, electricity can be increased
Pond cost, it is therefore desirable to strengthen graphene powder modifying and decorating Graphene catalytic capability.
So, there is provided a kind of modifies three-dimensional grapheme powder of nitrogen plasma has turned into the skill of this area urgent need to resolve
Art problem.
The content of the invention
In order to solve above-mentioned shortcoming and defect, it is an object of the invention to provide a kind of nitrogen plasma it is modifies three
Tie up the preparation method of graphene powder.
The present invention also aims to provide by the preparation side of the modifies three-dimensional grapheme powder of above-mentioned nitrogen plasma
The modifies three-dimensional grapheme powder of nitrogen plasma that method is prepared.
It is quick as dyestuff the present invention also aims to provide the modifies three-dimensional grapheme powder of above-mentioned nitrogen plasma
Change application of the solar cell to electrode material.
The purpose of the present invention is again to provide a kind of DSSC, and it is included by above-mentioned nitrogen gas plasma
Modified three-dimensional grapheme powder prepare to electrode.
To reach above-mentioned purpose, on the one hand, the invention provides a kind of modifies three-dimensional grapheme powder of nitrogen plasma
The preparation method of body, it is comprised the following steps：
(1) the bottom electricity that, the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity
Extremely go up, adjustment top electrodes cause to keep a suitable spacing between bottom electrode and top electrodes, remove chamber air, then
To being passed through nitrogen in chamber；
(2), after after pressure stability in plasma apparatus cavity, open high-voltage DC power supply with stabilization produce nitrogen etc. from
Daughter atmosphere, and the nitrogen gas plasma modification of three-dimensional grapheme powder is carried out under the atmosphere, after treatment terminates, obtain
The modifies three-dimensional grapheme powder of the nitrogen plasma.
According to preparation method of the present invention, wherein, drying described in step (1) is this area routine operation, this hair
It is bright that specific requirement is not made to drying, as long as guarantee can completely remove bigger serface three-dimensional grapheme powder contained humidity i.e.
Can, in the specific embodiment of the invention, the drying course is realized in vacuum drying oven, and drying temperature is 40 DEG C, drying time
It is 2h.
According to preparation method of the present invention, wherein, plasma apparatus used by the present invention are used for this area
Conventional equipment.
According to preparation method of the present invention, it is preferable that the bigger serface three-dimensional grapheme powder is with side
The three-dimensional grapheme powder of edge topological defect structure, its specific surface area is 1500-2000m2/g。
According to preparation method of the present invention, in the specific embodiment of the invention, bigger serface three-dimensional stone used
Black alkene powder is using fluid bed chemical vapor deposition method (Guoqing Ning etal, Gram-scale synthesis of
nanomesh grapheme with high surface area and its application in
Supercapacitor electrodes, Chem Commun, 2011,47,5976-5978) growth bigger serface it is three-dimensional
Graphene powder.
According to preparation method of the present invention, wherein, it is this area that chamber air operation is removed described in step (1)
Routine operation, the present invention does not make specific requirement to it, as long as guarantee can eliminate chamber air, of the invention specific
In implementation method, removing chamber air operation includes step in detail below：
First the air in chamber is drained using vavuum pump, then passes to nitrogen, then again drain nitrogen, to eliminate sky
Gas.
According to preparation method of the present invention, it is preferable that the spacing between the bottom electrode and top electrodes is 4-
8mm。
According to preparation method of the present invention, it is preferable that to being passed through in chamber after nitrogen in holding chamber room in step (1)
Pressure be 450-500Pa.
According to preparation method of the present invention, it is preferable that the flow of nitrogen described in step (1) is 150-200sccm/
min。
According to preparation method of the present invention, it is preferable that the voltage of high-voltage DC power supply described in step (2) is 450-
500V。
According to preparation method of the present invention, it is preferable that the place of nitrogen gas plasma modification described in step (2)
Reason temperature is 30-50 DEG C, and process time is 15-40min.
Wherein, room temperature is substantially remained in incipient stage plasma apparatus cavity, with the extension in reaction time, equipment
Temperature can somewhat increase, and temperature ranges are at 30-50 DEG C.
On the other hand, present invention also offers the three-dimensional grapheme raw powder's production technology that above-mentioned nitrogen plasma is modifies
The modifies three-dimensional grapheme powder of the nitrogen plasma for preparing；
Preferably, the specific surface area of the modifies three-dimensional grapheme powder of the nitrogen plasma is 1800-2000m2/ g, hole
Volume is 2.8-3.1cm3g-1, aperture is 2-9nm, and conductance is 3000-3200S m-1。
Another aspect, it is quick as dyestuff present invention also offers the modifies three-dimensional grapheme powder of above-mentioned nitrogen plasma
Change application of the solar cell to electrode material.
Another further aspect, present invention also offers a kind of DSSC, it is included by the nitrogen plasma
Modifies three-dimensional grapheme powder prepare to electrode.
The present invention is based on nitrogen gas plasma modified 3 D graphene powder, and three-dimensional grapheme structure is not being changed as far as possible
On the premise of it is carried out it is surface modified, it is ensured that modified grapheme material still have excellent electric conductivity；
Meanwhile, the modifies three-dimensional grapheme powder of the nitrogen plasma for preparing of the invention also has larger ratio table
Area is (more than 1800m2g-1)；
Additionally, during nitrogen gas plasma modifying and decorating, (changing voltage to realize by controlling the intensity of plasma
), on the premise of substantially three-dimensional grapheme structure is not destroyed, the present invention can realize skirt selectivity doping nitrogen-atoms and draw
Enter nitrogen-atoms defect sites, because the carbon atom activity at edge is comparatively higher, can be easier and the nitrogen original in plasma
Son is combined, therefore makes modifies three of the nitrogen plasma that the present invention is obtained with reference to hetero atom nitrogen and abundant edge topological defect
Dimension graphene powder has excellent electrocatalysis characteristic.
Meanwhile, the preparation method of nitrogen gas plasma modified 3 D graphene powder provided by the present invention is close to room temperature
At a temperature of can carry out, and easy easily operation can be realized being prepared on a large scale, with stronger universality.
The modifies three-dimensional grapheme powder of the nitrogen plasma that is prepared using the present invention is used as to electrode material group
Dress DSSC, and then replace conventional electrode materials Pt, cell photovoltaic efficiency can be obviously improved, reduce battery
Production cost.
Brief description of the drawings
Fig. 1 schemes for the SEM of the bigger serface three-dimensional grapheme powder prepared in the embodiment of the present invention 1；
Fig. 2 schemes for the Raman of the bigger serface three-dimensional grapheme powder prepared in the embodiment of the present invention 1；
Fig. 3 schemes for the XPS of the bigger serface three-dimensional grapheme powder prepared in the embodiment of the present invention 1；
Fig. 4 is the SEM of the modifies three-dimensional grapheme powder of the nitrogen plasma prepared in the embodiment of the present invention 2
Figure；
Fig. 5 is the Raman of the modifies three-dimensional grapheme powder of the nitrogen plasma prepared in the embodiment of the present invention 2
Figure；
Fig. 6 is the XPS of the modifies three-dimensional grapheme powder of the nitrogen plasma prepared in the embodiment of the present invention 2
Figure；
Fig. 7 is the SEM of the modifies three-dimensional grapheme powder of the nitrogen plasma prepared in the embodiment of the present invention 3
Figure；
Fig. 8 is the Raman of the modifies three-dimensional grapheme powder of the nitrogen plasma prepared in the embodiment of the present invention 3
Figure；
Fig. 9 is the XPS of the modifies three-dimensional grapheme powder of the nitrogen plasma prepared in the embodiment of the present invention 3
Figure；
Figure 10 is the photoelectric current-photovoltage curve map of solar cell I in the embodiment of the present invention 5；
Figure 11 is the photoelectric current-photovoltage curve map of solar cell II in the embodiment of the present invention 5；
Figure 12 is the photoelectric current-photovoltage curve map of solar cell III in the embodiment of the present invention 5；
Figure 13 is the photoelectric current-photovoltage curve comparison figure of solar cell III and IV in the embodiment of the present invention 5；
Figure 14 is a typical photoelectric current-photovoltage curve map (photovoltaic curve map)；
Figure 15 is plasma apparatus structural representation provided by the present invention.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, in conjunction with detail below
Embodiment and Figure of description technical scheme is carried out it is described further below, but it is not intended that to it is of the invention can
The restriction of practical range.
Embodiment 1
Present embodiments provide a kind of using vertical fluidized bed chemical vapor deposition method growth bigger serface three-dimensional graphite
The method of alkene powder, it is comprised the following steps：
Under normal pressure, Ar (1000sccm/min) is passed through, heating furnace in fluid bed is warming up to 950 DEG C, heating rate is 5
℃/min；After reaching reaction temperature, CH is passed through4Gas (800sccm/min)；
Simultaneously 20g magnesium oxide templates, reaction time 20min are added from fluid bed top；
After reaching the reaction time, stopping is passed through CH4Gas, stops heating, naturally cools to room temperature.Burner hearth is opened, is taken out
Removing template is removed in black product, pickling purifying, is placed on after filtering in vacuum drying oven and is dried 10h in 50 DEG C and remove moisture removal completely；
So as to obtain bigger serface three-dimensional grapheme powder material, the specific surface area of the graphene powder raw material is 1900m2/ g, hole
Volume is 2.91cm3g-1, aperture is 4.5nm, and conductance is 3000S m-1。
The bigger serface three-dimensional grapheme powder material prepared to the present embodiment is scanned Electronic Speculum (SEM) respectively
Analysis, Raman (Raman) analysis and element (XPS) analysis, bigger serface three-dimensional grapheme powder SEM figure, Raman figure and
XPS figures respectively as shown in Figure 1-Figure 3, wherein, the ordinate of Raman figures is intensity (Intensity), abscissa is Raman shift
(Raman shift)；The ordinate of XPS figures is intensity (Intensity), abscissa is electron binding energy (Binding
energy)。
As can be seen that the bigger serface three-dimensional grapheme powder material for preparing of the present embodiment is true from Fig. 1-Fig. 3
It is real that there is edge defect structure.
Embodiment 2
Present embodiments provide a kind of modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma, it include with
Lower step：
(1) the bigger serface three-dimensional grapheme powder for, preparing embodiment 1 is placed in vacuum drying oven in 40 DEG C of bakings
Dry 2h, to remove moisture removal completely；
(2) the bigger serface three-dimensional grapheme powder after drying, is placed in plasma apparatus (structural representation such as figure
Shown in 15) on bottom electrode in chamber, adjustment top electrodes cause to be kept between bottom electrode and top electrodes the spacing be
6mm, first drains chamber air followed by vavuum pump, then passes to nitrogen to normal pressure, then again drains nitrogen, finally
Nitrogen is passed through to cavity indoor pressure as 470Pa by 170sccm/min of flow again；
(3), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply adjusts voltage to 480V, with
Stabilization produces nitrogen gas plasma atmosphere, and the modifies place of nitrogen plasma of three-dimensional grapheme powder is carried out under the atmosphere
Reason, after 38 DEG C for the treatment of 15min, obtains the modifies three-dimensional grapheme powder of the nitrogen plasma, wherein, the nitrogen plasma
The specific surface area of modifies three-dimensional grapheme powder is 1921m2g-1, pore volume is 3.07cm3g-1, aperture is 4.5nm, conductive
Rate is 3075S m-1。
The modifies three-dimensional grapheme powder of the nitrogen plasma that is prepared to the present embodiment is scanned Electronic Speculum respectively
(SEM) analysis, Raman (Raman) analysis and element (XPS) analysis, the modifies three-dimensional grapheme powder of nitrogen plasma
SEM figures, Raman figures and XPS figures respectively as Figure 4-Figure 6, wherein, the ordinate of Raman figures is intensity (Intensity),
Abscissa is Raman shift (Raman shift)；The ordinate of XPS figures is intensity (Intensity), abscissa is with reference to energy
(Binding energy)。
Embodiment 3
Present embodiments provide a kind of modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma, it include with
Lower step：
(1) the bigger serface three-dimensional grapheme powder for, preparing embodiment 1 is placed in vacuum drying oven in 40 DEG C of bakings
Dry 2h, to remove moisture removal completely；
(2) the bottom electricity that, the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity
Extremely go up, adjustment top electrodes cause that it is 6mm that spacing is kept between bottom electrode and top electrodes, followed by vavuum pump first by chamber
Room air is drained, and then passes to nitrogen to normal pressure, then again drains nitrogen, finally logical by 170sccm/min of flow again
It is 470Pa to enter nitrogen to cavity indoor pressure；
(3), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply adjusts voltage to 480V, with
Stabilization produces nitrogen gas plasma atmosphere, and the modifies place of nitrogen plasma of three-dimensional grapheme powder is carried out under the atmosphere
Reason, after 38 DEG C for the treatment of 40min, obtains the modifies three-dimensional grapheme powder of the nitrogen plasma, wherein, the nitrogen plasma
The specific surface area of modifies three-dimensional grapheme powder is 1917m2g-1, pore volume is 3.04cm3g-1, aperture is 4.7nm, conductive
Rate is 3175S m-1。
The modifies three-dimensional grapheme powder of the nitrogen plasma that is prepared to the present embodiment is scanned Electronic Speculum respectively
(SEM) analysis, Raman (Raman) analysis and element (XPS) analysis, the modifies three-dimensional grapheme powder of nitrogen plasma
SEM figures, Raman figures and XPS figures respectively as shown in figs. 7 to 9, wherein, the ordinate of Raman figures is intensity (Intensity),
Abscissa is Raman shift (Raman shift)；The ordinate of XPS figures is intensity (Intensity), abscissa is with reference to energy
(Binding energy)。
As can be seen that the bigger serface three-dimensional grapheme powder in the present invention is through nitrogen gas plasma from Fig. 1,4,7
After modification, there is no significant change in its structure.
As can be seen that the bigger serface three-dimensional grapheme powder in the present invention is through nitrogen gas plasma from Fig. 2,5,8
After modification, the ratio between D peak intensities angle value and G peak intensity angle value there occurs change, as process time increases, D peak intensities angle value and G peaks
The ratio between intensity level increases, and after illustrating bigger serface three-dimensional grapheme powder through nitrogen gas plasma modification, there is nitrogen really
The introducing in atom defect site.
As can be seen that the bigger serface three-dimensional grapheme powder in the present invention is through nitrogen gas plasma from Fig. 3,6,9
After modification, occur the peak of obvious nitrogen in XPS figures, illustrate during nitrogen plasma treatment, there is miscellaneous original really
In the bigger serface three-dimensional grapheme powder being introduced into after modification of sub- nitrogen.
Embodiment 4
The invention provides a kind of modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma, it includes following
Step：
(1) the bigger serface three-dimensional grapheme powder for, preparing embodiment 1 is placed in vacuum drying oven in 40 DEG C of bakings
Dry 2h, to remove moisture removal completely；
(2) the bottom electricity that, the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity
Extremely go up, adjustment top electrodes cause that it is 4mm that spacing is kept between bottom electrode and top electrodes, followed by vavuum pump first by chamber
Room air is drained, and then passes to nitrogen to normal pressure, then again drains nitrogen, finally logical by 170sccm/min of flow again
It is 470Pa to enter nitrogen to cavity indoor pressure；
(3), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply adjusts voltage to 480V, with
Stabilization produces nitrogen gas plasma atmosphere, and the modifies place of nitrogen plasma of three-dimensional grapheme powder is carried out under the atmosphere
Reason, after treatment 40min, obtains the modifies three-dimensional grapheme powder of the nitrogen plasma.
Embodiment 5
The invention provides a kind of modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma, it includes following
Step：
(1) the bigger serface three-dimensional grapheme powder for, preparing embodiment 1 is placed in vacuum drying oven in 40 DEG C of bakings
Dry 2h, to remove moisture removal completely；
(2) the bottom electricity that, the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity
Extremely go up, adjustment top electrodes cause that it is 8mm that spacing is kept between bottom electrode and top electrodes, followed by vavuum pump first by chamber
Room air is drained, and then passes to nitrogen to normal pressure, then again drains nitrogen, finally logical by 170sccm/min of flow again
It is 470Pa to enter nitrogen to cavity indoor pressure；
(3), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply adjusts voltage to 480V, with
Stabilization produces nitrogen gas plasma atmosphere, and the modifies place of nitrogen plasma of three-dimensional grapheme powder is carried out under the atmosphere
Reason, after treatment 40min, obtains the modifies three-dimensional grapheme powder of the nitrogen plasma.
Contrast preparation example 1
Present embodiments provide a kind of modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma, it include with
Lower step：
(1) the bigger serface three-dimensional grapheme powder for, preparing embodiment 1 is placed in vacuum drying oven in 40 DEG C of bakings
Dry 2h, to remove moisture removal completely；
(2) the bottom electricity that, the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity
Extremely go up, adjustment top electrodes cause that it is 6mm that spacing is kept between bottom electrode and top electrodes, followed by vavuum pump first by chamber
Room air is drained, and then passes to nitrogen to normal pressure, then again drains nitrogen, finally logical by 170sccm/min of flow again
It is 470Pa to enter nitrogen to cavity indoor pressure；
(3), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply adjusts voltage to 400V, with
Stabilization produces nitrogen gas plasma atmosphere, and the modifies place of nitrogen plasma of three-dimensional grapheme powder is carried out under the atmosphere
Reason, after treatment 40min, obtains the modifies three-dimensional grapheme powder of the nitrogen plasma.
Contrast preparation example 2
Present embodiments provide a kind of modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma, it include with
Lower step：
(1) the bigger serface three-dimensional grapheme powder for, preparing embodiment 1 is placed in vacuum drying oven in 40 DEG C of bakings
Dry 2h, to remove moisture removal completely；
(2) the bottom electricity that, the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity
Extremely go up, adjustment top electrodes cause that it is 6mm that spacing is kept between bottom electrode and top electrodes, followed by vavuum pump first by chamber
Room air is drained, and then passes to nitrogen to normal pressure, then again drains nitrogen, nitrogen to cavity indoor pressure is finally passed through again and is
470Pa；
(3), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply adjusts voltage to 550V, with
Stabilization produces nitrogen gas plasma atmosphere, and the modifies place of nitrogen plasma of three-dimensional grapheme powder is carried out under the atmosphere
Reason, after treatment 40min, obtains the modifies three-dimensional grapheme powder of the nitrogen plasma.
Contrast preparation example 3
The invention provides a kind of modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma, it includes following
Step：
(1) the bigger serface three-dimensional grapheme powder for, preparing embodiment 1 is placed in vacuum drying oven in 40 DEG C of bakings
Dry 2h, to remove moisture removal completely；
(2) the bottom electricity that, the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity
Extremely go up, adjustment top electrodes cause that it is 8mm that spacing is kept between bottom electrode and top electrodes, followed by vavuum pump first by chamber
Room air is drained, and then passes to nitrogen to normal pressure, then again drains nitrogen, nitrogen to cavity indoor pressure is finally passed through again and is
300Pa；
(3), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply adjusts voltage to 480V, with
Stabilization produces nitrogen gas plasma atmosphere, and the modifies place of nitrogen plasma of three-dimensional grapheme powder is carried out under the atmosphere
Reason, after treatment 40min, obtains the modifies three-dimensional grapheme powder of the nitrogen plasma.
Contrast preparation example 4
The invention provides a kind of modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma, it includes following
Step：
(1) the bigger serface three-dimensional grapheme powder for, preparing embodiment 1 is placed in vacuum drying oven in 40 DEG C of bakings
Dry 2h, to remove moisture removal completely；
(2) the bottom electricity that, the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity
Extremely go up, adjustment top electrodes cause that it is 6mm that spacing is kept between bottom electrode and top electrodes, followed by vavuum pump first by chamber
Room air is drained, and then passes to nitrogen to normal pressure, then again drains nitrogen, nitrogen to cavity indoor pressure is finally passed through again and is
550Pa；
(3), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply adjusts voltage to 480V, with
Stabilization produces nitrogen gas plasma atmosphere, and the modifies place of nitrogen plasma of three-dimensional grapheme powder is carried out under the atmosphere
Reason, after treatment 40min, obtains the modifies three-dimensional grapheme powder of the nitrogen plasma.
Knowable to above-mentioned preparation embodiment 2-5 and contrast preparation example 1-4, for voltage, if voltage is too big, wait from
Sub- intensity is too big, influence, and the present invention can be produced to be adjusted by judging the brightness of the starting the arc structure of three-dimensional grapheme material
Control voltage, if voltage is too small, is unable to the starting the arc, therefore applied voltage of the present invention is 450-500V.
For electrode spacing, spacing is smaller, and produced plasma attack is stronger, it is also possible to destroy three-dimensional graphite
The structure of alkene material, but spacing is too big, and the plasma starting the arc is weaker, therefore coordination electrode spacing of the present invention is 4-8mm.
For nitrogen pressure, if nitrogen pressure is too small, it is not easy to produce nitrogen plasma atmosphere, but press
Too greatly, the intensity of plasma can also become larger to power, and then be possible to destroy the structure of three-dimensional grapheme material, because
This, it is 450-500Pa that the present invention controls nitrogen pressure.
Embodiment 6
The present embodiment has carried out the assembling of DSSC, and it is comprised the following steps：
Wherein, 1, the preparation of light anode is comprised the following steps：
20min is cleaned by ultrasonic to FTO electro-conductive glass using acetone, deionized water and ethanol successively.After drying, will be clean
FTO rests on the TiCl of 40mM4In the aqueous solution, 70 DEG C of oil bath 30min make FTO surfaces form one layer of TiO2Compacted zone.
After the completion of, with ethanol rinse FTO surfaces, and it is put into Muffle furnace and calcines 30min in 450 DEG C.Treat FTO natural coolings
Afterwards, with screen printing technique by commercial TiO212 μm of (particle diameters of sensitizing layer slurry：~20nm) and TiO22 μm of reflecting layer slurry (~
300nm or so) successively it is printed on the TiO on FTO2Fine and close layer surface, is then placed in calcining 30min in 500 DEG C in Muffle furnace.
After after natural cooling, will be with TiO2FTO be put into the 0.3mM N719 dyestuff ethanol solutions that prepare in advance, room
Temperature immersion 16h, then, after the FTO glass that will be taken out is with ethanol rinse, that is, obtains TiO2Light anode.
2nd, the preparation to electrode film is comprised the following steps：
Bigger serface three-dimensional grapheme powder material, embodiment 2, implementation that 20mg embodiments 1 are prepared are taken respectively
The modifies three-dimensional hole graphene powder sample of nitrogen plasma that example 3 is prepared, in adding 10mL isopropanols, ultrasound point
Dissipate 1h and form uniform dispersion；
The above-mentioned dispersion liquids of 5mL are drawn with 10mL syringes, electrospray device (conventional equipment used by this area) is then placed in
In, it is 120 μ L min to control feed rate by micro-injection pump-1, it is 5cm to control horizontal range between needle point and FTO；
High-voltage DC power supply is opened, setting voltage value is 9kV, the time of electron spray is controlled for 5min, so as to prepare 5
The N doping three-dimensional grapheme (the modifies three-dimensional hole Graphene of nitrogen plasma) of μ m thick is to electrode film uniform load
In on FTO, be designated as respectively A to electrode film/FTO (the bigger serface three-dimensional grapheme powder prepared using embodiment 1 as
To electrode material), B is to electrode film/FTO (modifies three-dimensional hole Graphenes of the nitrogen plasma that is prepared with embodiment 2
Powder is used as to electrode material) and C to electrode film/FTO (modifies three-dimensionals of the nitrogen plasma that is prepared with embodiment 3
Hole graphene powder is used as to electrode material)；
Then three pieces for obtaining are placed in tube furnace to electrode film/FTO, heat 30min in 200 DEG C under Ar atmosphere, most
N doping three-dimensional hole Graphene is obtained eventually to electrode.
3rd, the assembling of DSSC is comprised the following steps：
The heat-sealing film of 35 μ m thicks is placed in the TiO for preparing2In/FTO light anodes, then will prepare to electrode film
(A, B and C) alignment is placed on heat-sealing film；
Then sealed under the conditions of 2MPa, 115 DEG C, constant temperature 30s with battery heat-seal machine；
Electrolyte is added drop-wise in the hole to the electrode back side with syringe finally, will electrolysis by the way of backfill is vacuumized
Liquid is injected between two electrodes.Wherein, electrolyte is to contain 0.05M I2, 0.1M LiI, 0.1M guanidinium isothiocyanates, 0.6M 1-
The acetonitrile solution of butyl -3- methylimidazoles iodide and 0.5M 4- tert .-butylpyridines；
Three pieces of DSSCs have been prepared in the present embodiment, be designated as respectively battery I (A to electrode film/
FTO), battery II (B is to electrode film/FTO) and battery III (C is to electrode film/FTO).
Embodiment 7
The present embodiment carries out performance test to the DSSC that embodiment 6 is prepared, and the test includes
Following steps：
By DSSC I-III packaged in embodiment 6 and this area it is conventional be to electrode material with Pt
The DSSC (being designated as battery IV) that material is prepared presss from both sides (solar cell test system with reserve battery respectively
Carry battery folders) battery plus-negative plate is clamped, test loop is formed, and be placed on the simulation in solar cell test system
Under sunshine, the solar cell test system for Beijing stand upright Han Guang companies production Zolix SS150A type sun optical analogs
Device, light intensity is 100mW cm-2；
Then, the digital sourcemeters of Keithlet 2601 of computer controls, the light of solar cell described in test record are accessed
Electric current-photovoltage curve.The photoelectric current of solar cell I-IV-photovoltage curve as shown in figures 10-13, in wherein Figure 10-12
Abscissa is voltage (Voltage), and ordinate is current density (Current density).
Correspondence solar cell photoelectric can be directly obtained from the photoelectric current-photovoltage curve map of the solar cell
The key index of performance：Short circuit current (Short-circuit current density, Jsc), open-circuit voltage (Open-
circuit voltage,Voc), fill factor, curve factor (Filling factor, FF) and electricity conversion (Power
conversion efficiency,PCE)；
Wherein, short circuit current is the intersection point numerical value of the curve and Y-axis in curve map；
Open-circuit voltage is the intersection point numerical value of the curve and X-axis in curve map；
Fill factor, curve factor is JoptAnd VoptProduct and JscAnd VocThe ratio between product；
Photoelectric transformation efficiency=short circuit current (Jsc) × open-circuit voltage (Voc) × fill factor, curve factor (FF)；On above-mentioned each ginseng
Several explanations, refer to Figure 14, wherein, when power output is maximum, corresponding current value is Jopt, now corresponding voltage
It is V to be worthopt。
In sum, the short circuit current (J of solar cell I-IV can be obtained by Figure 10-13sc), open-circuit voltage (Voc)、
The data such as fill factor, curve factor (FF) and electricity conversion (PCE), see the table below shown in 1.
Table 1
Can be clearly seen from table 1, by the modifies three-dimensional hole graphene powder of nitrogen plasma as to electrode
The electricity conversion of the DSSC that material is prepared is obviously improved；Conventional with this area is right with Pt
The DSSC battery IV that electrode material is prepared is compared, and it is modifies by nitrogen plasma that the present invention is provided
Three-dimensional hole graphene powder as the DSSC prepared to electrode material electricity conversion
Also it is obviously improved.
Claims (10)
1. the modifies three-dimensional grapheme raw powder's production technology of a kind of nitrogen plasma, it is comprised the following steps：
(1), on the bottom electrode that the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus cavity,
Adjustment top electrodes cause to keep a suitable spacing between bottom electrode and top electrodes, remove chamber air, then to chamber
Interior is passed through nitrogen；
(2), after after pressure stability in plasma apparatus cavity, opening high-voltage DC power supply produces nitrogen gas plasma with stabilization
Atmosphere, and the nitrogen gas plasma modification of three-dimensional grapheme powder is carried out under the atmosphere, after treatment terminates, obtain described
The modifies three-dimensional grapheme powder of nitrogen plasma.
2. preparation method according to claim 1, it is characterised in that the bigger serface three-dimensional grapheme powder is tool
There is the three-dimensional grapheme powder of edge defect structure, its specific surface area is 1500-2000m2/g。
3. preparation method according to claim 1 and 2, it is characterised in that between the bottom electrode and top electrodes
Spacing is 4-8mm.
4. preparation method according to claim 1 and 2, it is characterised in that to being protected after nitrogen is passed through in chamber in step (1)
It is 450-500Pa to hold the pressure in chamber.
5. preparation method according to claim 1 and 2, it is characterised in that the flow of nitrogen described in step (1) is 150-
200sccm/min。
6. preparation method according to claim 1 and 2, it is characterised in that the electricity of high-voltage DC power supply described in step (2)
It is 450-500V to press.
7. preparation method according to claim 1 and 2, it is characterised in that nitrogen plasma is modifies described in step (2)
The treatment temperature for the treatment of is 30-50 DEG C, and process time is 15-40min.
8. the modifies three-dimensional grapheme raw powder's production technology of nitrogen plasma described in any one of claim 1-7 is prepared
The modifies three-dimensional grapheme powder of nitrogen plasma；
Preferably, the specific surface area of the modifies three-dimensional grapheme powder of the nitrogen plasma is 1800-2000m2/ g, pore volume
It is 2.8-3.1cm3g-1, aperture is 2-9nm, and conductance is 3000-3200S m-1。
9. the modifies three-dimensional grapheme powder of nitrogen plasma described in claim 8 is used as DSSC pair
The application of electrode material.
10. a kind of DSSC, it is characterised in that the DSSC is included by claim 8
The modifies three-dimensional grapheme powder of described nitrogen plasma prepare to electrode.
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