CN106744898B - A kind of three-dimensional grapheme powder that nitrogen plasma is modifies and its preparation and application - Google Patents
A kind of three-dimensional grapheme powder that nitrogen plasma is modifies and its preparation and application Download PDFInfo
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- CN106744898B CN106744898B CN201611110475.1A CN201611110475A CN106744898B CN 106744898 B CN106744898 B CN 106744898B CN 201611110475 A CN201611110475 A CN 201611110475A CN 106744898 B CN106744898 B CN 106744898B
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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Abstract
The present invention provides a kind of three-dimensional grapheme powder that nitrogen plasma is modifies and its preparation and application, itself the following steps are included: (1), the bigger serface three-dimensional grapheme powder after drying is placed on the bottom electrode in plasma apparatus cavity, adjustment top electrodes to keep a suitable spacing between bottom electrode and top electrodes, chamber air is removed, then is passed through nitrogen into chamber；(2), after pressure in plasma apparatus cavity is stablized, it opens high-voltage DC power supply and generates nitrogen gas plasma atmosphere to stablize, and the nitrogen gas plasma modification of three-dimensional grapheme powder is carried out under the atmosphere, after treatment obtains the modifies three-dimensional grapheme powder of the nitrogen plasma.The modifies three-dimensional grapheme powder of the nitrogen plasma being prepared using the present invention, which is used as, assembles dye-sensitized solar cells to electrode material, and then replaces conventional electrode materials Pt, can be obviously improved cell photovoltaic efficiency, reduce battery production cost.
Description
Technical field
The present invention relates to a kind of three-dimensional grapheme powder that nitrogen plasma is modifies and its preparation and application, belong to graphite
Alkene material and its preparation and application technical field.
Background technique
Three-dimensional grapheme powder has good electric conductivity, big specific surface area, low cost and to a certain extent
Electro catalytic activity, be considered as ideal dye-sensitized solar cells to electrode material, but itself if it is desired to provide compared with
Good catalytic activity, it is required larger to thickness of electrode, and this is unfavorable for the subsequent encapsulation and practical application of battery, will increase electricity
Pond cost, it is therefore desirable to enhance graphene powder modifying and decorating graphene catalytic capability.
So providing the skill that a kind of three-dimensional grapheme powder that nitrogen plasma is modifies has become this field urgent need to resolve
Art problem.
Summary of the invention
In order to solve the above shortcomings and deficiencies, the purpose of the present invention is to provide a kind of nitrogen plasma it is modifies three
Tie up the preparation method of graphene powder.
The object of the invention is also to provide the preparation sides by the modifies three-dimensional grapheme powder of above-mentioned nitrogen plasma
The modifies three-dimensional grapheme powder of the nitrogen plasma that method is prepared.
The object of the invention is also to provide the modifies three-dimensional grapheme powder of above-mentioned nitrogen plasma is quick as dyestuff
Change application of the solar battery to electrode material.
The purpose of the present invention is to provide a kind of dye-sensitized solar cells again comprising by above-mentioned nitrogen gas plasma
Modified three-dimensional grapheme powder be prepared to electrode.
In order to achieve the above objectives, on the one hand, the present invention provides a kind of three-dimensional grapheme powder that nitrogen plasma is modifies
The preparation method of body comprising following steps:
(1), the bigger serface three-dimensional grapheme powder after drying is placed in the electricity of the bottom in plasma apparatus cavity
On extremely, adjustment top electrodes to keep a suitable spacing between bottom electrode and top electrodes, remove chamber air, then
Nitrogen is passed through into chamber；
(2), after pressure in plasma apparatus cavity is stablized, open high-voltage DC power supply with stablize generate nitrogen etc. from
Daughter atmosphere, and the nitrogen gas plasma modification of three-dimensional grapheme powder is carried out under the atmosphere, after treatment obtains
The modifies three-dimensional grapheme powder of the nitrogen plasma.
Preparation method according to the present invention, wherein drying described in step (1) is this field routine operation, this hair
It is bright that specific requirement is not made to drying, as long as guaranteeing that bigger serface three-dimensional grapheme powder contained humidity can be completely removed i.e.
Can, in the specific embodiment of the invention, which realizes in vacuum drying oven, and drying temperature is 40 DEG C, drying time
For 2h.
Preparation method according to the present invention, wherein plasma apparatus used in the present invention is what this field used
Conventional equipment.
Preparation method according to 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, specific surface area 1500-2000m2/g。
Preparation method according to the present invention, in the specific embodiment of the invention, bigger serface three-dimensional stone used
Black alkene powder is using fluidized 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.
Preparation method according to the present invention, wherein the operation of removing chamber air described in step (1) is this field
Routine operation, the present invention do not make specific requirement to it, as long as guaranteeing to eliminate chamber air, of the invention specific
In embodiment, the removing chamber air operation comprising the following specific steps
First the indoor air of chamber is drained using vacuum pump, nitrogen is then passed to, then again drains nitrogen, to eliminate sky
Gas.
Preparation method according to the present invention, it is preferable that the spacing between the bottom electrode and top electrodes is 4-
8mm。
Preparation method according to the present invention, it is preferable that be passed through in step (1) into chamber after nitrogen in holding chamber room
Pressure be 450-500Pa.
Preparation method according to the present invention, it is preferable that the flow of nitrogen described in step (1) is 150-200sccm/
min。
Preparation method according to the present invention, it is preferable that the voltage of high-voltage DC power supply described in step (2) is 450-
500V。
Preparation method according to the present invention, it is preferable that the place of nitrogen gas plasma modification described in step (2)
Managing temperature is 30-50 DEG C, and the processing time is 15-40min.
Wherein, room temperature, with the extension of reaction time, equipment are substantially remained in incipient stage plasma apparatus cavity
Temperature can slightly increase, and temperature ranges are at 30-50 DEG C.
On the other hand, the three-dimensional grapheme raw powder's production technology modifies the present invention also provides above-mentioned nitrogen plasma
The modifies three-dimensional grapheme powder of the nitrogen plasma being prepared；
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 2-9nm, conductivity is 3000-3200S m-1。
Another aspect, the present invention also provides the modifies three-dimensional grapheme powder of above-mentioned nitrogen plasma is quick as dyestuff
Change application of the solar battery to electrode material.
In another aspect, the present invention also provides a kind of dye-sensitized solar cells comprising by the nitrogen plasma
Modifies three-dimensional grapheme powder be prepared to electrode.
The present invention is based on nitrogen gas plasma modified 3 D graphene powders, are not changing three-dimensional grapheme structure as far as possible
Under the premise of modification is surface modified to it, ensure that modified grapheme material still has excellent electric conductivity；
Meanwhile the modifies three-dimensional grapheme powder of the nitrogen plasma that is prepared of the present invention also has and biggish compares table
Area is (more than 1800m2g-1)；
In addition, the intensity by controlling plasma (changes voltage to realize during nitrogen gas plasma modifying and decorating
), under the premise of unobvious destruction three-dimensional grapheme structure, the present invention can be realized 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 former with the nitrogen in plasma
Son combines, therefore hetero atom nitrogen and edge topological defect abundant is combined to make modifies three of obtained nitrogen plasma of the invention
Tieing up 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 it is easy to be easy to operate, can be realized and be prepared on a large scale, there is stronger universality.
The modifies three-dimensional grapheme powder of the nitrogen plasma being prepared using the present invention is used as to electrode material group
Dye-sensitized solar cells is filled, and then replaces conventional electrode materials Pt, cell photovoltaic efficiency can be obviously improved, reduces battery
Production cost.
Detailed description of the invention
Fig. 1 is the SEM figure for the bigger serface three-dimensional grapheme powder being prepared in the embodiment of the present invention 1；
Fig. 2 is the Raman figure for the bigger serface three-dimensional grapheme powder being prepared in the embodiment of the present invention 1；
Fig. 3 is the XPS figure for the bigger serface three-dimensional grapheme powder being prepared in the embodiment of the present invention 1；
Fig. 4 is the SEM for the three-dimensional grapheme powder that the nitrogen plasma that is prepared is modifies in the embodiment of the present invention 2
Figure；
Fig. 5 is the Raman for the three-dimensional grapheme powder that the nitrogen plasma that is prepared is modifies in the embodiment of the present invention 2
Figure；
Fig. 6 is the XPS for the three-dimensional grapheme powder that the nitrogen plasma that is prepared is modifies in the embodiment of the present invention 2
Figure；
Fig. 7 is the SEM for the three-dimensional grapheme powder that the nitrogen plasma that is prepared is modifies in the embodiment of the present invention 3
Figure；
Fig. 8 is the Raman for the three-dimensional grapheme powder that the nitrogen plasma that is prepared is modifies in the embodiment of the present invention 3
Figure；
Fig. 9 is the XPS for the three-dimensional grapheme powder that the nitrogen plasma that is prepared is modifies in the embodiment of the present invention 3
Figure；
Figure 10 is photoelectric current-photovoltage curve graph of solar battery I in the embodiment of the present invention 5；
Figure 11 is photoelectric current-photovoltage curve graph of solar battery II in the embodiment of the present invention 5；
Figure 12 is photoelectric current-photovoltage curve graph of solar battery III in the embodiment of the present invention 5；
Figure 13 is photoelectric current-photovoltage curve comparison figure of solar battery III and IV in the embodiment of the present invention 5；
Figure 14 is a typical photoelectric current-photovoltage curve graph (photovoltaic curve graph)；
Figure 15 is plasma apparatus structural schematic diagram provided by the present invention.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now in conjunction in detail below
Embodiment and Figure of description carry out following detailed description to technical solution of the present invention, but should not be understood as can to of the invention
The restriction of practical range.
Embodiment 1
It present embodiments provides a kind of using vertical fluidized bed chemical vapor deposition method growth bigger serface three-dimensional graphite
The method of alkene powder comprising following steps:
Under normal pressure, it is passed through Ar (1000sccm/min), heating furnace in fluidized bed is warming up to 950 DEG C, heating rate 5
℃/min；After reaching reaction temperature, it is passed through CH4Gas (800sccm/min)；
20g magnesium oxide template, reaction time 20min is added from fluidized bed top simultaneously；
After reaching the reaction time, stopping is passed through CH4Gas stops heating, cooled to room temperature.Burner hearth is opened, is taken out
Black product, pickling purifying remove removing template, are placed it in vacuum drying oven after filtering and completely remove moisture in 50 DEG C of drying 10h；
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 4.5nm, conductivity is 3000S m-1。
Electronic Speculum (SEM) is scanned respectively to the bigger serface three-dimensional grapheme powder material that the present embodiment is prepared
Analysis, Raman (Raman) analysis and element (XPS) analysis, bigger serface three-dimensional grapheme powder SEM figure, Raman figure and
XPS figure is as shown in Figure 1-Figure 3 respectively, wherein the ordinate of Raman figure is intensity (Intensity), abscissa is Raman shift
(Raman shift)；The ordinate of XPS figure is intensity (Intensity), abscissa is electron binding energy (Binding
energy)。
It is true to can be seen that the bigger serface three-dimensional grapheme powder material that the present embodiment is prepared from Fig. 1-Fig. 3
It is real that there is edge defect structure.
Embodiment 2
Present embodiments provide a kind of three-dimensional grapheme raw powder's production technology that nitrogen plasma is modifies comprising with
Lower step:
(1), the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared is placed in vacuum drying oven and is dried in 40 DEG C
Dry 2h, to completely remove moisture；
(2), the bigger serface three-dimensional grapheme powder after drying is placed in plasma apparatus (structural schematic diagram such as figure
Shown in 15) on the indoor bottom electrode of chamber, adjustment top electrodes to keep the spacing be between bottom electrode and top electrodes
6mm first drains chamber air followed by vacuum pump, then passes to nitrogen to normal pressure, then again drains nitrogen, finally
It is again that 170sccm/min is passed through nitrogen to cavity indoor pressure as 470Pa with flow；
(3), after pressure in plasma apparatus cavity is stablized, opening high-voltage DC power supply adjusting voltage to 480V, with
Stablize and generate nitrogen gas plasma atmosphere, and carries out the modifies place of nitrogen plasma of three-dimensional grapheme powder under the atmosphere
It manages, after 38 DEG C of processing 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 3.07cm3g-1, aperture 4.5nm, conduction
Rate is 3075S m-1。
The modifies three-dimensional grapheme powder of the nitrogen plasma that the present embodiment is prepared is scanned Electronic Speculum respectively
(SEM) analysis, Raman (Raman) analysis and element (XPS) analysis, the modifies three-dimensional grapheme powder of nitrogen plasma
SEM figure, Raman figure and XPS figure respectively it is as shown in Figure 4-Figure 6, wherein the ordinate of Raman figure be intensity (Intensity),
Abscissa is Raman shift (Raman shift)；The ordinate of XPS figure is intensity (Intensity), abscissa is in conjunction with energy
(Binding energy)。
Embodiment 3
Present embodiments provide a kind of three-dimensional grapheme raw powder's production technology that nitrogen plasma is modifies comprising with
Lower step:
(1), the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared is placed in vacuum drying oven and is dried in 40 DEG C
Dry 2h, to completely remove moisture；
(2), the bigger serface three-dimensional grapheme powder after drying is placed in the electricity of the bottom in plasma apparatus cavity
On extremely, adjustment top electrodes to keep spacing between bottom electrode and top electrodes to be 6mm, followed by vacuum pump first by chamber
Room air is drained, and is then passed to nitrogen to normal pressure, is then again drained nitrogen, finally led to again with flow for 170sccm/min
Entering nitrogen to cavity indoor pressure is 470Pa；
(3), after pressure in plasma apparatus cavity is stablized, opening high-voltage DC power supply adjusting voltage to 480V, with
Stablize and generate nitrogen gas plasma atmosphere, and carries out the modifies place of nitrogen plasma of three-dimensional grapheme powder under the atmosphere
It manages, after 38 DEG C of processing 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 3.04cm3g-1, aperture 4.7nm, conduction
Rate is 3175S m-1。
The modifies three-dimensional grapheme powder of the nitrogen plasma that the present embodiment is prepared is scanned Electronic Speculum respectively
(SEM) analysis, Raman (Raman) analysis and element (XPS) analysis, the modifies three-dimensional grapheme powder of nitrogen plasma
SEM figure, Raman figure and XPS figure respectively as shown in figs. 7 to 9, wherein the ordinate of Raman figure be intensity (Intensity),
Abscissa is Raman shift (Raman shift)；The ordinate of XPS figure is intensity (Intensity), abscissa is in conjunction with energy
(Binding energy)。
From the bigger serface three-dimensional grapheme powder that can be seen that in Fig. 1,4,7 in the present invention through nitrogen gas plasma
After modification, significant change does not occur for structure.
From the bigger serface three-dimensional grapheme powder that can be seen that in Fig. 2,5,8 in the present invention through nitrogen gas plasma
After modification, the ratio between D peak intensity angle value and G peak intensity angle value are changed, as the processing time increases, D peak intensity angle value and the peak G
The ratio between intensity value increases, and illustrates that bigger serface three-dimensional grapheme powder after nitrogen gas plasma modification, there is nitrogen really
The introducing in atom defect site.
From the bigger serface three-dimensional grapheme powder that can be seen that in Fig. 3,6,9 in the present invention through nitrogen gas plasma
After modification, occur the peak of apparent nitrogen in XPS figure, during illustrating nitrogen plasma treatment, there is miscellaneous original really
In the bigger serface three-dimensional grapheme powder of sub- nitrogen being introduced into after modification.
Embodiment 4
The present invention provides a kind of three-dimensional grapheme raw powder's production technologies that nitrogen plasma is modifies comprising following
Step:
(1), the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared is placed in vacuum drying oven and is dried in 40 DEG C
Dry 2h, to completely remove moisture；
(2), the bigger serface three-dimensional grapheme powder after drying is placed in the electricity of the bottom in plasma apparatus cavity
On extremely, adjustment top electrodes to keep spacing between bottom electrode and top electrodes to be 4mm, followed by vacuum pump first by chamber
Room air is drained, and is then passed to nitrogen to normal pressure, is then again drained nitrogen, finally led to again with flow for 170sccm/min
Entering nitrogen to cavity indoor pressure is 470Pa；
(3), after pressure in plasma apparatus cavity is stablized, opening high-voltage DC power supply adjusting voltage to 480V, with
Stablize and generate nitrogen gas plasma atmosphere, and carries out the modifies place of nitrogen plasma of three-dimensional grapheme powder under the atmosphere
Reason obtains the modifies three-dimensional grapheme powder of the nitrogen plasma after handling 40min.
Embodiment 5
The present invention provides a kind of three-dimensional grapheme raw powder's production technologies that nitrogen plasma is modifies comprising following
Step:
(1), the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared is placed in vacuum drying oven and is dried in 40 DEG C
Dry 2h, to completely remove moisture；
(2), the bigger serface three-dimensional grapheme powder after drying is placed in the electricity of the bottom in plasma apparatus cavity
On extremely, adjustment top electrodes to keep spacing between bottom electrode and top electrodes to be 8mm, followed by vacuum pump first by chamber
Room air is drained, and is then passed to nitrogen to normal pressure, is then again drained nitrogen, finally led to again with flow for 170sccm/min
Entering nitrogen to cavity indoor pressure is 470Pa；
(3), after pressure in plasma apparatus cavity is stablized, opening high-voltage DC power supply adjusting voltage to 480V, with
Stablize and generate nitrogen gas plasma atmosphere, and carries out the modifies place of nitrogen plasma of three-dimensional grapheme powder under the atmosphere
Reason obtains the modifies three-dimensional grapheme powder of the nitrogen plasma after handling 40min.
Compare preparation example 1
Present embodiments provide a kind of three-dimensional grapheme raw powder's production technology that nitrogen plasma is modifies comprising with
Lower step:
(1), the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared is placed in vacuum drying oven and is dried in 40 DEG C
Dry 2h, to completely remove moisture；
(2), the bigger serface three-dimensional grapheme powder after drying is placed in the electricity of the bottom in plasma apparatus cavity
On extremely, adjustment top electrodes to keep spacing between bottom electrode and top electrodes to be 6mm, followed by vacuum pump first by chamber
Room air is drained, and is then passed to nitrogen to normal pressure, is then again drained nitrogen, finally led to again with flow for 170sccm/min
Entering nitrogen to cavity indoor pressure is 470Pa；
(3), after pressure in plasma apparatus cavity is stablized, opening high-voltage DC power supply adjusting voltage to 400V, with
Stablize and generate nitrogen gas plasma atmosphere, and carries out the modifies place of nitrogen plasma of three-dimensional grapheme powder under the atmosphere
Reason obtains the modifies three-dimensional grapheme powder of the nitrogen plasma after handling 40min.
Compare preparation example 2
Present embodiments provide a kind of three-dimensional grapheme raw powder's production technology that nitrogen plasma is modifies comprising with
Lower step:
(1), the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared is placed in vacuum drying oven and is dried in 40 DEG C
Dry 2h, to completely remove moisture；
(2), the bigger serface three-dimensional grapheme powder after drying is placed in the electricity of the bottom in plasma apparatus cavity
On extremely, adjustment top electrodes to keep spacing between bottom electrode and top electrodes to be 6mm, followed by vacuum pump first by chamber
Room air is drained, and is then passed to nitrogen to normal pressure, is then again drained nitrogen, being finally passed through nitrogen to cavity indoor pressure again is
470Pa；
(3), after pressure in plasma apparatus cavity is stablized, opening high-voltage DC power supply adjusting voltage to 550V, with
Stablize and generate nitrogen gas plasma atmosphere, and carries out the modifies place of nitrogen plasma of three-dimensional grapheme powder under the atmosphere
Reason obtains the modifies three-dimensional grapheme powder of the nitrogen plasma after handling 40min.
Compare preparation example 3
The present invention provides a kind of three-dimensional grapheme raw powder's production technologies that nitrogen plasma is modifies comprising following
Step:
(1), the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared is placed in vacuum drying oven and is dried in 40 DEG C
Dry 2h, to completely remove moisture；
(2), the bigger serface three-dimensional grapheme powder after drying is placed in the electricity of the bottom in plasma apparatus cavity
On extremely, adjustment top electrodes to keep spacing between bottom electrode and top electrodes to be 8mm, followed by vacuum pump first by chamber
Room air is drained, and is then passed to nitrogen to normal pressure, is then again drained nitrogen, being finally passed through nitrogen to cavity indoor pressure again is
300Pa；
(3), after pressure in plasma apparatus cavity is stablized, opening high-voltage DC power supply adjusting voltage to 480V, with
Stablize and generate nitrogen gas plasma atmosphere, and carries out the modifies place of nitrogen plasma of three-dimensional grapheme powder under the atmosphere
Reason obtains the modifies three-dimensional grapheme powder of the nitrogen plasma after handling 40min.
Compare preparation example 4
The present invention provides a kind of three-dimensional grapheme raw powder's production technologies that nitrogen plasma is modifies comprising following
Step:
(1), the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared is placed in vacuum drying oven and is dried in 40 DEG C
Dry 2h, to completely remove moisture；
(2), the bigger serface three-dimensional grapheme powder after drying is placed in the electricity of the bottom in plasma apparatus cavity
On extremely, adjustment top electrodes to keep spacing between bottom electrode and top electrodes to be 6mm, followed by vacuum pump first by chamber
Room air is drained, and is then passed to nitrogen to normal pressure, is then again drained nitrogen, being finally passed through nitrogen to cavity indoor pressure again is
550Pa；
(3), after pressure in plasma apparatus cavity is stablized, opening high-voltage DC power supply adjusting voltage to 480V, with
Stablize and generate nitrogen gas plasma atmosphere, and carries out the modifies place of nitrogen plasma of three-dimensional grapheme powder under the atmosphere
Reason obtains the modifies three-dimensional grapheme powder of the nitrogen plasma after handling 40min.
From above-mentioned preparation embodiment 2-5 and comparison preparation example 1-4 it is found that for voltage, if voltage is too big, wait from
Sub- intensity is too big, can have an impact to the structure of three-dimensional grapheme material, and the present invention is adjusted by judging the brightness of the starting the arc
Voltage is controlled, 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 generated plasma attack is stronger, it is also possible to destroy three-dimensional graphite
The structure of alkene material, but spacing is too big, 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 generate 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, which controls nitrogen pressure,.
Embodiment 6
The present embodiment has carried out the assembling of dye-sensitized solar cells comprising following steps:
Wherein, 1, light anode preparation the following steps are included:
20min successively is cleaned by ultrasonic to FTO electro-conductive glass using acetone, deionized water and ethyl alcohol.It, will be clean after drying
FTO rests on the TiCl of 40mM4In aqueous solution, 70 DEG C of oil bath 30min make the surface FTO form one layer of TiO2Compacted zone.
After the completion, the surface FTO is rinsed with ethyl alcohol, and be put into Muffle furnace in 450 DEG C of calcining 30min.To FTO natural cooling
Afterwards, with screen printing technique by commercial TiO212 μm of sensitizing layer slurry (partial size :~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 Muffle furnace in 500 DEG C of calcining 30min.
After natural cooling, will have TiO2FTO be put into the 0.3mM N719 dyestuff ethanol solution prepared in advance, room
Temperature impregnate 16h, then, by after the ethyl alcohol rinse of the FTO glass of taking-up to get arrive TiO2Light anode.
2, to the preparation of electrode film the following steps are included:
The bigger serface three-dimensional grapheme powder material that takes 20mg embodiment 1 to be prepared respectively, is implemented embodiment 2
The modifies three-dimensional hole graphene powder sample of the nitrogen plasma that example 3 is prepared is added in 10mL isopropanol, ultrasound point
It dissipates 1h and forms uniform dispersion；
The above-mentioned dispersion liquid of 5mL is drawn with 10mL syringe, is then placed in electrospray device (conventional equipment used in this field)
In, controlling feed rate by micro-injection pump is 120 μ L min-1, controlling horizontal distance between needle point and FTO is 5cm；
High-voltage DC power supply is opened, sets voltage value as 9kV, the time for controlling electron spray is 5min, to be prepared 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 denoted as respectively A to electrode film/FTO (using the bigger serface three-dimensional grapheme powder that embodiment 1 is prepared as
To electrode material), B is to electrode film/FTO (modifies three-dimensional hole graphene of the nitrogen plasma being prepared with embodiment 2
Powder is as to electrode material) and C to electrode film/FTO (modifies three-dimensional of the nitrogen plasma being prepared with embodiment 3
Hole graphene powder is used as to electrode material)；
Then obtain three pieces are placed in tube furnace electrode film/FTO, in 200 DEG C of heating 30min under Ar atmosphere, most
N doping three-dimensional hole graphene is obtained eventually to electrode.
3, dye-sensitized solar cells assembling the following steps are included:
The heat-sealing film of 35 μ m thicks is placed in the TiO prepared2In/FTO light anode, then it will prepare to electrode film
(A, B and C) alignment is placed on heat-sealing film；
Then it is sealed under the conditions of 2MPa, 115 DEG C, constant temperature 30s with battery heat-seal machine；
Finally electrolyte is added drop-wise in the hole to the electrode back side with syringe, it will electrolysis by the way of vacuumizing backfill
Liquid is injected between two electrodes.Wherein, electrolyte is containing 0.05M I2, 0.1M LiI, 0.1M guanidinium isothiocyanate, 0.6M 1-
The acetonitrile solution of butyl -3- methylimidazole iodide and 0.5M 4- tert .-butylpyridine；
Three pieces of dye-sensitized solar cells have been prepared in the present embodiment, be denoted 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 dye-sensitized solar cells that embodiment 6 is prepared in the present embodiment is tested for the property, which includes
Following steps:
By dye-sensitized solar cells I-III packaged in embodiment 6 and this field it is conventional be to electrode material with Pt
Expect that the dye-sensitized solar cells (being denoted as battery IV) being prepared presss from both sides (solar cell test system with reserve battery respectively
Included battery folders) battery plus-negative plate is clamped, test loop is formed, and place it in the simulation in solar cell test system
Under sunlight, the solar cell test system be Beijing stand upright Han Guang company production Zolix SS150A type sun optical analog
Device, light intensity are 100mW cm-2；
Then, 2601 digital sourcemeter of Keithlet of computer control, the light of solar battery described in test record are accessed
Electric current-photovoltage curve.The photoelectric current of solar battery I-IV-photovoltage curve as shown in figures 10-13, wherein in Figure 10-12
Abscissa is voltage (Voltage), and ordinate is current density (Current density).
Corresponding solar cell photoelectric can be directly obtained from photoelectric current-photovoltage curve graph of the solar battery
The key index of performance: short circuit current (Short-circuit current density, Jsc), open-circuit voltage (Open-
circuit voltage,Voc), fill factor (Filling factor, FF) and incident photon-to-electron conversion efficiency (Power
conversion efficiency,PCE)；
Wherein, short circuit current is the intersection point numerical value of Y-axis in the curve and curve graph；
Open-circuit voltage is the intersection point numerical value of X-axis in the curve and curve graph；
Fill factor is JoptAnd VoptProduct and JscAnd VocThe ratio between product；
Photoelectric conversion efficiency=short circuit current (Jsc) × open-circuit voltage (Voc) × fill factor (FF)；About above-mentioned each ginseng
Several explanations, please refers to Figure 14, wherein when output power maximum, corresponding current value is Jopt, corresponding voltage at this time
Value is Vopt。
In conclusion by the short circuit current (J of the available solar battery I-IV of Figure 10-13sc), open-circuit voltage (Voc)、
The data such as fill factor (FF) and incident photon-to-electron conversion efficiency (PCE), see the table below shown in 1.
Table 1
It can be clearly seen from table 1, be used as by the modifies three-dimensional hole graphene powder of nitrogen plasma to electrode
The incident photon-to-electron conversion efficiency for the dye-sensitized solar cells that material is prepared is obviously improved；With this field it is conventional be pair with Pt
The dye-sensitized solar cells battery IV that electrode material is prepared is compared, provided by the invention modifies by nitrogen plasma
Incident photon-to-electron conversion efficiency of the three-dimensional hole graphene powder as the dye-sensitized solar cells that electrode material is prepared
Also it is obviously improved.
Claims (1)
1. a kind of three-dimensional grapheme raw powder's production technology that nitrogen plasma is modifies comprising following steps:
(1), the bigger serface three-dimensional grapheme powder after drying is placed on the bottom electrode in plasma apparatus cavity,
Adjustment top electrodes to keep a suitable spacing between bottom electrode and top electrodes, remove chamber air, then to chamber
Interior is passed through nitrogen；
(2), after pressure in plasma apparatus cavity is stablized, high-voltage DC power supply is opened to stablize and generates nitrogen gas plasma
Atmosphere, and the nitrogen gas plasma modification of three-dimensional grapheme powder is carried out under the atmosphere, after treatment obtains described
The modifies three-dimensional grapheme powder of nitrogen plasma；
The bigger serface three-dimensional grapheme powder is the three-dimensional grapheme powder with edge defect structure, specific surface area
For 1500-2000m2/g；
Spacing between the bottom electrode and top electrodes is 4-8mm；
The indoor pressure of holding chamber is 450-500Pa after being passed through nitrogen in step (1) into chamber；
The flow of nitrogen described in step (1) is 150-200sccm/min；
The voltage of high-voltage DC power supply described in step (2) is 450-500V；
The treatment temperature of nitrogen gas plasma modification described in step (2) is 30-50 DEG C, and the processing time is 15-40min.
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| CN110357085B (en) * | 2019-08-15 | 2020-04-24 | 常州机电职业技术学院 | Graphene surface plasma modification treatment device and treatment method |
| CN112724710A (en) * | 2021-01-15 | 2021-04-30 | 贵州玖碳科技有限公司 | Plasma graphene powder surface modification process |
| CN113593917A (en) * | 2021-07-23 | 2021-11-02 | 阜阳师范大学 | Synthesis method of cellular three-dimensional graphene and application of cellular three-dimensional graphene in quasi-solid-state dye-sensitized solar cell |
| CN115092919A (en) * | 2022-06-21 | 2022-09-23 | 贵州玖碳科技有限公司 | Production process of plasma graphene powder |
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