CN104465113A - Nitrogen-doped graphene counter electrode preparing method and application of nitrogen-doped graphene counter electrode in dye-sensitized solar cell - Google Patents
Nitrogen-doped graphene counter electrode preparing method and application of nitrogen-doped graphene counter electrode in dye-sensitized solar cell Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to the field of photovoltaic conversion and discloses a nitrogen-doped graphene thin-film counter electrode preparing method. Particularly, a heterogeneous hydrothermal reaction is conducted on oxidized graphene and urea under the acid environment to obtain nitrogen-doped graphene sizing, and a scraper method is used for preparing a counter electrode. The invention further discloses the application of the counter electrode in a dye-sensitized solar cell. The nitrogen-doped graphene thin-film counter electrode preparing method and the application of the counter electrode in the dye-sensitized solar cell have the advantages that the short circuit density current of the dye-sensitized solar cell is improved, the defect that traditional carbon material counter electrode fill factors are low is overcome, the production cost is reduced, and wide application of the dye-sensitized solar cell is facilitated.
Description
[technical field]
The invention belongs to the application of DIC material in photoelectric conversion technique field, be specifically related to a kind of preparation method of nitrogen-doping graphene counter electrode and the application as counter electrode of dye sensitization battery thereof.
[background technology]
dye-sensitized solar cells becomes the film photovoltaic device of new generation with potential commercial value with its simple manufacturing process, low production cost and higher photoelectric conversion efficiency.Typical dye-sensitized solar cells is made up of electrode the titanium deoxid film of organic (or inorganic) dye sensitization, liquid iodophor electrolyte and platinum.Wherein, although iodine electrolyte has good redox active and higher ion diffusion rates, but this type of electrolyte also exists defects such as absorbing shortwave light, corroding metal wire and too high oxidation-reduction potential, have impact on the raising of sensitized cells efficiency and the long-time stability of battery component.
In recent years, a large amount of non-iodine oxidation-reduction pairs is applied in dye-sensitized cell system, with make up iodine electrolyte apply in dye-sensitized cell in defect.Typical non-iodine oxidation-reduction pair comprise cobalt complex electricity to, nickel complex electricity to, copper complex electricity to and disulphide Organic Electricity equity.Some researchs show, at present conventional platinum is to electrode pair part non-iodine oxidation-reduction pair, and such as copper complex electricity is lower to the catalytic activity that, disulphide Organic Electricity is right, and it is right with the use of forming sensitized cells with these electricity to be unsuitable for.In order to address this problem, various carbon materials, such as carbon black, carbon nano-tube, Graphene etc. have been widely used in the preparation of catalysis non-iodine electrolyte redox reaction to electrode.The application of carbon back to electrode not only increases non-iodine sensitized cells photoelectric conversion efficiency and considerably reduces the production cost to electrode than platinum electrode.
At carbon in electrode material, nitrogen-doping graphene counter electrode receives extensive attention with its high catalytic activity and high stability.At present, nitrogen-doped graphene prepared by Hydrothermal Synthesis route prepared by the nitrogen-doped graphene being applied to sensitized cells easily forms Graphene gel, dried Graphene gel cannot uniform coating and bonding to electrode in preparation, and then have impact on its application in sensitized cells.
[summary of the invention]
To the object of the invention is for nitrogen-doped graphene as Problems existing in counter electrode of dye sensitization battery materials application, provide a kind of heterogeneous hydrothermal method synthetic nitrogen doped graphene and based on this Graphene to electrode fabrication.Nitrogen-doped graphene film prepared by doctor blade method can be convenient to use to electrode by this technology.Will to application of electrode after DSSC, overcome the defect of the uneven and bonding difficulty of film, increased substantially battery short-circuit current density, open circuit voltage and photoelectric conversion efficiency, there is significant technique effect.
Concrete technical scheme of the present invention is as follows:
A preparation method for nitrogen-doping graphene counter electrode, comprises following two steps:
1) preparation of nitrogen-doped graphene slurry
Be 20-30 %(atomic percentages by the oxygen atom content adopting Hummer method to prepare) graphene oxide powder, be dissolved under mechanical agitation in deionized water, be made into the solution that concentration is 0.5-3 mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, add 1-10 g urea and 2-16 g mass percent concentration is the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
o1-20 h is reacted under C.The nitrogen-doped graphene sediment deionized water formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0, wherein the volume ratio of deionized water and ethanol is 0.2-5.0.Azepine graphene suspension is placed in centrifuge centrifugation under 3500rpm and within 30 minutes, obtains azepine Graphene slurry, its mass concentration is 60-90%.
2) use doctor blade method to coat on the FTO electro-conductive glass of 1.5cm × 2cm square resistance 15 Ω by gained nitrogen-doped graphene slurry in step 1), use adhesive tape by the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace and sinters 2 hours at 80-400 DEG C, obtained nitrogen-doping graphene counter electrode;
Above-mentioned nitrogen-doping graphene counter electrode can be applicable in DSSC, and its application process is:
Nano-crystalline titanium dioxide slurry is coated on the FTO conductive glass surface through cleaning, drying, in the titanium deoxid film that 450 DEG C of sintering obtain.Film heating is formed dioxy electric polarization titanium film in 24-48 hour and as light anode to immersing in light-sensitive coloring agent after 70-90 DEG C to adsorb, using above-mentioned obtained nitrogen-doping graphene counter electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate.
Wherein cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
Advantage of the present invention and good effect:
The present invention with nitrogen-doped graphene for have prepared nitrogen-doping graphene counter electrode to electrode material, and be applied to DSSC, nitrogen-doped graphene has the active and good conductive capability of either high redox concurrently, both combinations were both improve and has done short circuit density electric current during electrode with graphene oxide, improve the conventional carbon material defect low to electrode fill factor, curve factor separately, again reduce preparation cost, there is significant technique effect, be conducive to the extensive use of DSSC.
[accompanying drawing explanation]
Fig. 1 is sensitized cells current density voltage curve prepared by embodiment 1.
Fig. 2 is sensitized cells current density voltage curve prepared by embodiment 2.
Fig. 3 is sensitized cells current density voltage curve prepared by embodiment 3.
Fig. 4 is sensitized cells current density voltage curve prepared by embodiment 4.
Fig. 5 is sensitized cells current density voltage curve prepared by embodiment 5.
Fig. 6 is sensitized cells current density voltage curve prepared by embodiment 6.
Fig. 7 is sensitized cells current density voltage curve prepared by embodiment 7.
Fig. 8 is sensitized cells current density voltage curve prepared by embodiment 8.
[embodiment]
embodiment 1:
Be that DSSC prepared by raw material with nitrogen-doped graphene, step is as follows:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder that the oxygen atom content adopting Hummer method to prepare is 29.4 at%, be dissolved under mechanical agitation in deionized water, be made into the solution of 1mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, the urea and the 5g mass percent concentration that add 6g are the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
oreact 2 hours under C.The deionized water of the nitrogen-doped graphene sediment volume ratio 1:1 formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0.Azepine graphene suspension being placed in centrifuge centrifugation under 3500rpm, within 30 minutes, can to obtain azepine Graphene mass concentration be 85% object.
2) to the preparation of electrode
On the FTO electro-conductive glass using doctor blade method to be coated by nitrogen-doped graphene slurry to be of a size of 1.5cm × 2cm square resistance 15 Ω, use adhesive tape will the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace in 350
oc temperature sinters 2 hours, obtained to electrode;
3) preparation of DSSC
Nano-crystalline titanium dioxide slurry is coated on the conductive glass surface of above-mentioned process, the titanium deoxid film obtained by high temperature sintering immerses after being heated to 80 DEG C in light-sensitive coloring agent to adsorb and forms dioxy electric polarization titanium films as light anode in 24 hours, using obtained to electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate; Described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
The photovoltaic performance test of this DSSC:
The photovoltaic performance test of battery is by drawing wire respectively in titanium dioxide membrane electrode provided with to electrode, being connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.156 cm
2.Export simulated solar irradiation with solar simulator (Oriel 91160-1000 (300W)), luminous intensity is adjusted to 100 mW/cm
2, record the current density voltage curve of this battery as shown in Figure 1.Show in figure: photoelectric conversion efficiency is 5.2 %, open circuit voltage is 710mV, and short circuit current density is 13.40 mAcm
-2, fill factor, curve factor is 0.55.
embodiment 2:
Be that DSSC prepared by raw material with nitrogen-doped graphene, step is as follows:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder that the oxygen atom content adopting Hummer method to prepare is 29.4 at%, be dissolved under mechanical agitation in deionized water, be made into the solution of 1mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, the urea and the 5g mass percent concentration that add 6g are the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
oreact 2 hours under C.The deionized water of the nitrogen-doped graphene sediment volume ratio 1:1 formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0.Azepine graphene suspension being placed in centrifuge centrifugation under 3500rpm, within 30 minutes, can to obtain azepine Graphene mass concentration be 85% object.
2) to the preparation of electrode
On the FTO electro-conductive glass using doctor blade method to be coated by nitrogen-doped graphene slurry to be of a size of 1.5cm × 2cm square resistance 15 Ω, use adhesive tape will the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace in 80
oc temperature sinters 2 hours, obtained to electrode;
3) preparation of DSSC
Nano-crystalline titanium dioxide slurry is coated on the conductive glass surface of above-mentioned process, the titanium deoxid film obtained by high temperature sintering immerses after being heated to 80 DEG C in light-sensitive coloring agent to adsorb and forms dioxy electric polarization titanium films as light anode in 24 hours, using obtained to electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate; Described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
The photovoltaic performance test of this DSSC:
The photovoltaic performance test of battery is by drawing wire respectively in titanium dioxide membrane electrode provided with to electrode, being connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.156 cm
2.Export simulated solar irradiation with solar simulator (Oriel 91160-1000 (300W)), luminous intensity is adjusted to 100 mW/cm
2, record the current density voltage curve of this battery as shown in Figure 2.Show in figure: photoelectric conversion efficiency is 3.5 %, open circuit voltage is 694 mV, and short circuit current density is 10.5 mAcm
-2, fill factor, curve factor is 0.48.
embodiment 3:
Be that DSSC prepared by raw material with nitrogen-doped graphene, step is as follows:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder that the oxygen atom content adopting Hummer method to prepare is 29.4 at%, be dissolved under mechanical agitation in deionized water, be made into the solution of 1mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, the urea and the 5g mass percent concentration that add 6g are the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
oreact 6 hours under C.The deionized water of the nitrogen-doped graphene sediment volume ratio 1:1 formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0.Azepine graphene suspension being placed in centrifuge centrifugation under 3500rpm, within 30 minutes, can to obtain azepine Graphene mass concentration be 85% object.
2) to the preparation of electrode
On the FTO electro-conductive glass using doctor blade method to be coated by nitrogen-doped graphene slurry to be of a size of 1.5cm × 2cm square resistance 15 Ω, use adhesive tape will the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace in 80
oc temperature sinters 2 hours, obtained to electrode;
3) preparation of DSSC
Nano-crystalline titanium dioxide slurry is coated on the conductive glass surface of above-mentioned process, the titanium deoxid film obtained by high temperature sintering immerses after being heated to 80 DEG C in light-sensitive coloring agent to adsorb and forms dioxy electric polarization titanium films as light anode in 24 hours, using obtained to electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate; Described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
The photovoltaic performance test of this DSSC:
The photovoltaic performance test of battery is by drawing wire respectively in titanium dioxide membrane electrode provided with to electrode, being connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.156 cm
2.Export simulated solar irradiation with solar simulator (Oriel 91160-1000 (300W)), luminous intensity is adjusted to 100 mW/cm
2, record the current density voltage curve of this battery as shown in Figure 3.Show in figure: photoelectric conversion efficiency is 6.2%, open circuit voltage is 799 mV, and short circuit current density is 12.5 mAcm
-2, fill factor, curve factor is 0.62.
embodiment 4:
Be that DSSC prepared by raw material with nitrogen-doped graphene, step is as follows:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder that the oxygen atom content adopting Hummer method to prepare is 29.4 at%, be dissolved under mechanical agitation in deionized water, be made into the solution of 1mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, the urea and the 5g mass percent concentration that add 6g are the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
oreact 12 hours under C.The deionized water of the nitrogen-doped graphene sediment volume ratio 1:1 formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0.Azepine graphene suspension being placed in centrifuge centrifugation under 3500rpm, within 30 minutes, can to obtain azepine Graphene mass concentration be 85% object.
2) to the preparation of electrode
On the FTO electro-conductive glass using doctor blade method to be coated by nitrogen-doped graphene slurry to be of a size of 1.5cm × 2cm square resistance 15 Ω, use adhesive tape will the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace in 350
oc temperature sinters 2 hours, obtained to electrode;
3) preparation of DSSC
Nano-crystalline titanium dioxide slurry is coated on the conductive glass surface of above-mentioned process, the titanium deoxid film obtained by high temperature sintering immerses after being heated to 80 DEG C in light-sensitive coloring agent to adsorb and forms dioxy electric polarization titanium films as light anode in 24 hours, using obtained to electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate; Described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
The photovoltaic performance test of this DSSC:
The photovoltaic performance test of battery is by drawing wire respectively in titanium dioxide membrane electrode provided with to electrode, being connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.156 cm
2.Export simulated solar irradiation with solar simulator (Oriel 91160-1000 (300W)), luminous intensity is adjusted to 100 mW/cm
2, record the current density voltage curve of this battery as shown in Figure 4.Show in figure: photoelectric conversion efficiency is 8.2%, open circuit voltage is 826 mV, and short circuit current density is 16.6 mAcm
-2, fill factor, curve factor is 0.60.
embodiment 5:
Be that DSSC prepared by raw material with nitrogen-doped graphene, step is as follows:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder that the oxygen atom content adopting Hummer method to prepare is 29.4 at%, be dissolved under mechanical agitation in deionized water, be made into the solution of 1mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, the urea and the 5g mass percent concentration that add 6g are the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
oreact 12 hours under C.The deionized water of the nitrogen-doped graphene sediment volume ratio 1:1 formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0.Azepine graphene suspension being placed in centrifuge centrifugation under 3500rpm, within 30 minutes, can to obtain azepine Graphene mass concentration be 85% object.
2) to the preparation of electrode
On the FTO electro-conductive glass using doctor blade method to be coated by nitrogen-doped graphene slurry to be of a size of 1.5cm × 2cm square resistance 15 Ω, use adhesive tape will the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace in 80
oc temperature sinters 2 hours, obtained to electrode;
3) preparation of DSSC
Nano-crystalline titanium dioxide slurry is coated on the conductive glass surface of above-mentioned process, the titanium deoxid film obtained by high temperature sintering immerses after being heated to 80 DEG C in light-sensitive coloring agent to adsorb and forms dioxy electric polarization titanium films as light anode in 24 hours, using obtained to electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate; Described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
The photovoltaic performance test of this DSSC:
The photovoltaic performance test of battery is by drawing wire respectively in titanium dioxide membrane electrode provided with to electrode, being connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.156 cm
2.Export simulated solar irradiation with solar simulator (Oriel 91160-1000 (300W)), luminous intensity is adjusted to 100 mW/cm
2, record the current density voltage curve of this battery as shown in Figure 5.Show in figure: photoelectric conversion efficiency is 7.7%, open circuit voltage is 818mV, and short circuit current density is 14.4 mAcm
-2, fill factor, curve factor is 0.66.
embodiment 6:
Be that DSSC prepared by raw material with nitrogen-doped graphene, step is as follows:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder that the oxygen atom content adopting Hummer method to prepare is 29.4 at%, be dissolved under mechanical agitation in deionized water, be made into the solution of 1mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, add 6g urea and 5g mass percent concentration is the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
oreact 18 hours under C.The deionized water of the nitrogen-doped graphene sediment volume ratio 1:1 formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0.Azepine graphene suspension being placed in centrifuge centrifugation under 3500rpm, within 30 minutes, can to obtain azepine Graphene mass concentration be 85% object.
2) to the preparation of electrode
On the FTO electro-conductive glass using doctor blade method to be coated by nitrogen-doped graphene slurry to be of a size of 1.5cm × 2cm square resistance 15 Ω, use adhesive tape will the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace in 350
oc temperature sinters 2 hours, obtained to electrode;
3) preparation of DSSC
Nano-crystalline titanium dioxide slurry is coated on the conductive glass surface of above-mentioned process, the titanium deoxid film obtained by high temperature sintering immerses after being heated to 80 DEG C in light-sensitive coloring agent to adsorb and forms dioxy electric polarization titanium films as light anode in 24 hours, using obtained to electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate; Described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
The photovoltaic performance test of this DSSC:
The photovoltaic performance test of battery is by drawing wire respectively in titanium dioxide membrane electrode provided with to electrode, being connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.156 cm
2.Export simulated solar irradiation with solar simulator (Oriel 91160-1000 (300W)), luminous intensity is adjusted to 100 mW/cm
2, record the current density voltage curve of this battery as shown in Figure 6.Show in figure: photoelectric conversion efficiency is 6.4%, open circuit voltage is 768 mV, and short circuit current density is 14.0 mAcm
-2, fill factor, curve factor is 0.59.
embodiment 7:
Be that DSSC prepared by raw material with nitrogen-doped graphene, step is as follows:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder that the oxygen atom content adopting Hummer method to prepare is 29.4 at%, be dissolved under mechanical agitation in deionized water, be made into the solution of 1mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, add 6g urea and 5g mass percent concentration is the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
oreact 18 hours under C.The deionized water of the nitrogen-doped graphene sediment volume ratio 1:1 formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0.Azepine graphene suspension being placed in centrifuge centrifugation under 3500rpm, within 30 minutes, can to obtain azepine Graphene mass concentration be 85% object.
2) to the preparation of electrode
On the FTO electro-conductive glass using doctor blade method to be coated by nitrogen-doped graphene slurry to be of a size of 1.5cm × 2cm square resistance 15 Ω, use adhesive tape will the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace in 80
oc temperature sinters 2 hours, obtained to electrode;
3) preparation of DSSC
Nano-crystalline titanium dioxide slurry is coated on the conductive glass surface of above-mentioned process, the titanium deoxid film obtained by high temperature sintering immerses after being heated to 80 DEG C in light-sensitive coloring agent to adsorb and forms dioxy electric polarization titanium films as light anode in 24 hours, using obtained to electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate; Described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
The photovoltaic performance test of this DSSC:
The photovoltaic performance test of battery is by drawing wire respectively in titanium dioxide membrane electrode provided with to electrode, being connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.156 cm
2.Export simulated solar irradiation with solar simulator (Oriel 91160-1000 (300W)), luminous intensity is adjusted to 100 mW/cm
2, record the current density voltage curve of this battery as shown in Figure 7.Show in figure: photoelectric conversion efficiency is 5.2%, open circuit voltage is 738 mV, and short circuit current density is 12.4 mAcm
-2, fill factor, curve factor is 0.57.
embodiment 8:
Be that DSSC prepared by raw material with nitrogen-doped graphene, step is as follows:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder that the oxygen atom content adopting Hummer method to prepare is 29.4 at%, be dissolved under mechanical agitation in deionized water, be made into the solution of 1mg/mL.Get the above-mentioned graphene oxide aqueous dispersions of 50mL, add 6g urea and 5g mass percent concentration is the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma.Said mixture is placed in polytetrafluoroethylene reactor, 180
oreact 6 hours under C.The deionized water of the nitrogen-doped graphene sediment volume ratio 1:1 formed after hydro-thermal reaction and alcohol mixed solution are washed till pH value and equal 7.0.Azepine graphene suspension being placed in centrifuge centrifugation under 3500rpm, within 30 minutes, can to obtain azepine Graphene mass concentration be 85% object.
2) to the preparation of electrode
On the FTO electro-conductive glass using doctor blade method to be coated by nitrogen-doped graphene slurry to be of a size of 1.5cm × 2cm square resistance 15 Ω, use adhesive tape will the THICKNESS CONTROL of coating Graphene pulp layer at 60um.Thereafter, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace in 350
oc temperature sinters 2 hours, obtained to electrode;
3) preparation of DSSC
Nano-crystalline titanium dioxide slurry is coated on the conductive glass surface of above-mentioned process, the titanium deoxid film obtained by high temperature sintering immerses after being heated to 80 DEG C in light-sensitive coloring agent to adsorb and forms dioxy electric polarization titanium films as light anode in 24 hours, using obtained to electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate; Described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
The photovoltaic performance test of this DSSC:
The photovoltaic performance test of battery is by drawing wire respectively in titanium dioxide membrane electrode provided with to electrode, being connected in the photovoltaic test system of battery.The light-receiving area of battery is 0.156 cm
2.Export simulated solar irradiation with solar simulator (Oriel 91160-1000 (300W)), luminous intensity is adjusted to 100 mW/cm
2, record the current density voltage curve of this battery as shown in Figure 8.Show in figure: photoelectric conversion efficiency is 7.4%, open circuit voltage is 812 mV, and short circuit current density is 14.8 mAcm
-2, fill factor, curve factor is 0.62.
Claims (8)
1. a preparation method for nitrogen-doping graphene counter electrode, is characterized in that, this method comprises the following steps:
1) preparation of nitrogen-doped graphene slurry
By the graphene oxide powder of certain oxygen atom content prepared by employing Hummer method, be dissolved under mechanical agitation in deionized water, be made into certain density graphene oxide aqueous dispersions,
Get the above-mentioned graphene oxide aqueous dispersions of 50mL, the urea and the mass fraction that add certain mass are the concentrated sulfuric acid of 98%, stir 15min, form graphene oxide hydro-thermal reaction presoma, above-mentioned presoma is placed in polytetrafluoroethylene reactor, 180
ocertain hour is reacted under C, then with deionized water and the alcohol mixed solution washing gained sediment of certain volume ratio, obtain the nitrogen-doped graphene suspension that pH value is 7.0, finally this nitrogen-doped graphene suspension is placed in centrifuge centrifugation under 3500rpm and within 30 minutes, obtains azepine Graphene slurry;
2) doctor blade method is used to coat on the FTO electro-conductive glass of 1.5cm × 2cm square resistance 15 Ω by gained nitrogen-doped graphene slurry in step 1), use adhesive tape by the THICKNESS CONTROL of coating Graphene pulp layer at 60um, then, the electro-conductive glass of load nitrogen-doped graphene is placed in Muffle furnace and fixs sintering 2 hours in one, obtained nitrogen-doping graphene counter electrode.
2. the preparation method of nitrogen-doping graphene counter electrode according to claim 1, is characterized in that: the oxygen atom content of described graphene oxide powder is 20-30 %(atomic percentages), graphene oxide aqueous dispersions concentration is 0.5-3 mg/mL.
3. the preparation method of nitrogen-doping graphene counter electrode according to claim 1, it is characterized in that: described urea addition is 1-10 g, the addition of the described concentrated sulfuric acid is 2-16 g.
4. the preparation method of nitrogen-doping graphene counter electrode according to claim 1, is characterized in that: described presoma is 1-20 h in the polytetrafluoroethylene reaction kettle for reaction time.
5. the preparation method of nitrogen-doping graphene counter electrode according to claim 1, is characterized in that: in described deionized water and alcohol mixed solution, the volume ratio of water and ethanol is 0.2-5.0.
6. the preparation method of nitrogen-doping graphene counter electrode according to claim 1, is characterized in that: the sintering temperature of electro-conductive glass in Muffle furnace of described load nitrogen-doped graphene is 80-400 DEG C.
7. an application for nitrogen-doping graphene counter electrode as claimed in claim 1, for the preparation of DSSC, is characterized in that: method is as follows,
Nano-crystalline titanium dioxide slurry is coated on the FTO conductive glass surface through cleaning, drying, in the titanium deoxid film that 450 DEG C of sintering obtain, film heating is formed dioxy electric polarization titanium film in 24-48 hour and as light anode to immersing in light-sensitive coloring agent after 70-90 DEG C to adsorb, using obtained nitrogen-doping graphene counter electrode as photocathode, light anode and to electrode between fill cobalt-based electrolyte and encapsulate.
8. the application of nitrogen-doping graphene counter electrode according to claim 7, is characterized in that: described cobalt-based is electrolytical consists of 0.25M Phen cobalt (II) lithium microcosmic salt { [Co (II) (phen)
3] (PF
6)
2, 0.05M Phen cobalt (III) lithium microcosmic salt { [Co (III) (phen)
3] (PF
6)
3, the acetonitrile solution of 0.1M bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and 1.0M tert .-butylpyridine (tBP).
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| CN106335890A (en) * | 2015-07-16 | 2017-01-18 | 中国石油化工股份有限公司 | Preparation method of phosphorus-doped graphene |
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| CN112768249A (en) * | 2020-12-30 | 2021-05-07 | 山东力诺光伏高科技有限公司 | Green and environment-friendly graphene solar cell and preparation method thereof |
| CN112768249B (en) * | 2020-12-30 | 2022-07-22 | 山东力诺光伏高科技有限公司 | Green and environment-friendly graphene solar cell and preparation method thereof |
| CN113155931A (en) * | 2021-04-09 | 2021-07-23 | 国家烟草质量监督检验中心 | Method for detecting chloride ions in tobacco and tobacco planting soil |
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