CN109585054A - The dry conductive carbon paste of green solvent Shift Method is applied to perovskite solar battery - Google Patents
The dry conductive carbon paste of green solvent Shift Method is applied to perovskite solar battery Download PDFInfo
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- CN109585054A CN109585054A CN201811517581.0A CN201811517581A CN109585054A CN 109585054 A CN109585054 A CN 109585054A CN 201811517581 A CN201811517581 A CN 201811517581A CN 109585054 A CN109585054 A CN 109585054A
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- solar battery
- perovskite solar
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a kind of green solvent Shift Methods to prepare conductive carbon paste technique, and is applied to perovskite solar battery.The perovskite solar battery structure include successively the substrate of lamination, transparent electrode, compacted zone and porous layer, perovskite light-absorption layer and carbon to electrode, wherein carbon to the making material of electrode be mainly it is a kind of replaced with organic solvent after dry conductive carbon paste, perovskite light-absorption layer is made of the photovoltaic material with perovskite structure.Preparation process is mainly innovated on preparing preparation of the carbon to electrode material.The preparation of carbon electrode material of the invention is only with the DBE solvent in dehydrated alcohol replacement business conductive carbon paste, it can carry out at room temperature, its simple process, efficiency and stability low in cost and improving battery, are suitable for the Ca-Ti ore type solar energy of various structures to electrode.
Description
Technical field
The present invention relates to perovskite technical field of solar batteries more particularly to a kind of perovskite solar battery carbon to electricity
The preparation method of pole material.
Background technique
With the continuous consumption of fossil energy, human world is faced with energy crisis and environmental pollution two large problems, faces
These problems, the scientists of countries in the world all replace fossil energy finding a kind of new clean reproducible energy.Cleaning
Renewable energy has wind energy, geothermal energy, tide energy, biomass energy and solar energy etc..First three is larger by regional impact, there is limitation
Property, biomass utilization rate is lower, and technology is immature and higher cost, and solar energy is without geographical restrictions, it is easy to use and
It is at low cost.The Land use systems of solar energy are mainly photoelectric conversion, and solar battery is exactly a kind of luminous energy to be converted to the one of electric energy
Kind device has many advantages, such as environmentally friendly, resourceful, cleaning is renewable, at low cost and conversion limitation is small between electric energy,
There is extraordinary prospect in practical application, therefore attracts attention extensively.Perovskite solar battery was in recent years
Since its higher transfer efficiency becomes the research hotspot of society, highest transfer efficiency has had reached 23.2%.
Traditional perovskite solar battery contains hole transmission layer (HTM) metal electrode, these electrode materials there is
Many problems, such as at high cost, stability is poor.Common HTM has Spiro-MeoTAD, P3HT and PTAA etc., these HTM
It is expensive, and keep stability test poor.Noble metal electrode, if Au is expensive and is not suitable for industrialized production, Ag
It is expensive and easy reacted with calcium titanium ore bed.Carbon material has rich reserves, at low cost, work function matching and stability good
The advantages that, it is the ideal substitute of above-mentioned noble metal.
The solvent in commercialized conductive carbon paste bought is DBE, and calcium titanium ore bed is easy to by this conductive carbon paste
Former solvent damage keeps the stability of battery and efficiency all bad.Business conductive carbon paste is directly dried to obtain carbon block body consolidation, then
There are a large amount of carbon block bodies to prevent it from contacting well with calcium titanium ore bed in the secondary carbon slurry dispersed with chlorobenzene, leads to battery efficiency not
It is good.And with the dry conductive carbon paste of green solvent Shift Method there is loose porous structure to be very easy to drying, and good dispersion,
Contact more consolidation with calcium titanium ore bed, what battery efficiency obtained is obviously improved.
Summary of the invention
After commercialized conductive carbon paste being handled the purpose of the present invention is to provide a kind of simple method be used for calcium
Production of the carbon of titanium ore solar battery to electrode, can not only reduce the corrosion to calcium titanium ore bed, additionally it is possible to make to electrode
There is better contact with calcium titanium ore bed.
The present invention, which also resides in, provides a kind of preparation method of perovskite solar battery, the carbon of the perovskite solar battery
Electrode integrality is more preferable, and contact is more preferable between light absorbing layer.
The present invention is realized by the following technical solutions.
A kind of conductive carbon paste for the green solvent replacement being used to prepare perovskite solar battery, preparation process is to incite somebody to action
The conductive carbon material of business is dispersed in dehydrated alcohol, to form uniform carbon pastes；Suction filtration is washed with dehydrated alcohol；And it is dry
The dry carbon pastes layer is to remove the organic solvent in the carbon pastes layer, to obtain carbon to electrode material.
Specifically, the ratio of conductive carbon paste and dehydrated alcohol is 1:10.
Specifically, it is formed by uniform carbon pastes dehydrated alcohol filtering and washing.
Specifically, obtained carbon slurry will be filtered and puts 60 DEG C of dry 1h in an oven.
Specifically, carbon dust is dispersed with chlorobenzene after weighing a certain amount of drying.
A kind of perovskite solar battery to electrode is prepared by the conductive carbon paste of novel dissolvent replacement.
The perovskite solar battery, which is characterized in that the perovskite solar battery includes stacking gradually
Conductive substrates, electron transfer layer, perovskite light-absorption layer and carbon to electrode.
Further, the conductive substrates include FTO, ITO and other flexible substrates.
Further, the electron transfer layer is by TiO2Compacted zone and TiO2Porous layer is successively spun on electro-conductive glass
It is made.
Further, the perovskite light-absorption layer is formed by the one step spin coating of methylamine lead iodine solution that concentration is 1 M.
Further, the carbon is to scratch after being dissolved by the conductive carbon paste of novel dissolvent replacement with chlorobenzene in calcium titanium to electrode
On ore bed.
It is led the invention has the following advantages: the purpose of the present invention is to provide a kind of simple methods by commercialized
Electrical carbon slurry is handled.Manufactured conductive carbon paste short texture is replaced with green solvent, is dispersed convenient for solvent, and remove solvent institute
Need temperature it is lower, the time shorten, manufactured perovskite battery performance be better than convection drying conductive carbon paste, especially filling because
Son and incident photon-to-electron conversion efficiency increase substantially, this is because this pass through the more loose softness of the replaced conductive carbon paste of solvent, with
The contact area of calcium titanium ore bed increases, and reduces charge recombination.
Detailed description of the invention
Fig. 1 is the picture of the business conductive carbon paste of convection drying.
Fig. 2 is the picture of conductive carbon paste dry after replacing business conductive carbon paste with green solvent.
Fig. 3 is the scanning electron microscope (SEM) photograph of the business conductive carbon paste of convection drying.
Fig. 4 is the scanning electron microscope (SEM) photograph of conductive carbon paste dry after replacing business conductive carbon paste with green solvent.
Fig. 5 is the scanning electron microscope in the perovskite solar battery section made of the business conductive carbon paste material of convection drying
Figure.
Fig. 6 is the perovskite solar energy of conductive carbon paste material production dry after replacing business conductive carbon paste with green solvent
The scanning electron microscope (SEM) photograph of battery cross sectional.
Fig. 7 is the business conductive carbon paste material and the business conductive carbon paste dry with green solvent Shift Method with convection drying
The J-V curve for the perovskite solar battery that material makes respectively.
Fig. 8 is the business conductive carbon paste material and the business conductive carbon paste dry with green solvent Shift Method with convection drying
The EIS curve for the perovskite solar battery that material makes respectively.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Test method as used in the following examples is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Carbon of the present invention is to electrode perovskite solar cell device structure, comprising: transparent conductive substrate, compacted zone,
Porous layer, perovskite light-absorption layer, carbon electrode.Preparation step is as follows.
Embodiment 1.
1) monolith FTO electro-conductive glass the cleaning of electro-conductive glass: is cut into 19*19 mm2Fritter, then it is clean with washing respectively
Essence, 20 min of deionized water, isopropanol and dehydrated alcohol supersound washing, 150 DEG C, 1 h drying.
2) preparation of compacted zone: by diisopropoxy bis-acetylacetonate titanium (75% aqueous isopropanol sieve grace) and anhydrous second
1 h of alcohol 1:10 volume ratio mixing ageing obtains mixed solution, this solution is spun in FTO conductive substrates and is added for 120 DEG C again
20 min of heat remove solvent.
3) 1.2 g TiO the preparation of porous layer: are weighed2Slurry (50nmTiO2Particle, terpinol, ethyl cellulose and the moon
Cinnamic acid 1.25:6:0.9:0.3wt%), 10 ml dehydrated alcohols of addition, which are uniformly mixed, is spun on FTO/p-TiO2Again 120 in substrate
DEG C heating 20 min remove solvent, then place into 5 DEG C/min in Muffle furnace and be heated to after 450 DEG C of 30 min of heat preservation again
5 DEG C/min is warming up to Temperature fall after 510 DEG C of 1 h of holding.
4) the 1:1 mixing in molar ratio of lead iodide and iodine methylamine the preparation of calcium titanium ore bed: is dissolved in the mixed of DMSO and DMF
In bonding solvent, obtains concentration and be the perovskite solution of 1 M, and be spun on FTO/p-TiO2/m-TiO2In substrate.
5) preparation of the carbon to electrode: the Shenzhen business conductive carbon paste 10g(east is big next) it is dispersed in 100ml dehydrated alcohol,
To form uniform carbon pastes；Suction filtration is washed three times with dehydrated alcohol, and re-dry is described organic molten in carbon pastes layer to remove
Agent, to obtain carbon to electrode material.Blade coating is in FTO/p- after weighing 0.5 g carbon dust, the 3 ml chlorobenzenes dispersion of production
TiO2 / m-TiO2 / CH3NH3PbI3In substrate, 60 DEG C of 10 min of heating remove solvent.
Embodiment 2.
A kind of perovskite solar battery of the invention, essentially identical with 1 embodiment of embodiment and effect, difference is only
Be: the material of carbon-coating is to directly heat removal solvent with business conductive carbon paste, then weighed 0.5 g and 3 ml chlorobenzenes are added
Dissolution is scratched as carbon material in FTO/p-TiO2 / m-TiO2 / CH3NH3PbI3In substrate, 60 DEG C of heating 10min are gone
Except solvent.
The J-V curve test data of made perovskite solar battery are as follows.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not only limited to above-mentioned implementation
Example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications without departing from the principle of the present invention are regarded as guarantor of the invention
Protect range.
Claims (9)
1. a kind of conductive carbon paste for the green solvent replacement for being used to prepare perovskite solar battery, which is characterized in that with one kind
Former solvent in organic solvent dissolution replacement business conductive carbon paste, preparation method includes the following steps:
1) in organic solvent by the conductive carbon material dispersion of business, to form uniform carbon pastes；
2) uniform sizing material of formation is subjected to filtering and washing and with the organic solvent washing of same step 1)；
3) dry to filter obtained carbon pastes to remove the organic solvent in the carbon pastes layer, to obtain carbon to electrode material
Material.
2. the conductive carbon of a kind of green solvent replacement for being used to prepare perovskite solar battery according to claim 1
Slurry, which is characterized in that the former solvent in the business conductive carbon paste is DBE, is produced by Shenzhen Dong great Lai company.
3. the conductive carbon of a kind of green solvent replacement for being used to prepare perovskite solar battery according to claim 1
Slurry, which is characterized in that the organic solvent is dehydrated alcohol.
4. a kind of perovskite solar battery, which is characterized in that perovskite solar battery is by claim 1 ~ 3 to electrode
Described in green solvent replacement conductive carbon paste preparation.
5. the perovskite solar battery according to claim 4, which is characterized in that the perovskite solar battery
Including the conductive substrates, electron transfer layer, perovskite light-absorption layer and the carbon that stack gradually to electrode.
6. according to perovskite solar battery described in claim 4,5, which is characterized in that the conductive substrates include FTO,
ITO and other flexible substrates.
7. according to perovskite solar battery described in claim 4,5, which is characterized in that the electron transfer layer is by TiO2
Compacted zone and TiO2Porous layer is successively spun on electro-conductive glass and is made.
8. according to perovskite solar battery described in claim 4,5, which is characterized in that the perovskite light-absorption layer is by dense
Degree is that the one step spin coating of methylamine lead iodine solution of 1 M forms.
9. according to perovskite solar battery described in claim 4,5, which is characterized in that the carbon electrode layer is by chlorobenzene
Made of the conductive carbon paste powder mixed liquor blade coating of the green solvent Shift Method preparation of dissolution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110635046A (en) * | 2019-09-23 | 2019-12-31 | 武汉理工大学 | Preparation method of carbon-based double-layer electrode and perovskite type solar cell |
| CN112614942A (en) * | 2021-01-08 | 2021-04-06 | 河南大学 | PEG-modified carbon electrode, preparation method thereof and perovskite battery prepared by using PEG-modified carbon electrode |
| CN113644208A (en) * | 2021-08-06 | 2021-11-12 | 河南大学 | A PEDOT: PSS (patterned sapphire substrate) -modified carbon electrode, preparation method thereof and perovskite battery prepared from PSS |
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Patent Citations (6)
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| JPH11135816A (en) * | 1997-10-31 | 1999-05-21 | Matsushita Battery Industrial Co Ltd | Manufacture of cds/cdte solar cell |
| CN104600197A (en) * | 2015-01-27 | 2015-05-06 | 武汉大学 | Preparation method of hole-free transmission material perovskite thin film heterojunction battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110635046A (en) * | 2019-09-23 | 2019-12-31 | 武汉理工大学 | Preparation method of carbon-based double-layer electrode and perovskite type solar cell |
| CN112614942A (en) * | 2021-01-08 | 2021-04-06 | 河南大学 | PEG-modified carbon electrode, preparation method thereof and perovskite battery prepared by using PEG-modified carbon electrode |
| CN113644208A (en) * | 2021-08-06 | 2021-11-12 | 河南大学 | A PEDOT: PSS (patterned sapphire substrate) -modified carbon electrode, preparation method thereof and perovskite battery prepared from PSS |
| CN113644208B (en) * | 2021-08-06 | 2023-09-22 | 河南大学 | PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using same |
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Application publication date: 20190405 |