CN104538552A - Perovskite solar cell and manufacturing method thereof - Google Patents
Perovskite solar cell and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a perovskite solar cell and a manufacturing method of the perovskite solar cell. The perovskite solar cell is provided with a conducting glass conducting layer, a barrier layer, a mesoporous layer, a counter electrode layer and a perovskite light-absorbing layer. The conducting glass conducting layer is divided into a positive electrode region and a negative electrode region by a piece of insulating tape, the positive electrode region of the conducting glass conducting layer is coated with the barrier layer, the mesoporous layer is located on the barrier layer, the mesoporous layer, the insulating tape and the positive electrode region of the conducting glass conducting layer are covered with the counter electrode layer, and the outer surface of the counter electrode layer is coated with the perovskite light-absorbing layer. The low-cost screen printing technology is fully utilized, the production process is simple, the energy consumption of the low-cost screen printing technology is much lower than that of the evaporation coating technology, and the manufacturing method of the perovskite solar cell is beneficial for large-scale production and has broad application prospects.
Description
Technical field
The present invention relates to technical field of solar batteries, is a kind of perovskite solar cell and preparation method thereof specifically.
Background technology
Up to now, the photoelectric conversion efficiency of the perovskite solar cell reported reaches 17.9%.As third generation solar cell, the feature that perovskite solar cell is prepared with its higher photoelectric conversion efficiency and low-cost and easy-to, receives the concern of more and more people.But, the mode depositing noble metal of the hot evaporation that conventional perovskite solar cell adopts is to electrode, it is no matter the energy consumption of material cost or preparation process, all quite high, in addition, conventional perovskite solar cell needs to use hole mobile material as electronic barrier layer, and hole mobile material is very expensive, current price exceedes 10 times of gold, and the problem of existence and stability difference.These all greatly hinder the commercialized development of perovskite solar cell.
Be in current perovskite solar cell preparation technology and first deposit perovskite light absorbent, finally use thermal evaporation techniques deposition to electrode layer, first deposit perovskite and hole transmission layer, when depositing again electrode layer, deposit and destroy calcium titanium ore bed and hole transmission layer to very possible in the process of electrode, there is the problem of loose contact or short circuit, these all can cause serious impact to the product quality of solar cell and qualification rate simultaneously.
Summary of the invention
The object of the invention is for above-mentioned deficiency of the prior art, a kind of perovskite solar cell with low cost is provided.
Another object of the present invention is to provide the preparation method that preparation technology is simple, have this perovskite solar cell with low cost of very high practical value.
The object of the invention is to be achieved through the following technical solutions:
A kind of perovskite solar cell, have electro-conductive glass conductive layer, barrier layer, mesoporous layer, to electrode layer and perovskite light-absorption layer, described electro-conductive glass conductive layer is separated into positive pole zone and negative regions by insulating tape, described barrier layer is coated on the negative regions of described electro-conductive glass conductive layer, described mesoporous layer is positioned on described barrier layer, in described positive pole zone electrode layer being covered in described mesoporous layer, insulating tape and electro-conductive glass conductive layer, described perovskite light-absorption layer is coated on the described outer surface to electrode layer.
In further design, the material on described barrier layer is fine and close titanium dioxide; The material of described mesoporous layer is mesoporous ZrO 2; The described material to electrode layer is mesoporous graphite carbon black mixt.
In further design, described stop thickness 18-22 nanometer, described mesoporous thickness 450-550 nanometer, described to electrode thickness 9-11 micron.
Further in design, described perovskite light-absorption layer adopts the coating of perovskite solution to form, described perovskite solution is the gamma-butyrolacton solution of lead iodide and iodine methylamine, and the molar concentration of lead iodide is 1.0-1.5 mol/L, and the molar concentration of iodine methylamine is 1.2-1.8 mol/L).
The preparation method of above-mentioned perovskite solar cell, comprises following concrete steps:
1), etching conductive glass conductive layer: use wavelength is that the infrared laser of 1064 nanometers etches a bar insulation band on electro-conductive glass conductive layer, makes the positive pole zone and the negative regions that conducting glass substrate are formed not conducting mutually.
2), spraying barrier layer: at 400 ~ 450 oC temperature, coating quality concentration is the titanium tetrachloride solution of 0.05-0.10% on the surface in the negative regions of electro-conductive glass, forms the titanium dioxide barrier layer of one deck densification after sintering.
3), mesoporous layer is printed: use screen printing technique, print one deck zirconium dioxide slurry over the barrier layer, in zirconium dioxide slurry, zirconium dioxide particle particle diameter is 60-100 nanometer, is incubated 30 minutes with ramp to 500 oC of 5 oC/ minutes, forms mesoporous layer after printing.
4), print electrode layer: use screen printing technique, the positive pole zone of mesoporous graphite carbon black and electro-conductive glass conductive layer prints one deck carbon pastes, be incubated 30 minutes with ramp to 420 oC of 8 oC/ minutes after printing, formed electrode layer.
5), perovskite light-absorption layer is applied: the ratio being 1:1.2 in the mol ratio of lead iodide and iodine methylamine will be dissolved in gamma-butyrolacton at lead iodide and iodine methylamine prepares perovskite solution, at 60oC-80oC temperature, to electrode layer outer surface one deck perovskite solution, after oven dry, namely obtain perovskite solar cell.
In further design, the compound method of zirconium dioxide slurry is: Zirconium dioxide powder and the ethyl cellulose of getting particle diameter 60-100 nanometer join in the mixed liquor of terpinol and ethanol, in planetary ball mill, ball milling took out after 24 hours, evaporative removal ethanol, namely zirconium dioxide slurry is obtained, wherein, the mass ratio of Zirconium dioxide powder and ethyl cellulose is 2:1, and the volume ratio of terpinol and ethanol is 2:1.
In further design, the compound method of carbon pastes is: mixed with carbon black by graphite, add the zirconium dioxide particle of 2% of graphite carbon black gross mass, be dispersed in the mixed liquor of terpinol and ethanol, after ultrasonic 40 minutes, ball milling 24 hours in planetary ball mill, evaporative removal ethanol, obtains carbon pastes, wherein, the mass ratio of graphite and carbon black is 13:4, and the volume ratio of terpinol and ethanol is 4:3.
The operation applying perovskite solution in step 5 can be carried out in horizontal thermal station.
The present invention has following outstanding beneficial effect:
Perovskite solar cell of the present invention adopts cheapness to instead of noble metal to electrode material to electrode material, and do not need to use expensive hole mobile material, significantly reduce cost, simultaneously, what adopt carbon pastes to prepare is more much bigger than the plate electrode of routine to the specific area of electrode layer, this is conducive to the exchange of electrode surface electric charge, effectively can reduce the internal resistance of device, makes prepared device have more excellent photoelectric conversion efficiency; Adopt meso-porous carbon material as skeleton, stablize, not easily deformation occur, in the process of deposition perovskite, mesoporous material layer can not change, and makes perovskite light absorbent simultaneously and has larger contact area to electrode, be conducive to charge-exchange.
The preparation method of perovskite solar cell of the present invention makes full use of the screen printing technique of low cost, and production technology is simple, and energy consumption far below evaporation coating technique, and is beneficial to large-scale production, has application prospect.First use printing technology to deposit electrode layer (top electrode layer) in preparation process, then the filling of perovskite light absorbent is carried out, adopt meso-porous carbon material as skeleton, stablize, not easily deformation occur, in the process of deposition perovskite, mesoporous material layer can not change, make perovskite light absorbent simultaneously and to electrode, there is larger contact area, be conducive to charge-exchange, efficiently avoid the problem may destroyed calcium titanium ore bed and hole transmission layer and product and occur loose contact or short circuit.
Accompanying drawing explanation
Fig. 1 is the vertical view of the perovskite solar cell that embodiment 1 obtains;
Fig. 2 is A-A cross-sectional view in Fig. 1 and Fig. 3;
Fig. 3 is the vertical view of the perovskite solar cell that embodiment 2 obtains;
In figure, the positive pole zone of 1-electro-conductive glass conductive layer, 2-insulating tape, the negative regions of 3-electro-conductive glass conductive layer, 4-barrier layer, the mesoporous layer of 5-, 6-to electrode layer, 7-perovskite light-absorption layer.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment 1
See Fig. 1 and Fig. 2, first, use infrared laser (wavelength 1064 nanometer) the distance insulating tape 2 that wherein cm place, edge 0.8 etching one is parallel with this limit on the FTO electro-conductive glass conductive layer being of a size of 2.0 cm × 2.0 cm, wide 0.05 cm of insulating tape 2, be divided into positive pole zone 1(to be of a size of 0.8 cm × 2.0 cm electro-conductive glass) and negative regions 3(be of a size of 1.2 cm × 2.0 cm), make conductive layer can not conducting completely, the electro-conductive glass after etching uses washing agent, distilled water and absolute ethyl alcohol to carry out ultrasonic cleaning successively.
Then under 450 oC temperature conditions in the negative regions 3 of electro-conductive glass the titanium tetrachloride solution of coating quality concentration 0.05% on the surface, form the barrier layer 4 of the densification of thick layer 22 nanometer.
Get Zirconium dioxide powder that 8g particle diameter is 60 nanometers and 4g ethyl cellulose joins in 30ml terpinol and 15mL ethanolic solution, in planetary ball mill, ball milling took out after 24 hours, evaporative removal ethanol, namely zirconium dioxide slurry is obtained, on above-mentioned barrier layer 4, the zirconium dioxide pulp layer that one deck is of a size of 0.8 cm × 0.8 cm is printed with the zirconium dioxide slurry prepared, be incubated 30 minutes with ramp to 500 oC of 5 oC/ minutes, after sintering, form the mesoporous layer 5 of thick 450 nanometers.
6.5g graphite is mixed with 2g carbon black, adds the zirconium dioxide particle of 2% of graphite carbon black gross mass, they are dispersed in 20g terpinol and 15g ethanol.After ultrasonic 40 minutes, ball milling 24 hours in planetary ball mill, utilizes Rotary Evaporators to be removed by ethanol wherein afterwards, obtains carbon pastes.On above-mentioned mesoporous layer 5, the carbon pastes layer that one deck is of a size of 0.6 cm × 1.1 cm is printed with the carbon pastes prepared, this carbon pastes major part covers on described zirconium dioxide mesoporous layer 5, another part covers in the positive pole zone 1 of electro-conductive glass, be incubated 30 minutes with ramp to 420 oC of 8 oC/ minutes, form the mesoporous graphite carbon black of porous after sintering to electrode layer 6.
Finally, prepare perovskite solution: by lead iodide and iodine methylamine in molar ratio the ratio of 1:1.2 be dissolved in gamma-butyrolacton and obtain perovskite solution; Be printed with mesoporous layer 5 by above-mentioned and be positioned in horizontal thermal station to the electro-conductive glass of electrode layer 6, temperature is set as 70 oC and is incubated; Electrode surface is being applied to the perovskite solution of 10 microlitres, and drying the perovskite light-absorption layer 7 forming thick 9 microns.Namely obtain based on carbon electrode and the perovskite solar cell without hole mobile material structure.
Embodiment 2
See Fig. 3 and Fig. 2, first use wavelength 1064 nanometer laser distance insulating tape 2 that wherein cm place, edge 1.1 etching one is parallel with this limit on the FTO electro-conductive glass conductive layer being of a size of 3.0 cm × 3.0 cm with infrared laser, wide 0.05 cm of insulating tape 2, be divided into positive pole zone 1(to be of a size of 1.1 cm × 3.0 cm electro-conductive glass) and negative regions 3(be of a size of 1.9 cm × 3.0 cm), make conductive layer can not conducting completely, the electro-conductive glass after etching uses washing agent, distilled water and absolute ethyl alcohol to carry out ultrasonic cleaning successively.
Then under 400 oC temperature conditions in the negative regions 3 of electro-conductive glass the titanium tetrachloride solution of coating quality concentration 0.1% on the surface, form the barrier layer 4 of the densification of thick layer 28 nanometer.
Get Zirconium dioxide powder that 8g particle diameter is 80 nanometers and 4g ethyl cellulose joins in 30ml terpinol and 15mL ethanolic solution, in planetary ball mill, ball milling took out after 24 hours, evaporative removal ethanol, namely zirconium dioxide slurry is obtained, on above-mentioned barrier layer 4, the zirconium dioxide pulp layer that one deck is of a size of 1.1 cm × 1.1 cm is printed with the zirconium dioxide slurry prepared, be incubated 30 minutes with ramp to 500 oC of 5 oC/ minutes, after sintering, form thick 550 mesoporous nano layers 5.
6.5g graphite is mixed with 2g carbon black, adds the zirconium dioxide particle of 2% of graphite carbon black gross mass, they are dispersed in 20g terpinol and 15g ethanol.After ultrasonic 40 minutes, ball milling 24 hours in planetary ball mill, utilizes Rotary Evaporators to be removed by ethanol wherein afterwards, obtains carbon pastes.On above-mentioned mesoporous layer 5, the carbon pastes layer that one deck is of a size of 1.1 cm × 1.8 cm is printed with the carbon pastes prepared, this carbon pastes major part covers on described zirconium dioxide mesoporous layer 5, another part covers in the positive pole zone 1 of electro-conductive glass, be incubated 30 minutes with ramp to 420 oC of 8 oC/ minutes, form the mesoporous graphite carbon black of porous after sintering to electrode layer 6.
Finally, prepare perovskite solution: by lead iodide and iodine methylamine in molar ratio the ratio of 1:1.2 be dissolved in gamma-butyrolacton and obtain perovskite solution; Be printed with mesoporous layer 5 by above-mentioned and be positioned in horizontal thermal station to the electro-conductive glass of electrode layer 6, temperature is set as 80 oC and is incubated; Electrode surface is being applied to the perovskite solution of 15 microlitres, and drying and dry the perovskite light-absorption layer 7 forming thick 11 microns.Namely obtain based on carbon electrode and the perovskite solar cell without hole mobile material structure.
Be more than preferred embodiment of the present invention, all changes done according to technical solution of the present invention, when the function produced does not exceed the scope of technical solution of the present invention, all belong to protection scope of the present invention.
Claims (8)
1. a perovskite solar cell, it is characterized in that, this solar cell have electro-conductive glass conductive layer, barrier layer, mesoporous layer, to electrode layer and perovskite light-absorption layer, described electro-conductive glass conductive layer is separated into positive pole zone and negative regions by insulating tape, described barrier layer is coated on the negative regions of described electro-conductive glass conductive layer, described mesoporous layer is positioned on described barrier layer, in described positive pole zone electrode layer being covered in described mesoporous layer, insulating tape and electro-conductive glass conductive layer, described perovskite light-absorption layer is coated on the described outer surface to electrode layer.
2. perovskite solar cell according to claim 1, is characterized in that, the material on described barrier layer is fine and close titanium dioxide; The material of described mesoporous layer is mesoporous ZrO 2; The described material to electrode layer is mesoporous graphite carbon black mixt.
3. perovskite solar cell according to claim 1, is characterized in that, described stop thickness 18-22 nanometer, and described mesoporous thickness 450-550 nanometer is described to electrode thickness 9-11 micron.
4. perovskite solar cell according to claim 1, it is characterized in that, described perovskite light-absorption layer adopts the coating of perovskite solution to form, described perovskite solution is the gamma-butyrolacton solution of lead iodide and iodine methylamine, the molar concentration of lead iodide is 1.0-1.5 mol/L, and the molar concentration of iodine methylamine is 1.2-1.8 mol/L).
5. the preparation method of perovskite solar cell described in the arbitrary claim of claim 1-4, is characterized in that, comprise following concrete steps:
1), etching conductive glass conductive layer: use wavelength is that the infrared laser of 1064 nanometers etches a bar insulation band on electro-conductive glass conductive layer, makes the positive pole zone and the negative regions that conducting glass substrate are formed not conducting mutually;
2), spraying barrier layer: at 400 ~ 450 oC temperature, coating quality concentration is the titanium tetrachloride solution of 0.05-0.10% on the surface in the negative regions of electro-conductive glass, forms the titanium dioxide barrier layer of one deck densification after sintering;
3), mesoporous layer is printed: use screen printing technique, print one deck zirconium dioxide slurry over the barrier layer, in zirconium dioxide slurry, zirconium dioxide particle particle diameter is 60-100 nanometer, is incubated 30 minutes with ramp to 500 oC of 5 oC/ minutes, forms mesoporous layer after printing;
4), print electrode layer: use screen printing technique, the positive pole zone of mesoporous layer, insulating tape and electro-conductive glass conductive layer prints one deck carbon pastes, be incubated 30 minutes with ramp to 420 oC of 8 oC/ minutes after printing, formed electrode layer;
5), perovskite light-absorption layer is applied: the ratio being 1:1.2 in the mol ratio of lead iodide and iodine methylamine will be dissolved in gamma-butyrolacton at lead iodide and iodine methylamine prepares perovskite solution, at 60oC-80oC temperature, to electrode layer outer surface one deck perovskite solution, after oven dry, namely obtain perovskite solar cell.
6. the preparation method of perovskite solar cell according to claim 5, it is characterized in that, the compound method of zirconium dioxide slurry is: Zirconium dioxide powder and the ethyl cellulose of getting particle diameter 60-100 nanometer join in the mixed liquor of terpinol and ethanol, in planetary ball mill, ball milling took out after 24 hours, evaporative removal ethanol, namely obtains zirconium dioxide slurry, wherein, the mass ratio of Zirconium dioxide powder and ethyl cellulose is 2:1, and the volume ratio of terpinol and ethanol is 2:1.
7. the preparation method of perovskite solar cell according to claim 5, it is characterized in that, the compound method of carbon pastes is: mixed with carbon black by graphite, adds the zirconium dioxide particle of 2% of graphite carbon black gross mass, be dispersed in the mixed liquor of terpinol and ethanol, after ultrasonic 40 minutes, ball milling 24 hours in planetary ball mill, evaporative removal ethanol, obtain carbon pastes, wherein, the mass ratio of graphite and carbon black is 13:4, and the volume ratio of terpinol and ethanol is 4:3.
8. the preparation method of perovskite solar cell according to claim 5, is characterized in that, applies operating in horizontal thermal station of perovskite solution and carry out in step 5.
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Cited By (10)
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| CN105140398A (en) * | 2015-07-02 | 2015-12-09 | 南京大学 | Back-contact perovskite solar cell |
| CN105870340A (en) * | 2016-04-19 | 2016-08-17 | 苏州黎元新能源科技有限公司 | Preparation method and application of perovskite thin film |
| CN106098141A (en) * | 2016-07-31 | 2016-11-09 | 武汉理工大学 | A kind of perovskite electric-conducting nickel paste used for solar batteries and preparation method thereof |
| CN107141221A (en) * | 2017-05-11 | 2017-09-08 | 北京大学深圳研究生院 | A kind of perovskite structural material and preparation method thereof, application |
| CN108258120A (en) * | 2018-01-12 | 2018-07-06 | 北京化工大学 | A kind of perovskite solar cell inexpensively stablized and the photoelectrocatalysidevice device of driving |
| CN108408712A (en) * | 2018-03-26 | 2018-08-17 | 厦门大学 | A kind of preparation method and application of carbon black and its carbon electrode |
| CN108922970A (en) * | 2018-06-30 | 2018-11-30 | 浙江浙能技术研究院有限公司 | A kind of mesoporous type perovskite solar battery and preparation method thereof |
| CN110581223A (en) * | 2018-06-11 | 2019-12-17 | 湖北万度光能有限责任公司 | Method for producing solar cell |
| CN110581222A (en) * | 2018-06-11 | 2019-12-17 | 湖北万度光能有限责任公司 | Preparation method of solar cell |
| CN111106246A (en) * | 2019-12-03 | 2020-05-05 | 南京大学 | Solar cell based on thiocyanate ion-containing pseudo-halide perovskite |
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| CN108922970A (en) * | 2018-06-30 | 2018-11-30 | 浙江浙能技术研究院有限公司 | A kind of mesoporous type perovskite solar battery and preparation method thereof |
| CN108922970B (en) * | 2018-06-30 | 2023-03-28 | 浙江浙能技术研究院有限公司 | Mesoporous perovskite solar cell and preparation method thereof |
| CN111106246A (en) * | 2019-12-03 | 2020-05-05 | 南京大学 | Solar cell based on thiocyanate ion-containing pseudo-halide perovskite |
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Application publication date: 20150422 |