CN104157786A - Perovskite type solar battery and preparation method thereof - Google Patents
Perovskite type solar battery and preparation method thereof Download PDFInfo
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- 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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Abstract
The invention discloses a perovskite type solar battery and a preparation method thereof. The perovskite type solar battery comprises a photo-anode, a sensitization layer, a hole transfer layer, and a counter electrode, wherein Cl and Br are doped in the sensitization layer of the perovskite type solar battery; the doping method comprises a two-step method or a three-step method; the doping materials forming the sensitization layer are selected from at least one of PbCl2 and PbBr2. According to the invention, the sensitization material can prevent perovskite from decomposing under the use condition of high temperature to improve the thermal stability of the perovskite and is low in price; the operating method is simple and convenient, the control is easy, and a new idea is provided for the research of the thermal stability of all-solid-state dye-sensitized solar batteries.
Description
Technical field
The invention belongs to chemical field, relate to a kind of solar cell material, be specifically related to a kind of Ca-Ti ore type solar cell and preparation method thereof.
Background technology
After 21 century, economic and society's fast development, the mankind are increasing to the demand of the energy, and energy problem has become the major issue that is related to human survival.Yet traditional fossil fuel (coal, oil, natural gas) is just because constantly a large amount of consumption is increasingly exhausted.The exploitation of renewable new forms of energy contributes to alleviate the pressure of world energy sources and environment, and solar energy is stock number maximum, distribution green regenerative energy sources the most widely.
Solar cell is realized the conversion of luminous energy and electric energy, and its development and utilization is applied solar energy one of the most effective approach.Solar cell volume is little, and conveniently moving is used the restriction that is not subject to region.The application form of solar cell is varied, can make large-scale power station, and realization is generated electricity by way of merging two or more grid systems, and can utilize again less battery component to user from far-off regions life electric energy is provided, or provide electric power safeguard to mobile communication equipment.At present, on market, the solar cell of dominate is mainly monocrystalline silicon and polysilicon solar cell, the production technology comparative maturity of these two kinds of batteries, and the photoelectric conversion efficiency of battery is higher, good stability (useful life is all more than 15 years).But silicon is that solar cell requirement material purity generally will be more than 99.9999%, and complex manufacturing technology, high cost, cannot realize ultra-large practical.
For present stage silicon be the Cost Problems of solar cell, since the nineties in last century, a kind of novel organic--the solar cell-DSSC of inorganic compounding is with low cost with it, prepares the extensive concern that easy feature has caused people.It is also considered to a kind of up-and-coming technology of utilizing solar energy.
1991, Lausanne, SUI Gao Deng engineering institute
professor's scientific research group is by porous TiO
2film is applied in this battery, and the photoelectric conversion efficiency of this battery is greatly improved, and has obtained breakthrough progress
deng, United States Patent (USP), publication number, WO9116719A-31Oct1991;
deng, United States Patent (USP), publication number, US005350644A-27Sep1994).The DSSC of unijunction structure and laminated construction has obtained respectively 11.18% and 15.09% photoelectric conversion efficiency (Progress In Photovoltaics:Research And Applications at present, 2006.V.14.429-442, Applied Physics Letters, 2006.V.88.203103-1-3).Ca-Ti ore type organic-inorganic composition CH
3nH
3pbI
3and derivative, have that band gap is adjustable, molar absorption coefficient is high and the many merits such as spectral absorption scope is wide, be expected to the conventional dyes in substituted dyes sensitization solar battery.
Summary of the invention
The object of this invention is to provide a kind of Ca-Ti ore type solar cell and preparation method thereof.
Ca-Ti ore type solar cell provided by the invention, comprises light anode, sensitizing layer, hole transmission layer and from the bottom to top successively to electrode;
Wherein, described smooth anode forms by described compact film or by described compact film and porous rete, and described porous rete is positioned on described compact film;
Wherein, the material that forms described sensitizing layer is periodo perovskite material CH
3nH
3pbI
3, the perovskite material of chlorine doping or the perovskite material of bromine doping.
In above-mentioned battery, the material that forms described compact film can be TiO
2;
The method that described compact film can provide according to following document is prepared: Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%, H.S.Kim, C.R.Lee, J.H.Im, K.B.Lee, T.Moehl, A.Marchioro, S.J.Moon, R.Humphry-Baker, J.H.Yum, J.E.Moser, M.Gratzel and N.G.Park, Scientific Reports, 2012, 2, 591. concrete steps are: adopt spin-coating method to prepare titanium dioxide dense film, the precursor solution of dense film is filled to conductive glass surface, at rotating speed, be under 3000rpm condition, to get rid of film 30s.After end, immediately film is placed into and on the hot plate that is preheating to 80 degree, heats 30min and be fully hydrolyzed, and at 500 degree, heating 60min.
The thickness of described compact film specifically can be 50nm.
The material that forms described porous rete is TiO
2, Al
2o
3or MgO; The thickness of described porous rete specifically can be 400nm;
Described hole transmission layer specifically can be comprised of following component: spiro-OMeTAD (2,29,7,79-tetrakis (N, N-di-p-methoxyphenylamine)-9,99-spirobifluorene) acetonitrile solution of 0.072g, 4-tert .-butylpyridine 37.5 μ L, two fluoroform sulfimide lithiums (the two fluoroform sulfimide lithiums of 520mg are dissolved in 1ml acetonitrile) 17.5 μ L and chlorobenzene 1mL;
The thickness of described hole transmission layer specifically can be 100nm;
Described is Au/Ag electrode or Au electrode to electrode; Described the thickness of electrode specifically be can be to 60nm
The thickness of described sensitizing layer is 2-500nm; .
In above-mentioned Ca-Ti ore type solar cell, light anode, hole transmission layer and the preparation method of electrode is to conventional method, can and obtain according to existing preparation method's preparation.
Described sensitizing layer also can be the sensitizing layer preparing by the following method.
The invention provides the method for preparing sensitizing layer in the described Ca-Ti ore type solar cell of preparation, be respectively two-step method or three-step approach;
Wherein, two-step method comprises the steps:
By PbCl
2+ PbI
2+ CH
3nH
3i or PbBr
2+ PbI
2+ CH
3nH
3i is scattered in after organic solvent, crosses leaching filtrate and obtains spin coating liquid I, and described spin coating liquid I is spin-coated on described smooth anode, and heating makes, after described organic solvent volatilization, gained film to be soaked in to CH
3nH
3in the aqueous isopropanol of I, react, then heating solvent evaporates is fallen after, obtain described sensitizing layer.
In above-mentioned two-step method, described organic solvent is all selected from least one in DMF, DMSO, ethanol and gamma-butyrolacton;
In described filtration step, the diameter of filter opening is 10-450nm, is specially 220nm;
In described spin coating step, spin coating rotating speed is 1500-7000rpm, is specially 5000rpm; Time is 20s-120s, is specially 60s.
Described spin coating liquid I specifically can be the spin coating liquid that organic solvent is DMF;
In described spin coating liquid I, PbCl
2concentration be 5-100mgml
-1, be specially 87.3mgml
-1;
PbI
2concentration be 250-550mgml
-1, be specially 400mgml
-1;
CH
3nH
3the concentration of I is 10-100mgml
-1, be specially 50mgml
-1;
CH
3nH
3the concentration of the aqueous isopropanol of I is 2-50mgml
-1, be specially 10-50mgml
-1.
Three-step approach comprises the steps:
By PbCl
2or PbBr
2be scattered in after organic solvent, cross leaching filtrate and obtain spin coating liquid II, more described spin coating liquid II is spin-coated on described smooth anode, heating makes after described organic solvent volatilization, then continues to use PbI
2solution gets rid of film, and gained film is soaked in to CH
3nH
3in the aqueous isopropanol of I, react, then heating solvent evaporates is fallen after, obtain described sensitizing layer.
In above-mentioned three-step approach, described organic solvent is all selected from least one in DMF, DMSO, ethanol and gamma-butyrolacton;
In described filtration step, the diameter of filter opening is 10-450nm, is specially 220nm;
In described spin coating step, spin coating rotating speed is 1500-7000rpm, is specially 5000rpm; Time is 20s-120s, is specially 60s.
Described spin coating liquid II specifically can be the spin coating liquid that organic solvent is DMF;
In described spin coating liquid II, PbCl
2or PbBr
2concentration be 5-100mgml
-1, be specifically 25mgml
-1;
Described PbI
2in solution, solvent is selected from least one in DMF, DMSO, ethanol and gamma-butyrolacton;
Described PbI
2in solution, PbI
2concentration be 250-550mgml
-1, be specially 463mgml
-1;
CH
3nH
3the concentration of the aqueous isopropanol of I is 2-50mgml
-1, be specially 150mgml
-1.
The course of reaction of above-mentioned two-step method and three-step approach is as follows:
xPbCl
2+(1-x)PbI
2+CH
3NH
3I＝＝＝CH
3NH
3PbCl
2xI
3-2x
xPbBr
2+(1-x)PbI
2+CH
3NH
3I＝＝＝CH
3NH
3PbBr
2xI
3-2x
Side reaction: PbCl
2+ 3CH
3nH
3i===CH
3nH
3pbI
3+ 2CH
3nH
3cl
PbCl
2+3CH
3NH
3I＝＝＝PbI
2+CH
3NH
3I+2CH
3NH
3Cl
The present invention, in existing all-solid-state dye-sensitized solar cell structure, has changed the composition as the sensitizing layer of extinction material of main part, in it forms, has mixed a small amount of Cl and Br element, has improved the atom matching degree of perovskite crystalline lattice and the thermal stability of material.And this based sensitisers material price is cheap, method of operation is easy, easily controls.Such sensitized material provides new thinking for all-solid-state dye-sensitized solar cell improves thermal stability.In a word, the present invention is photoelectric conversion efficiency and the thermal stability of boost device significantly, and with low cost, significant for the practical application of all-solid-state dye-sensitized solar cell.
Accompanying drawing explanation
Fig. 1 is that blank battery 1 is to the J-V curve of all solid state sensitization solar battery device of blank battery 3 and embodiment 1 to embodiment 6.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
PbI used in following embodiment
2purity be 98%-99.999%; Be specially 99.9985%;
PbCl
2purity be 98%-99.999%; Be specially 99.999%;
PbBr
2purity be 98%-99.999%; Be specially 99.98%;
CH
3nH
3the purity of I is more than 97%; Specifically according to document 6.5%efficient perovskite quantum-dot-sensitized solar cell.J.H.Im, C.R.Lee, J.W.Lee, S.W.Park and N.G.Park, Nanoscale, 2011,3,4088 – 4093 synthesize and purify, and purity reaches more than 98%;
The purity of DMF is 98%-99.999%; Be specially 99.9%, super dry;
The purity of isopropyl alcohol is 98%-99.999%; Be specially 99.9%.
Whether all raw materials all can be bought and obtain from open commercial sources.
Reference examples 1, one-step method are prepared unadulterated TiO
2the all solid state sensitization solar battery of light anode (being also control cell 1)
1) prepare light anode
The preparation of a, compact film:
The method that can provide according to following document is prepared: Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%, H.S.Kim, C.R.Lee, J.H.Im, K.B.Lee, T.Moehl, A.Marchioro, S.J.Moon, R.Humphry-Baker, J.H.Yum, J.E.Moser, M.Gratzel and N.G.Park, Scientific Reports, 2012,2,591. concrete steps are:
Adopting spin-coating method to prepare titanium dioxide dense film, the precursor solution of dense film is filled to conductive glass surface, is under 3000rpm condition, to get rid of film 30s at rotating speed.After end, immediately film is placed into and on the hot plate that is preheating to 80 degree, heats 30min and be fully hydrolyzed, and at 500 degree, heating 60min.The thickness 50nm of compact film.
The preparation of b, porous rete:
Perforated membrane comprises TiO
2, MgO, Al
2o
3three kinds of perforated membranes.
I. according to conventional method, be prepared TiO
2the method that perforated membrane can provide according to following document is prepared: Sequential deposition as a route to high-performanceperovskite-sensitized solar cells, J.Burschka, N.Pellet, S.Moon, R.H.Baker, P.Gao, M.K.Nazeeruddin, M.Graetze, Nature, 2013,499,316. concrete steps are:
Acid process slurry is used absolute ethyl alcohol according to mass ratio 1/3 dilution, and perforated membrane slurry is coated on the film surface that step a obtains, and rotating speed is spin coating 30s under 7000rpm condition.After end, by film transfer, to hot plate, 500 degree heat 60min, and the thickness of porous rete is 400nm.
Ii. according to conventional method, be prepared Al
2o
3the method that perforated membrane can provide according to following document is prepared: Efficient hybrid solar cells based on meso-superstructuredorganometalhalideperovskites, M.M.Lee, J.Teuscher, T.Miyasaka, T.N.Murakami and H.J.Snaith, Science, 2012,338,643-647. concrete steps are:
The Al that is 30-40nm by the particle diameter of purchase
2o
3particle is dispersed in ethanol solution, by document addition, adds after terpinol, ethyl cellulose and stirs and ultrasonic dispersion, revolves to steam to obtain Al
2o
3original slurry.Use absolute ethyl alcohol according to mass ratio 1/1.5 dilution gained slurry, perforated membrane slurry is coated on to the film surface that step a obtains, rotating speed is spin coating 30s under 7000rpm condition.After end, by film transfer, to hot plate, 500 degree heat 60min, and the thickness of porous rete is 400nm.
Iii. according to conventional method, be prepared, the preparation process of MgO perforated membrane is as follows:
With above-mentioned Al
2o
3the preparation method of original slurry is identical, with the MgO particle that the particle diameter of buying is 30-40nm, prepare the original slurry of MgO, according to using absolute ethyl alcohol according to mass ratio 1/2 dilution, perforated membrane slurry is coated on the film surface that step a obtains, and rotating speed is spin coating 30s under 7000rpm condition.After end, by film transfer, to hot plate, 500 degree heat 60min, and the thickness of porous rete is 400nm.
2) preparation of sensitizing layer:
By the presoma PbI of perovskite
2according to 463mgml
-1concentration be dissolved in DMF, the film surface that solution coat obtains to step b, is 5000rpm at rotating speed during spin coating, the time is 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree, be cooled to room temperature, be immersed in CH
3nH
360s in the aqueous isopropanol of I, and rinse with isopropyl alcohol, brownish black film obtained.Two-step method is prepared film forming.Be placed on the hot plate of 70 ℃ and heat 30min, obtain sensitizing layer.
3) prepare hole transmission layer
In step 2) surperficial spin coating one deck hole transmission layer of gained sensitizing layer, during spin coating, adopt 1s to accelerate to 4000rpm, keep 30s, spin coating finishes rear placement and spends the night, the material that forms hole transmission layer is fully permeated, and the thickness of this hole transmission layer of gained is 100nm;
Wherein, hole transmission layer is comprised of by proportioning various components, specific as follows: spiro-OMeTAD (2,29,7,79-tetrakis (N, N-di-p-methoxyphenylamine)-9,99-spirobifluorene) acetonitrile solution of 0.072g, 4-tert .-butylpyridine 37.5 μ L, two fluoroform sulfimide lithiums (the two fluoroform sulfimide lithiums of 520mg are dissolved in 1ml acetonitrile) 17.5 μ L and chlorobenzene 1mL.
4) preparation is to electrode
In step 4) vacuum evaporation gold on gained hole transmission layer, evaporation rate is
vacuum degree is at 1.0*10
-3below Pa, gold electrode thickness is 60nm, obtains Ca-Ti ore type solar cell (being control cell 1).
At AM1.5,100mWcm
-2under illumination, with ZAHNER CIMPS, carry out the J-V performance curve of test battery, as shown in Fig. 1 curve b, the short-circuit current density that obtains battery is 16.8mAcm
-2, open circuit voltage is 0.74V, and fill factor, curve factor is 0.72, and photoelectric conversion efficiency is 8.76%.
Reference examples 2, one-step method are prepared the TiO of Cl doping
2the all solid state sensitization solar battery of light anode (being also control cell 2)
According to the step of reference examples 1, only by step 2) experimental technique make following change:
The presoma of perovskite is by PbCl
2and CH
3nH
3the DMF of I (DMF) mixed solution forms, wherein PbCl
2concentration is 87.3mgml
-1, CH
3nH
3i concentration is 150mgml
-1.The film surface that solution coat obtains to step b, spin coating rotating speed is 1500rpm, the time is 30s.One step completes into film preparation.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 100 degree, be cooled to room temperature, obtain sensitizing layer.
At AM1.5,100mWcm
-2under illumination, with the J-V performance curve of KEITHLEY 4200 these batteries of test, as shown in fig. 1, the short-circuit current density that obtains battery is 22.0mAcm
-2, open circuit voltage is 0.74V, and fill factor, curve factor is 0.55, and photoelectric conversion efficiency is 8.79%.
Reference examples 3, one-step method are prepared the TiO of Br doping
2the all solid state sensitization solar battery of light anode (being also control cell 3)
According to the step of control cell 1, only by step 2) experimental technique make following change.PbBr
2and CH
3nH
3the DMF of I (DMF) mixed solution, wherein PbBr
2concentration is 87.3mgml
-1, CH
3nH
3i concentration is 150mgml
-1.The film surface that solution coat obtains to step b, spin coating rotating speed is 1500rpm, the time is 30s.One-step method is prepared film forming.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 100 degree, be cooled to room temperature, obtain sensitizing layer.
At AM1.5,100mWcm
-2under illumination, with the J-V performance curve of KEITHLEY 4200 these batteries of test, as shown in fig. 1, the short-circuit current density that obtains battery is 18.3mAcm
-2, open circuit voltage is 0.88V, and fill factor, curve factor is 0.52, and photoelectric conversion efficiency is 8.30%.
Embodiment 1, two-step method are prepared the TiO of Cl doping
2the all solid state sensitization solar battery of light anode
According to the step of reference examples 2, only by step 2) experimental technique make following change:
PbCl
2, PbI
2and CH
3nH
3the DMF mixed solution of I, wherein PbCl
2concentration is 87.3mgml
-1, PbI
2concentration is 400mgml
-1, CH
3nH
3i concentration is 50mgml
-1.The film surface that solution coat obtains to step b, spin coating rotating speed is 5000rpm, the time is 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree, be cooled to room temperature, be immersed in 10mgml
-1cH
3nH
360s in the aqueous isopropanol of I, and rinse with isopropyl alcohol, brownish black film obtained.Two-step method is prepared film forming.Be placed on the hot plate of 70 ℃ and heat 30min, obtain sensitizing layer.
At AM1.5,100mWcm
-2under illumination, with the J-V performance curve of KEITHLEY 4200 these batteries of test, as shown in fig. 1, the short-circuit current density that obtains battery is 20.8mAcm
-2, open circuit voltage is 0.82V, and fill factor, curve factor is 0.59, and photoelectric conversion efficiency is 10.1%.
Embodiment 2, two-step method are prepared the TiO of Br doping
2the all solid state sensitization solar battery of light anode
According to the step of reference examples 3, only by step 2) experimental technique make following change.PbBr
2, PbI
2and CH
3nH
3the DMF mixed solution of I, wherein PbBr
2concentration is 87.3mgml
-1, PbI
2concentration is 400mgml
-1, CH
3nH
3i concentration is 50mgml
-1.The film surface that solution coat obtains to step b, spin coating rotating speed is 5000rpm, the time is 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree, be cooled to room temperature, be immersed in 10mgml
-1cH
3nH
360s in the aqueous isopropanol of I, and rinse with isopropyl alcohol, brownish black film obtained.Two-step method is prepared film forming.Be placed on the hot plate of 70 ℃ and heat 30min, obtain sensitizing layer.
At AM1.5,100mWcm
-2under illumination, with the J-V performance curve of KEITHLEY 4200 these batteries of test, as shown in fig. 1, the short-circuit current density that obtains battery is 22.9mAcm
-2, open circuit voltage is 0.81V, and fill factor, curve factor is 0.53, and photoelectric conversion efficiency is 9.83%.
Embodiment 3, three-step approach are prepared the TiO of Cl doping
2the all solid state sensitization solar battery of light anode
According to the step of reference examples 2, only by step 2) experimental technique make following change.PbCl
2dMF solution, PbCl
2concentration is 25mgml
-1.The film surface that solution coat obtains to step b, spin coating rotating speed is 5000rpm, the time is 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree.Use PbI
2concentration is 463mgml
-1dMF solution, 5000rpm gets rid of film 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree.Be cooled to room temperature, and be immersed in CH
3nH
360s in the aqueous isopropanol of I, and rinse with isopropyl alcohol, brownish black film obtained.Three-step approach is prepared film forming.Be placed on the hot plate of 70 ℃ and heat 30min, obtain sensitizing layer.
At AM1.5,100mWcm
-2under illumination, with KEITHLEY4200, test the J-V performance curve of this battery, as shown in fig. 1, the short-circuit current density that obtains battery is 23.9mAcm
-2, open circuit voltage is 0.82V, and fill factor, curve factor is 0.67, and photoelectric conversion efficiency is 13.3%.
Embodiment 4, three-step approach are prepared the TiO of Br doping
2the all solid state sensitization solar battery of light anode
According to the step of reference examples 3, only by step 2) experimental technique make following change.PbBr
2dMF solution, PbBr
2concentration is 25mgml
-1.The film surface that solution coat obtains to step b, spin coating rotating speed is 5000rpm, the time is 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree.Use PbI
2concentration is 463mgml
-1dMF solution, 5000rpm gets rid of film 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree.Be cooled to room temperature, and be immersed in CH
3nH
360s in the aqueous isopropanol of I, and rinse with isopropyl alcohol, brownish black film obtained.Three-step approach is prepared film forming.Be placed on the hot plate of 70 ℃ and heat 30min, obtain sensitizing layer.
At AM1.5,100mWcm
-2under illumination, with KEITHLEY4200, test the J-V performance curve of this battery, as shown in fig. 1, the short-circuit current density that obtains battery is 21.5mAcm
-2, open circuit voltage is 0.75V, and fill factor, curve factor is 0.60, and photoelectric conversion efficiency is 9.58%.
Embodiment 5, three-step approach are prepared the Al of Cl doping
2o
3the all solid state sensitization solar battery of light anode
According to the step of reference examples 2, by TiO
2light anode changes Al into
2o
3light anode, and to step 2) experimental technique is made following change.PbCl
2dMF solution, PbCl
2concentration is 25mgml
-1.The film surface that solution coat obtains to step b, spin coating rotating speed is 5000rpm, the time is 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree.Use PbI
2concentration is 463mgml
-1dMF solution, 5000rpm gets rid of film 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree.Be cooled to room temperature, and be immersed in CH
3nH
360s in the aqueous isopropanol of I, and rinse with isopropyl alcohol, brownish black film obtained.Three-step approach is prepared film forming.Be placed on the hot plate of 70 ℃ and heat 30min, obtain sensitizing layer.
At AM1.5,100mWcm
-2under illumination, with KEITHLEY4200, test the J-V performance curve of this battery, as shown in fig. 1, the short-circuit current density that obtains battery is 22.0mAcm
-2, open circuit voltage is 0.88V, and fill factor, curve factor is 0.52, and photoelectric conversion efficiency is 9.88%.
Embodiment 6, three-step approach are prepared all solid state sensitization solar battery of MgO light anode of Cl doping
According to the step of reference examples 2, by TiO
2light anode changes MgO light anode into, and to step 2) experimental technique make following change.PbCl
2dMF solution, PbCl
2concentration is 25mgml
-1.The film surface that solution coat obtains to step b, spin coating rotating speed is 5000rpm, the time is 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree.Use PbI
2concentration is 463mgml
-1dMF solution, 5000rpm gets rid of film 60s.After end, immediately film transfer is heated after 30min to being warmed up in advance on the hot plate of 70 degree.Be cooled to room temperature, and be immersed in CH
3nH
360s in the aqueous isopropanol of I, and rinse with isopropyl alcohol, brownish black film obtained.Three-step approach is prepared film forming.Be placed on the hot plate of 70 ℃ and heat 30min, obtain sensitizing layer.
At AM1.5,100mWcm
-2under illumination, with KEITHLEY4200, test the J-V performance curve of this battery, as shown in fig. 1, the short-circuit current density that obtains battery is 20.4mAcm
-2, open circuit voltage is 0.88V, and fill factor, curve factor is 0.55, and photoelectric conversion efficiency is 9.86%.
The J-V parameter of all solid state sensitization solar battery device of table 1, blank battery, embodiment 1 to embodiment 6
| ? | J SC/mA?cm -2 | V OC/V | PCE | FF |
| Control cell 1 | 16.8 | 0.74 | 8.76％ | 0.72 |
| Control cell 2 | 22.0 | 0.74 | 8.79％ | 0.55 |
| Control cell 3 | 18.3 | 0.88 | 8.30％ | 0.52 |
| Embodiment 1 | 20.8 | 0.82 | 10.1％ | 0.59 |
| Embodiment 2 | 22.9 | 0.81 | 9.83％ | 0.53 |
| Embodiment 3 | 23.9 | 0.82 | 13.3％ | 0.67 |
| Embodiment 4 | 21.5 | 0.75 | 9.58％ | 0.60 |
| Embodiment 5 | 22.0 | 0.88 | 9.88％ | 0.52 |
| Embodiment 6 | 20.4 | 0.88 | 9.86％ | 0.55 |
As from the foregoing, after Cl and Br doping treatment by two-step method and three-step approach, the short circuit current of device generally improves, and improves the thermally-stabilised raising of device after doping mainly due to device temperature in test process.The doping method of two-step method and three-step approach is compared performance with traditional periodo two-step method with doping one-step method remarkable lifting.Open circuit voltage also has the raising of certain limit, the photovoltaic performance index of comprehensive above device, and the electricity conversion of device improves.
The stability that all solid state sensitization solar battery of table 2, blank battery, embodiment 1 to embodiment 6 is modified device efficiency
| ? | PCE-40℃ | PCE-150℃ | Efficiency conservation rate |
| Control cell 1 | 8.76％ | 0.56％ | 6.4％ |
| Control cell 2 | 8.79％ | 4.3％ | 48.9％ |
| Control cell 3 | 8.30％ | 5.1％ | 61.5％ |
| Embodiment 1 | 10.1％ | 6.7％ | 66.3％ |
| Embodiment 2 | 9.83％ | 5.9％ | 60.0％ |
| Embodiment 3 | 13.3％ | 9.7％ | 72.9％ |
| Embodiment 4 | 9.58％ | 7.1％ | 74.1％ |
| Embodiment 5 | 9.88％ | 6.8％ | 68.8％ |
| Embodiment 6 | 9.86％ | 7.9％ | 80.1％ |
As from the foregoing, after Cl and Br doping treatment, the stability of device efficiency generally improves, mainly due to Cl and Br atom doped after, the matching degree of perovskite crystalline lattice improves, and causes the thermal stability of crystal to improve, thereby the stability of device is improved.Meanwhile, use the sensitizing layer that doping method obtains to use at Al
2o
3with on MgO light anode, can obtain equally the good perovskite solar cell of stability.
Claims (9)
1. a Ca-Ti ore type solar cell, comprises light anode, sensitizing layer, hole transmission layer and from the bottom to top successively to electrode;
Wherein, described smooth anode forms by compact film or by compact film and porous rete, and described porous rete is positioned on described compact film;
It is characterized in that: the material that forms described sensitizing layer is periodo perovskite material CH
3nH
3pbI
3, the perovskite material of chlorine doping or the perovskite material of bromine doping.
2. battery according to claim 1, is characterized in that: the material that forms described porous rete is TiO
2, Al
2o
3or MgO;
Described is Au/Ag electrode or Au electrode to electrode;
The thickness of described sensitizing layer is 2-500nm.
3. battery according to claim 1 and 2, is characterized in that: described sensitizing layer is for obtaining according to the arbitrary described method preparation of claim 4-9.
4. a method of preparing sensitizing layer in the arbitrary described Ca-Ti ore type solar cell of claim 1-3, comprises the steps:
By PbCl
2+ PbI
2+ CH
3nH
3i or PbBr
2+ PbI
2+ CH
3nH
3i is scattered in after organic solvent, crosses leaching filtrate and obtains spin coating liquid I, and described spin coating liquid I is spin-coated on described smooth anode, and heating makes, after described organic solvent volatilization, gained film to be soaked in to CH
3nH
3in the aqueous isopropanol of I, react, then heating solvent evaporates is fallen after, obtain described sensitizing layer.
5. method according to claim 4, is characterized in that: described organic solvent is all selected from least one in DMF, DMSO, ethanol and gamma-butyrolacton;
In described filtration step, the diameter of filter opening is 10-450nm, is specially 220nm;
In described spin coating step, spin coating rotating speed is 1500-7000rpm, is specially 5000rpm; Time is 20s-120s, is specially 60s.
6. according to the method described in claim 4 or 5, it is characterized in that: described spin coating liquid I is that organic solvent is the spin coating liquid of DMF;
In described spin coating liquid I, PbCl
2concentration be 5-100mgml
-1, be specially 87.3mgml
-1;
PbI
2concentration be 250-550mgml
-1, be specially 400mgml
-1;
CH
3nH
3the concentration of I is 10-100mgml
-1, be specially 50mgml
-1;
CH
3nH
3the concentration of the aqueous isopropanol of I is 2-50mgml
-1, be specially 10-50mgml
-1.
7. a method of preparing sensitizing layer in the arbitrary described Ca-Ti ore type solar cell of claim 1-3, comprises the steps:
By PbCl
2or PbBr
2be scattered in after organic solvent, cross leaching filtrate and obtain spin coating liquid II, more described spin coating liquid II is spin-coated on described smooth anode, heating makes after described organic solvent volatilization, then continues to use PbI
2solution gets rid of film, and gained film is soaked in to CH
3nH
3in the aqueous isopropanol of I, react, then heating solvent evaporates is fallen after, obtain described sensitizing layer.
8. method according to claim 7, is characterized in that: described organic solvent is all selected from least one in DMF, DMSO, ethanol and gamma-butyrolacton;
In described filtration step, the diameter of filter opening is 10-450nm, is specially 220nm;
In described spin coating step, spin coating rotating speed is 1500-7000rpm, is specially 5000rpm; Time is 20s-120s, is specially 60s.
9. according to the method described in claim 7 or 8, it is characterized in that: described spin coating liquid II is that organic solvent is the spin coating liquid of DMF;
In described spin coating liquid II, PbCl
2or PbBr
2concentration be 5-100mgml
-1, be specifically 25mgml
-1;
Described PbI
2in solution, solvent is selected from least one in DMF, DMSO, ethanol and gamma-butyrolacton;
Described PbI
2in solution, PbI
2concentration be 250-550mgml
-1, be specially 463mgml
-1;
CH
3nH
3the concentration of the aqueous isopropanol of I is 2-50mgml
-1, be specially 150mgml
-1.
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