CN104900809A - Carbon counter electrode perovskite solar cell and manufacturing method thereof - Google Patents
Carbon counter electrode perovskite solar cell and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a carbon counter electrode perovskite solar cell. The cell includes a photoanode, a counter electrode and a cavity transmission layer. The counter electrode is carbon cloth, which sequentially undergoes NiO precursor mixed solution dipping processing and reaction processing, so the cavity transmission layer formed by NiO nanosheets is evenly and densely adhered to the carbon cloth. The carbon cloth is embedded to a TiO2 porous layer in the photoanode. Provided is alto a method of manufacturing a carbon counter electrode perovskite solar cell. The method includes the steps: preparing a cavity transmission layer, performing dipping processing on carbon cloth in a precursor mixed solution, performing reaction processing, and placing the carbon cloth to which the precursor mixed solution is adhered in a high-pressure reaction vessel for reaction; then taking out the carbon cloth, and cleaning and drying the carbon cloth; and finally performing annealing processing, and obtaining the carbon cloth to which the cavity transmission layer is adhered. Contact areas among layers in the cell are effectively increased, and the photoelectric conversion efficiency is finally improved.
Description
Technical field
The invention belongs to technical field of micro-nano manufacture, be specifically related to a kind of 3D half built-in carbon to electrode perovskite solar cell and preparation method thereof.
Background technology
Perovskite solar cell is a kind of novel solar battery, is the nova of photovoltaic art that DSSC develops of continuing.It adopts the organic-metallic halide with perovskite structure as the light-sensitive material of battery.This material has the wide absorption spectrum covering visible wavelength range, and has outstanding advantages in opto-electronic conversion performance.Perovskite material can adopt solution to prepare, and its technique is simple, can reduce the process costs preparing solar cell.Perovskite solar cell was produced out beginning from 2009, electricity conversion has risen to 20.4% from initial 3.8%, its theoretical electricity conversion reaches as high as 50%, being 2 times of the solar cell transformation efficiency sold in the market, is current very one of promising photovoltaic technology of tool.
At present, preparing the method for perovskite solar cell to electrode is: adopt electron beam evaporation technique to plate one deck gold or silver to collect the hole that illumination excites generation at battery surface.Electron beam evaporation technique needs high vacuum degree, adds the continuous consumption of Precious Metals-Gold and silver, makes solar cell preparation cost higher, hinder the popularization of battery, be unfavorable for the large-scale development of battery.
Carbon is rich content in the earth's crust, and with gold and silver have close work function, in theory can with carbon replace gold, silver as perovskite solar cell to electrode.2013, the grand seminar of Central China University of Science and Technology Korea Spro propose first using material with carbon element as to application of electrode in perovskite solar cell, and achieve the electricity conversion of 6.64%.Follow-up its improves perovskite and battery structure again and achieves the electricity conversion of 12.8%, and its achievement is published on " SCIENCE " periodical in July, 2014.Simultaneously, other seminars many have also made many effort at carbon to electrode perovskite area of solar cell.In April, 2014, Qingbo professor Meng of the Chinese Academy of Sciences proposes a kind of full carbon without hole mobile material to electrode perovskite solar cell, and obtains the electricity conversion of 10.2%.Similar, in August in the same year, the Tingli Ma seminar of Dalian University of Technology improves commercial electroconductive carbon pastes, makes it be applicable to the preparation of perovskite solar cell to electrode, and achieves the electricity conversion of 9.08%.Meanwhile, carbon nano-tube film prepared by Subodh G.Mhaisalkar seminar realization CVD as perovskite solar cell to electrode, and achieve the electricity conversion of 9.90%.
But, the solar cell of this carbon to electrode belongs to the structure of the heterogeneous joint of a kind of plane, the contact between layers of this structure to battery requires high, the conductive carbon film prepared by conductive carbon pastes screen printing mode is owing to being subject to the impact of graphite granule, its usual indentation in contact interface place, limit the collection of photo-generated carrier, photogenerated current and fill factor, curve factor can be affected greatly, finally can affect its electricity conversion, this efficiency being also this type of battery reaches temporarily also fails to surmount gold, silver is as the electricity conversion reached the battery of electrode.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of half built-in carbon to electrode perovskite solar cell and preparation method thereof, its object is to, adopt carbon cloth as to electrode, this carbon cloth is successively through NiO precursor mixed solution impregnation process and reaction treatment, thus make the hole transmission layer that attachment NiO nanometer sheet evenly dense on every root fiber of carbon cloth is formed, correspondingly improve perovskite solar cell hole-transporting layer, the contact area of sensitizing layer, to solve in prior art carbon thus to the contact interface indentation of the solar cell of electrode, thus limit the technical problem of photo-generated carrier collection.
For achieving the above object, according to one aspect of the present invention, provide a kind of carbon to electrode perovskite solar cell, it comprise conductive substrates, light anode, to electrode and be all positioned at light anode and to interelectrode hole transmission layer and sensitizing layer, described smooth anode comprises TiO
2compacted zone and TiO
2porous layer, described is carbon cloth to electrode, and this carbon cloth successively through NiO precursor mixed solution impregnation process and reaction treatment, thus makes the hole transmission layer that attachment evenly dense on this carbon cloth is made up of NiO nanometer sheet; Described carbon cloth is embedded in the TiO of described smooth anode
2in porous layer; Described sensitizing layer is periodo perovskite or chlorine adulterated with Ca and Ti ore.
In above inventive concept, carbon cloth is successively through NiO precursor mixed solution impregnation process and reaction treatment, thus make the hole transmission layer that attachment NiO nanometer sheet evenly dense on every root fiber of carbon cloth is formed, formed using carbon cloth as the main body to electrode, and the micro-nano hierarchy of one of grown on carbon fibers NiO nanometer sheet at carbon cloth.This structure has larger specific area, in cell manufacturing process, in the nanocrystalline gap effectively penetrated between structure of perovskite, can improve perovskite light-sensitive material preferably and to the contact situation between electrode.
Preferably, described TiO
2porous layer thickness is 500nm ~ 5 μm, described TiO
2dense layer thickness is 20nm ~ 40nm.
Preferably, described precursor mixed solution is for include 9 ~ 11mmol/L NiCl simultaneously
26H
2o, 30 ~ 50mmol/L CO (NH
2)
2and 15 ~ 25mmol/L NH
4the aqueous solution of F.
Preferably, described conductive substrates refers to that surface sputtering has the glass of tin indium oxide (ITO) or Fluorin doped tin ash (FTO).
According to second aspect of the present invention, provide and a kind ofly prepare the method for carbon described above to electrode perovskite solar cell, it is characterized in that, comprise the steps:
Hole transmission layer preparation process: in precursor mixed solution, impregnation process is performed to clean carbon cloth; Then perform reaction treatment, inserted in autoclave by the carbon cloth being stained with described raw material mixed solution and react, reaction temperature is 120 DEG C ~ 140 DEG C, and the reaction time is 7h ~ 10h; Then take out carbon cloth from autoclave to carry out cleaning and drying; Finally perform annealing in process, obtain the carbon cloth being attached with hole transmission layer;
Light anode preparation process: first prepare TiO in conductive substrates
2compacted zone, then prepare TiO
2porous layer;
To electrode preparation process: at TiO
2before porous layer drying, by the carbon cloth press-in TiO prepared through hole transmission layer preparation process
2in porous layer, form carbon cloth and be embedded in TiO
2the intermediate structure of porous layer, performs annealing in process to intermediate structure, obtains battery intermediary device;
The preparation process of sensitizing layer: first make the carbon cloth of described battery intermediary device floods sensitizing layer starting material solution, and make this sensitizing layer starting material solution penetrate into TiO through the carbon cloth of intermediary device
2porous layer, then performs reaction treatment, to obtain the sensitizing layer of periodo perovskite or chlorine adulterated with Ca and Ti ore.
In above inventive concept, perform impregnation process to clean carbon cloth in precursor mixed solution, precursor mixed solution is 9 ~ 11mmol/L NiCl
26H
2o, 30 ~ 50mmol/L CO (NH
2)
2and 15 ~ 25mmol/L NH
4the aqueous solution of F, then react in autoclave, reaction temperature is 120 DEG C ~ 140 DEG C, reaction time is 7h ~ 10h, first flood, on the every root carbon fiber that ensure that carbon cloth, to be stained with presoma easy for dipping, after control reaction condition and temperature, can nano level NiO sheet be obtained, and ensure that nano NiO sheet and carbon cloth together constitute a kind of micro-nano hierarchy of three-dimensional.
Further, in hole transmission layer preparation process, the temperature of annealing in process is 340 DEG C ~ 360 DEG C, and annealing time is 1.5 ~ 2.5h.Hole transmission layer is annealed, and makes NiO nanometer sheet single crystallization.
Further, in light anode preparation process, screen printing mode is adopted to prepare TiO
2porous layer.
Further, in the preparation process of sensitizing layer, adopt one-step method to prepare the sensitizing layer of periodo perovskite or chlorine adulterated with Ca and Ti ore, described one-step method is:
First make in the carbon cloth dipping sensitizing layer starting material solution of described battery intermediary device, this sensitizing layer starting material solution penetrates into TiO through the carbon cloth of intermediary device
2in porous layer, then dry at 60 DEG C ~ 70 DEG C, complete sensitizing layer preparation;
Described sensitizing layer starting material solution comprises CH
3nH
3i and PbI
2mol ratio is the gamma-butyrolacton mixed solution of 1:1, and CH
3nH
3i and PbI
2the quality of having reacted the perovskite of rear acquisition accounts for 39 ~ 42% of whole solution quality;
Described sensitizing layer starting material solution also comprises CH
3nH
3i and PbCl
2mol ratio is dimethyl formamide (DMF) mixed solution of 3:1, and CH
3nH
3i and PbCl
2what reaction terminated that the quality of the chlorine adulterated with Ca and Ti ore of rear acquisition accounts for whole solution quality is 40 ~ 44%.
Further, in the preparation process of sensitizing layer, adopt two step method to prepare the sensitizing layer of periodo perovskite or chlorine adulterated with Ca and Ti ore, described two step method is:
First the PbI of 450 ~ 480mgml-1 is configured respectively
2dimethyl formamide solution and the CH of 9 ~ 11mgml-1
3nH
3the aqueous isopropanol of I; Then 80 ~ 100 μ LPbI are got
2dimethyl formamide solution drip in the battery between the carbon cloth surfaces of device, treat that its spontaneous carbon cloth through intermediary device penetrates into TiO
2after in porous layer, dry at 60 DEG C ~ 70 DEG C; Then the battery intermediary device after oven dry is inserted in aqueous isopropanol and infiltrate; Finally take out battery intermediary device, and insert containing CH
3nH
310min ~ 15min in the aqueous isopropanol of I.
In general, the above technical scheme conceived by the present invention compared with prior art, can obtain following beneficial effect:
1, adopt and as carbon, prepared by perovskite solar cell to electrode by the carbon cloth of carbon fiber knit, carbon cloth is tridimensional network, its conductivity is strong, flexible, carbon cloth is through solution impregnation process and reaction treatment, can be used as substrate deposition hole transmission layer, the carbon fiber of carbon cloth is prepared the hole transmission layer of NiO nanometer sheet as solar cell, nanometer sheet is evenly dense to be attached on every root carbon fiber of carbon cloth, carbon cloth and NiO nanometer sheet is made to together constitute a kind of micro-nano hierarchy of three-dimensional, such structural rate surface area is large, perovskite high adsorption capacity, can well improve contact condition between heterogeneous joint, thus overcome the solar cell of carbon to electrode in prior art and belong to the structure of the heterogeneous joint of plane, its contact interface indentation, thus limit the problem of the collection of photo-generated carrier.
2, on the carbon fiber of carbon cloth, the hole transmission layer of NiO nanometer sheet as solar cell is prepared, can by controlling reaction condition, reaction temperature is made to be 120 DEG C ~ 140 DEG C, reaction time is 7h ~ 10h, thus nanometer sheet pattern can be controlled preferably, improve the contact area of hole transmission layer and sensitizing layer, correspondingly improve electricity conversion, and its preparation method is simple, one-step method or two-step method is adopted to prepare perovskite sensitizing layer, method is simple, can prepare by solution, and the large area being applicable to battery is produced.
The THICKNESS CONTROL of 3.TiO2 porous membrane is in 500nm ~ 5 μm, and test proves, such thickness range can preferably for supporting carbon to electrode and perovskite sensitizing layer.
Accompanying drawing explanation
Fig. 1 be in the embodiment of the present invention a kind of carbon to the structural representation of electrode perovskite solar cell;
Fig. 2 be in the embodiment of the present invention a kind of carbon to the comparison diagram of electrode perovskite solar cell properties.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each execution mode of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Fig. 1 be in the embodiment of the present invention a kind of carbon to the structural representation of electrode perovskite solar cell, as seen from the figure, it comprise conductive substrates, light anode, to electrode and be all positioned at light anode and to interelectrode hole transmission layer and sensitizing layer, light anode comprises TiO
2compacted zone and TiO
2porous layer is carbon cloth to electrode, and carbon cloth is tridimensional network, and its conductivity is strong, flexible.The hole transmission layer that attachment evenly dense on carbon cloth is made up of NiO nanometer sheet, carbon cloth and NiO nanometer sheet together constitute a kind of micro-nano hierarchy of three-dimensional.Described carbon cloth is embedded in the TiO of described smooth anode
2in porous layer; Described sensitizing layer is positioned at TiO
2porous layer.
Embodiment 1
Hole transmission layer preparation process: by the carbon cloth bought respectively ultrasonic cleaning 15min in acetone, absolute ethyl alcohol, deionized water, after under 100 DEG C of environment dry for standby.What the hole transmission layer of battery adopted is the NiO nanometer sheet that hydro thermal method generates.In raw material mixed solution, perform impregnation process to clean carbon cloth, described raw material mixed solution is for being 10mmol/L NiCl
26H
2o, 40mmol/L CO (NH
2)
2and 20mmol/L NH
4the aqueous solution of F; Then perform reaction treatment, inserted in autoclave by the carbon cloth being stained with described raw material mixed solution and react, reaction temperature is 120 DEG C, and the reaction time is 8h; To be cooled to room temperature, take out carbon cloth from autoclave, and with ethanol and washed with de-ionized water for several times, remove the impurity of surface deposition, after put into the vacuum drying chamber oven dry 12h that temperature is 60 DEG C.Complete cleaning and drying, perform annealing in process, annealing furnace hollow carbon cloth being put into 350 DEG C burns 2h, obtains the carbon cloth being attached with hole transmission layer.
Light anode preparation process: first prepare TiO in conductive substrates
2compacted zone, then prepare TiO
2porous layer.
First, need to prepare TiO
2the presoma of compacted zone, the ethanolic solution of filling a prescription as including 0.254mol/L isopropyl titanate and 0.02mol/L HCl.Secondly, be fixed on spin coating instrument by the conductive substrates after cleaning, in the present embodiment, conductive substrates refers to that surface sputtering has the glass of Fluorin doped tin ash (FTO), and drips TiO
2the presoma of compacted zone, after with the rotating speed spin coating 1min of 3000r/min.After film after spin coating is dried on the hot plate of 150 DEG C, then the 30min that anneals under putting into annealing furnace 500 DEG C of conditions.The compacted zone film thickness obtained is 20nm.
Then, TiO is adopted
2slurry (DSL.18NR-T, 20nm, Dyesol, Australia), prepare film forming by screen printing technique, controlling the thickness of film is 1 μm.The present invention adopts TiO
2loose structure adheres to perovskite sensitizing layer as support.
To electrode preparation process: after silk screen printing porous layer, at TiO
2before porous layer drying, the carbon cloth press-in TiO of hole transmission layer will be attached with
2in porous layer, form carbon cloth and be embedded in TiO
2the intermediate structure of porous layer, performs annealing in process to intermediate structure, under 500 DEG C of conditions, is incubated 30min, promotes TiO2 loose structure single crystallization, obtains pure anatase crystal, obtain battery intermediary device;
The preparation process of sensitizing layer: perovskite sensitizing layer adopts one-step method to be prepared, preparation periodo perovskite material CH
3nH
3pbI
3.Its constituent is CH
3nH
3i and PbI
2mol ratio is the gamma-butyrolacton solution of 1:1, and adjustment gamma-butyrolacton solution content, makes CH
3nH
3i and PbI
2the quality of having reacted the perovskite of rear acquisition accounts for 40% of whole solution quality.The solution configured above is fully mixed 12h at 60 DEG C, obtains yellow clarified solution.Afterwards, get the surface that 100 these solution of μ L drip counter electrode of battery after annealing, make that perovskite presoma is spontaneous penetrates into light anode TiO
2in porous membrane.Finally, battery is put into air dry oven dry 2h at 60 DEG C, in dry run, the yellow-covered solution of battery forms dark brown film gradually, means the formation gradually of perovskite crystal.
Embodiment 2
Hole transmission layer preparation process: by the carbon cloth bought respectively ultrasonic cleaning 15min in acetone, absolute ethyl alcohol, deionized water, after under 100 DEG C of environment dry for standby.What the hole transmission layer of battery adopted is the NiO nanometer sheet that hydro thermal method generates.In raw material mixed solution, perform impregnation process to clean carbon cloth, described raw material mixed solution is for being 9mmol/L NiCl
26H
2o, 50mmol/L CO (NH
2)
2and 25mmol/L NH
4the aqueous solution of F; Then perform reaction treatment, inserted in autoclave by the carbon cloth being stained with described raw material mixed solution and react, reaction temperature is 130 DEG C, and the reaction time is 10h; To be cooled to room temperature, take out carbon cloth from autoclave, and with ethanol and washed with de-ionized water for several times, remove the impurity of surface deposition, after put into the vacuum drying chamber oven dry 12h that temperature is 60 DEG C.Complete cleaning and drying, perform annealing in process, annealing furnace hollow carbon cloth being put into 360 DEG C burns 1.5h, obtains the carbon cloth being attached with hole transmission layer.
Light anode preparation process: first prepare TiO in conductive substrates
2compacted zone, then prepare TiO
2porous layer.
First, the presoma preparing TiO2 compacted zone is needed, the ethanolic solution of filling a prescription as including 0.254mol/L isopropyl titanate and 0.02mol/L HCl.Secondly, be fixed on spin coating instrument by the conductive substrates after cleaning, in the present embodiment, conductive substrates refers to that surface sputtering has the glass of tin indium oxide (ITO), and drips TiO
2the presoma of compacted zone, after with the rotating speed spin coating 1min of 3000r/min.After film after spin coating is dried on the hot plate of 150 DEG C, then the 30min that anneals under putting into annealing furnace 500 DEG C of conditions.The compacted zone film thickness obtained is 30nm.
Then, adopt the slurry (DSL.18NR-T, 20nm, Dyesol, Australia) of TiO2, prepare film forming by screen printing technique, the thickness controlling film is 5 μm.The present invention adopts TiO2 loose structure to adhere to perovskite sensitizing layer as support.
To electrode preparation process: after silk screen printing porous layer, at TiO
2before porous layer drying, the carbon cloth press-in TiO of hole transmission layer will be attached with
2in porous layer, form carbon cloth and be embedded in TiO
2the intermediate structure of porous layer, performs annealing in process to intermediate structure, under 500 DEG C of conditions, is incubated 30min, promotes TiO
2loose structure single crystallization, obtains pure anatase crystal, obtains battery intermediary device;
The preparation process of sensitizing layer:
Perovskite sensitizing layer adopts one-step method to be prepared.Preparation chlorine adulterated with Ca and Ti ore material.Its constituent is CH
3nH
3i and PbCl
2mol ratio is dimethyl formamide (DMF) solution of 3:1, CH
3nH
3i and PbCl
2what reaction terminated that the quality of the chlorine adulterated with Ca and Ti ore of rear acquisition accounts for whole solution quality is 40%.The solution configured above is fully mixed 12h at 60 DEG C, obtains yellow clarified solution.Afterwards, get the surface that 100 these solution of μ L drip counter electrode of battery after annealing, make that perovskite presoma is spontaneous penetrates into light anode TiO
2in porous membrane.Finally, battery is put into air dry oven dry 2h at 60 DEG C, in dry run, the yellow-covered solution of battery forms dark brown film gradually, means the formation gradually of perovskite crystal.
Embodiment 3
Hole transmission layer preparation process: by the carbon cloth bought respectively ultrasonic cleaning 15min in acetone, absolute ethyl alcohol, deionized water, after under 100 DEG C of environment dry for standby.What the hole transmission layer of battery adopted is the NiO nanometer sheet that hydro thermal method generates.In raw material mixed solution, perform impregnation process to clean carbon cloth, described raw material mixed solution is for being 11mmol/L NiCl
26H
2o, 30mmol/L CO (NH
2)
2and 15mmol/L NH
4the aqueous solution of F; Then perform reaction treatment, inserted in autoclave by the carbon cloth being stained with described raw material mixed solution and react, reaction temperature is 140 DEG C, and the reaction time is 7h; To be cooled to room temperature, take out carbon cloth from autoclave, and with ethanol and washed with de-ionized water for several times, remove the impurity of surface deposition, after put into the vacuum drying chamber oven dry 12h that temperature is 60 DEG C.Complete cleaning and drying, perform annealing in process, annealing furnace hollow carbon cloth being put into 340 DEG C burns 2.5h, obtains the carbon cloth being attached with hole transmission layer.
Light anode preparation process: first prepare TiO in conductive substrates
2compacted zone, then prepare TiO
2porous layer.
First, need to prepare TiO
2the presoma of compacted zone, the ethanolic solution of filling a prescription as including 0.254mol/L isopropyl titanate and 0.02mol/L HCl.Secondly, the FTO after cleaning is fixed on spin coating instrument, and drips TiO
2the presoma of compacted zone, after with the rotating speed spin coating 1min of 3000r/min.After film after spin coating is dried on the hot plate of 150 DEG C, then the 30min that anneals under putting into annealing furnace 500 DEG C of conditions.The compacted zone film thickness obtained is 40nm.
Then, TiO is adopted
2slurry (DSL.18NR-T, 20nm, Dyesol, Australia), prepare film forming by screen printing technique, controlling the thickness of film is 500nm.The present invention adopts TiO
2loose structure adheres to perovskite sensitizing layer as support.
To electrode preparation process: after silk screen printing porous layer, at TiO
2before porous layer drying, the carbon cloth press-in TiO of hole transmission layer will be attached with
2in porous layer, form carbon cloth and be embedded in TiO
2the intermediate structure of porous layer, performs annealing in process to intermediate structure, under 500 DEG C of conditions, is incubated 30min, promotes TiO
2loose structure single crystallization, obtains pure anatase crystal, obtains battery intermediary device;
The preparation process of sensitizing layer:
Perovskite sensitizing layer adopts the two-step method of periodo perovskite material to be prepared.
First respectively 462mgml is configured
-1pbI
2dimethyl formamide solution and 10mgml
-1cH
3nH
3the aqueous isopropanol of I; Then 100 μ LPbI are got
2dimethyl formamide solution drip in the battery between the carbon cloth surfaces of device, treat that its spontaneous carbon cloth through intermediary device penetrates into TiO
2after in porous layer, and dry at 70 DEG C.Then the battery intermediary device after oven dry is inserted in aqueous isopropanol and infiltrate; Finally take out battery intermediary device, and insert containing CH
3nH
310min in the aqueous isopropanol of I.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare hole transmission layer, light anode and carbon to electrode, unlike the one-step preparation process of the periodo perovskite material adopted in sensitizing layer preparation process, adjustment gamma-butyrolacton solution content, makes CH
3nH
3i and PbI
2the quality of having reacted the perovskite of rear acquisition accounts for 42% of whole solution quality.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare hole transmission layer, light anode and carbon to electrode, unlike the one-step preparation process of the periodo perovskite material adopted in sensitizing layer preparation process, adjustment gamma-butyrolacton solution content, makes CH
3nH
3i and PbI
2the quality of having reacted the perovskite of rear acquisition accounts for 39% of whole solution quality.
Embodiment 6
Adopt the method identical with embodiment 2 to prepare hole transmission layer, light anode and carbon to electrode, unlike the one-step preparation process of the chlorine adulterated with Ca and Ti ore material adopted in sensitizing layer preparation process, adjustment dimethyl formamide solution content, makes CH
3nH
3i and PbI
2the quality of having reacted the perovskite of rear acquisition accounts for 42% of whole solution quality.
Embodiment 7
Adopt the method identical with embodiment 2 to prepare hole transmission layer, light anode and carbon to electrode, unlike the one-step preparation process of the chlorine adulterated with Ca and Ti ore material adopted in sensitizing layer preparation process, adjustment dimethyl formamide solution content, makes CH
3nH
3i and PbI
2the quality of having reacted the perovskite of rear acquisition accounts for 44% of whole solution quality.
Embodiment 8
The method identical with embodiment 3 is adopted to prepare hole transmission layer, light anode and carbon to electrode, the two-step method preparation technology unlike the periodo perovskite material adopted in sensitizing layer preparation process:
First respectively 450mgml is configured
-1pbI
2dimethyl formamide solution and 9mgml
-1cH
3nH
3the aqueous isopropanol of I; Then 80 μ LPbI are got
2dimethyl formamide solution drip in the battery between the carbon cloth surfaces of device, treat that its spontaneous carbon cloth through intermediary device penetrates into TiO
2after in porous layer, and dry at 70 DEG C.Then the battery intermediary device after oven dry is inserted in aqueous isopropanol and infiltrate; Finally take out battery intermediary device, and insert containing CH
3nH
315min in the aqueous isopropanol of I.
Embodiment 9
The method identical with embodiment 3 is adopted to prepare hole transmission layer, light anode and carbon to electrode, the two-step method preparation technology unlike the periodo perovskite material adopted in sensitizing layer preparation process:
First respectively 480mgml is configured
-1pbI
2dimethyl formamide solution and 11mgml
-1cH
3nH
3the aqueous isopropanol of I; Then 90 μ LPbI are got
2dimethyl formamide solution drip in the battery between the carbon cloth surfaces of device, treat that its spontaneous carbon cloth through intermediary device penetrates into TiO
2after in porous layer, and dry at 70 DEG C.Then the battery intermediary device after oven dry is inserted in aqueous isopropanol and infiltrate; Finally take out battery intermediary device, and insert containing CH
3nH
315min in the aqueous isopropanol of I.
By battery prepared by embodiment 1, embodiment 2 and embodiment 3, carry out battery performance test, obtain the comparison diagram of the result of the test described in table 1 and battery performance as shown in Figure 2, the carbon cloth wherein for control cell is modified without NiO nanometer sheet electrode.Associative list 1 and Fig. 2 known, the introducing of hole transmission layer NiO nanometer sheet can promote the separation of photo-generated carrier on energy level, thus improves the open circuit voltage of battery, secondly because its larger specific area, increase the contact area of electrode and perovskite light-sensitive material, short circuit current obviously increases.Chlorine adulterated with Ca and Ti ore material is compared periodo material and is had wider absorption spectrum, so can obtain higher electricity conversion.The perovskite photosensitive layer adopting two-step method to prepare can more effectively penetrate in light anodic porous structure, and compare one-step method, method is more excellent.
The experimental result of table 1. battery examples
| Jsc/mA cm-2 | Voc/V | FF | PCE | |
| Embodiment 1 | 18.8 | 0.74 | 0.31 | 4.31％ |
| Embodiment 2 | 19.9 | 0.84 | 0.4 | 6.63％ |
| Embodiment 3 | 19.1 | 0.90 | 0.36 | 6.13％ |
| Control cell | 11.9 | 0.66 | 0.36 | 2.83％ |
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. carbon is to an electrode perovskite solar cell, it comprise conductive substrates, light anode, to electrode and be all positioned at light anode and to interelectrode hole transmission layer and sensitizing layer, described smooth anode comprises TiO
2compacted zone and TiO
2porous layer, is characterized in that,
Described is carbon cloth to electrode, and this carbon cloth successively through NiO precursor mixed solution impregnation process and reaction treatment, thus makes this carbon cloth to adhere to equably the hole transmission layer be made up of NiO nanometer sheet; Described carbon cloth is embedded in the TiO of described smooth anode
2in porous layer; Described sensitizing layer is periodo perovskite or chlorine adulterated with Ca and Ti ore.
2. a kind of carbon as claimed in claim 1 is to electrode perovskite solar cell, it is characterized in that, described TiO
2porous layer thickness is 500nm ~ 5 μm, described TiO
2dense layer thickness is 20nm ~ 40nm.
3. a kind of carbon as claimed in claim 1 or 2 is to electrode perovskite solar cell, it is characterized in that, described precursor mixed solution is for include 9mmol/L ~ 11mmol/L NiCl simultaneously
26H
2o, 30mmol/L ~ 50mmol/L CO (NH
2)
2and 15mmol/L ~ 25mmol/L NH
4the aqueous solution of F.
4. a kind of carbon as claimed in claim 3 is to electrode perovskite solar cell, it is characterized in that, described conductive substrates refers to that surface sputtering has the glass of tin indium oxide or Fluorin doped tin ash.
5. prepare carbon as described in one of claim 1-4, to a method for electrode perovskite solar cell, to it is characterized in that, comprise the steps:
Hole transmission layer preparation process: in precursor mixed solution, impregnation process is performed to clean carbon cloth; Then perform reaction treatment, inserted in autoclave by the carbon cloth being stained with described raw material mixed solution and react, reaction temperature is 120 DEG C ~ 140 DEG C, and the reaction time is 7h ~ 10h; Then take out carbon cloth from autoclave to carry out cleaning and drying; Finally perform annealing in process, obtain the carbon cloth being attached with hole transmission layer;
Light anode preparation process: first prepare TiO in conductive substrates
2compacted zone, then prepare TiO
2porous layer;
To electrode preparation process: at TiO
2before porous layer drying, by the carbon cloth press-in TiO prepared through hole transmission layer preparation process
2in porous layer, form carbon cloth and be embedded in TiO
2the intermediate structure of porous layer, performs annealing in process to intermediate structure, obtains battery intermediary device;
The preparation process of sensitizing layer: first make the carbon cloth of described battery intermediary device floods sensitizing layer starting material solution, and make this sensitizing layer starting material solution penetrate into TiO through the carbon cloth of intermediary device
2porous layer, then performs reaction treatment, to obtain the sensitizing layer of periodo perovskite or chlorine adulterated with Ca and Ti ore.
6. method as claimed in claim 5, it is characterized in that, in hole transmission layer preparation process, the temperature of annealing in process is 340 DEG C ~ 360 DEG C, and annealing time is 1.5 ~ 2.5h.
7. method as described in claim 5 or 6, is characterized in that, in light anode preparation process, adopts screen printing mode to prepare TiO
2porous layer.
8. method as described in claim 5 or 6, is characterized in that, in the preparation process of sensitizing layer, adopt one-step method to prepare the sensitizing layer of periodo perovskite or chlorine adulterated with Ca and Ti ore, described one-step method is:
First make in the carbon cloth dipping sensitizing layer starting material solution of described battery intermediary device, this sensitizing layer starting material solution penetrates into TiO through the carbon cloth of intermediary device
2in porous layer, then dry at 60 DEG C ~ 70 DEG C, complete sensitizing layer preparation;
Described sensitizing layer starting material solution comprises CH
3nH
3i and PbI
2mol ratio is the gamma-butyrolacton mixed solution of 1:1, and CH
3nH
3i and PbI
2the quality of having reacted the perovskite of rear acquisition accounts for 39 ~ 42% of whole solution quality;
Described sensitizing layer starting material solution also comprises CH
3nH
3i and PbCl
2mol ratio is dimethyl formamide (DMF) mixed solution of 3:1, and CH
3nH
3i and PbCl
2what reaction terminated that the quality of the chlorine adulterated with Ca and Ti ore of rear acquisition accounts for whole solution quality is 40 ~ 44%.
9. method as described in claim 5 or 6, is characterized in that, in the preparation process of sensitizing layer, adopt two step method to prepare the sensitizing layer of periodo perovskite or chlorine adulterated with Ca and Ti ore, described two step method is:
First the PbI of 450 ~ 480mgml-1 is configured respectively
2dimethyl formamide solution and the CH of 9 ~ 11mgml-1
3nH
3the aqueous isopropanol of I; Then 80 ~ 100 μ LPbI are got
2dimethyl formamide solution drip in the battery between the carbon cloth surfaces of device, treat that its spontaneous carbon cloth through intermediary device penetrates into TiO
2after in porous layer, dry at 60 DEG C ~ 70 DEG C; Then the battery intermediary device after oven dry is inserted in aqueous isopropanol and infiltrate; Finally take out battery intermediary device, and insert containing CH
3nH
310min ~ 15min in the aqueous isopropanol of I.
10. method as described in claim 5 or 6, is characterized in that, described precursor mixed solution is for include 9mmol/L ~ 11mmol/L NiCl simultaneously
26H
2o, 30mmol/L ~ 50mmol/L CO (NH
2)
2and 15mmol/L ~ 25mmol/L NH
4the aqueous solution of F.
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