CN108899422B - HxMoO3-yNano material, HxMoO3-yElectrode and solar battery and preparation method comprising it - Google Patents

HxMoO3-yNano material, HxMoO3-yElectrode and solar battery and preparation method comprising it Download PDF

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CN108899422B
CN108899422B CN201810672757.3A CN201810672757A CN108899422B CN 108899422 B CN108899422 B CN 108899422B CN 201810672757 A CN201810672757 A CN 201810672757A CN 108899422 B CN108899422 B CN 108899422B
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王欢
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Shenzhen Institute of Advanced Technology of CAS
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Abstract

This application involves technical field of solar batteries.Disclose a kind of novel HxMoO3‑yNano material, the H comprising the nano materialxMoO3‑yMembrane electrode and perovskite solar battery and their preparation method comprising the electrode.The nano material includes HxMoO3‑yThe nanobelt that the diameter of formation is 50~190nm, length is 0.1~20 μm can form a kind of H to electrode that may be used as perovskite solar battery by itxMoO3‑yMembrane electrode.The work content of this new electrode materials is more matched with the energy level of perovskite, effectively reduces charge transmission potential barrier；Secondly, the electric conductivity of the new material is better than carbon electrode, charge can be more effectively collected；Again, compared with Au/Ag electrode, the lower production costs of the new electrode materials.By using this novel HxMoO3‑yElectrode is prepared for perovskite solar battery, especially can be applied in the perovskite solar battery of no hole transmission layer, the perovskite solar battery of available efficient stable.

Description

HxMoO3-yNano material, HxMoO3-yElectrode and solar battery and system comprising it Preparation Method
Technical field
The present invention relates to technical field of solar batteries.More specifically, it is related to a kind of HxMoO3-yNano material, HxMoO3-yElectrode and the solar battery comprising the electrode and preparation method thereof.
Background technique
Solar battery is the device that solar energy is directly become to electric energy, development experience three phases: the first generation is Silicon systems solar battery based on crystalline silicon.Since energy consumption is high in silicon systems solar battery manufacturing process, it is big to pollute, then plus The production technology of upper complexity and high production cost, are not able to satisfy large-scale application demand still.For this purpose, being developed with copper Indium gallium selenium (CIGS) and cadmium telluride (CdTe) are the second generation compound film solar battery of representative.With first generation solar-electricity Pond is compared, and the expected cost of second generation solar battery is lower, insufficient but there is also critical material element crustal abundances, device Stability and lower efficiency the problems such as, limit its application popularization.Therefore, it is necessary to greatly develop to be based on novel photovoltaic material bodies The solar battery technology of new generation of system and working mechanism.It here include organic solar batteries, dye sensitization of solar electricity Pond, hybrid perovskite solar battery etc..Wherein hybrid perovskite solar battery is sent out in recent years Exhibition rapidly, the photoelectric conversion efficiency of perovskite solar battery from 3.8% be initially reported till now 22.1%, imitating The polysilicon solar cell for having developed many decades and compound film solar battery are produced the equalizer in rate, to become most The solar battery technology of new generation of commercial application prospect.
Au or Ag or C material are used to electrode in existing hybrid halide perovskite solar battery Material, wherein though Au or Ag are excellent conductor materials, as expensive noble metal, apply in perovskite solar-electricity Higher cost in pond, and the work content of Au or Ag does not extremely match actually with perovskite.On the other hand, C-material is in the earth's crust Rich content, electric conductivity it is higher and cheap, but there is also certain energy level difference between its work content and perovskite, charge is passed Defeated process has certain potential barrier, causes lower using C as the open-circuit voltage of the perovskite solar battery of electrode.Therefore, it is badly in need of seeking Look for the electrode material of a kind of good conductivity, the matched novel stabilising of work content.
Summary of the invention
Therefore, and work content unmatched problem expensive in view of the above-mentioned electrode material for solar battery, purport of the present invention A kind of novel H is being providedxMoO3-yElectrode material and preparation method thereof and solar battery comprising the electrode, are keeping On the basis of the photoelectric conversion efficiency of battery, the higher cost and stability problem of existing perovskite solar battery are solved, is obtained Lower production costs and efficient perovskite solar battery.
In order to achieve the goal above, one aspect of the present invention provides a kind of HxMoO3-yNano material, the nano material packet Containing HxMoO3-yThe nanobelt that the diameter of formation is 50~190nm, length is 0.1~20 μm, 0 < x≤1,0≤y≤1.
Another aspect of the present invention provides a kind of HxMoO3-yThe preparation method of nano material, the method includes walking as follows It is rapid:
Molybdenum powder is reacted into 2-4h with hydrogen peroxide；
After acquired solution is carried out 0.5~3d of hydro-thermal reaction at 140~200 DEG C, is cleaned and dried；And
Acetic acid is added in products therefrom after to drying, after adding 3~5d of HI reaction, is cleaned and is dried.
Another aspect of the present invention provides a kind of HxMoO3-yMembrane electrode, the membrane electrode include the HxMoO3-yIt receives Rice material.
Preferably, the membrane electrode with a thickness of 1~10 μm.
Preferably, the membrane electrode is as solar battery to electrode.
Another aspect of the present invention provides a kind of HxMoO3-yThe preparation method of membrane electrode, the method includes such as Lower step:
By HxMoO3-yNano material, which is scattered in organic solvent, obtains dispersion liquid, and the nano material includes HxMoO3-yShape At diameter be 50~190nm, the nanobelt that length is 0.1~20 μm, 0 < x≤1,0≤y≤1；
The dispersion liquid is formed into film by spraying or spin coating.
On the one hand of the invention also provides a kind of solar battery, the structure of the solar battery includes: from the bottom to top Electrically conducting transparent substrate, hole blocking layer, mesoporous electron transfer layer, mesoporous framework layer and electrode layer, wherein the mesoporous framework layer There is perovskite light absorbent with infiltration in electrode layer, the electrode layer is to include HxMoO3-yThe H of nano materialxMoO3-yThin-film electro Pole, the nano material include HxMoO3-yThe nanobelt that the diameter of formation is 50~190nm, length is 0.1~20 μm, 0 < x ≤ 1,0≤y≤1.
Preferably, the perovskite light absorbent is ABX3, A=CH3NH3、NH2CHNH2, or mixtures thereof Cs；B=Pb or Or mixtures thereof Sn；Or mixtures thereof X=I, Br, Cl, CN, SCN.
On the one hand of the invention also provides a kind of preparation method of solar battery, the method includes walking as follows It is rapid: to prepare electrically conducting transparent substrate；
Hole blocking layer is formed in the electrically conducting transparent substrate；
Mesoporous electron transfer layer is formed on the hole blocking layer；
Mesoporous framework layer is formed on the mesoporous electron transfer layer；
Electrode layer is formed on the mesoporous framework layer；And
Solution containing perovskite light absorbent is penetrated into the mesoporous framework layer and electrode layer and is annealed,
Wherein, the electrode layer is to include HxMoO3-yThe H of nano materialxMoO3-yMembrane electrode, the nano material include HxMoO3-yThe nanobelt that the diameter of formation is 50~190nm, length is 0.1~20 μm, 0 < x≤1,0≤y≤1.
On the one hand of the invention also provides a kind of solar battery, the structure of the solar battery includes: from the bottom to top Electrically conducting transparent substrate, hole blocking layer, mesoporous electron transfer layer, mesoporous framework layer, perovskite light-absorption layer and electrode layer, wherein The electrode layer is to include HxMoO3-yThe H of nano materialxMoO3-yMembrane electrode, the nano material include HxMoO3-yIt is formed The nanobelt that diameter is 50~190nm, length is 0.1~20 μm, 0 < x≤1,0≤y≤1.
Preferably, the perovskite light-absorption layer is by ABX3Material is formed, A=CH3NH3、NH2CHNH2, or mixtures thereof Cs； Or mixtures thereof B=Pb or Sn；Or mixtures thereof X=I, Br, Cl, CN, SCN.
On the one hand of the invention also provides a kind of preparation method of above-mentioned solar battery, the method includes walking as follows It is rapid: to prepare electrically conducting transparent substrate；
Hole blocking layer is formed in the electrically conducting transparent substrate；
Mesoporous electron transfer layer is formed on the hole blocking layer；
Mesoporous framework layer is formed on the mesoporous electron transfer layer；
Perovskite light-absorption layer is formed on the mesoporous framework layer；And
Electrode layer is formed on the perovskite light-absorption layer,
Wherein, the electrode layer is to include HxMoO3-yThe H of nano materialxMoO3-yMembrane electrode, the nano material include HxMoO3-yThe nanobelt that the diameter of formation is 50~190nm, length is 0.1~20 μm, 0 < x≤1,0≤y≤1.
Beneficial effect
The application has been prepared by adjusting molybdenum powder and hydrogen peroxide and HI is sour reacts with suitable dimension HxMoO3-yNano material, the HxMoO3-yNano material can form film, the electrode as perovskite solar battery, this The work content of new electrode materials is more matched with the energy level of perovskite, effectively reduces charge transmission potential barrier；Secondly, the novel-section The electric conductivity of material is better than carbon electrode, can more effectively collect charge；Again, compared with Au/Ag electrode, the new electrode materials Lower production costs.By using this novel HxMoO3-yElectrode is prepared for perovskite solar battery, can especially answer For in the perovskite solar battery of no hole transmission layer, the perovskite solar battery of available efficient stable.
Detailed description of the invention
From detailed description with reference to the accompanying drawing, it will be more clearly understood above-mentioned and other purposes of the invention, Feature and other advantages, wherein
Fig. 1 shows the H of the preparation of embodiment 1xMoO3-yThe scanning electron microscope (SEM) photograph of nanobelt；
Fig. 2 shows the solar cell device structural schematic diagrams of the embodiment of the present invention 2, wherein 1 electrically conducting transparent substrate, 2 Hole blocking layer, 3 mesoporous electron transfer layers, 4 mesoporous framework layers and 5HxMoO3-yTo electrode layer；
Fig. 3 shows the solar cell device structural schematic diagram of the embodiment of the present invention 3, wherein 1 electrically conducting transparent substrate, 2 Hole blocking layer, 3 mesoporous electron transfer layers, 4 mesoporous framework layers, 5 perovskite light-absorption layers, 6HxMoO3-yTo electrode layer.
Specific embodiment
Existing perovskite solar battery generallys use metallic gold or silver or carbon material as electrode material, still, this Several electrode work contents are not to match very much, and gold or ag material are also costly.This application provides a kind of novel HxMoO3-yNano material may be used as the electrode material of perovskite solar battery.
H provided by the present applicationxMoO3-yNano material includes HxMoO3-yThe diameter of formation is 50~190nm, length 0.1 ~20 μm of nanobelt, preferably diameter are 100-150nm, and length is 1~10 μm, wherein 0 < x≤1,0≤y≤1, preferably 0.1≤x≤1.By by the size Control of nanobelt in the range, such HxMoO3-yThe thin-film electro of nano material preparation Pole can be adapted for perovskite solar battery.Work as HxMoO3-yThe diameter and length of nanobelt obtain not in this range Film roughness is larger, is not suitable for the electrode material as solar battery.
The HxMoO3-yNano material generates molybdenum trioxide by reacting molybdenum powder with hydrogen peroxide, then anti-with HI again It should prepare, specifically comprise the following steps:
Molybdenum powder is set to react 2-4h with hydrogen peroxide；
After acquired solution is carried out 0.5~3d of hydro-thermal reaction at 140~200 DEG C, is cleaned and dried；And Xiang Gan Acetic acid is added in products therefrom after dry, after adding 3~5d of HI reaction, is cleaned and is dried.
More specifically, molybdenum powder and H can be made first2O2It is stirred to react 2~4h, the preferably reaction can be under condition of ice bath It carries out, available orange clear solution after reaction, the ratio of molybdenum powder and hydrogen peroxide can be 1:10-1:20 (weight/volume Than), that is, for example, 1g molybdenum powder can be diluted in the H that 10mL is added in 10mL water thereto again2O2Or 20mL is added in 1g molybdenum powder H2O2In.Then hydro-thermal reaction is carried out to obtained solution, solution can be specifically fitted into reaction kettle, 140~200 0.5~3d of hydro-thermal reaction under the conditions of DEG C, available milky white product after this step then carry out gained milky white product clear It washes and dries, preferably can be dry with being placed on after deionized water and washes of absolute alcohol 1~3 time in drying box respectively, it can be with Obtain MoO3White powder.It carries out obtaining blackish green solution in processing 3~5 days finally, HI is added into obtained white powder, Preferably, MoO3Reaction ratio with hydroiodic acid HI can be 1:10-1:20 (weight/volume), more specifically, can be such as It is reacted with following ratio, weighs the MoO of 0.1g320mL acetic acid reaction 2h is added in white powder thereto, then molten to mixing The HI that 2mL is added in liquid carries out 3~5d of processing, and then the solution is cleaned and dried, can specifically use bicarbonate respectively Sodium water solution, deionized water, dehydrated alcohol, which are placed in drying box after successively cleaning 3 times, obtains blackish green powder, as HxMoO3-yNano material.By the selected reaction condition of the application, the H with aforementioned dimensions can be obtainedxMoO3-yNanometer material Material.
In preparation HxMoO3-yDuring material, when hydrothermal temperature is lower than 140 DEG C, the reaction time is less than 0.5d, water Thermal response is not thorough, and has more byproduct residue wherein.When hydrothermal temperature is higher than 200 DEG C, the reaction time is greater than 3d, obtains The size of the product arrived is larger, is unfavorable for obtaining uniform HxMoO3-yMembrane electrode.
Utilize the H of the applicationxMoO3-yNano material can prepare a kind of novel HxMoO3-yMembrane electrode, the membrane electrode H comprising the applicationxMoO3-yNano material.The HxMoO3-yThe thickness of membrane electrode can be 1~10 μm, preferably 4~6 μm. The thickness of membrane electrode is controlled in the range, it is ensured that effective extraction of charge in device.Prepared HxMoO3-yIt is thin Membrane electrode may be used as solar battery to electrode, be preferably used as perovskite solar battery to electrode.HxMoO3-yHave Higher conductivity and hole mobility, the membrane electrode work content being consequently formed more are matched with the energy level of perovskite, can be dropped Low charge transmits potential barrier；And excellent electric conductivity, charge can be more effectively collected, while cost is also very cheap.
According to some embodiments of the application, HxMoO3-yMembrane electrode can be prepared via a method which, by the application HxMoO3-yNano material, which is scattered in organic solvent, obtains dispersion liquid, and the dispersion liquid is passed through spraying or spin coating shape At film.Preferably, dispersion liquid can be formed using selected from one of chlorobenzene, isopropanol or ethyl alcohol or a variety of organic solvents. Such electrode preparation method simple process, does not need expensive equipment and complicated condition is conducive to drop convenient for the assembling of device The production cost of low solar battery.
Utilize HxMoO3-yMembrane electrode, some embodiments of the application provide a kind of solar battery, and structure is under Supreme includes: electrically conducting transparent substrate, hole blocking layer, mesoporous electron transfer layer, mesoporous framework layer and electrode layer, wherein described Infiltration has perovskite light absorbent in mesoporous framework layer and electrode layer, and the electrode layer is HxMoO3-yMembrane electrode.
Preferably, the perovskite light absorbent is ABX3, A=CH3NH3、NH2CHNH2, or mixtures thereof Cs；B=Pb or Or mixtures thereof Sn；Or mixtures thereof X=I, Br, Cl, CN, SCN.
Preferably, the electrically conducting transparent substrate is FTO electro-conductive glass or ITO electro-conductive glass.
Preferably, the hole blocking layer is densification TiO2Layer, more preferentially, densification TiO2Layer with a thickness of 40~ 100nm。
Preferably, the mesoporous electron transfer layer is TiO2、ZnO、SnO2Or CdS film layer, it is highly preferred that the mesoporous electronics Transport layer with a thickness of 400~600nm.
Preferably, the mesoporous framework layer is Al2O3Or ZrO2Layer, it is highly preferred that the mesoporous framework layer with a thickness of 40~ 600nm。
It is above-mentioned to contain HxMoO3-yThe solar battery of membrane electrode can be prepared via a method which: prepare electrically conducting transparent Substrate；
Hole blocking layer is formed in the electrically conducting transparent substrate；
Mesoporous electron transfer layer is formed on the hole blocking layer；
Mesoporous framework layer is formed on the mesoporous electron transfer layer；
Electrode layer is formed on the mesoporous framework layer；And
Solution containing perovskite light absorbent is penetrated into the mesoporous framework layer and electrode layer and is annealed.
More specifically, the preparation electrically conducting transparent substrate can be the step of cleaning to electrically conducting transparent substrate.For example, FTO or ITO electro-conductive glass substrate can be placed in ultrasonic cleaning machine and be cleaned, it is highly preferred that can be successively weak with PH=8~10 Akaline liquid dish washing liquid, deionized water, dehydrated alcohol, acetone respectively clean 5~20 minutes.Cleaning to electrically conducting transparent substrate can It is carried out with the other methods that can be used using this field.
It, can be by by the solution spraying of organic titanium source in the step of forming hole blocking layer in the electrically conducting transparent substrate In electrically conducting transparent substrate and heat progress, the organic titanium source can be such as isopropyl titanate, more specifically, for example can be with The FTO electro-conductive glass substrate cleaned up is heated at 400~600 DEG C, the isopropyl titanate of 0.01~0.05mol/L is different Propanol solution sprays in this substrate, heats 20~60 minutes, forms the fine and close TiO of 40~100nm thickness2Hole blocking layer.
The mesoporous electron transfer layer can be TiO2、ZnO、SnO2Or CdS film layer, it can be by by raw material such as TiO2、 ZnO、SnO2Or the slurry of CdS dilutes by a certain percentage with organic solvent such as dehydrated alcohol, and dilution is then spin-coated on sky On the barrier layer of cave, then heats 20~120 minutes and prepare on 400~600 DEG C of warm table.
The preparation of the mesoporous framework layer can be by by the material of mesoporous framework layer such as Al2O3Or ZrO2Solution rotation It is coated on mesoporous electron transfer layer and prepares.
Then, by HxMoO3-yDispersion liquid spin coating is sprayed on the mesoporous framework layer, is added under the conditions of 40~200 DEG C Heat 10~70 minutes, can be obtained HxMoO3-yMembrane electrode.As it was noted above, the HxMoO3-yDispersion liquid can be by by this Shen H pleasexMoO3-yNano material, which is scattered in organic solvent, to be obtained.It preferably, can be using selected from chlorobenzene, isopropanol or ethyl alcohol One of or a variety of organic solvents formed dispersion liquid.
Finally, the solution containing perovskite light absorbent can be penetrated into the mesoporous framework layer and electrode layer and moved back Fire.It specifically, can be by configured perovskite solution drop coating in HxMoO3-yIt penetrates into through capillary action on electrode, 70~200 DEG C are annealed 10~60 minutes, and the novel H is finally obtainedxMoO3-yElectrode perovskite solar battery.Preferred calcium Titanium ore material is as previously mentioned, can be ABX3, wherein A=CH3NH3、NH2CHNH2, or mixtures thereof Cs；B=Pb or Sn or its Mixture；Or mixtures thereof X=I, Br, Cl, CN, SCN.
Utilize HxMoO3-yMembrane electrode, other of the application are embodiments further provide a kind of solar battery, knot Structure includes: electrically conducting transparent substrate, hole blocking layer, mesoporous electron transfer layer, mesoporous framework layer, perovskite light-absorption layer from the bottom to top And electrode layer, wherein the electrode layer is to include HxMoO3-yThe H of nano materialxMoO3-yMembrane electrode.
Wherein, electrically conducting transparent substrate, hole blocking layer, mesoporous electron transfer layer and mesoporous framework layer and its preparation be above Through being described in detail, omit herein.
In some embodiments, the perovskite light-absorption layer can be ABX3Layer, wherein A=CH3NH3、 NH2CHNH2、 Or mixtures thereof Cs；Or mixtures thereof B=Pb or Sn；Or mixtures thereof X=I, Br, Cl, CN, SCN, the preferably described perovskite Light-absorption layer with a thickness of 100~800nm.This perovskite light-absorption layer can be by by ABX3Perovskite solution is heavy using a step spin coating Area method or two step spin-deposit process or vapor phase method are deposited on mesoporous framework layer, are annealed 10~60 minutes and are obtained at 70~200 DEG C.
Finally, by HxMoO3-yDispersion liquid spin coating is sprayed on the perovskite light-absorption layer, under the conditions of 40~200 DEG C Heating 10~70 minutes, can be obtained HxMoO3-yMembrane electrode, and finally obtain the novel HxMoO3-yElectrode perovskite solar energy Battery.As it was noted above, the HxMoO3-yDispersion liquid can be by by the H of the applicationxMoO3-yNano material is scattered in organic solvent In obtain.Preferably, dispersion liquid can be formed using selected from one of chlorobenzene, isopropanol or ethyl alcohol or a variety of organic solvents.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing and specific implementation Example, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain this hair It is bright, it is not intended to limit the present invention.Particular technique or condition are not specified in embodiment, it is described according to the literature in the art Technology or conditions or carried out according to product description.Reagents or instruments used without specified manufacturer is that can lead to Cross the conventional products of commercially available acquisition.Term as used herein "and/or" includes appointing for one or more relevant listed items Meaning and all combinations.
Embodiment 1:HxMoO3-yThe preparation of nano material
As follows, H is preparedxMoO3-yPowder:
(1) H of 20mL is added in 1g molybdenum powder2O2In, make molybdenum powder and H under condition of ice bath2O2It is stirred to react 2~4h.
(2) above-mentioned solution is fitted into reaction kettle, hydro-thermal reaction 2d under the conditions of 180 DEG C obtains milky white product.
(3) dry with being placed on after deionized water and washes of absolute alcohol 3 times in drying box respectively to above-mentioned milky white product It is dry to obtain MoO3White powder.
(4) MoO of 0.1g is weighed320mL acetic acidreaction 2h is added thereto, then is added into mixed solution for white powder The HI of 2mL carry out processing 5d obtain blackish green solution, respectively with saturated sodium bicarbonate aqueous solution, deionized water, dehydrated alcohol according to It is placed in drying box after secondary cleaning 3 times and obtains blackish green powder, as HxMoO3-yPowder.Obtained HxMoO3-yPattern such as Shown in Fig. 1.
Embodiment 2: the preparation of perovskite solar battery SC-1
As follows, it is prepared for the perovskite solar battery SC-1 of device architecture shown in Fig. 2, as shown in Fig. 2, its Including electrically conducting transparent substrate, hole blocking layer, mesoporous electron transfer layer, mesoporous framework layer and the electrode being sequentially distributed from bottom to up Layer, perovskite light absorbent are filled into mesoporous framework layer and electrode layer:
(1) clean: by FTO electro-conductive glass substrate be placed in ultrasonic cleaning machine successively with PH=8 alkalescent liquid detergent, Deionized water, dehydrated alcohol, acetone respectively clean 5 minutes；
(2) prepared by hole blocking layer: the FTO electro-conductive glass substrate cleaned up is heated at 500 DEG C, it will be configured The isopropyl titanate aqueous isopropanol of 0.05mol/L sprays in this substrate, heats 20 minutes formation about 60nm densification TiO2It is empty Cave barrier layer；
(3) mesoporous electron transfer layer preparation: by TiO2Slurry and dehydrated alcohol are diluted according to mass ratio 1:2.5, will be diluted Liquid is spin-coated on TiO2On hole blocking layer, is heated 30 minutes on 550 DEG C of warm table and obtain the mesoporous TiO of 400nm2Electronics passes Defeated layer；
(4) prepared by mesoporous framework layer: by Al2O3Solution, which is spin-coated on electronic barrier layer, forms the mesoporous of one layer of 400nm Al2O3Casing play；
(5)HxMoO3-yIt prepared by electrode: by H prepared by embodiment 1xMoO3-yNano material is dispersed in chlorobenzene and is formed The dispersion liquid is spin-coated on the mesoporous framework layer by dispersion liquid, is heated 15 minutes, is obtained with a thickness of 6 μm under the conditions of 100 DEG C HxMoO3-yElectrode.
(6) ABX in battery is filled3Perovskite material preparation: in the H of the solar batteryxMoO3-yTo electrode surface CH after instilling 2 μ L heating3NH3PbI3Perovskite material heats 30 minutes at 100 DEG C, and perovskite material solvent is made to volatilize Obtain solid perovskite solar battery.
Embodiment 3: the preparation of perovskite solar battery SC-2
As follows, it is prepared for the perovskite solar battery SC-2 of device architecture shown in Fig. 3, as shown in figure 3, its Including be sequentially distributed from bottom to up electrically conducting transparent substrate, hole blocking layer, mesoporous electron transfer layer, mesoporous framework layer, calcium titanium Mine light-absorption layer and electrode layer:
(1) it cleans: FTO transparent conducting glass substrate is placed in ultrasonic cleaning machine successively with PH=10 alkalescent liquid Dish washing liquid, deionized water, dehydrated alcohol, acetone respectively clean 10 minutes；
(2) prepared by hole blocking layer: the FTO electro-conductive glass substrate cleaned up is heated at 500 DEG C, it will be configured The isopropyl titanate aqueous isopropanol of 0.01mol/L sprays in this substrate, heats 30 minutes formation about 100nm densification TiO2It is empty Cave barrier layer；
(3) mesoporous electron transfer layer preparation: on the barrier layer prepared, by TiO2Slurry and dehydrated alcohol according to Mass ratio 1:3.0 dilution, is spin-coated on TiO for dilution2On hole blocking layer, heated on 500 DEG C of warm table 40 minutes To the mesoporous TiO of 300nm2Electron transfer layer；
(4) prepared by mesoporous framework layer: by ZrO2Solution is spin-coated on mesoporous electron transfer layer, is annealed under the conditions of 450 DEG C, Form the mesoporous ZrO of one layer of 600nm2Casing play；
(5) prepared by perovskite light-absorption layer: taking the CH of 100 μ L3NH3PbI3Perovskite material is spin-coated on mesoporous framework layer, Under 100 DEG C of environment, heats 30 minutes, perovskite material solvent is made to volatilize to form the perovskite light-absorption layer of one layer of 300nm；
(7)HxMoO3-yIt prepared by electrode: by H prepared by embodiment 1xMoO3-yNano material is dispersed in shape in isopropanol At dispersion liquid, which is sprayed on the perovskite light-absorption layer, is heated 10 minutes under the conditions of 70 DEG C, obtain with a thickness of 7 μm of HxMoO3-yElectrode.It ultimately forms containing HxMoO3-yTo the perovskite solar battery of the efficient stable of electrode.
The major parameter of solar battery characterization is short-circuit current density (Jsc), open-circuit voltage (Voc), fill factor (FF) With photoelectric conversion efficiency (PCE).Wherein, JscRefer to the photoelectric current generated when unit area circuit is in short circuit, VocFor circuit Photovoltage when in open circuit, FF are expressed as the ratio between maximal input and limited output power of battery i.e.Jopt Current density when for peak power output, VoptVoltage when for peak power output.PCE refers to solar battery by the sun It can be converted into the ratio of electric energy, be expressed as the peak power output P of batterymaxWith incident optical power PinRatio i.e.: Wherein, PinThe incidence under the conditions of solar irradiation to commonly use AM1.5 Energy density is 100mW cm-2。
Prepared perovskite solar battery SC-1 is characterized, above-mentioned parameter is tested.
SC-1 being placed under the solar simulator of standard and is tested, the voltage range of scanning is -0.1~1.1V, Scanning speed is 50mv/s.It is found by test, the open-circuit voltage V of perovskite solar battery SC-1ocFor 0.95V, short circuit Current density, JscFor 22.5mA cm-2, fill factor FF is 0.66, photoelectric conversion efficiency 14.1%.Compared to pyrocarbon electricity The open-circuit voltage of 0.90 V of the perovskite solar battery of pole, the open-circuit voltage V of SC-1ocIt is higher.
The foregoing is merely better embodiments of the invention, are not intended to limit the invention, all of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within spirit and principle.

Claims (6)

1. a kind of solar battery, the structure of the solar battery includes: electrically conducting transparent substrate, hole barrier from the bottom to top Layer, mesoporous electron transfer layer, mesoporous framework layer and electrode layer, wherein infiltration has calcium titanium in the mesoporous framework layer and electrode layer Mine light absorbent, the electrode layer are to include HxMoO3-yThe H of nano materialxMoO3-yMembrane electrode, the nano material include HxMoO3-yThe nanobelt that the diameter of formation is 50~190nm, length is 0.1~20 μm, 0 < x≤1,0≤y≤1.
2. solar battery as described in claim 1, wherein the perovskite light absorbent is ABX3, A=CH3NH3、 NH2CHNH2, or mixtures thereof Cs；Or mixtures thereof B=Pb or Sn；Or mixtures thereof X=I, Br, Cl, CN, SCN.
3. a kind of preparation method of solar battery described in claim 1, described method includes following steps: preparing transparent lead Electric substrate；
Hole blocking layer is formed in the electrically conducting transparent substrate；
Mesoporous electron transfer layer is formed on the hole blocking layer；
Mesoporous framework layer is formed on the mesoporous electron transfer layer；
Electrode layer is formed on the mesoporous framework layer；
And the solution containing perovskite light absorbent is penetrated into the mesoporous framework layer and electrode layer and is annealed.
4. a kind of solar battery, the structure of the solar battery includes: electrically conducting transparent substrate, hole barrier from the bottom to top Layer, mesoporous electron transfer layer, mesoporous framework layer, perovskite light-absorption layer and electrode layer, wherein the electrode layer be comprising HxMoO3-yThe H of nano materialxMoO3-yMembrane electrode, the nano material include HxMoO3-yThe diameter of formation be 50~190nm, The nanobelt that length is 0.1~20 μm, 0 < x≤1,0≤y≤1.
5. solar battery as claimed in claim 4, wherein the perovskite light-absorption layer is by ABX3Material is formed, A= CH3NH3、NH2CHNH2, or mixtures thereof Cs；Or mixtures thereof B=Pb or Sn；Or mixtures thereof X=I, Br, Cl, CN, SCN.
6. a kind of preparation method of solar battery as claimed in claim 4, wherein described method includes following steps: preparing Electrically conducting transparent substrate；
Hole blocking layer is formed in the electrically conducting transparent substrate；
Mesoporous electron transfer layer is formed on the hole blocking layer；
Mesoporous framework layer is formed on the mesoporous electron transfer layer；
Perovskite light-absorption layer is formed on the mesoporous framework layer；And
Electrode layer is formed on the perovskite light-absorption layer.
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