A kind of perovskite solar battery and preparation method thereof
Technical field
The invention belongs to technical field of solar batteries more particularly to a kind of perovskite solar battery and its preparation sides
Method.
Background technique
In recent years, organic inorganic hybridization perovskite material is because of its high absorptivity, the current-carrying that forbidden bandwidth is adjustable, high
Transport factor etc. is excellent and has good prospect, and this kind of current highest of solar battery efficiency has reached 22.1%, root
According to the efficiency also very big room for promotion of theoretical prediction perovskite solar battery.
Perovskite solar battery is usually by transparent electrode, hole transmission layer, perovskite light-absorption layer, electron transfer layer, gold
Belong to electrode and constitutes p-i-n structure.Hole mobile material can be effectively improved Schottky contacts, form good Ohmic contact, have
The transporting holes of effect reduce the Carrier recombination of interface, improve the efficiency of device.Although many organic hole materials are answered
The problems such as in perovskite battery, but organic material itself usually has stability poor, is unfavorable for large scale preparation, such as pass
On the one hand the organic hole transport material PEDOT:PSS of system can corrode transparent electrode surface in acidity, on the other hand have again and inhale
It is moist that device stability is had an impact.NiOx as a kind of inorganic semiconductor material because it has each high hole injection rate, properly
Level structure and solution processable the features such as be now widely used for perovskite solar battery.
In realizing process of the present invention, at least there are the following problems in the prior art for inventor's discovery:
Many organic hole materials are applied in perovskite battery, but organic material itself usually has stability
Difference, the problems such as being unfavorable for large scale preparation.
Summary of the invention
The object of the present invention is to provide a kind of perovskite solar batteries, have the relatively high and stable property of photoelectric conversion efficiency
Preferable advantage.
It is a further object to provide the preparation methods of the perovskite solar battery.
As shown in Figure 1, a kind of perovskite solar battery, carries out heat to hole transmission layer using redox graphene and moves back
Fire;The perovskite battery includes CH3NH3PbI3Film and hole transmission layer;The hole transmission layer is NiOx hole transport
Layer, the NiOx hole transmission layer includes NiOx film.
Preferably, the perovskite solar battery includes conductive glass layer, hole transmission layer, the bromine mixing set gradually
CH3NH3PbI3Film, PCBM film and metal electrode.
Preferably, CH is prepared using spin-coating method3NH3PbI3Layer.
Preferably, PCBM electron transfer layer is prepared using spin coating method, with a thickness of 50~100nm.
It preferably, is 280 DEG C to the annealing temperature of NiOx hole transmission layer.
Preferably, the metal electrode metal Ag electrode layer of the perovskite solar battery prepares gold using vapour deposition method
Belong to Ag electrode layer 106, with a thickness of 120nm.
Preferably, the perovskite battery includes CH3NH3PbI3Film and hole transmission layer;The NiOx hole transmission layer
Including NiOx film;The step of preparation method of perovskite solar battery includes: the NiOx for preparing the hole transmission layer
Precursor liquid;The precursor liquid of the hole transmission layer is prepared according to the following steps: acetic acid nickel by powder and the ethanol amine as cosolvent
It is dissolved in the solution for obtaining that concentration is 0.2M in glycol monoethyl ether, is placed at room temperature after solution is stirred 2h at a temperature of 65 DEG C
For 24 hours, the precursor liquid of NiOx is finally obtained.
Preferably, the step of preparation method of perovskite solar battery further include: after the precursor liquid for preparing NiOx, preparation
Based on redox graphene annealing NiOx film.
Preferably, the step of preparation method of perovskite solar battery include: prepare graphene annealing NiOx film after,
CH is prepared using spin-coating method on the hole transport layer3NH3PbI3Film;In the CH3NH3PbI3Spin-coating method is used on film
PCBM layers of preparation;Metal electrode is prepared using vapour deposition method on the PCBM layer, obtains perovskite battery.
Preferably, the step of preparation method of perovskite solar battery includes: that preparation is moved back based on redox graphene
Fiery NiOx film;
It is described to be prepared according to the following steps based on redox graphene annealing NiOx film: to add in the precursor liquid of NiOx
Enter a certain proportion of rGO as spare.Tu two layers of NiOx and of short duration after 280 DEG C of annealing is revolved on FTO, in third layer rotation Tu
When rotation Tu joined the NiOx precursor liquid of rGO, and finally 480 DEG C at a temperature of anneal 2 hours.
Above-mentioned technical proposal is had the following beneficial effects: because using being annealed using redox graphene to NiOx
Technological means improve the short circuit current of battery and fill out so reached the boundary defect for reducing hole transport layer surface
The factor is filled, to improve the technical effect of the transfer efficiency of battery;Simultaneously because NiOx is full-inorganic technology oxide, battery
Stability be also improved.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the structural schematic diagram for the perovskite solar battery that the embodiment of the present invention 1 provides;
Fig. 2 is that the X-ray photoelectron spectroscopic analysis (XPS) for the perovskite solar battery that the embodiment of the present invention 1 provides is bent
Line chart (curve graph of each element relative amount in film);Dotted line indicates in the nickel oxide film by graphene thermal annealing
Oxygen content;Solid line indicates the oxygen content in common nickel oxide film.Abscissa indicates electron binding energy, and unit is electron volts
(eV);Ordinate indicates that photoelectron intensity, unit are volume unit (a.u.).
Fig. 3 be the perovskite solar battery that provides of the embodiment of the present invention 1 VA characteristic curve figure (i.e. current density and
The curve graph of voltage relationship);Dotted line indicates the perovskite using the nickel oxide that graphene thermal makes annealing treatment as hole transmission layer too
The VA characteristic curve of positive energy battery;Solid line indicates the perovskite solar battery using common nickel oxide as hole transmission layer
VA characteristic curve.Abscissa indicates voltage, and unit is volt (V);Ordinate indicates current density, unit mA/cm2。
Fig. 4 is the dark current curve graph for the perovskite solar battery that the embodiment of the present invention 1 provides;Dotted line is indicated with graphite
Dark current curve of the nickel oxide of alkene thermal anneal process as the perovskite solar battery of hole transmission layer;Solid line is with common oxygen
Change dark current curve of the nickel as the perovskite solar battery of hole transmission layer.Abscissa indicates voltage, and unit is volt
(V);Ordinate indicates current density, unit mA/cm2。
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention provides a kind of solar batteries, including hole transmission layer, electron transfer layer and light-absorption layer;The sun
Energy battery is perovskite solar battery;The hole transmission layer is that the NiOx (nickel oxide) of redox graphene thermal annealing is thin
Film;The electron transfer layer is PCBM (fullerene derivate) film;The light-absorption layer is CH3NH3PbI3(organic inorganic hybridization
Perovskite structure film).
The present invention is not particularly limited the source of all raw materials, is commercially available.
I.e. a kind of perovskite solar battery carries out thermal annealing to hole transmission layer using redox graphene;It is described
Perovskite battery includes CH3NH3PbI3Film and hole transmission layer;The hole transmission layer is NiOx hole transmission layer, the sky
Cave transport layer includes NiOx film.The present invention anneals to NiOx using redox graphene, reduces hole transmission layer
The boundary defect on surface, improves the short circuit current and fill factor of battery, to improve the transfer efficiency of battery.
Preferably, the perovskite solar battery includes conductive glass layer, hole transmission layer, the bromine mixing set gradually
CH3NH3PbI3Film, PCBM film and metal electrode;All material be all it is commercially available, it is universal and be easy to buy without specifically limited.
Preferably, CH is prepared using spin-coating method3NH3PbI3Layer can make film more smooth using spin-coating method preparation.
Preferably, PCBM electron transfer layer, with a thickness of 50~100nm, this level of thickness are prepared using spin coating method
Battery size can be made smaller, also improve the transfer efficiency of battery.
It preferably, is 280 DEG C to the annealing temperature of NiOx hole transmission layer, the stability of battery is improved.
Preferably, metal electrode metal Ag (silver) electrode layer of the perovskite solar battery, using vapor deposition legal system
Standby metal Ag electrode layer 106, with a thickness of 120nm, preparing metal layer using vapour deposition method can make metal layer more uniform, be conducive to
Reduce the surface defect of battery.
A kind of the step of preparation method of perovskite solar battery, the preparation method of perovskite solar battery includes:
The precursor liquid of the NiOx of the hole transmission layer is prepared, precursor liquid manufacture craft is simple, and various raw materials are universal.
Preferably, the perovskite battery includes CH3NH3PbI3Film and hole transmission layer;The NiOx hole transmission layer
Including NiOx film;The step of preparation method of perovskite solar battery includes: that preparation is annealed based on redox graphene
The precursor liquid of NiOx film, the hole transmission layer is prepared according to the following steps: acetic acid nickel by powder and the ethyl alcohol as cosolvent
Amine is dissolved in the solution for obtaining that concentration is 0.2M in glycol monoethyl ether, puts at room temperature after solution is stirred 2h at a temperature of 65 DEG C
Set the precursor liquid for finally obtaining NiOx for 24 hours;This film is selected, the stability of battery is also improved.
Preferably, the step of preparation method of perovskite solar battery includes: on the hole transport layer using rotation
Coating prepares CH3NH3PbI3Film;In the CH3NH3PbI3PCBM layers are prepared using spin-coating method on film;PCBM layers described
It is upper that metal electrode is prepared using vapour deposition method, obtain perovskite battery.Nickel oxide of this perovskite battery compared to conventional anneal
As having higher short circuit current and fill factor for the battery of hole transmission layer, therefore also there is higher transfer efficiency.
Preferably, the step of preparation method of perovskite solar battery includes: that preparation is moved back based on redox graphene
NiOx film performance can be improved using annealing process in fiery NiOx film.
It is described to be prepared according to the following steps based on redox graphene annealing NiOx film: to add in the precursor liquid of NiOx
Enter a certain proportion of rGO (graphene powder) as spare.Two layers of NiOx of Tu and of short duration is revolved on FTO (fin oxide condutire glass)
After 280 DEG C of annealing, rotation Tu joined the NiOx precursor liquid of rGO when third layer revolves Tu, and finally in 480 DEG C of temperature
Lower annealing 2 hours.This preparation method is simple and convenient, improves the short circuit current and fill factor of battery.
Wherein, the perovskite battery is perovskite battery well known to those skilled in the art, has no special limit
It makes, preferred translucent perovskite battery in the present invention;The perovskite battery more preferably include the conductive glass layer set gradually,
Hole transmission layer, CH3NH3PbI3Film, PCBM layers and metal electrode.
The conductive glass layer is conductive glass layer well known to those skilled in the art, has no special limitation, this
Stannic oxide (FTO) electro-conductive glass of fluorine is preferably mixed in invention.
Hole transmission layer is provided on the electro-conductive glass;The hole transmission layer is the NiOx of full-inorganic, the present invention
Thermal annealing is carried out to NiOx film using redox graphene;The hole transmission layer with a thickness of 50nm.
CH is provided on the hole transmission layer3NH3PbI3Film;The CH3NH3PbI3Film is those skilled in the art
Well known CH3NH3PbI3Film has no special limitation.
The CH3NH3PbI3Electron transfer layer is provided on film;The electron transfer layer is that those skilled in the art are ripe
The electron transfer layer known has no special limitation, is preferably PCBM layers in the present invention;PCBM layers of the thickness is preferably
50~100nm, more preferably 50~80nm are further preferably 50~60nm.
Metal electrode is set on PCBM layers described;The metal electrode is metal electrode well known to those skilled in the art,
Its depositing operation does not damage perovskite, has no special limitation, is preferably Ag electrode in the present invention, with a thickness of 120nm.
Perovskite solar battery in the present invention includes hole transmission layer, electron transfer layer and light-absorption layer;The sun
Energy battery is perovskite solar battery;The hole transmission layer is the NiOx film of redox graphene thermal annealing;It is described
Electron transfer layer is PCBM film;The light-absorption layer is CH3NH3PbI3Film.Compared with prior art, innovative point of the invention
It is to anneal to NiOx using redox graphene, reduces the boundary defect of hole transport layer surface, improve electricity
The short circuit current and fill factor in pond, so that the transfer efficiency of battery is improved, simultaneously because NiOx is the oxidation of full-inorganic technology
The stability of object, battery is also improved.
The present invention also provides a kind of preparation methods of above-mentioned perovskite solar battery, comprising:
S1) preparation is based on redox graphene annealing NiOx film
The precursor liquid of the hole transmission layer is prepared according to the following steps: acetic acid nickel by powder and the ethanol amine as cosolvent
It is dissolved in the solution for obtaining that concentration is 0.2M in glycol monoethyl ether, is placed at room temperature after solution is stirred 2h at a temperature of 65 DEG C
For 24 hours, the precursor liquid of NiOx is finally obtained.
It is described to be prepared according to the following steps based on redox graphene annealing NiOx film: to add in the precursor liquid of NiOx
Enter a certain proportion of rGO as spare.Tu two layers of NiOx and of short duration after 280 DEG C of annealing is revolved on FTO, in third layer rotation Tu
When rotation Tu joined the NiOx precursor liquid of rGO, and finally 480 DEG C at a temperature of anneal 2 hours.
S2 perovskite solar battery) is prepared
The perovskite battery is prepared according to the following steps: preparing hole transport using the method in S1 on electro-conductive glass
Layer;CH is prepared using spin-coating method on the hole transport layer3NH3PbI3Film;In the CH3NH3PbI3Using rotation on film
Coating prepares PCBM layers;Metal electrode is prepared using vapour deposition method on the PCBM layer, obtains perovskite battery.
In order to further illustrate the present invention, with reference to embodiments to a kind of perovskite solar battery provided by the invention
It is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
Referring to Fig. 1;Fig. 1 is the structural schematic diagram of perovskite solar battery;Wherein 101 be the stannic oxide for mixing fluorine
FTO electro-conductive glass, 102 be NiOx film, and 102 be the NiOx film for being mixed with rGO, and 103 be perovskite CH3NH3PbI3Layer, 104
It is Ag electrode layer for PCBM electron transfer layer, 105.
Preparation is based on redox graphene annealing NiOx film:
(1) Tu NiOx is revolved on FTO and is annealed 10 minutes at 280 DEG C, is repeated twice;
(2) the NiOx solution that Tu is mixed with rGO is revolved on NiOx film, is put into annealing furnace after ten minutes in 280 DEG C of annealing
In at 480 DEG C anneal 2 hours.
Prepare perovskite battery:
(1) after preparing two layers of NiOx film 102 using spin-coating method on the stannic oxide FTO electro-conductive glass 101 of mixing fluorine
The NiOx film 103 that one layer is mixed with rGO is prepared again and is used as hole transmission layer, and thickness is about 50nm.
(2) CH is prepared using spin-coating method3NH3PbI3Layer 104.
(3) PCBM electron transfer layer 105 is prepared using spin coating method, with a thickness of 50~100nm.
(4) metal Ag electrode layer 106 is prepared using vapour deposition method, with a thickness of 120nm.
In instances, perovskite solar energy is prepared by preparing nickel oxide in the way of conventional anneal as hole transmission layer
As a comparison, I-V curve comparison diagram as shown in Figure 2 is it is found that the nickel oxide conduct annealed using redox graphene for battery
The perovskite solar battery of hole transmission layer compared to conventional anneal nickel oxide as having for the battery of hole transmission layer
Higher short circuit current and fill factor, therefore also have higher transfer efficiency.Known to XPS curve comparison figure as shown in Figure 3,
Redox graphene, which is annealed, reduces the oxygen defect at nickel oxide interface, and the ratio of oxygen defect is reduced to 0.81 from 0.97.Oxidation
Oxygen defect in nickel can capture hole, cause charge transmission bad, the reduction of oxygen defect improves carrier transport efficiency.By scheming
Dark-state current curve comparison diagram shown in 4 using nickel oxide surfaces defect after the annealing of anodic oxidation graphene thermal it is found that reduced, secretly
State electric current is substantially reduced.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.