CN106935710A - A kind of perovskite solar cell with High-current output under extremely low temperature - Google Patents
A kind of perovskite solar cell with High-current output under extremely low temperature Download PDFInfo
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Abstract
The invention discloses a kind of perovskite solar cell with High-current output under extremely low temperature, including conductive transparent substrate, inorganic electronic transport layer, barrier layer, inorganic hole-transporting layer and carbon electrode；Wherein, inorganic electronic transport layer, barrier layer, inorganic hole-transporting layer and carbon electrode are filled with perovskite light absorbent；Conductive transparent substrate is used to transmit electronics, inorganic electronic transport layer is used to extract the electronics in perovskite light absorbent and transmit, the function of barrier layer is to prevent electronics from occurring to be combined in the interface of inorganic electronic transport layer and inorganic hole-transporting layer with hole, inorganic hole-transporting layer is used for the extraction in hole, and carbon electrode is used to transmit electric charge；The perovskite solar cell that the present invention is provided remains to normal work under the extremely low temperature less than thermodynamic temperature 160K and has larger current to export, it is adaptable to the field of scientific research and Reconnaissance Survey is carried out under extremely low temperature.
Description
Technical field
The invention belongs to photoelectron material and device arts, have under extremely low temperature more particularly, to one kind
The perovskite solar cell of High-current output.
Background technology
Green, safe and reproducible solar energy makes photovoltaic generation be the ideal for solving mankind's energy crisis and environmental pollution
Scheme；High-photoelectric transformation efficiency and low manufacturing cost are to popularize two preconditions of photovoltaic generation in an all-round way.Therefore, have concurrently efficiently
The solar cell of rate and characteristic of low cost is the target that people constantly pursue.
At present, commercial solar cell commercially prevailing silicon solar cell can not still meet low cost with
The demand that efficiency and stability are taken into account；Perovskite solar cell quickly grew at nearly 2 years, one has been started in the world and has been ground
Study carefully upsurge.Perovskite structural material is because band gap is adjustable, with absorptivity high and bipolarity carrier mobility and can
Prepared by solwution method the features such as, enables the preparation method of the simple structure of perovskite solar cell and low cost to obtain light high
Photoelectric transformation efficiency.
Hybrid perovskite, the advantage of organic and inorganic component both is combined in an intramolecular,
Both the physical characteristics such as inorganic component mobility higher, heat endurance, dielectricity and relatively low energy gap had been remained, but it is simultaneous
Has organic component (such as：Organic ammonium salt) excellent self assembly and film forming.Therefore, with single inorganic or organic material phase
Than hybrid perovskite has the significant advantages such as preparation process is simple, low cost and large area film forming.
Hybrid perovskite solar cell, compared with other types of solar cell, its device architecture tool
There is diversity, mesoporous perovskite solar cell, formal flat board perovskite solar cell, trans flat board perovskite can be divided into too
Four kinds of structures such as positive energy battery, homojunction perovskite solar cell, its device architecture is various, comes from above-mentioned organic/inorganic miscellaneous
Change perovskite material in itself as light absorbent while, and with electronics and hole mobility high and be easy to film forming etc. and show
The advantage of work.
Although having larger advantage on current perovskite solar battery efficiency, perovskite material has unstability,
Water vapour in air can accelerate the decomposition of perovskite material；And it is applied to the organic hole transmission of perovskite solar cell
Layer poor performance, performance of the extreme influence to perovskite solar cell under extremely low temperature under extremely low temperature.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, there is big electricity the invention provides one kind under extremely low temperature
The perovskite solar cell of output is flowed, its object is to solve existing perovskite solar cell less than thermodynamic temperature
The problem of no current output under the extremely low temperature of 160K.
To achieve the above object, according to one aspect of the present invention, there is provided one kind has high current under extremely low temperature
The perovskite solar cell of output, including from lower from the conductive transparent substrate for above stacking gradually, inorganic electronic transport layer, obstruct
Layer, inorganic hole-transporting layer and carbon electrode；Wherein, inorganic electronic transport layer, barrier layer, inorganic hole-transporting layer and carbon electrode are equal
Filled with perovskite light absorbent；
Conductive transparent substrate is used to transmit electronics, and inorganic electronic transport layer is used to extract the electronics in perovskite light absorbent
And transmit, the function of barrier layer is to prevent electronics with hole in inorganic electronic transport layer and the interface of inorganic hole-transporting layer
Occur to be combined, inorganic hole-transporting layer is used for the extraction in hole, carbon electrode is used to transmit electric charge.
Preferably, above-mentioned perovskite solar cell, the material of its conductive transparent substrate is FTO electro-conductive glass；It is inorganic
Electron transfer layer is the TiO filled with perovskite light absorbent2Mesoporous layer, barrier layer is filled with perovskite light absorbent
Al2O3Mesoporous layer, inorganic hole-transporting layer is the mesoporous layers of NiO filled with perovskite light absorbent, carbon electrode material be filled with
The carbon black and graphite of perovskite light absorbent.
Preferably, above-mentioned perovskite solar cell, inorganic electronic transport layer, barrier layer, inorganic hole-transporting layer and
The perovskite light absorbent of carbon electrode filling is CH3NH3PbI3Perovskite.
To realize the object of the invention, it is another aspect of this invention to provide that there is high current under providing a kind of extremely low temperature
The preparation method of the perovskite solar cell of output, comprises the following steps：
(1) blank mould is prepared；Including following sub-step：
(1.1) by FTO electro-conductive glass cleaning, dryings, as transparent conductive substrate；
(1.2) by TiO2Slurry is printed onto in transparent conductive substrate, and sintering forms inorganic with hole on hot plate
Electron transfer layer；
(1.3) by Al2O3Slurry is printed onto in inorganic electronic transport layer, and sintering forms the resistance with hole on hot plate
Interlayer；
(1.4) NiO slurries are printed onto on barrier layer, sintering forms the inorganic hole with hole and transmits on hot plate
Layer；
(1.5) carbon pastes are printed onto on inorganic hole-transporting layer, sintering forms carbon electrode on hot plate, obtain blank
Mould；
(2) by CH3NH3I and PbI2According to mol ratio 1：1 is dissolved in dimethylformamide and to stir acquisition uniform molten
Liquid, uniform solution is dropped on blank mould and heated, and obtains perovskite solar cell.
Preferably, the preparation method of above-mentioned perovskite solar cell, its step (1.2), step (1.3), step
(1.4) process of sintering is specific as follows：
125 degrees Celsius were warmed up to by 15 minutes, 10 minutes are incubated；375 were warmed up to by 15 minutes from 125 degrees Celsius to take the photograph
Family name's degree, is incubated 10 minutes；450 degrees Celsius were warmed up to from 375 degrees Celsius by 15 minutes, 10 minutes are incubated；Risen from 450 degrees Celsius
Temperature is incubated 30 minutes to 500 degrees Celsius.
Preferably, the preparation method of above-mentioned perovskite solar cell, CH3NH3The preparation of I comprises the following steps：
A () is by methylamine and HI according to mol ratio 1：2~3 hours are reacted under 0~3 degree Celsius after 1 mixing；
B be evaporated for the reactant that step (a) is obtained by (), obtain CH3NH3I；
C CH that () obtains to step (b)3NH3I carries out Diethyl ether recrystallization treatment；
D the product of step (c) is dried to form CH by ()3NH3I powder.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show
Beneficial effect：
(1) there is the perovskite solar cell of High-current output, by being used under the extremely low temperature that the present invention is provided
Titanium ore material there is less exciton binding energy, low temperature thermodynamic voltage effect under exciton can just occur dissociation generation from
By electric charge；And perovskite material sheet has less dielectric constant under extremely low temperature, so as to reduce in extremely low temperature
The series resistance of the lower electric charge transmission of degree；Test demonstrates the perovskite solar cell of present invention offer less than thermodynamic temperature
Still there is current density to be not less than 10mA`cm under the extremely low temperature of 160K-2Output current, overcome traditional mono-crystalline silicon solar electricity
Pond and the organic solar batteries limitation without opto-electronic conversion under extremely low temperature；Also, perovskite provided by the present invention is too
The structure of positive energy battery can well stop the moisture in air, intercept decomposition of the moisture in air to perovskite material,
The stability of perovskite battery can be greatly improved；
(2) there is the preparation method of the perovskite solar cell of High-current output under the extremely low temperature that the present invention is provided,
It prepares blank mould using simple silk-screen printing in preparing, form purely inorganic hole mobile material；Existing perovskite
Organic hole transmission layer, and organic hole transport material are used solar cell at low temperature almost without electric conductivity more, therefore
Have influence on the performance of whole perovskite solar cell；Perovskite solar cell prepared by the present invention, the transmission of its inorganic hole
Layer be influenced by temperature it is smaller, performance is kept under extremely low temperature stably, prepared perovskite solar cell is in extremely low temperature
Also larger electric current can be produced under degree.
Brief description of the drawings
Fig. 1 is the structure of the perovskite solar cell with High-current output under extremely low temperature that embodiment 1 is provided
Schematic diagram；
Fig. 2 is for the perovskite solar cell that embodiment 1 is provided is from open-circuit voltage to short circuit current fast direction is swept
Current density voltage curve schematic diagram under direction；
Fig. 3 is for the perovskite solar cell that embodiment 1 is provided is from short circuit current to open-circuit voltage fast direction is swept
Current density voltage curve schematic diagram under direction.
In all of the figs, identical reference be used for represent identical element or structure, wherein：1- transparency electrodes,
2- inorganic electronic transport layers, 3- barrier layers, 4- inorganic hole-transporting layers, 5- carbon electrodes.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each implementation method
Not constituting conflict each other can just be mutually combined.
There is the perovskite solar cell of High-current output, its structure is as schemed under a kind of extremely low temperature that embodiment is provided
Shown in 1, including from lower from the conductive transparent substrate for above stacking gradually, inorganic electronic transport layer, barrier layer, inorganic hole-transporting layer
And carbon electrode；In the present embodiment, the material of conductive transparent substrate is FTO electro-conductive glass；Inorganic electronic transport layer is filled with calcium
The TiO of titanium ore light absorbent2Mesoporous layer, barrier layer is the Al filled with perovskite light absorbent2O3Mesoporous layer, inorganic hole is passed
Defeated layer is the mesoporous layers of NiO filled with perovskite light absorbent, and carbon electrode material is the carbon black filled with perovskite light absorbent
And graphite.
There is the preparation side of the perovskite solar cell of High-current output under a kind of extremely low temperature that embodiment 1 is provided
Method, comprises the following steps：
(1) blank mould is prepared；Including following sub-step：
(1.1) by FTO electro-conductive glass cleaning, dryings, as transparent conductive substrate；
(1.2) by TiO2Slurry is printed onto in transparent conductive substrate, and sintering forms inorganic with hole on hot plate
Electron transfer layer；
Sintering process is specially：125 degrees Celsius were warmed up to by 15 minutes, 10 minutes are incubated；Taken the photograph from 125 by 15 minutes
Family name's degree is warmed up to 375 degrees Celsius, is incubated 10 minutes；450 degrees Celsius were warmed up to from 375 degrees Celsius by 15 minutes, 10 points are incubated
Clock；500 degrees Celsius are warmed up to from 450 degrees Celsius, 30 minutes are incubated, the inorganic electronic transport layer with hole is formed；
(1.3) by Al2O3Slurry is printed onto in inorganic electronic transport layer, and sintering forms the resistance with hole on hot plate
Interlayer；
Sintering process is specially：125 degrees Celsius are raised within 15 minutes, 10 minutes are incubated, then risen within 15 minutes from 125 degrees Celsius
To 375 degrees Celsius, 10 minutes are incubated, then 450 degrees Celsius, insulation 10 minutes, finally from 450 are raised within 15 minutes from 375 degrees Celsius
500 degrees Celsius degree Celsius are warmed up to, 30 minutes are incubated, the barrier layer with hole is formed；
(1.4) NiO slurries are printed onto on barrier layer, sintering forms the inorganic hole with hole and transmits on hot plate
Layer；
Sintering process is specially：125 degrees Celsius were warmed up to by 15 minutes, 10 minutes are incubated；Taken the photograph from 125 by 15 minutes
Family name's degree is warmed up to 375 degrees Celsius for 15 minutes, is incubated 10 minutes；450 degrees Celsius were warmed up to from 375 degrees Celsius by 15 minutes, are protected
Temperature 10 minutes；500 degrees Celsius are warmed up to from 450 degrees Celsius, 30 minutes are incubated, the inorganic hole-transporting layer with hole is formed.
(1.5) carbon pastes are printed onto on inorganic hole-transporting layer, 400 degrees Celsius is raised within 30 minutes on hot plate, protected
Temperature 30 minutes, forms carbon electrode；
(2) by CH3NH3I and PbI2According to mol ratio 1：1 is dissolved in dimethylformamide and stirs, will be uniform
Solution is dropped on blank mould, is heated 30 minutes at 70 DEG C, obtains perovskite solar cell.
Wherein, CH3NH3I prepares bag and obtains according to following methods；
A () is by methylamine and HI according to mol ratio 1：After 1 mixing 2~3 hours are reacted at 0~3 degree Celsius；
B reactant that () obtains step (a) obtained CH in 50~55 degrees Celsius of lower rotary evaporations 1~2 hour3NH3I；
C CH that () obtains to step (b)3NH3I carries out Diethyl ether recrystallization treatment；
D () in 60~65 degrees Celsius of dryings 24~48 hours, forms dry CH to the product of step (c)3NH3I powder.
The preparation method of the perovskite solar cell that 2~embodiment of embodiment 6 is provided and the technique phase of embodiment 1
Together, difference is the technological parameter in sintering process；The system of the perovskite solar cell that 2~embodiment of embodiment * is provided
The technological parameter of the sintering process of Preparation Method is as shown in the following chart：
The technological parameter list of sintering process in 2~embodiment of embodiment 6
Fig. 2 is that perovskite solar cell prepared by above-described embodiment 1 is from open-circuit voltage to short-circuit electricity fast direction is swept
Current density voltage curve schematic diagram under stream direction；Test condition is：Lamp source is AM1.5, and active layer effective area is
0.09cm2, speed is swept for 20mVs-1, it is to be carried out to short circuit current direction from open-circuit voltage to sweep fast direction, and test temperature is thermodynamics
Temperature 160K；
Fig. 3 is that perovskite solar cell prepared by above-described embodiment 2 is from short circuit current to open circuit fast direction is swept
Current density voltage curve schematic diagram under voltage direction；Test condition is：Lamp source is AM1.5, and active layer effective area is
0.09cm2, speed is swept for 20mVs-1, it is to be carried out to open-circuit voltage direction from short circuit current to sweep fast direction, and test temperature is thermodynamics
Temperature 160K；
From figures 2 and 3, it will be seen that in the case where test temperature is for the condition of work of 160K, either sweeping fast direction from short circuit
Electric current is carried out to open-circuit voltage direction, or is carried out to short circuit current direction from open-circuit voltage, and the perovskite solar cell is equal
There is larger short circuit current, almost no current is defeated under extremely low temperature to overcome organic cavity transmission layer perovskite solar cell
The defect for going out.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include
Within protection scope of the present invention.
Claims (6)
1. it is a kind of under extremely low temperature with High-current output perovskite solar cell, it is characterised in that including from it is lower from
On the conductive transparent substrate, inorganic electronic transport layer, barrier layer, inorganic hole-transporting layer and the carbon electrode that stack gradually；The nothing
Machine electron transfer layer, barrier layer, inorganic hole-transporting layer and carbon electrode are filled with perovskite light absorbent；
The conductive transparent substrate is used to transmit electronics, and the inorganic electronic transport layer is used to extracting in perovskite light absorbent
Electronics is simultaneously transmitted, and the barrier layer is used to prevent electronics with hole at inorganic electronic transport layer and the interface of inorganic hole-transporting layer
Place occurs to be combined, and the inorganic hole-transporting layer is used for the extraction in hole, and the carbon electrode is used to transmit electric charge.
2. perovskite solar cell as claimed in claim 1, it is characterised in that the material of the conductive transparent substrate is
FTO electro-conductive glass；The inorganic electronic transport layer is the TiO filled with perovskite light absorbent2Mesoporous layer, barrier layer is filling
There is the Al of perovskite light absorbent2O3Mesoporous layer, inorganic hole-transporting layer is the mesoporous layers of NiO filled with perovskite light absorbent,
The material of carbon electrode is carbon black and graphite filled with perovskite light absorbent.
3. perovskite solar cell as claimed in claim 1 or 2, it is characterised in that the inorganic electronic transport layer, resistance
The perovskite light absorbent of interlayer, inorganic hole-transporting layer and carbon electrode filling is CH3NH3PbI3Perovskite.
4. it is a kind of as described in any one of claims 1 to 3 under extremely low temperature with High-current output perovskite solar energy
The preparation method of battery, it is characterised in that comprise the following steps：
(1) blank mould, including following sub-step are prepared：
(1.1) by FTO electro-conductive glass cleaning, dryings, as transparent conductive substrate；
(1.2) by TiO2Slurry is printed onto in transparent conductive substrate, and sintering forms the inorganic electronic transport layer with hole；
(1.3) by Al2O3Slurry is printed onto in inorganic electronic transport layer, and sintering forms the barrier layer with hole；
(1.4) NiO slurries are printed onto on barrier layer, sintering forms the inorganic hole-transporting layer with hole；
(1.5) carbon pastes are printed onto on inorganic hole-transporting layer, sintering forms carbon electrode on hot plate, obtain blank mould；
(2) by CH3NH3I and PbI2According to mol ratio 1：1 is dissolved in dimethylformamide and stirs the uniform solution of acquisition, will
Uniform solution is dropped on the blank mould and heated, and obtains perovskite solar cell.
5. the preparation method of perovskite solar cell as claimed in claim 4, it is characterised in that the method for the sintering is such as
Under：
First stage：125~130 degrees Celsius were warmed up to by 15~20 minutes, 10~15 minutes are incubated；
Second stage：375~380 degrees Celsius were warmed up to from 125~130 degrees Celsius by 15~20 minutes, 10~15 points are incubated
Clock；
Phase III：450~455 degrees Celsius were warmed up to from 375~400 degrees Celsius by 15~20 minutes, 10~15 points are incubated
Clock；
Fourth stage：500~505 degrees Celsius are warmed up to from 450~455 degrees Celsius, 30~35 minutes are incubated.
6. the preparation method of the perovskite solar cell as described in claim 4 or 5, it is characterised in that the CH3NH3I's
Preparation comprises the following steps：
A () is by methylamine and HI according to mol ratio 1：After 1 mixing 2~3 hours are reacted at 0~3 degree Celsius；
B be evaporated for the reactant that step (a) is obtained by (), obtain CH3NH3I；
C CH that () obtains to step (b)3NH3I carries out Diethyl ether recrystallization treatment；
D the product of step (c) is dried to form CH by ()3NH3I powder.
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Cited By (5)
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| CN107337607A (en) * | 2017-07-14 | 2017-11-10 | 北京理工大学 | A kind of preparation method of methylpyridinium iodide ammonium |
| CN108807693A (en) * | 2018-05-23 | 2018-11-13 | 河南理工大学 | A kind of perovskite solar cell and preparation method thereof of low cost high stability |
| CN109490371A (en) * | 2018-11-28 | 2019-03-19 | 中国华能集团有限公司 | A kind of methylamine monitor and preparation method thereof |
| CN110061140A (en) * | 2019-04-11 | 2019-07-26 | 宁波大学 | A kind of stratiform NiO base carbon electrode perovskite solar battery and preparation method thereof |
| CN110176542A (en) * | 2019-06-11 | 2019-08-27 | 中国矿业大学 | Perovskite battery Organic-inorganic composite hole transport film and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107337607A (en) * | 2017-07-14 | 2017-11-10 | 北京理工大学 | A kind of preparation method of methylpyridinium iodide ammonium |
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| CN108807693A (en) * | 2018-05-23 | 2018-11-13 | 河南理工大学 | A kind of perovskite solar cell and preparation method thereof of low cost high stability |
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| CN109490371A (en) * | 2018-11-28 | 2019-03-19 | 中国华能集团有限公司 | A kind of methylamine monitor and preparation method thereof |
| CN110061140A (en) * | 2019-04-11 | 2019-07-26 | 宁波大学 | A kind of stratiform NiO base carbon electrode perovskite solar battery and preparation method thereof |
| CN110176542A (en) * | 2019-06-11 | 2019-08-27 | 中国矿业大学 | Perovskite battery Organic-inorganic composite hole transport film and preparation method thereof |
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