CN109786558A - A kind of Ca-Ti ore type solar battery and preparation method thereof - Google Patents
A kind of Ca-Ti ore type solar battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Ca-Ti ore type solar batteries and preparation method thereof, the Ca-Ti ore type solar battery, including FTO layer, hole transmission layer, calcium titanium ore bed, electron transfer layer, BCP layers and the electrode being cascading from bottom to top, the calcium titanium ore bed is the calcium titanium ore bed obtained through overdoping aminoquinolines, and the calcium titanium ore bed material after the doping is Csx(HC(NH2)2)(1‑x)PbI3And CH3NH3PbI3At least one of, wherein 0≤x≤1.The solar battery dopant material is cheap, and operating method is easy, is easy to control；It increases short circuit current, fill factor and the open-circuit voltage of device, provides new thinking for the stability of perovskite solar battery and the research of transformation efficiency.
Description
Technical field
The invention belongs to perovskite area of solar cell, and in particular to a kind of Ca-Ti ore type solar battery and its preparation
Method.
Background technique
After 21 century, economy and society are fast-developing, and demand of the mankind to the energy is increasing.However, traditional change
Stone fuel (coal, petroleum, natural gas) is just increasingly exhausted because constantly largely consuming, and energy problem has become restriction human society
The bottleneck of development.The exploitation of renewable new energy helps to alleviate the pressure of world energy sources and environment, and solar energy is stock number
Maximum, the most commonly used green regenerative energy sources of distribution.More and more countries come into effect " sunlight program ", develop solar energy
Resource seeks the new power of economic development.
Solar battery can be converted into luminous energy electric energy, and the exploitation of solar battery is most effective using solar energy
One of approach.Solar battery is small in size, and conveniently moving is used and is not limited by regions.It both can be solar-electricity
Pond is made into large-scale power station, and realization is generated electricity by way of merging two or more grid systems, and can easily be used with less battery component to remote districts
Family provides life electric energy, or provides electric power safeguard to mobile communication equipment.Currently, occupying the sun of leading position on the market
Energy battery is mainly monocrystalline silicon and polysilicon solar cell, the production technology comparative maturity of both batteries, the photoelectricity of battery
Transfer efficiency is higher, and stability is good (service life is all at 15 years or more).But silicon systems solar battery is severe to raw material requirement
It carves, purity generally will be 99.9999% or more, and complex manufacturing technology, cost remain high, and cost of electricity-generating is higher, can not
Realize ultra-large functionization.
Summary of the invention
The purpose of the present invention is to provide a kind of Ca-Ti ore type solar battery, another object is to provide the Ca-Ti ore type sun
Can battery preparation method, by perovskite adulterate aminoquinolines improve Ca-Ti ore type solar battery efficiency and
Stability.
A kind of Ca-Ti ore type solar battery, including FTO layer, the hole transmission layer, calcium being cascading from bottom to top
Titanium ore layer, electron transfer layer, BCP layers and electrode；The calcium titanium ore bed is the calcium obtained through overdoping aminoquinolines
Titanium ore layer, the calcium titanium ore bed material after the doping are Csx(HC(NH2)2)(1-x)PbI3And CH3NH3PbI3At least one of,
Wherein 0≤x≤1.
Further, the aminoquinolines are 2- aminoquinoline, 3- aminoquinoline, 5- aminoquinoline and 8-
Any one in aminoquinoline.
Further, the material of the electron transfer layer is PCBM.
Further, the material of the electrode is the one of which in gold and silver.
Further, the BCP layer material is 2,9- dimethyl -4,7- diphenyl -1,10- ferrosin.
Further, described FTO layers with a thickness of 450nm, hole transmission layer (NiOX) with a thickness of 10-50nm, calcium titanium ore bed
With a thickness of 300-400nm, electron transfer layer (PCBM) with a thickness of 50-100nm, BCP layers with a thickness of the thickness for 6nm and electrode
For 120nm.
A kind of Ca-Ti ore type preparation method of solar battery, the method includes the preparation of calcium titanium ore bed, the perovskite
The preparation of layer includes the following steps:
1) preparation of perovskite precursor solution: by presoma PbI2、HC(NH2)2I and CsI be dissolved in gamma-butyrolacton with
In the solution of dimethyl sulfoxide mixing, it is uniformly mixed, obtains precursor solution；
2) addition aminoquinolines are into the perovskite precursor solution until concentration is 0.001-100mg/
mL；
3) step 2) acquired solution is filtered, filtrate is spun on hole transmission layer (NiOX) on, and 5s- before the end
Chlorobenzene is added dropwise in 40s；
4) step 3) floating coat film is finally heated to 30min after annealing on 100 DEG C of hot plate, obtains doping amino quinoline
The calcium titanium ore bed of quinoline class compound.
Further, the perovskite precursor solution the preparation method comprises the following steps: by presoma PbI2、HC(NH2)2I and CsI
According to molal weight than the proportional arrangement for 1.1:1:0.1, weighs 1.5mol presoma and be dissolved in 1L with gamma-butyrolacton and diformazan
Base sulfoxide volume ratio is to be uniformly mixed in the solution of 7:3, obtains the precursor solution that concentration is 1.5mol/L.
Further, solution filters in step 3), and the filter aperture used of filtering is 10-440nm.
Further, the filter aperture used of filtering is 220nm.
Further, 300 μ L chlorobenzenes are added dropwise in 10s before preferably terminating in the step 3).
Further, in the spin coating, spin coating revolving speed is 2000-6000rpm, spin-coating time 15s-60s.
Further, spin coating revolving speed is preferably 4000rpm, and spin-coating time is preferably 30s.
In above-mentioned Ca-Ti ore type solar battery, electron transfer layer, gold or silver electrode and BCP layers of preparation method are normal
Rule method can be prepared according to existing preparation method.
It can refer to following document:
In situ induced core/shell stabilized hybrid perovskites via gallium
(III)acetylacetonate intermediate towards highly efficient and stable solar
cells.Energy Environ.Sci.,2018,11,286.
In battery structure, the structure of perovskite material itself is particularly important, and can the electron hole pair that generated in perovskite
Efficiently separating and transmitting has significant impact to device transformation efficiency.In addition to this, it is thin also to receive calcium titanium ore bed for device stability
The influence of membrane structure.Changing and optimize this body structure of perovskite thin film material by doping method is to improve device efficiency and stabilization
One of the main means of property.
Aminoquinolines are excellent luminescent material and electron donor and transmission material, are entrained in perovskite solution
In, the grain boundaries of perovskite are filled in, compensate for the low defect of perovskite material electron transport ability, and resonate by Foster
Energy transfer (FRET) enhances current-carrying quantum splitting and transmission, therefore improves the transformation efficiency of perovskite solar energy.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) by being doped to calcium titanium ore bed, the final raising for realizing device transformation efficiency.
(2) such dopant material is cheap, and operating method is easy, is easy to control, while such decorative material is calcium titanium
The stability of mine solar battery and the research of transformation efficiency provide new thinking.
(3) by doping, the electric current of device and open pressure be all obviously improved, substantially increase the performance of battery.
Detailed description of the invention
Fig. 1 is battery structure figure.
Fig. 2 is control cell and embodiment 1 (2- aminoquinoline), embodiment 4 (3- aminoquinoline), reality in comparative example 1
It applies the perovskite solar battery of example 5 (5- aminoquinoline) and embodiment 6 (8- aminoquinoline) and its adulterates the J-V song of device
Line.
Specific embodiment
Further to illustrate technological means and its effect adopted by the present invention, below in conjunction with preferred implementation of the invention
Example to further illustrate the technical scheme of the present invention, but the present invention is not limited in scope of embodiments.
Comparative example 1, the perovskite solar battery for preparing the doping of 2- aminoquinoline
1) hole transmission layer (NiO is preparedX)
Specific steps are as follows: the nickel acetate of 125mg is molten into 5ml ethyl alcohol, be added 30 μ L ethanol amines, it is to be dissolved completely after,
Filtering.
The ethanol solution of the nickel acetate prepared is spin-coated on FTO layers of glass, after heating 30min on 400 DEG C of hot plate
Annealing, hole transmission layer (NiO obtainedX) thickness be about 50nm.
2) preparation of adulterated with Ca and Ti ore layer
By presoma PbI2、HC(NH2)2I and CsI, than the proportional arrangement for 1.1:1:0.1, is weighed according to molal weight
1.5mol is dissolved in 1L with gamma-butyrolacton and dimethyl sulfoxide volume ratio as in the solution of 7:3, uniformly mixed, obtaining concentration is
The precursor solution of 1.5mol/L., precursor solution is spun to hole transmission layer film surface, revolving speed is when spin coating
4000rpm, spin-coating time 30s.300 μ L chlorobenzenes are added dropwise in 10s before spin coating terminates, and finally heat on 100 DEG C of hot plate
30min obtains calcium titanium ore bed after annealing.
3) electron transfer layer is prepared
On obtained calcium titanium ore bed, one layer of electron transfer layer of spin coating, revolving speed is 2000rpm when spin coating, and spin-coating time is
30s, the gained hole transmission layer with a thickness of 50-100nm；Wherein, electron transfer layer is made of following material: by 15mg's
PCBM is dissolved in 1mL chlorobenzene.
4) BCP layers are prepared
The isopropanol saturated solution of spin coating BCP on gained electron transfer layer, revolving speed is 4000rpm, spin coating when spin coating
Time is 30s, and BCP layers obtained with a thickness of 1-10nm, preferably 6nm.
5) Ag/Au electrode is deposited
In vacuum degree 1.0 × 10-3Pa is hereinafter, evaporation rate isUnder the conditions of, the electrode evaporation on BCP layer, vapor deposition
Obtained thickness of electrode is 120nm.
In AM1.5,100mW/cm2The J-V performance curve for testing battery under illumination with solar simulator, such as Fig. 2 institute
Show, the short-circuit current density that battery is obtained under the conditions of blank is 19.60mA/cm2, open-circuit voltage 0.91V, fill factor is
0.71, photoelectric conversion efficiency 13.06%.
Embodiment 1
Remaining step is identical as comparative example 1, by presoma PbI in step 2)2、HC(NH2)2I and CsI is according to a mole matter
Amount weighs 1.5mol presoma and is dissolved in 1L with gamma-butyrolacton and dimethyl sulfoxide volume than the proportional arrangement for being 1.1:1:0.1
Than being uniformly mixed in the solution for 7:3, the precursor solution that concentration is 1.5mol/L is obtained, 2- aminoquinoline is then added and arrives
Until concentration is 0.001mg/ml, filtering in above-mentioned precursor solution.Filtrate is spun to hole transmission layer film surface, spin coating
When revolving speed be 4000rpm, time 30s.300 μ L chlorobenzenes are added dropwise in 10s before terminating, and finally heat on 100 DEG C of hot plate
30min obtains the calcium titanium ore bed of doping 2- aminoquinoline after annealing.
In AM1.5,100mW/cm2The J-V performance curve for testing the battery under illumination with KEITHLEY 2400, in Fig. 2
Shown, the short-circuit current density for obtaining battery is 21.83mA/cm2, open-circuit voltage 0.96V, fill factor 0.76, photoelectricity
Transfer efficiency is 16.16%.
Embodiment 2
Remaining step is identical as comparative example 1, by presoma PbI in step 2)2、HC(NH2)2I and CsI is according to a mole matter
Amount weighs 1.5mol presoma and is dissolved in 1L with gamma-butyrolacton and dimethyl sulfoxide volume than the proportional arrangement for being 1.1:1:0.1
Than being uniformly mixed in the solution for 7:3, the precursor solution that concentration is 1.5mol/L is obtained, 2- aminoquinoline is then added and arrives
Until concentration is 1mg/mL, filtering in above-mentioned precursor solution.Filtrate is spun to hole transmission layer film surface, when spin coating turns
Speed is 4000rpm, time 30s.300 μ L chlorobenzenes are added dropwise in 10s before spin coating terminates, and finally heat on 100 DEG C of hot plate
30min obtains doping 2- aminoquinoline calcium titanium ore bed.
In AM1.5,100mW/cm2The J-V performance curve for testing the battery under illumination with KEITHLEY 2400, in Fig. 2
Shown, the short-circuit current density for obtaining battery is 21.93mA/cm2, open-circuit voltage 0.97V, fill factor 0.79, photoelectricity
Transfer efficiency is 17.16%.
Embodiment 3
Remaining step is identical as comparative example 1, by presoma PbI in step 2)2、HC(NH2)2I and CsI is according to a mole matter
Amount weighs 1.5mol presoma and is dissolved in 1L with gamma-butyrolacton and dimethyl sulfoxide volume than the proportional arrangement for being 1.1:1:0.1
Than being uniformly mixed in the solution for 7:3, the precursor solution that concentration is 1.5mol/L is obtained.Then addition 2- aminoquinoline arrives
Until concentration is 100mg/ml, filtering in above-mentioned precursor solution.Filtrate is spun to hole transmission layer film surface, when spin coating
Revolving speed is 4000rpm, time 30s.300 μ L chlorobenzenes are added dropwise in 10s before terminating, and finally heat 30min on 100 DEG C of hot plate,
Doping 2- aminoquinoline calcium titanium ore bed is obtained after annealing.
In AM1.5,100mW/cm2The J-V performance curve for testing the battery under illumination with KEITHLEY 2400, in Fig. 2
Shown, the short-circuit current density for obtaining battery is 22.08mA/cm2, open-circuit voltage 1.00V, fill factor 0.79, photoelectricity
Transfer efficiency is 17.36%.
Embodiment 4, the perovskite solar battery for preparing the doping of 3- aminoquinoline
The step of according to embodiment 1, only changes step 2) doping 2- aminoquinoline used into 3- aminoquinoline.Add 3- ammonia
Base quinoline is into precursor solution until concentration is 1mg/mL.
In AM1.5,100mW/cm2The J-V performance curve for testing the battery under illumination with KEITHLEY 2400, in Fig. 2
Shown, the short-circuit current density for obtaining battery is 22.10mA/cm2, open-circuit voltage 0.95V, fill factor 0.75, photoelectricity
Transfer efficiency is 15.96%.
Embodiment 5, the perovskite solar battery for preparing the doping of 5- aminoquinoline
The step of according to embodiment 1, only changes step 2) doping 2- aminoquinoline used into 5- aminoquinoline.Add 5- ammonia
Base quinoline is into precursor solution until concentration is 1mg/mL.
In AM1.5,100mW/cm2The J-V performance curve for testing the battery under illumination with KEITHLEY 2400, in Fig. 2
Shown, the short-circuit current density for obtaining battery is 21.52mA/cm2, open-circuit voltage 0.95V, fill factor 0.77, photoelectricity
Transfer efficiency is 16.11%.
Embodiment 6, the perovskite solar battery for preparing the doping of 8- aminoquinoline
The step of according to embodiment 1, only changes step 2) doping 2- aminoquinoline used into 8- aminoquinoline.Add 8- ammonia
Base quinoline is into precursor solution until concentration is 1mg/mL.
In AM1.5,100mW/cm2The J-V performance curve for testing the battery under illumination with KEITHLEY 2400, in Fig. 2
Shown, the short-circuit current density for obtaining battery is 22.15mA/cm2, open-circuit voltage 0.97V, fill factor 0.78, photoelectricity
Transfer efficiency is 17.30%.
The J-V parameter of table 1, the perovskite solar battery of embodiment 1 to embodiment 4 and its doping device
| JSC/mA cm-2 | VOC/V | PCE | FF | |
| Comparative example 1 | 19.60 | 0.91 | 13.06% | 0.71 |
| Embodiment 1 | 21.83 | 0.96 | 16.16% | 0.76 |
| Embodiment 2 | 21.93 | 0.97 | 17.16% | 0.79 |
| Embodiment 3 | 22.08 | 1.00 | 17.36% | 0.79 |
| Embodiment 4 | 22.10 | 0.95 | 15.96% | 0.75 |
| Embodiment 5 | 21.52 | 0.95 | 16.11% | 0.79 |
| Embodiment 6 | 22.15 | 0.97 | 17.30% | 0.78 |
From the foregoing, it will be observed that short circuit current, fill factor and the open-circuit voltage of device generally improve by after doping treatment.It is comprehensive
The photovoltaic performance index of the above device is closed, the incident photon-to-electron conversion efficiency of device improves.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of Ca-Ti ore type solar battery, including FTO layer, hole transmission layer, the calcium titanium being cascading from bottom to top
Ore bed, electron transfer layer, BCP layers and electrode, which is characterized in that the calcium titanium ore bed is through overdoping aminoquinolines
Obtained calcium titanium ore bed, the calcium titanium ore bed material after the doping are Csx(HC(NH2)2)(1-x)PbI3And CH3NH3PbI3In extremely
Few one kind, wherein 0≤x≤1.
2. Ca-Ti ore type solar battery according to claim 1, which is characterized in that the aminoquinolines
For 2- aminoquinoline, 3- aminoquinoline, any one in 5- aminoquinoline and 8- aminoquinoline.
3. Ca-Ti ore type solar battery according to claim 1, which is characterized in that the material of the electron transfer layer is
PCBM。
4. Ca-Ti ore type solar battery according to claim 1, which is characterized in that the material of the electrode is Jin Heyin
In one of which.
5. Ca-Ti ore type solar battery according to claim 1, which is characterized in that the BCP layer material is 2,9- bis-
Methyl -4,7- diphenyl -1,10- ferrosin.
6. Ca-Ti ore type solar battery according to any one of claims 1 to 5, which is characterized in that the FTO thickness degree
For 450nm, thickness of hole transport layer 10-50nm, calcium titanium ore bed are with a thickness of 300-400nm, electron transport layer thickness 50-
100nm, BCP layers with a thickness of 6nm and electrode with a thickness of 120nm.
7. a kind of preparation method of Ca-Ti ore type solar battery, which is characterized in that the method includes the preparation of calcium titanium ore bed,
The preparation of the calcium titanium ore bed includes the following steps:
1) preparation of perovskite precursor solution: by presoma PbI2、HC(NH2)2I and CsI are dissolved in gamma-butyrolacton and diformazan
In the solution of base sulfoxide mixing, it is uniformly mixed, obtains perovskite precursor solution；
2) addition aminoquinolines are into the perovskite precursor solution until concentration is 0.001-100mg/mL；
3) step 2) acquired solution is filtered, filtrate is spun on hole transmission layer, and chlorobenzene is added dropwise in 5s-40s before the end；
4) step 3) floating coat film is finally heated to 30min after annealing on 100 DEG C of hot plate, obtains doping aminoquinolines
The calcium titanium ore bed of compound.
8. the preparation method of Ca-Ti ore type solar battery according to claim 7, which is characterized in that before the perovskite
Drive liquid solution the preparation method comprises the following steps: by presoma PbI2、HC(NH2)2I and CsI is according to molal weight than the ratio for 1.1:1:0.1
Example configuration weighs 1.5mol presoma and is dissolved in 1L with gamma-butyrolacton and dimethyl sulfoxide volume ratio to mix in the solution of 7:3
Close the precursor solution for uniformly obtaining that concentration is 1.5mol/L.
9. the preparation method of Ca-Ti ore type solar battery according to claim 7, which is characterized in that solution in step 3)
Filtering, the filter aperture used of filtering is 10-440nm.
10. the preparation method of Ca-Ti ore type solar battery according to claim 7, which is characterized in that in the spin coating,
Spin coating revolving speed is 2000-6000rpm, spin-coating time 15s-60s.
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