CN108615815A - NiO bases compacted zone, perovskite solar cell and preparation method thereof - Google Patents
NiO bases compacted zone, perovskite solar cell and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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Abstract
The present invention discloses a kind of NiO bases compacted zone, perovskite solar cell and preparation method thereof, and perovskite solar cell includes conductive substrates, NiO bases compacted zone, perovskite light-absorption layer, electron transfer layer, interface-modifying layer, metal electrode；Preparation method is as follows：It is dry after conductive substrates are cleaned；Nickelous nitrate hexahydrate and Gerhardite are dissolved in organic solvent, and combustion adjuvant is added, is stirred evenly to get precursor solution；Precursor solution is deposited on conductive substrates with cold nebulization pyrolysismethod, up to NiO base compacted zones after annealing；It is sequentially prepared perovskite light-absorption layer, electron transfer layer, interface-modifying layer and metal electrode on NiO base compacted zones.The NiO bases compacted zone of the present invention can large area prepare, and do not need high-temperature process, while even compact, good conductivity, and the battery device performance of perovskite solar cell prepared by NiO base compacted zones is used to significantly improve, and its stability also significantly improves.
Description
Technical field
The present invention relates to technical field of solar batteries, and in particular to a kind of NiO bases compacted zone, perovskite solar cell
And preparation method thereof.
Background technology
It becomes increasingly conspicuous with the increasingly in short supply and environmental problem of the energy, people are to new energy especially solar cell
Study growing interest.Perovskite solar cell from 2009 for the first time report since, with its low cost, can solution method prepare,
Extensive concern simple for process and by researcher, energy conversion efficiency rapid are promoted to present by initial 3.8%
22.7%.However, constantly promoted simultaneously in efficiency, the stability of device be always limit its commercial applications it is crucial because
Element.
In order to solve the problems, such as that device stability, scientific research personnel have done many trials.Wherein, made using inorganic p-type material
The stability of device can be improved for hole transmission layer.In numerous inorganic p-type materials, NiO is because preparation method is various, energy
Level position is suitable, good chemical stability receives extensive research.But the electric conductivity of NiO films is poor, and it is big at present
The preparation of the NiO films of majority report is prepared using spin-coating method, and the uniformity of film prepared is poor, is unfavorable for large area
The preparation of film, and along with the high temperature anneal process.
In view of this, provide it is a kind of can large area prepare the preparation method of even compact and the NiO films of good conductivity
As technical problem urgently to be resolved hurrily at this stage.
Invention content
In state natural sciences fund (51672094,51661135023), state key development project
Under the support energetically of (2016YFC0205002) and Central China University of Science and Technology's autonomous innovation research foundation (2016JCTD111), this hair
It is bright that a kind of NiO bases compacted zone, perovskite solar cell and preparation method thereof are provided, solve covering for NiO films in the prior art
The technical barrier that lid is poor, preparation temperature is high, electric conductivity is not high.
To reach above-mentioned technical purpose, the present invention provides a kind of preparation method of NiO bases compacted zone, includes the following steps：
S21, Nickelous nitrate hexahydrate and Gerhardite are dissolved in organic solvent, and combustion adjuvant is added, stirred evenly, i.e.,
Obtain precursor solution；
S22, precursor solution is deposited on conductive substrates with cold nebulization pyrolysismethod, is caused up to NiO bases after annealing
Close layer.
The present invention also provides a kind of NiO bases compacted zone, the method for being prepared as described above is prepared.
The present invention also provides a kind of perovskite solar cells, including be cascading from the bottom to top conductive substrates,
NiO bases compacted zone, perovskite light-absorption layer, electron transfer layer, interface-modifying layer, metal electrode, the NiO bases compacted zone is by above-mentioned
Preparation method is arranged in conductive substrates.
The present invention also provides a kind of preparation methods of perovskite solar cell, include the following steps：
S1, it is dried after cleaning conductive substrates；
S2, NiO base compacted zones are set in conductive substrates by the preparation method of NiO base compacted zones；
S3, perovskite light-absorption layer is prepared on NiO base compacted zones；
S4, electron transfer layer is prepared on perovskite light-absorption layer；
S5, interface-modifying layer is prepared on the electron transport layer；
S6, metal electrode is prepared on interface-modifying layer.
Compared with prior art, NiO bases compacted zone of the invention can large area prepare, and do not need high-temperature process, simultaneously
Even compact, good conductivity, and the battery device performance of the perovskite solar cell of NiO base compacted zones preparation is used significantly to carry
Height, and its stability also significantly improves.
Description of the drawings
Fig. 1 is the dimensional structure diagram of the perovskite solar cell of the present invention；
Fig. 2 is thermogravimetric-differential scanning amount thermal map of the presoma of the present embodiment 1；
Fig. 3 is the scanning electron microscope comparison of the conductive substrates of the present embodiment 1 and the NiO base compacted zones prepared in conductive substrates
Figure；
Fig. 4 is the X ray diffracting spectrum of the present embodiment 1 and the NiO base compacted zones of the preparation of embodiment 2；
Fig. 5 is the current density voltage curve comparison of the present embodiment 1 and the perovskite solar cell of the preparation of embodiment 2
Figure；
Fig. 6 is the performance uniformity profiles versus figure of the present embodiment 1 and the perovskite solar cell of the preparation of embodiment 2；
Fig. 7 is the stability contrast figure of the present embodiment 1 and the perovskite solar cell of the preparation of embodiment 2.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
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.
The present invention provides a kind of perovskite solar cells comprising the conductive base being cascading from the bottom to top
Bottom, NiO bases compacted zone, perovskite light-absorption layer, electron transfer layer, interface-modifying layer, metal electrode；Wherein, the perovskite is inhaled
Photosphere is ABX3, A CH3NH3 +、CH(NH2)2 +、Cs+At least one of, B Pb2+、Sn2+At least one of, X Cl-、
Br-、I-At least one of；The electron transfer layer is fullerene derivate film PC61CM and/or PC71BM；It repaiies at the interface
It is LIF, BCP, TiO to adorn layerxAt least one of；The metal electrode is Ag and/or Al.
The specific preparation method of perovskite solar cell is as follows：
S1, it is dried after cleaning conductive substrates；
Specifically, the present embodiment is surpassed with glass cleaning solution, deionized water, industrial alcohol, absolute ethyl alcohol, acetone respectively successively
Sonication 20min after the completion of processing, is dried up with dry nitrogen, is preserved for use；It is existing often that other can also be used in the present embodiment
Rule mode is cleaned, is dried.
S2, NiO base compacted zones are set in conductive substrates；
NiO base compacted zones are prepared as follows：
S21, Nickelous nitrate hexahydrate and Gerhardite are dissolved in organic solvent, and combustion adjuvant is added, stirred evenly, i.e.,
Obtain precursor solution；
After Nickelous nitrate hexahydrate and Gerhardite are added in organic solvent, need to add after it is completely dissolved
Combustion adjuvant, and need after being stirred at room temperature 10~12 hours, you can obtain the forerunner that solute concentration is 0.01~0.5mol/L
Liquid solution, and wherein atomic ratio Cu:(Ni+Cu)=0~10%, preferably 2~8%, more preferably 4~6%.Wherein, it needs
Illustrate, when Cu contents are 0, then the corresponding Gerhardite amount being added is zero.
Wherein, combustion adjuvant described in the present embodiment is acetylacetone,2,4-pentanedione, urea, at least one of glycine, described organic molten
Agent is at least one of ethylene glycol monomethyl ether, acetonitrile, ethylene glycol.
S22, precursor solution is deposited on conductive substrates with cold nebulization pyrolysismethod, is caused up to NiO bases after annealing
Close layer, and NiO bases compacted zone described in the present embodiment is NiO films.
When carrying out spray pyrolysis using cold nebulization pyrolysismethod, in order to improve the NiO base compacted zones formed after spray pyrolysis
Even compact, the spraying nebulizer gas pressure of the present embodiment spray pyrolysis is 0.1~0.5Mpa, nozzle diameter size be 0.1~
0.5mm, nozzle to thermal station distance be 10~40cm, spraying total amount be 20~100mL.
Wherein, the annealing is the 30~90min that anneals at a temperature of 250~350 DEG C, may make conductive substrates
The upper NiO films for forming crystalline state.
The present embodiment prepares NiO films by the above method, realizes the low temperature preparation of NiO films, i.e., 250~
350 DEG C of preparations, which obviate traditional high temperature to prepare (500 DEG C or more), while by the way of spray pyrolysis, can prepare
The large area NiO films of even densification, and Copper-cladding Aluminum Bar is realized by the Gerhardite of addition, the conduction of nickel oxide can be changed
Property, improve the performance and stability of device.
S3, perovskite light-absorption layer is prepared on NiO base compacted zones；
Mole ratio is 1 by the present embodiment:1 to 1:3 PbX2Powder and AX powder mixed dissolution are in DMF, DMSO or two
In the mixed solution of person, and stirring obtains the APbX that Pb molar concentrations are 1~2mol/L to dissolving at 10~70 DEG C3Solution；
By above-mentioned APbX3Solution is spin-coated on NiO base compacted zones, and the rotating speed of spin coating is 4000~6000 revolutions per seconds, the time is 10~30
Second；Then with 100~200 DEG C of heating plate 5~30min of annealing, cooled to room temperature is to get perovskite light-absorption layer.
S4, electron transfer layer is prepared on perovskite light-absorption layer；
The present embodiment weighs a certain amount of PCBM and incorporates in chlorobenzene, the solution of 10~30mg/ml is configured to, at 30~50 DEG C
The PCBM solution of preparation is spin-coated on perovskite light-absorption layer by lower stirring to dissolving, and the rotating speed of spin coating is 2000~4000 turns/
Second, time are 10~30 seconds；Then with 70 DEG C of heating plate 5~30min of annealing, cooled to room temperature is to get electron-transport
Layer.
S5, interface-modifying layer is prepared on the electron transport layer；
The present embodiment incorporates BCP in methanol, is configured to saturated solution, the BCP saturated solutions of preparation are spin-coated on PCBM
On electron transfer layer, spin coating rotating speed is 1000~6000 revolutions per seconds, the time is 10~30 seconds；Then 70 DEG C of heating plates annealing 5~
30min, cooled to room temperature is to get interface-modifying layer.
S6, metal electrode is prepared on interface-modifying layer；
Thermal evaporation apparatus pressure is evacuated to 1*10 by the present embodiment-5~5*10-4After Pa, evaporation power supply is opened, by Ag or Al heat
In hydatogenesis to BCP interface-modifying layers, deposition rate is 0.1~0.5 angstroms per second, and deposition thickness is 100~300nm, and area is
1.0124cm2。
NiO bases compacted zone and perovskite solar cell manufactured in the present embodiment have more preferably property for convenience of description
Can, now carry out following examples：
Embodiment 1：NiO bases compacted zone and perovskite solar cell are prepared using cold nebulization pyrolysismethod, specifically, pressing
Above-mentioned steps S1~S6 prepares NiO bases compacted zone and perovskite solar cell respectively.
As shown in Fig. 2, it is in the NiO base compacted zone preparation process of the present embodiment 1, thermogravimetric-differential of presoma scans
Calorimetric figure, as shown in Figure 2, presoma start to decompose at 250~350 DEG C, and form NiO films.
As shown in figure 3, it is in the NiO base compacted zone preparation process of the present embodiment 1, conductive substrates and in conductive substrates
The scanning electron microscope comparison diagram of the NiO base compacted zones of preparation is located at right side wherein being the scanning electron microscope (SEM) photograph of conductive substrates positioned at left side
It is that the scanning electron microscope (SEM) photograph for having NiO base compacted zones is prepared in conductive substrates, by above-mentioned comparison diagram it is found that using the present embodiment 1
NiO films prepared by preparation method can be uniformly covered in conductive substrates.
Embodiment 2：NiO films and perovskite solar cell are prepared using traditional spin-coating method, specially by above-mentioned steps
Step S2 in S1~S6 is replaced using following steps S2 '：
S2 ', NiO base compacted zones are prepared in conductive substrates；
The present embodiment 2 is by nickel acetate and ethanol amine in molar ratio 1:1, which is dissolved in ethyl alcohol, forms nickel ion concentration as 0.05mol/L
Precursor solution；Above-mentioned precursor solution is deposited on by spin-coating method in conductive substrates, at a temperature of 250~350 DEG C
30~90min of annealing is deposited on the NiO base compacted zones in conductive substrates to obtain the final product.
NiO bases compacted zone and perovskite solar cell prepared by above-described embodiment 1 and embodiment 2 are compared as follows
Test：Wherein, embodiment 1 is divided to for two embodiments：Embodiment 1, atomic ratio Cu in precursor solution:(Ni+Cu)=
5%, it corresponds to and copper is mixed with cold nebulization pyrolysis in figure below；Embodiment 2, atomic ratio Cu in precursor solution:(Ni+Cu)=0,
Its correspondence is pyrolyzed with cold nebulization in figure below.
And embodiment 2 is prepared using existing conventional method, i.e., is prepared using existing conventional spin-coating method, and
It corresponds to traditional spin coating in figure below.
One, X ray diffracting spectrum compares
NiO bases compacted zone prepared by the embodiment 2 of the present embodiment 1 and embodiment 2 is subjected to X-ray under the same conditions
Diffracting spectrum is tested, ranging from 10~70 ° of test angle, and test voltage 40kV, test electric current are 40mA, and test result is asked
Referring to Fig. 4, by above-mentioned Fig. 4 it is found that NiO base compacted zones prepared by the present embodiment 1 have more preferably performance.
Two, current density voltage curve comparison diagram
Perovskite solar cell prepared by the embodiment 1 of the present embodiment 1 and 2 and embodiment 2 is under the same conditions
Current density-voltage test is carried out, at the standard conditions (AM1.5,100mW/cm2) tested, test result please refers to
Fig. 5, as shown in Figure 5, the perovskite solar cell current voltage characteristics having the same that the present embodiment 1 is prepared with embodiment 2.
Three, performance uniformity profiles versus schemes
Perovskite solar cell prepared by the embodiment 1 of the present embodiment 1 and 2 and embodiment 2 is under the same conditions
Current density-voltage test is carried out, at the standard conditions (AM1.5,100mW/cm2) tested, the performance measured is joined
Number (current density, open-circuit voltage, fill factor and energy conversion efficiency) carries out analysis of Uniformity comparison respectively, and comparing result is asked
Refering to Fig. 6, it will be appreciated from fig. 6 that perovskite solar cell prepared by the cold nebulization pyrolysismethod in the present embodiment 1 is with better
Performance, and using embodiment 1 when its performance more preferably.
Four, stability contrast figure
Perovskite solar cell prepared by the present embodiment 1 and embodiment 2 is subjected to stability test under the same conditions,
Testing standard is：It will prepare and unpackaged device is placed in vacuum glove box and preserves, it is at regular intervals that device is initial,
Current density-voltage test carried out to device in regular air environment, registering device can transfer efficiency (PCE), and draw
Comparison diagram, comparison diagram is referring to Fig. 7, as shown in Figure 7, the perovskite sun prepared by the cold nebulization pyrolysismethod in the present embodiment 1
Energy battery obviously has better stability, and more preferably using its stability when embodiment 1.
The specific implementation mode of present invention described above, is not intended to limit the scope of the present invention..Any basis
The various other corresponding changes and deformation that the technical concept of the present invention is made, should be included in the guarantor of the claims in the present invention
It protects in range.
Claims (9)
1. a kind of preparation method of NiO bases compacted zone, which is characterized in that include the following steps：
S21, Nickelous nitrate hexahydrate and Gerhardite are dissolved in organic solvent, and combustion adjuvant is added, stirred evenly to get preceding
Drive liquid solution；
S22, precursor solution is deposited on conductive substrates with cold nebulization pyrolysismethod, up to NiO base compacted zones after annealing.
2. preparation method as described in claim 1, which is characterized in that a concentration of the 0.01 of the precursor solution~
0.5mol/L, and wherein atomic ratio Cu:(Ni+Cu)=0~10%.
3. preparation method as described in claim 1, which is characterized in that the spraying nebulizer gas pressure in the cold nebulization pyrolysismethod
For 0.1~0.5Mpa, nozzle diameter size be 0.1~0.5mm, the distance of nozzle to thermal station is 10~40cm, spraying total amount is
20~100mL.
4. preparation method as described in claim 1, which is characterized in that the combustion adjuvant is in acetylacetone,2,4-pentanedione, urea, glycine
At least one, the organic solvent is ethylene glycol monomethyl ether, acetonitrile, at least one of ethylene glycol.
5. preparation method as described in claim 1, which is characterized in that the annealing is at a temperature of 250~350 DEG C
Anneal 30~90min.
6. a kind of NiO bases compacted zone, which is characterized in that prepared by any preparation method of claim 1~6.
7. a kind of perovskite solar cell, which is characterized in that including be cascading from the bottom to top conductive substrates, NiO
Base compacted zone, perovskite light-absorption layer, electron transfer layer, interface-modifying layer, metal electrode, the NiO bases compacted zone are wanted by right
1~6 any preparation method is asked to be arranged in conductive substrates.
8. perovskite solar cell as described in claim 1, which is characterized in that the perovskite light-absorption layer is ABX3, A is
CH3NH3 +、CH(NH2)2 +、Cs+At least one of, B Pb2+、Sn2+At least one of, X Cl-、Br-、I-In at least one
Kind；The electron transfer layer is fullerene derivate film PC61CM and/or PC71BM；The interface-modifying layer be LIF, BCP,
TiOxAt least one of；The metal electrode is Ag and/or Al.
9. a kind of preparation method of perovskite solar cell, which is characterized in that include the following steps：
S1, it is dried after cleaning conductive substrates；
S2, NiO base compacted zones are set in conductive substrates by claim 1~6 any preparation method；
S3, perovskite light-absorption layer is prepared on NiO base compacted zones；
S4, electron transfer layer is prepared on perovskite light-absorption layer；
S5, interface-modifying layer is prepared on the electron transport layer；
S6, metal electrode is prepared on interface-modifying layer.
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| CN114715958A (en) * | 2022-03-08 | 2022-07-08 | 华能新能源股份有限公司 | Spray pyrolysis method of nickel oxide and perovskite solar cell |
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| CN114715958B (en) * | 2022-03-08 | 2024-04-02 | 华能新能源股份有限公司 | Spray pyrolysis method of nickel oxide and perovskite solar cell |
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