CN107993848B - Based on the titania-doped perovskite solar battery and preparation method thereof of nickel - Google Patents
Based on the titania-doped perovskite solar battery and preparation method thereof of nickel Download PDFInfo
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- CN107993848B CN107993848B CN201711088549.0A CN201711088549A CN107993848B CN 107993848 B CN107993848 B CN 107993848B CN 201711088549 A CN201711088549 A CN 201711088549A CN 107993848 B CN107993848 B CN 107993848B
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention belongs to minute manufacturing correlative technology fields, and it discloses the preparation methods based on the titania-doped perovskite solar battery of nickel, method includes the following steps: (1) starts the cleaning processing conductive substrates；(2) immersion method is used to deposit the titania-doped film of nickel of Rutile Type in the conductive substrates to form light anode, annealing temperature is 450 DEG C~500 DEG C；(3) in the surface spin coating perovskite precursor solution of the light anode, and heated to obtain light absorbing layer；(4) one layer of CuPc is deposited to form hole transmission layer on the surface of the light absorbing layer；(5) it is formed a film by silk-screen printing commercialization carbon paddle to form carbon on the hole transport layer to electrode layer, is thus terminated.The present invention further relates also to the perovskite solar battery titania-doped based on nickel.Present invention decreases production costs, substantially increase the performance and stability of battery, are conducive to the large-scale commercial production of battery.
Description
Technical field
The invention belongs to minute manufacturing correlative technology fields, more particularly, to a kind of titania-doped based on nickel
Perovskite solar battery and preparation method thereof.
Background technique
The energy is one of the three big basic resources of human survival and social development, and the most commonly used energy of modern society is still
It is fossil energy, on the one hand, conventional fossil fuel is depleted；On the other hand, the environmental pollution of combustion of fossil fuel bring is tight
The living environment of this mankind is threatened again.And solar energy will be accounted for as cleaning, sustainable new energy in following energy resource structure
Research and application according to most important status, therefore to heliotechnics is increasingly extensive.
By long-term research with development, solar battery experienced first generation crystal silicon based solar battery, second is based on
The thin-film solar cells of CuInGaSe, CdTe etc. and third generation quantum dot solar cell epoch.However, these solar-electricities
Pond all haves the defects that itself, for example silica-based solar cell is there are high production cost, production process energy consumption is big, environment is dirty
The problems such as dye is serious, the cost recovery time is long；In second generation thin-film solar cells, containing very deficient in the earth's crust in CuInGaSe
Weary element In and Ga, is unfavorable for the extensive sustainable development of such battery, and contains important element Cd in CdTe, will cause ring
Border pollution problem；There are quantum dots to prepare more difficult, the lower problem of efficiency for quantum dot solar cell.Nowadays efficient, cheap,
The novel solar battery technology of environmental protection, such as paint vehicle sensitization solar battery, organic solar batteries, perovskite solar battery
Technology continues to bring out, wherein burning the hotest to the research of perovskite solar battery.
2009, Japanese Miyasaka et al. was during studying sensitization solar battery, for the first time using with calcium titanium
The organic metal halide CH of mine structure3NH3PbBr3And CH3NH3PbI3As sensitizer, perovskite solar battery has been pulled open
The prelude of research.In recent years, perovskite solar battery technology achieves the progress advanced by leaps and bounds, energy conversion efficiency
Have been over paint vehicle sensitization solar battery, organic solar batteries etc., nearest Korea Research Institute of Chemical Technology (KRICT) and South Korea
The perovskite solar battery cell highest transformation efficiency of Wei Shan University of Science and Technology (UNIST) exploitation has been more than current up to 22.1%
The level of the technology CuInGaSe thin film solar cell of comparative maturity.In addition to high conversion efficiency, perovskite solar battery
There is also it is at low cost, can solution preparation, the hot spots such as all solid state, for preparation can roll-to-roll mass production the flexible perovskite sun
Energy battery creates condition, and therefore, it is the existing business sun that perovskite solar battery, which has very bright industrialization prospect,
The competitor of the energy optimal potentiality of battery.
Currently, in perovskite solar battery preparation field, because of TiO2With at low cost, preparation process is simple, properly
Conduction band and and valence band, excellent light transmittance and high physics and the advantages that chemical stability, height is widely used in high efficiency battery
The Anatase TiO of temperature sintering2As light anode.But pure TiO2There are conductivity is low and defect state density height etc. lacks for film
Point, and by TiO2These defects can be effectively improved by being doped processing, prepare TiO compared to traditional high temperature sintering2Light sun
Pole, the TiO of some low temperature preparation techniques such as low temperature CBD technique preparation2Have the shortcomings that crystallinity is not high, and is based on low temperature preparation
TiO2Battery there are fill factors it is low, dim light performance is poor, magnetic hysteresis is larger the disadvantages of.
In addition, most popular organic hole transport material such as spiro-OMeTAD, PTAA etc., structure are expensive at this stage
And charge transport properties are poor, the organic additive used to improve its performance easily aoxidizes in air, further drops
The low stability of battery.Thermal evaporation noble metal gold or silver are generallyd use to prepare to electrode, energy consumption is higher, and thermal evaporation is past
Toward condition of high vacuum degree is needed, along with the consumption of noble metal, so that battery preparation cost is higher, it is unfavorable for the extensive system of battery
It is standby, difficulty is brought to the industrialization of battery.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, it is titania-doped based on nickel that the present invention provides a kind of
A kind of production is studied and devised to perovskite solar battery and preparation method thereof based on the preparation characteristic of existing light anode
Cost is relatively low and the higher perovskite solar battery and preparation method thereof titania-doped based on nickel of stability test.This
The nickel doped rutile phase TiO that invention is prepared using CBD method2As light anode, and high temperature sintering is carried out to it to improve crystallization
Degree, not only increases its charge transport ability, also improves TiO2Surface topography, and then promote and be deposited in light anode
The well-crystallized of perovskite, the experimental results showed that the short circuit current of battery and fill factor all obtain larger raising；Use phase
Stability and the better ternary mixed-cation perovskite persursor material of thermal stability enhance the stabilization of prepared battery
Property；Using cheap and high stability CuPc and carbon respectively as hole transmission layer and to electrode material, have instead of expensive
Machine high-molecular hole conduction material and noble metal both reduce production cost, further improve the stabilization of battery to electrode
Property.
To achieve the above object, according to one aspect of the present invention, a kind of calcium titania-doped based on nickel is provided
The preparation method of titanium ore solar battery, method includes the following steps:
(1) conductive substrates are provided, and etch groove in the conductive substrates；
(2) it is dried up after being cleaned to the conductive substrates, UV ozone processing then is carried out to the conductive substrates；
(3) the titania-doped film of nickel of Rutile Type is deposited in the conductive substrates using immersion method, and carried out
Annealing, to form light anode, wherein annealing temperature is 450 DEG C~500 DEG C；
(4) in the surface spin coating perovskite precursor solution of the light anode, and heated mixed to obtain ternary
Cations calcium titanium ore bed, i.e. light absorbing layer；The ternary mixed-cation calcium titanium ore bed is Cs0.05(MA0.17FA0.83)0.95Pb
(I0.83Br0.17)3；
(5) under vacuum condition, one layer of CuPc is deposited on the surface of the light absorbing layer, to form hole transmission layer；
(6) it is formed a film by silk-screen printing commercialization carbon paddle to form carbon on the hole transport layer to electrode layer, it is thus complete
At the preparation based on the titania-doped perovskite solar battery of nickel.
Further, the annealing temperature is 500 DEG C.
Further, the conductive substrates include substrate glass and the FTO conductive layer being arranged in the substrate glass, institute
Groove is stated through the FTO conductive layer, and adjacent to one end of the conductive substrates；The light anode setting is conductive in the FTO
Layer covers the side wall wall surface of the groove, the side wall wall surface and the base far from the surface of the substrate glass simultaneously
Sheet glass is intersected vertically by the surface region that the light anode covers.
Further, step (2) is specifically includes the following steps: be respectively cleaned by ultrasonic institute with acetone, ethyl alcohol, deionized water respectively
It states conductive substrates 10 minutes~15 minutes, is then dried up with nitrogen stream, then UV ozone processing 20 is carried out to the conductive substrates
Minute~30 minutes.
Further, it is put vertically after step (3) is specifically includes the following steps: the conductive substrates are fixed by retainer
It sets in the beaker for filling growth solution, then the beaker is placed in thermostat water bath, and by the reaction of the growth solution
At 70 DEG C~75 DEG C, growth time is 2.5 hours~3.5 hours for temperature control, is finally annealed 0.5 hour~1 hour.
Further, the source Ti of the growth-promoting media is TiCl4, nickel doped source is NiCl2·6H2O, wherein TiCl4Concentration
For 0.2mol/L~0.3mol/L, NiCl2·6H2The concentration of O is 0mol/L~0.013mol/L.
Further, the concentration of the perovskite precursor solution is 1.25mol/L~1.3mol/L.
Further, evaporation rate control exists
Other side according to the invention provides a kind of perovskite solar-electricity titania-doped based on nickel
Pond, the perovskite solar battery are using perovskite solar battery titania-doped based on nickel as described above
Preparation method preparation.
Further, the light anode with a thickness of 150nm~200nm；The hole transmission layer with a thickness of 35nm~
40nm；The carbon is to electrode layer with a thickness of 10 μm~30 μm.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, base provided by the invention
It is mainly had the advantages that in titania-doped perovskite solar battery of nickel and preparation method thereof
1. using the nickel doped rutile phase TiO of high temperature sintering2As light anode, CBD method prepares Rutile Type TiO2And it is right
It mixes nickel, then through high temperature sintering to improve TiO2The crystallinity of layer is put forward for the first time with the technique system for reducing defect state；Secondly, phase
Compared with the Anatase TiO of slab construction2, Rutile Type TiO2Film has bigger surface area, can be between calcium titanium ore bed
It is formed and is in close contact, therefore be more advantageous to the migration of photo-generated carrier；Finally, nickel doping can change TiO2Fermi level,
The concentration of free carrier is promoted, TiO is improved2Electric conductivity and electron transfer rate, improve TiO2The interfacial characteristics of film promote
Into the crystallization of perovskite, to reduce the electronic defects density of states and unfavorable charge recombination；In addition, this CBD mixes nickel mode
Advantage also resides in TiCl4The strong acidic environment generated when hydrolysis can effectively prevent the formation of NiO resistive layer from mixing through testing and verification
Effect is best when miscellaneous concentration is 0.01M nickel, and battery peak efficiency reaches 17.46%, and the efficiency is in the carbon-based calcium titanium being currently known
It is highest in mine solar battery；
2. using ternary mixed-cation perovskite as light absorbing layer, compared to widely used MAPbI3Perovskite,
Ternary mixed-cation perovskite Cs0.5(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3With more suitable energy band and higher steady
It is qualitative, experiments verify that, using ternary mixed-cation perovskite as light absorbing layer, it not only can effectively promote the short of battery
The major parameters such as road electric current and open-circuit voltage, can also greatly improve the stability of battery；
3. using inexpensively and high stability CuPc be used as hole transport layer material, substitution it is widely used it is expensive with
Unstable organic polymer hole mobile material can not only greatly reduce production cost, but also can promote the stability of battery, have
Conducive to the large-scale commercial production of battery；
4. replacing expensive gold or silver to make both to reduce electrode material using the carbon of cheap, high conductivity and high stability
Production cost, and the stability of battery is improved, carbon forms a film to electrode by low temperature silk-screen printing, on the one hand reduce production
Energy consumption, on the other hand can also be by controlling accurate control of the number realization of silk-screen printing to carbon layers having thicknesses.
Detailed description of the invention
Fig. 1 is the system for the perovskite solar battery titania-doped based on nickel that better embodiment of the present invention provides
The flow diagram of Preparation Method；
Fig. 2 is prepared using the preparation method of the perovskite solar battery titania-doped based on nickel in Fig. 1
Structural schematic diagram based on the titania-doped perovskite solar battery of nickel；
(a), (b) in Fig. 3 are undoped with TiO respectively2And the perovskite sun titania-doped based on nickel in Fig. 1
Can battery the CBD growth 3h that is related to of preparation method, nickel doping concentration is 0.01M, at 100 DEG C annealing 1h preparation with a thickness of
The Rutile Type TiO of 150nm~200nm2Scanning electron microscope diagram.
In all the appended drawings, identical appended drawing reference is used to denote the same element or structure, in which: 1- substrate glass,
2-FTO conductive layer, 3- light anode, 4- light absorbing layer, 5- hole transmission layer, 6- carbon is to electrode layer.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention 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.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Please refer to Fig. 1, Fig. 2 and Fig. 3, the perovskite titania-doped based on nickel that better embodiment of the present invention provides
The preparation method of solar battery, the nickel doped rutile phase TiO for using CBD method to prepare2It is carried out as light anode, and to it
High temperature sintering not only increases its charge transport ability, also improves TiO to improve crystallinity2Surface topography, and then promote
It is deposited on the well-crystallized of the perovskite in light anode, the experimental results showed that the short circuit current of battery and fill factor all obtain
Larger raising；Using phase stability and the better ternary mixed-cation perovskite persursor material of thermal stability, enhance
The stability of prepared battery；Using cheap and high stability CuPc and carbon respectively as hole transmission layer and to electrode material
Material both reduces production cost, further instead of expensive organic polymer hole mobile material and noble metal to electrode
Improve the stability of battery.
The preparation method of the perovskite solar battery titania-doped based on nickel mainly comprises the steps that
Step 1 provides conductive substrates, and etches groove in the conductive substrates.Specifically, FTO conduction glass is provided
For glass as conductive substrates, the conductive substrates include substrate glass 1 and the FTO conductive layer 2 that is arranged in the substrate glass 1,
The groove runs through the FTO conductive layer 2, and one end of the neighbouring conductive substrates；Use concentration for 2mol/L~2.5mol/
The dilute hydrochloric acid and zinc powder of L is handled the conductive layer of the conductive substrates to etch the groove.Wherein, FTO conduction glass
Glass is that sputtering has one layer of Fluorin doped SnO in silicon boryl substrate glass2The glass of conductive layer.
Step 2 dries up after cleaning to the conductive substrates, then carries out at UV ozone to the conductive substrates
Reason.Specifically, respectively it is cleaned by ultrasonic the conductive substrates 10 minutes~15 minutes with acetone, ethyl alcohol, deionized water respectively, then uses
Nitrogen stream drying, then UV ozone is carried out to the conductive substrates and is handled 20 minutes~30 minutes.
Step 3 deposits the titania-doped film of nickel of Rutile Type using immersion method in the conductive substrates, with
Form light anode 3.Specifically, the conductive substrates are placed on after fixed to the beaker for filling growth solution vertically by retainer
In, then the beaker is placed in thermostat water bath, and the reaction temperature of the growth solution is controlled at 70 DEG C~75 DEG C, it is raw
For a long time it is 2.5 hours~3.5 hours, finally anneals 0.5 hour~1 hour, annealing temperature is 450 DEG C~500 DEG C, preferably
It is 500 DEG C.The source Ti of the growth-promoting media is TiCl4, nickel doped source is NiCl2·6H2O, wherein TiCl4Concentration be 0.2mol/
L~0.3mol/L, NiCl2·6H2The concentration of O is 0mol/L~0.013mol/L.The light anode 3 with a thickness of 150nm~
200nm.In present embodiment, the light anode 3 is arranged on surface of the FTO conductive layer 2 far from the substrate glass 1,
The table that its side wall wall surface for covering the groove simultaneously, the side wall wall surface and the substrate glass 1 are covered by the light anode 3
Face region intersects vertically.
Step 4 in the surface spin coating perovskite precursor solution of the light anode 3, and is heated to obtain three
First mixed-cation calcium titanium ore bed, i.e. light absorbing layer 4.In present embodiment, the concentration of the perovskite precursor solution is
1.25mol/L~1.3mol/L.
Specifically, after the 60 μ L perovskite precursor solutions of μ L~80 are added dropwise on the surface of the light anode 3, then with revolving speed
1000rpm~1500rpm spin coating 8s~10s, then with revolving speed 6000rpm spin coating 20s~22s, with revolving speed 6000rpm spin coating
The 130 μ L chlorobenzenes of μ L~140 are added dropwise at the 14th~15 second as anti-solvent, then will be deposited with the conductive base of calcium titanium ore bed again
45 minutes~55 minutes Cs to form high-crystallinity are heated at 100 DEG C~102 DEG C in bottom0.05(MA0.17FA0.83)0.95Pb
(I0.83Br0.17)3Calcium titanium ore bed, i.e. light absorbing layer 4.The whole preparation process of the light absorbing layer 4 is in the hand for being full of nitrogen
It is carried out in casing.
Under vacuum condition, one layer of CuPc is deposited on the surface of the light absorbing layer 4, to form hole transport in step 5
Layer 5.Specifically, pressure is less than 10-3Under the high vacuum condition of Pa, a layer thickness is deposited on the surface of the light absorbing layer 4 it is
The CuPc of 35nm~40nm exists as hole transmission layer 5, evaporation rate control
Step 6, is formed a film by silk-screen printing commercialization carbon paddle to form carbon on the hole transport layer to electrode layer 6, by
This completes the preparation based on the titania-doped perovskite solar battery of nickel.Specifically, thickness of the carbon to electrode layer 6
It is 10 μm~30 μm；The carbon covers surface of the hole transmission layer 5 far from the conductive substrates, the sky to electrode layer 6
Cave transport layer 5 is neighbouring adjacent to one end of the groove and the light anode 3 adjacent to one end of the groove, the light absorbing layer 4
One end of the groove.
The present invention also provides the perovskite solar battery titania-doped based on nickel, the perovskite solar batteries
It is to be prepared using the preparation method as described above based on the titania-doped perovskite solar battery of nickel.
With several specific embodiments, the present invention is further described in detail below.
Embodiment 1
The preparation method for the perovskite solar battery titania-doped based on nickel that first embodiment of the invention provides
It mainly comprises the steps that
11. using concentration is the dilute hydrochloric acid of 2mol/L and zinc powder to conductive substrates using FTO electro-conductive glass as conductive substrates
FTO conductive layer handled, to etch groove.
12. being respectively cleaned by ultrasonic conductive substrates 15 minutes with acetone, ethyl alcohol, deionized water respectively, then dried up with nitrogen stream,
UV ozone is carried out to FTO conductive layer again to handle 30 minutes.
13. being placed in the beaker for filling growth solution vertically after conductive substrates are fixed by retainer, then will be described
Beaker is placed in thermostat water bath, and by reaction temperature control at 70 DEG C, growth time is 3 hours, finally annealing 0.5~1
Hour, annealing temperature was 500 DEG C to form light anode.Wherein, the TiCl in the growth-promoting media4Concentration and NiCl2·6H2O's
Concentration is respectively 0.2mol/L and 0mol/L.
14. after 70 μ L perovskite precursor solutions are added dropwise in the surface of the light anode, first with 1000rpm low speed spin coating
10s, then with 6000rpm high speed spin coating 22s, the 130 μ L chlorobenzenes of μ L~140 are added dropwise at the 15th second of high speed spin coating as anti-molten
Then the conductive substrates for being deposited with calcium titanium ore bed are heated 45 minutes Cs to form high-crystallinity by agent at 100 DEG C0.05
(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3Calcium titanium ore bed, i.e. light absorbing layer.The whole preparation process of the light absorbing layer is being filled
It is carried out in the glove box of full nitrogen.
15. pressure is less than 10-3The CuPc layer conduct of 35nm thickness is deposited under the high vacuum condition of Pa, on the light absorbing layer
Hole transmission layer, evaporation rate control exist
16. by silk-screen printing commercialization carbon slurry film forming the FTO conductive layer one end and the hole transmission layer it is upper
Surface forms carbon to electrode layer, and then completes entirely to adulterate TiO based on low temperature nickel2Perovskite solar battery preparation.Institute
The solvent drying temperature for the carbon slurry stated is set as 85 DEG C.
Embodiment 2
The preparation method for the perovskite solar battery titania-doped based on nickel that second embodiment of the invention provides
It mainly comprises the steps that
21. using concentration is the dilute hydrochloric acid of 2mol/L and zinc powder to conductive substrates using FTO electro-conductive glass as conductive substrates
FTO conductive layer handled, to etch groove.
22. being respectively cleaned by ultrasonic the conductive substrates 15 minutes with acetone, ethyl alcohol, deionized water respectively, nitrogen stream is then used
Drying, then UV ozone is carried out to FTO conductive layer and is handled 30 minutes.
23. being placed in the beaker for filling growth solution vertically after conductive substrates are fixed by retainer, then will be described
Beaker is placed in thermostat water bath, and by reaction temperature control at 70 DEG C, growth time is 3 hours, finally annealing 0.5~1
Hour, annealing temperature was 500 DEG C to form light anode.Wherein, the TiCl in the growth-promoting media4Concentration and NiCl2·6H2O's
Concentration is respectively 0.2mol/L and 0.004mol/L.
24. after 70 μ L perovskite precursor solutions are added dropwise in the surface of the light anode, first with 1000rpm low speed spin coating
10s, then with 6000rpm high speed spin coating 22s, the 130 μ L chlorobenzenes of μ L~140 are added dropwise at the 15th second of high speed spin coating as anti-molten
Then the conductive substrates for being deposited with calcium titanium ore bed are heated 45 minutes Cs to form high-crystallinity by agent at 100 DEG C0.05
(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3Calcium titanium ore bed, i.e. light absorbing layer.The whole preparation process of the light absorbing layer is being filled
It is carried out in the glove box of full nitrogen.
25. pressure is less than 10-3The CuPc layer conduct of 35nm thickness is deposited under the high vacuum condition of Pa, on the light absorbing layer
Hole transmission layer, evaporation rate control exist
26. by silk-screen printing commercialization carbon slurry film forming the FTO conductive layer one end and the hole transmission layer it is upper
Surface forms carbon to electrode layer, and then completes entirely to adulterate TiO based on low temperature nickel2Perovskite solar battery preparation.Institute
The solvent drying temperature for the carbon slurry stated is set as 85 DEG C.
Embodiment 3
The preparation method for the perovskite solar battery titania-doped based on nickel that third embodiment of the invention provides
It mainly comprises the steps that
31. using concentration is the dilute hydrochloric acid of 2mol/L and zinc powder to conductive substrates using FTO electro-conductive glass as conductive substrates
FTO conductive layer handled, to etch groove.
32. being respectively cleaned by ultrasonic the conductive substrates 15 minutes with acetone, ethyl alcohol, deionized water respectively, nitrogen stream is then used
Drying, then UV ozone is carried out to FTO conductive layer and is handled 30 minutes.
33. being placed in the beaker for filling growth solution vertically after conductive substrates are fixed by retainer, then will be described
Beaker is placed in thermostat water bath, and by reaction temperature control at 70 DEG C, growth time is 3 hours, finally annealing 0.5~1
Hour, annealing temperature was 500 DEG C to form light anode.Wherein, the TiCl in the growth-promoting media4Concentration and NiCl2·6H2O's
Concentration is respectively 0.2mol/L and 0.007mol/L.
34. after 70 μ L perovskite precursor solutions are added dropwise in the surface of the light anode, first with 1000rpm low speed spin coating
10s, then with 6000rpm high speed spin coating 22s, the 130 μ L chlorobenzenes of μ L~140 are added dropwise at the 15th second of high speed spin coating as anti-molten
Then the conductive substrates for being deposited with calcium titanium ore bed are heated 45 minutes Cs to form high-crystallinity by agent at 100 DEG C0.05
(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3Calcium titanium ore bed, i.e. light absorbing layer.The whole preparation process of the light absorbing layer is being filled
It is carried out in the glove box of full nitrogen.
35. pressure is less than 10-3The CuPc layer conduct of 35nm thickness is deposited under the high vacuum condition of Pa, on the light absorbing layer
Hole transmission layer, evaporation rate control exist
36. by silk-screen printing commercialization carbon slurry film forming the FTO conductive layer one end and the hole transmission layer it is upper
Surface forms carbon to electrode layer, and then completes entirely to adulterate TiO based on low temperature nickel2Perovskite solar battery preparation.Institute
The solvent drying temperature for the carbon slurry stated is set as 85 DEG C.
Embodiment 4
The preparation method for the perovskite solar battery titania-doped based on nickel that first embodiment of the invention provides
It mainly comprises the steps that
41. using concentration is the dilute hydrochloric acid of 2mol/L and zinc powder to conductive substrates using FTO electro-conductive glass as conductive substrates
FTO conductive layer handled, to etch groove.
42. being respectively cleaned by ultrasonic conductive substrates 15 minutes with acetone, ethyl alcohol, deionized water respectively, then dried up with nitrogen stream,
UV ozone is carried out to FTO conductive layer again to handle 30 minutes.
43. being placed in the beaker for filling growth solution vertically after conductive substrates are fixed by retainer, then will be described
Beaker is placed in thermostat water bath, and by reaction temperature control at 70 DEG C, growth time is 3 hours, finally annealing 0.5~1
Hour, annealing temperature was 500 DEG C to form light anode.Wherein, the TiCl in the growth-promoting media4Concentration and NiCl2·6H2O's
Concentration is respectively 0.2mol/L and 0.01mol/L.
44. after 70 μ L perovskite precursor solutions are added dropwise in the surface of the light anode, first with 1000rpm low speed spin coating
10s, then with 6000rpm high speed spin coating 22s, the 130 μ L chlorobenzenes of μ L~140 are added dropwise at the 15th second of high speed spin coating as anti-molten
Then the conductive substrates for being deposited with calcium titanium ore bed are heated 45 minutes Cs to form high-crystallinity by agent at 100 DEG C0.05
(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3Calcium titanium ore bed, i.e. light absorbing layer.The whole preparation process of the light absorbing layer is being filled
It is carried out in the glove box of full nitrogen.
45. pressure is less than 10-3The CuPc layer conduct of 35nm thickness is deposited under the high vacuum condition of Pa, on the light absorbing layer
Hole transmission layer, evaporation rate control exist
46. by silk-screen printing commercialization carbon slurry film forming the FTO conductive layer one end and the hole transmission layer it is upper
Surface forms carbon to electrode layer, and then completes entirely to adulterate TiO based on low temperature nickel2Perovskite solar battery preparation.Institute
The solvent drying temperature for the carbon slurry stated is set as 85 DEG C.
Embodiment 5
The preparation method for the perovskite solar battery titania-doped based on nickel that fifth embodiment of the invention provides
It mainly comprises the steps that
51. using concentration is the dilute hydrochloric acid of 2mol/L and zinc powder to conductive substrates using FTO electro-conductive glass as conductive substrates
FTO conductive layer handled, to etch groove.
52. being respectively cleaned by ultrasonic conductive substrates 15 minutes with acetone, ethyl alcohol, deionized water respectively, then dried up with nitrogen stream,
UV ozone is carried out to FTO conductive layer again to handle 30 minutes.
53. being placed in the beaker for filling growth solution vertically after conductive substrates are fixed by retainer, then will be described
Beaker is placed in thermostat water bath, and by reaction temperature control at 70 DEG C, growth time is 3 hours, finally annealing 0.5~1
Hour, annealing temperature was 500 DEG C to form light anode.Wherein, the TiCl in the growth-promoting media4Concentration and NiCl2·6H2O's
Concentration is respectively 0.2mol/L and 0.013mol/L.
54. after 70 μ L perovskite precursor solutions are added dropwise in the surface of the light anode, first with 1000rpm low speed spin coating
10s, then with 6000rpm high speed spin coating 22s, the 130 μ L chlorobenzenes of μ L~140 are added dropwise at the 15th second of high speed spin coating as anti-molten
Then the conductive substrates for being deposited with calcium titanium ore bed are heated 45 minutes Cs to form high-crystallinity by agent at 100 DEG C0.05
(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3Calcium titanium ore bed, i.e. light absorbing layer.The whole preparation process of the light absorbing layer is being filled
It is carried out in the glove box of full nitrogen.
55. pressure is less than 10-3The CuPc layer conduct of 35nm thickness is deposited under the high vacuum condition of Pa, on the light absorbing layer
Hole transmission layer, evaporation rate control exist
56. by silk-screen printing commercialization carbon slurry film forming the FTO conductive layer one end and the hole transmission layer it is upper
Surface forms carbon to electrode layer, and then completes entirely to adulterate TiO based on low temperature nickel2Perovskite solar battery preparation.Institute
The solvent drying temperature for the carbon slurry stated is set as 85 DEG C.
Embodiment 6
The preparation method for the perovskite solar battery titania-doped based on nickel that sixth embodiment of the invention provides
It mainly comprises the steps that
61. using concentration is the dilute hydrochloric acid of 2mol/L and zinc powder to conductive substrates using FTO electro-conductive glass as conductive substrates
FTO conductive layer handled, to etch groove.
62. being respectively cleaned by ultrasonic conductive substrates 15 minutes with acetone, ethyl alcohol, deionized water respectively, then dried up with nitrogen stream,
UV ozone is carried out to FTO conductive layer again to handle 30 minutes.
63. being placed in the beaker for filling growth solution vertically after conductive substrates are fixed by retainer, then will be described
Beaker is placed in thermostat water bath, and by reaction temperature control at 70 DEG C, growth time is 3 hours, finally annealing 0.5~1
Hour, annealing temperature was 500 DEG C to form light anode.Wherein, the TiCl in the growth-promoting media4Concentration and NiCl2·6H2O's
Concentration is respectively 0.2mol/L and 0.01mol/L.
64. after 70 μ L perovskite precursor solutions are added dropwise in the surface of the light anode, first with 1000rpm low speed spin coating
10s, then with 6000rpm high speed spin coating 22s, the 130 μ L chlorobenzenes of μ L~140 are added dropwise at the 15th second of high speed spin coating as anti-molten
Then the conductive substrates for being deposited with calcium titanium ore bed are heated 45 minutes Cs to form high-crystallinity by agent at 100 DEG C0.05
(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3Calcium titanium ore bed, i.e. light absorbing layer.The whole preparation process of the light absorbing layer is being filled
It is carried out in the glove box of full nitrogen.
65. pressure is less than 10-3The CuPc layer conduct of 40nm thickness is deposited under the high vacuum condition of Pa, on the light absorbing layer
Hole transmission layer, evaporation rate control exist
66. by silk-screen printing commercialization carbon slurry film forming the FTO conductive layer one end and the hole transmission layer it is upper
Surface forms carbon to electrode layer, and then completes entirely to adulterate TiO based on low temperature nickel2Perovskite solar battery preparation.Institute
The solvent drying temperature for the carbon slurry stated is set as 85 DEG C.
The results are shown in Table 1 for above embodiments:
Table 1
The perovskite solar battery and preparation method thereof titania-doped based on nickel provided by the invention, uses
The nickel doped rutile phase TiO of CBD method preparation2High temperature sintering is carried out to improve crystallinity as light anode, and to it, is not only increased
Its strong charge transport ability, also improves TiO2Surface topography, and then promote the perovskite being deposited in light anode
Well-crystallized, the experimental results showed that the short circuit current of battery and fill factor all obtain larger raising；Using phase stability and
The better ternary mixed-cation perovskite persursor material of thermal stability enhances the stability of prepared battery；Using honest and clean
The CuPc and carbon of valence and high stability are empty instead of expensive organic polymer respectively as hole transmission layer and to electrode material
Hole transport materials and noble metal both reduce production cost, further improve the stability of battery to electrode.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the perovskite solar battery titania-doped based on nickel, which is characterized in that this method packet
Include following steps:
(1) conductive substrates are provided, and etch groove in the conductive substrates；
(2) it is dried up after being cleaned to the conductive substrates, UV ozone processing then is carried out to the conductive substrates；
(3) the titania-doped film of nickel of Rutile Type is deposited in the conductive substrates using immersion method, and annealed
Processing, to form light anode, wherein annealing temperature is 450 DEG C~500 DEG C；
(4) in the surface spin coating perovskite precursor solution of the light anode, and heated to obtain ternary mixing sun
Ion calcium titanium ore bed, i.e. light absorbing layer；The ternary mixed-cation calcium titanium ore bed is Cs0.05(MA0.17FA0.83)0.95Pb
(I0.83Br0.17)3；
(5) under vacuum condition, one layer of CuPc is deposited on the surface of the light absorbing layer, to form hole transmission layer；
(6) film forming is starched to form carbon on the hole transport layer to electrode layer by silk-screen printing commercialization carbon, thus completes base
In the preparation of the titania-doped perovskite solar battery of nickel.
2. the preparation method as described in claim 1 based on the titania-doped perovskite solar battery of nickel, feature
Be: the annealing temperature is 500 DEG C.
3. the preparation method as described in claim 1 based on the titania-doped perovskite solar battery of nickel, feature
Be: the conductive substrates include substrate glass and the FTO conductive layer being arranged in the substrate glass, and the groove runs through institute
State FTO conductive layer, and one end of the neighbouring conductive substrates；The light anode is arranged in the FTO conductive layer far from the base
On the surface of sheet glass, the side wall wall surface of the groove is covered simultaneously, the side wall wall surface and the substrate glass are described
The surface region of light anode covering intersects vertically.
4. the preparation side of the perovskite solar battery titania-doped based on nickel as described in any one of claims 1-3
Method, it is characterised in that: step (2) specifically includes the following steps: being respectively cleaned by ultrasonic with acetone, ethyl alcohol, deionized water respectively described in
It conductive substrates 10 minutes~15 minutes, is then dried up with nitrogen stream, then UV ozone is carried out to the conductive substrates and handles 20 points
Clock~30 minute.
5. the preparation side of the perovskite solar battery titania-doped based on nickel as described in any one of claims 1-3
Method, it is characterised in that: step (3) is specifically includes the following steps: by the conductive substrates by placing vertically after retainer fixation
It is placed in thermostat water bath in the beaker for filling growth solution, then by the beaker, and by the reaction temperature of the growth solution
At 70 DEG C~75 DEG C, growth time is 2.5 hours~3.5 hours for degree control, is finally annealed 0.5 hour~1 hour.
6. the preparation method as claimed in claim 5 based on the titania-doped perovskite solar battery of nickel, feature
Be: the source Ti of the growth-promoting media is TiCl4, nickel doped source is NiCl2·6H2O, wherein TiCl4Concentration be 0.2mol/L~
0.3mol/L, NiCl2·6H2The concentration of O is greater than 0mol/L and is less than or equal to 0.013mol/L.
7. the preparation side of the perovskite solar battery titania-doped based on nickel as described in any one of claims 1-3
Method, it is characterised in that: the concentration of the perovskite precursor solution is 1.25mol/L~1.3mol/L.
8. the preparation side of the perovskite solar battery titania-doped based on nickel as described in any one of claims 1-3
Method, it is characterised in that: evaporation rate control exists
9. a kind of perovskite solar battery titania-doped based on nickel, it is characterised in that: the perovskite solar-electricity
Pond is using the preparation side such as the described in any item perovskite solar batteries titania-doped based on nickel of claim 1-8
Method preparation.
10. the perovskite solar battery titania-doped based on nickel as claimed in claim 9, it is characterised in that: described
Light anode with a thickness of 150nm~200nm；The hole transmission layer with a thickness of 35nm~40nm；The carbon is to electrode layer
With a thickness of 10 μm~30 μm.
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| CN105448524A (en) * | 2014-09-05 | 2016-03-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Silver-doped organometallic perovskite material, solar cell and manufacturing method thereof |
| CN105870336A (en) * | 2016-06-01 | 2016-08-17 | 华东师范大学 | Mesoporous perovskite solar cell |
| CN106410046A (en) * | 2016-12-12 | 2017-02-15 | 吉林大学 | Perovskite solar cell containing hydrophilic electrode modification layer and preparation method |
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| CN105448524A (en) * | 2014-09-05 | 2016-03-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Silver-doped organometallic perovskite material, solar cell and manufacturing method thereof |
| CN105870336A (en) * | 2016-06-01 | 2016-08-17 | 华东师范大学 | Mesoporous perovskite solar cell |
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