CN108878655A - A kind of fibrous type perovskite solar battery and the preparation method and application thereof - Google Patents
A kind of fibrous type perovskite solar battery and the preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
Abstract
The present invention relates to a kind of fibrous type perovskite solar battery and the preparation method and application thereof, which successively includes from inside to outside in the radial direction thereof using centered on the titanium silk as electrode：As the titanium silk of electrode, titanium dioxide dense layer, TiO 2 porous layer, perovskite crystal layer, hole transmission layer, and as the thin au to electrode.The energy conversion efficiency (up to 9%) that fibrous type perovskite solar energy produced by the present invention is greatly promoted, and large scale preparation can be relatively easily carried out, provides effective guarantee to be further applied to the fields such as wearable device, smart home.
Description
Technical field
The invention belongs to technical field of solar batteries more particularly to a kind of efficiently large-sized fibrous type perovskite sun
Energy battery and preparation method thereof.
Background technique
In today of wearable device fast development, higher want also proposed for portable energy supply equipment
It asks.The current most common energy supply mode is to be embedded in wearable device using lithium battery, but need in face of filling often
The worry of electricity.If the power generation facilities such as solar battery can be integrated into wearable device, or it is woven into clothing
In, then cooperate the energy storage devices such as lithium battery or supercapacitor, it will be able to realize round-the-clock continual work.Regardless of being collection
It at into wearable device, is still woven into clothing, the flexible solar battery of fibrous type is all ideal device shape
State, therefore developing fibrous type solar battery is the previous urgent demand of mesh.
In various solar battery technologies, perovskite solar battery is a nova in recent years.On the one hand, calcium titanium
The preparation method of mine solar battery is simple, of less demanding to machinery equipment, and cost is relatively low；And at the same time, also possessing can be with
The energy conversion efficiency of shoulder compared with silicon solar cell, the energy conversion efficiency of plane perovskite solar battery is most at present
Height can achieve 22%.Therefore, perovskite material is the ideal material for preparing fibrous type solar battery, and all solid state
Structure be also beneficial to the encapsulation and long-term use in later period.But since fiber curved surface film forming and plane film forming difference are very big,
The perovskite crystal film layer of acquisition is generally second-rate, and other function layer is there is also serious defect, thus current device efficiency
It is still within a lower level.
104009105 A of Chinese patent publication No. CN discloses a kind of linear perovskite solar battery and its preparation side
Method, is an electrode using stainless steel wire, finally wraps up transparent carbon nanotube grid as another electrode, prepares coaxial line
Shape perovskite solar battery.105047822 A of Chinese patent publication No. application publication number CN discloses a kind of flexible fiber shape
Perovskite solar battery and preparation method thereof, using two carbon nano-tube fibres respectively as working electrode and to electrode phase
Mutually winding is assembled into flexible fiber shape perovskite solar battery.But the energy for the fibrous type perovskite solar battery that they are obtained
It measures transfer efficiency and all there was only 3% or so, the market demand can't be better meet.
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide it is a kind of efficiently large-sized fibrous type perovskite solar battery and its preparation
Method.The energy conversion efficiency (up to 9%) that the fibrous type perovskite solar energy that the present invention obtains greatly is promoted, and can
Relatively easily to carry out large scale preparation, provided effectively to be further applied to the fields such as wearable device, smart home
It ensures.
The present invention adopts the following technical scheme that：
A kind of fibrous type perovskite solar battery, using centered on the Titanium silk as cathode, in the radial direction thereof
Successively include from inside to outside：The Titanium silk as cathode, titanium dioxide dense layer, TiO 2 porous layer, perovskite
Crystal layer, hole transmission layer, and as the thin au to electrode.
Further, the cross section of the titanium silk can be made required shape as needed, such as round or approximate circle,
Oval, rectangular, polygon or irregular shape etc., it is preferably circular or approximate circle.
Further, the cross section of the titanium silk is round or approximate circle, a diameter of 200-300 μm, preferably 250
μm。
Further, the titanium dioxide dense layer, TiO 2 porous layer, perovskite crystal layer, hole transmission layer, thin
The thickness of layer gold is respectively 50-100nm, 200-400nm, 300-500nm, 100-200nm, 10-20nm.
Further, the titanium dioxide dense layer can directly be made by the Titanium silk original position electric heating as electrode
?.The titanium dioxide dense layer of different-thickness can be prepared by control heating temperature, time.
Further, the TiO 2 porous layer can pass through the titanium dioxide coating glue on the titanium dioxide dense layer
Body and be made.Pass through revolving speed when control colloidal tio 2 concentration, application temperature, coating time, coating number and coating etc.
Condition can prepare the TiO 2 porous layer of different-thickness.
In the present invention, the perovskite crystal layer, the meaning of hole transmission layer are identical as this field conventional sense.
Specifically, the general structure of the perovskite crystal is ABX3, A is organic cation such as methylamine, carbonamidine etc.；B is
Metal cation such as Pb2+、Sn2+Deng；X is halide anion such as I-, Br-, Cl-Deng.
In a specific embodiment of the invention, the perovskite crystal is first ammonia lead iodine (CH3NH3PbI3)。
The perovskite crystal layer can be prepared by conventional method in that art.
It is first to coat PbI on TiO 2 porous layer in a specific embodiment of the invention2-xClxSolution, so
After heat solvent flashing, be prepared into PbI2-xClxLayer (x=0~0.5)；Then under vacuum conditions, generation is reacted with iodine methylamine
Perovskite crystal layer.By suitable control reaction condition, the perovskite crystal layer of required thickness can be prepared.
In solar battery of the present invention, the main function of perovskite crystal layer is to absorb luminous energy, carries out photoelectricity and turns
Change, generates electrons and holes.
Further, the substance for constituting hole transmission layer is mainly spiro-OMeTAD, can be by by above-mentioned system
It is standby to immerse 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell at the device containing perovskite crystal layer
It is made in the chlorobenzene solution of two fluorenes (i.e. spiro-OMeTAD).
Further, thin au can be prepared by conventional method in that art (such as magnetron sputtering, magnetic control sputtering device can be used).
Further, wire (preferably spun gold) is also wound in the thin au as to electrode, being used for will
Electric current export.
Further, the thickness of each layer of fibrous type perovskite solar battery is respectively：Compacted zone 50-100nm,
Porous layer 200-400nm, perovskite crystal layer 300-500nm, hole transmission layer 100-200nm, thin au 10-20nm.
The present invention also provides a kind of preparation methods of fibrous type perovskite solar battery as described above, including walk as follows
Suddenly：
1) Titanium silk is taken, titanium dioxide dense layer is prepared on its surface in electric heating in situ；
2) the titanium dioxide coating colloid on the titanium dioxide dense layer, prepares TiO 2 porous layer；
3) PbI is coated on the TiO 2 porous layer2-xClxPbI is made after heating solvent flashing in solution2-xClxLayer；
X=0~0.5；Under vacuum conditions, by iodine methylamine heating sublimation, with made PbI2-xClxGas phase reaction occurs and generates calcium
Titanium ore crystal layer；
4) the resulting device of step 3) is immersed into hole mobile material 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl)
Amino] -9,9'- spiral shell, two fluorenes (i.e. spiro-OMeTAD) chlorobenzene solution in, prepare hole transmission layer；
5) using the resulting device surface magnetron sputtering thin au of step 4) as to electrode.
Further, the above method also alternatively, further include in the thin au as to electrode wind wire it is (excellent
It is selected as spun gold).
In above-mentioned preparation method：
Further, step 1) the titanium silk is as described above, its diameter is preferably 200~300nm；And/or electricity in situ adds
The temperature of heat is 400~500 DEG C, and heating time is 1~3min.This step can be realized on Tu Siji.
Further, the purity of step 1) the titanium silk is 99% or more.
Further, step 1) can in advance polish titanium silk, then successively be cleaned up with acetone, EtOH Sonicate.
As shown in Fig. 2, self-control used applies silk machine, and both ends are synchronous rotary in a specific embodiment of the invention
Motor, can constant current or voltage input, and with adjustable speed reciprocating motion base station.
Further, the step 2) colloidal tio 2 can be used commercial titanium dioxide pulp dilution prepare (such as
Dyesol company 18NR-T commercial titanium dioxide slurry), solvent is ethyl alcohol, propyl alcohol or isopropanol, titania slurry and solvent
Mass ratio be 1:4~1:8；(such as horizontal coating) can be coated on Tu Siji as shown in Figure 2.To better ensure that
Effect is coated, temperature is 120~150 DEG C (can reach the temperature by heating titanium silk) when titanium dioxide coating colloid；Further
Ground, rotation speed are 0.5~1r/s, and movement speed is 0.5~3cm/s；General coating number is 2~14 times.
Further, the step 3) PbI2-xClxConcentration be 1~1.5mol/L, (x=0~0.5), solvent can be used
DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide) or GBL (gamma-butyrolacton)；Further, PbI is coated2- xClxThe method of solution includes：0.5~1cm/s first is coated at a slow speed 2~4 times at room temperature, and then 1~2cm/s quickly coats 4~8
It is secondary.The temperature for heating solvent flashing is 100~120 DEG C；General heating 10min or so can volatilize solvent.
Further, the step 3) vacuum condition：Vacuum degree 50Pa is hereinafter, it is preferred that 30~50Pa of vacuum degree；Reaction temperature
Degree is 110-130 DEG C.After the reaction was completed, can under inert atmosphere protection (such as 120 DEG C of 30~60min of heating) to remove surface
Remaining iodine methylamine.
Specifically, step 3) can be reacted in vacuum heater, as shown in figure 3, the vacuum heater has
Place desiccant and and the branch pipe of iodine methylamine can be condensed, sample cell can be heated properly, and inside has and can place fibre
The bracket of dimensional device.
Further, the composition of step 4) the spiro-OMeTAD chlorobenzene solution includes：Spiro-OMeTAD, chlorobenzene,
LiTFSI (double trifluoromethanesulfonimide lithiums), acetonitrile, TBP.
Further, step 5) the magnetron sputtering condition is d.c. sputtering, 100~150W of power；Time is generally 20
~30s；It, can be by the device obtained by step 4) with the speed axis of 0.5~2r/s to keep thin au more uniform when magnetron sputtering
To horizontally rotating.
Specifically, the preparation method of above-mentioned fibrous type perovskite solar battery, includes the following steps：
1) the titanium silk that diameter is 200~300nm, purity is 99% or more is taken, is polished using sand paper (such as 5000 mesh), so
It is successively cleaned up, is fixed on Tu Siji using acetone, EtOH Sonicate afterwards, titanium dioxide is prepared on its surface in electric heating in situ
Compacted zone；Electrically heated temperature is 400~500 DEG C, and heating time is 1~3min；
2) 120~150 DEG C are heated in step 1) obtained device, the device is made to keep 0.5~1r/s of rotation speed,
Titanium dioxide coating colloid on the titanium dioxide dense layer of the device, prepares TiO 2 porous layer；When coating, make described two
Movement speed of the titanium oxide colloid in the titanium dioxide dense layer axial direction is 0.5~3cm/s, and coating number is 2~14 times；
The colloidal tio 2 is by 18NR-T commercial titanium dioxide slurry and solvent in mass ratio 1:4~1:8 are made, and the solvent is
Ethyl alcohol, propyl alcohol or isopropanol；
3) two steps coat PbI on the TiO 2 porous layer of step 2) obtained device at room temperature2-xClxSolution：Make first
The PbI2-xClxMovement speed of the solution in the TiO 2 porous layer axial direction is 0.5~1cm/s, is applied to 2~4
It is secondary；Adjusting the movement speed later is 1~2cm/s, is applied to 4~8 times；After the completion of coating, waved in 100~120 DEG C of heating
Dry solvent, is made PbI2-xClxLayer；The PbI2-xClxSolution concentration be 1~1.5mol/L, x=0~0.5, solvent DMF,
DMSO or GBL；
4) step 3) obtained device is placed in vacuum heater, is evacuated to 30~50Pa, be heated to 110~130
DEG C make iodine methylamine distil and with the PbI on the device2-xClxOccur gas phase reaction (the General reactions time is 3~4 hours), it is raw
At perovskite crystal layer；Later, under inert gas protection in 120 DEG C of temperature heating (general 30~60min) to remove surface
Remaining iodine methylamine；
5) step 4) obtained device is immersed to a period of time (example in the chlorobenzene solution of hole mobile material spiro-OMeTAD
Such as 30-60s) it takes out afterwards, prepare hole transmission layer；The chlorobenzene solution of the spiro-OMeTAD by spiro-OMeTAD,
LiTFSI, acetonitrile, TBP and solvent chlorobenzene are made, and concentration is respectively：70-80mg/ml,8-10mg/ml,10-20μl/ml,
20-30μl/ml；
6) step 5) obtained device is placed in magnetic control sputtering device, makes the device with the speed of 0.5~2r/s in axial direction
On horizontally rotate, under d.c. sputtering mode, adjustment power be 100~150W, 20~30s of time, sputtering thin au be used as to electricity
Pole；
Alternatively, further winding spun gold in the thin au as to electrode.
The invention also includes the fibrous type perovskite solar batteries of above method preparation.
The invention also includes above-mentioned fibrous type perovskite solar batteries in wearable device, building fitment material for family, outdoor
The application in power generator field, concrete application include：Clothing, knapsack, wrist strap, the spectacle-frame of integrated fibers solar battery；Collection
At the window, curtain, barn door of fiber solar battery；Use the photovoltaic tree etc. of fiber solar battery.
The present invention is by directly preparing titanium dioxide dense layer, more uniform cause in titanium silk surface in situ electrothermal oxidation
Close, adhesiveness is good；The perovskite crystal layer of gas phase auxiliary law preparation, has better film forming, and tie in fibrous substrate
Crystalloid amount is high；Use thin au as to electrode, energy level more matches, and has better electronic transmission performance.It is overall and
Speech, compared with prior art, the fibrous type perovskite solar battery that method of the present invention is prepared have by a relatively large margin
Improved efficiency, incident photon-to-electron conversion efficiency can achieve 9% or more, and preparation condition is simple, be suitable for the extensive system of industrialization
It is standby.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of fibrous type perovskite solar battery of the present invention；
Wherein, 1：Titanium silk substrate, 2：Titanium dioxide dense layer, 3：TiO 2 porous layer, 4：Calcium titanium ore bed, 5：Hole passes
Defeated layer, 6：Gold is to electrode；
Fig. 2, which is that the present invention is used, applies silk machine structural schematic diagram；
Wherein, 7：Synchronous rotation motor, 8：Adjustable speed movable drill base, 9：Fibrous substrate；
Fig. 3 is vacuum heater schematic diagram used in the present invention；
Wherein, 10：Heating tube, 11：Sample cell, 12：Sample holder, 13：Fibre cell device, 14：Vacuum cock, 15：
Iodine methylamine, 16：Desiccant；
Fig. 4 is the sample holder schematic diagram of vacuum heater used in the present invention；
Wherein, 17：Tetrafluoroethene plate, 18：Groove, 19：Hollowed out area；
Fig. 5 is the perovskite crystal layer SEM exterior view of fibrous type perovskite solar battery prepared by the present invention；
Fig. 6 is the perovskite crystal layer SEM sectional view of fibrous type perovskite solar battery prepared by the present invention；
Fig. 7 is the J-V curve for the fibrous type perovskite solar battery that embodiment 1 is prepared, and battery efficiency is
9.8%；
Fig. 8 is the continuous power curve of output for the fibrous type perovskite solar battery that embodiment 1 is prepared；
Fig. 9 is the continuous bending performance for the fibrous type perovskite solar battery that embodiment 1 is prepared, in bending 500
It still is able to retain 90% or more performance after secondary；
Figure 10 is the J-V curve for the fibrous type perovskite solar battery that embodiment 2 is prepared, and battery efficiency is
9.2%；
Figure 11 is the surface the perovskite crystal layer SEM shape for the fibrous type perovskite solar battery that comparative example is prepared
Looks；
Figure 12 is the J-V curve for the fibrous type perovskite solar battery that comparative example is prepared, and battery efficiency is
3.9%.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
Painting silk machine schematic diagram used in fibrous type perovskite solar battery is prepared below as shown in Fig. 2, including：Synchronous rotation
Rotating motor 7, adjustable speed movable drill base 8, fibrous substrate 9；It further, further include power supply, it is constant to be inputted to titanium silk substrate
Current or voltage.
Vacuum heater schematic diagram used in fibrous type perovskite solar battery is prepared below as shown in figure 3, including：
Heating tube 10, sample cell 11, sample holder 12, fibre cell device 13, vacuum cock 14, iodine methylamine 15, desiccant 16；Its
In, the schematic diagram of sample holder 12 is as shown in figure 4, tetrafluoroethene plate 17, groove 18, hollowed out area 19.
The structure of fibrous type perovskite solar battery of the present invention as shown in Figure 1, using centered on the titanium silk 1 as electrode,
Successively include from inside to outside in the radial direction thereof：As the titanium silk 1 of battery cathode, titanium dioxide dense layer 2, titanium dioxide is more
Aperture layer 3, perovskite crystal layer 4, hole transmission layer 5, and as the thin au 6 to electrode；It further include in gold to being twined outside electrode
Around spun gold (not shown), for electric current to be exported.Wherein, SEM such as Fig. 5, the Fig. 6 on 4 surface of perovskite crystal layer and section
It is shown.The thickness of each layer of fibrous type perovskite solar battery is respectively：Titanium dioxide dense layer 50-100nm, titanium dioxide are more
Aperture layer 200-400nm, perovskite crystal layer 300-500nm, hole transmission layer 100-200nm, thin au 10-20nm.
Embodiment 1
Taking diameter is 250nm, and the titanium silk that purity is 99.9% is polished using the sand paper of 5000 mesh, then successively uses third
Ketone, EtOH Sonicate cleaning.It is fixed on painting silk machine shown in Fig. 2, electrically heated temperature is 500 DEG C, heating time 1min, former
Position prepares titanium dioxide dense layer.By 18NR-T commercial titanium dioxide slurry, the ethyl alcohol that 6.5 times of quality are added is diluted, system
At colloidal tio 2；On Tu Siji shown in Fig. 2, titanium silk is heated to 120 DEG C, makes titanium silk rotation speed in the radial direction
For 0.5r/s, colloidal tio 2 is loaded into the adjustable speed movable drill base 8 on painting silk machine shown in Fig. 2, makes it in titanium silk
Axis move up speed be 0.5cm/s, coat 10 times, prepare TiO 2 porous layer.Use DMF as solvent, configures dense
Degree is the PbI of 1.5mol/L2-xClxSolution (PbI2:PbCl2=4:1, mass ratio).Two steps coat PbI at room temperature2-xClxSolution：
By PbI2-xClxSolution stowage makes it in the axial direction of titanium silk first in the adjustable speed movable drill base 8 on painting silk machine shown in Fig. 2
On, coating 2 times at a slow speed with 0.5cm/s first, 2cm/s quickly coats 4 times later, then 100 DEG C of heating 10min solvent flashings,
Prepare PbI2-xClxLayer.In vacuum heater shown in Fig. 3,50Pa is evacuated to reaction system, being heated to 120 DEG C makes
The distillation of iodine methylamine and and PbI2-xClxGas phase reaction occurs, the reaction time is 4 hours, generates perovskite crystal layer；Later, lazy
Lower 120 DEG C of heating 40min are to remove iodine methylamine remained on surface for property gas shield.Using spiro-OMeTAD, chlorobenzene,
LiTFSI, acetonitrile, TBP configure the chlorobenzene solution of hole mobile material spiro-OMeTAD, and device immerses in solution after 30-60s
It takes out, prepares hole transmission layer.Finally, axially being horizontally rotated in magnetic control sputtering device with the speed of 0.5r/s, d.c. sputtering mould
Under formula, adjustment power is 125W, time 25s, and sputtering thin au is used as to electrode；To which fibrous type perovskite solar-electricity be made
Pond.
AM1.5 of the fibrous type perovskite solar battery manufactured in the present embodiment in Yamashita Denso YDC-50A
Under simulated solar light source, device performance test is carried out using 2000 multimeter of Keithley.The J-V curve of obtained device is such as
Shown in Fig. 7, in figure, open-circuit voltage 0.97V, short-circuit current density 13.92mA/cm2, fill factor 0.73, photoelectricity turn
Changing efficiency is 9.86%.Meanwhile obtained fibrous type solar cell device can carry out stable continuous power output, continue
Power output curve is as shown in Figure 8.
The device that method through this embodiment is prepared has better stability and bent performance, such as Fig. 9 institute
Show, still is able to retain 90% or more starting efficiency after continuous bending 500 times.In practical application, for wearable device,
Outdoor application equipment, bending use etc., all have better adaptability.
Embodiment 2
Taking diameter is 250nm, and the titanium silk that purity is 99.9% is polished using the sand paper of 5000 mesh, then successively uses third
Ketone, EtOH Sonicate cleaning.It is fixed on painting silk machine shown in Fig. 2, electrically heated temperature is 500 DEG C, heating time 1min, former
Position prepares titanium dioxide dense layer.By 18NR-T commercial titanium dioxide slurry, the ethyl alcohol that 8 times of quality are added is diluted, is made
Colloidal tio 2；On Tu Siji shown in Fig. 2, titanium silk is heated to 120 DEG C, makes titanium silk rotation speed in the radial direction
Colloidal tio 2 is loaded into the adjustable speed movable drill base 8 on painting silk machine shown in Fig. 2, makes it in titanium silk by 0.5r/s
It is 2cm/s that axis, which moves up speed, coats 8 times, prepares TiO 2 porous layer.
Use DMF:DMSO=5:1 (mass ratio) is used as mixed solvent, and configuration concentration is the PbI of 1.5mol/L2-xClxIt is molten
Liquid (PbI2:PbCl2=4:1, mass ratio).
Two steps coat PbI at room temperature2-xClxSolution：By PbI2-xClxSolution stowage is in adjustable on painting silk machine shown in Fig. 2
In fast movable drill base 8, make it in the axial direction of titanium silk first, is coated at a slow speed with 0.5cm/s 2 times first, 2cm/s is quickly applied later
It covers 4 times, then 120 DEG C of heating 10min solvent flashings, prepare PbI2-xClxLayer.In vacuum heater shown in Fig. 3,
50Pa is evacuated to reaction system, being heated to 120 DEG C makes the distillation of iodine methylamine and and PbI2-xClxGas phase reaction occurs, when reaction
Between be 3 hours, generate perovskite crystal layer；Later, under inert gas protection 120 DEG C of heating 40min to remove remained on surface
Iodine methylamine.Configure hole mobile material spiro-OMeTAD's using spiro-OMeTAD, chlorobenzene, LiTFSI, acetonitrile, TBP
Chlorobenzene solution, device immerses in solution to be taken out after 30-60s, prepares hole transmission layer.Finally, in magnetic control sputtering device, with
The speed of 0.5r/s axially horizontally rotates, and under d.c. sputtering mode, adjustment power is 125W, time 25s, sputters thin au conduct
To electrode；To which fibrous type perovskite solar battery be made.The device performance of battery is as shown in Figure 10, incident photon-to-electron conversion efficiency
It can achieve 9.2%.
Comparative example 1
Prepare perovskite crystal layer using a traditional step czochralski method, the preparation method and embodiment 1 of other function layer,
2 is identical, and concrete operation step is as follows：
Taking diameter is 250nm, and the titanium silk that purity is 99.9% is polished using the sand paper of 5000 mesh, then successively uses third
Ketone, EtOH Sonicate cleaning.It is fixed on painting silk machine shown in Fig. 2, electrically heated temperature is 500 DEG C, heating time 1min, former
Position prepares titanium dioxide dense layer.By 18NR-T commercial titanium dioxide slurry, the ethyl alcohol that 8 times of quality are added is diluted, is made
Colloidal tio 2；On Tu Siji shown in Fig. 2, titanium silk is heated to 120 DEG C, makes titanium silk rotation speed in the radial direction
Colloidal tio 2 is loaded into the adjustable speed movable drill base 8 on painting silk machine shown in Fig. 2, makes it in titanium silk by 0.5r/s
It is 2cm/s that axis, which moves up speed, coats 8 times, prepares TiO 2 porous layer.
Use DMF as solvent, PbCl2And CH3NH3I configures one-step method perovskite precursor solution as solute, wherein
PbCl2Mass fraction be 15%, CH3NH3The mass fraction of I is 25%.Room temperature coats perovskite precursor solution in next step：It will
The device for preparing TiO 2 porous layer is impregnated into 1min in perovskite precursor solution, takes out solvent flashing.By back
The device of perovskite precursor solution 100 DEG C of heating 60min in thermal station have been coated, the perovskite precursor film layer of coating is converted into
The SEM surface topography of perovskite crystal film layer, calcium titanium ore bed is as shown in figure 11.Using spiro-OMeTAD, chlorobenzene, LiTFSI,
The chlorobenzene solution of acetonitrile, TBP configuration hole mobile material spiro-OMeTAD, device immerses in solution to be taken out after 30-60s, is made
Standby hole transmission layer.Finally, axially being horizontally rotated in magnetic control sputtering device with the speed of 0.5r/s, under d.c. sputtering mode, adjust
Whole power is 125W, time 25s, and sputtering thin au is used as to electrode；To which fibrous type perovskite solar battery be made.Battery
Device performance such as Figure 12 it is all, energy conversion efficiency 3.9%.The main reason for device performance is bad be crystal transformation not
Completely, and crystallization shape is poor, so that carrier effectively can not be generated and be transmitted, eventually leads to electric current and voltage is lower.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of fibrous type perovskite solar battery, which is characterized in that using centered on the Titanium silk as cathode, in its diameter
Successively include from inside to outside on direction：The Titanium silk as cathode, titanium dioxide dense layer are TiO 2 porous
Layer, perovskite crystal layer, hole transmission layer, and as the thin au to electrode；Alternatively, in the thin layer as to electrode
Wire is also wound on gold, for exporting electric current.
2. fibrous type perovskite solar battery according to claim 1, which is characterized in that the cross section of the titanium silk is
Round or approximate circle, oval, rectangular, polygon or irregular shape；Preferably, the cross section of the titanium silk be it is round or
It is approximate circle, a diameter of 200-300 μm, more preferably 250 μm.
3. fibrous type perovskite solar battery according to claim 1 or 2, which is characterized in that the titanium dioxide causes
Close layer, TiO 2 porous layer, perovskite crystal layer, hole transmission layer, thin au thickness be respectively 50-100nm, 200-
400nm、300-500nm、100-200nm、10-20nm。
4. fibrous type perovskite solar battery according to claim 1-3, which is characterized in that the perovskite
The general structure of crystal is ABX3, A is organic cation；B is metal cation；X is halide anion；And/or the composition
The substance of hole transmission layer is mainly spiro-OMeTAD；
Preferably, A is methylamine or carbonamidine；And/or B Pb2+Or Sn2+；And/or X I-, Br-Or Cl-；
It is highly preferred that the perovskite crystal is first ammonia lead iodine CH3NH3PbI3。
5. a kind of preparation method of fibrous type perovskite solar battery, which is characterized in that include the following steps：
1) Titanium silk is taken, titanium dioxide dense layer is prepared on its surface in electric heating in situ；
2) the titanium dioxide coating colloid on the titanium dioxide dense layer, prepares TiO 2 porous layer；
3) PbI is coated on the TiO 2 porous layer2-xClxPbI is made after heating solvent flashing in solution2-xClxLayer；X=0
~0.5；Under vacuum conditions, by iodine methylamine heating sublimation, with made PbI2-xClxGas phase reaction occurs and generates perovskite
Crystal layer；
4) the resulting device of step 3) is immersed in the chlorobenzene solution of hole mobile material spiro-OMeTAD, prepares hole transport
Layer；
5) using the resulting device surface magnetron sputtering thin au of step 4) as to electrode；
Alternatively, further including winding wire in the thin au as to electrode.
6. preparation method according to claim 5, which is characterized in that in step 1), the titanium silk diameter is 200-300 μ
M, preferably 250 μm；And/or electrically heated temperature in situ is 400~500 DEG C, heating time is 1~3min.
7. preparation method according to claim 5 or 6, which is characterized in that in step 2), the colloidal tio 2 is by two
Titania slurry and solvent in mass ratio 1:4~1:8 are made；And/or
Temperature when titanium dioxide coating colloid is 120~150 DEG C；Rotation speed be 0.5~1r/s, movement speed be 0.5~
3cm/s；Coating 2~14 times；And/or
Step 3) the PbI2-xClxConcentration is 1~1.5mol/L, and x=0~0.5, solvent is selected from DMF, DMSO or GBL；It is preferred that
Ground coats PbI2-xClxThe method of solution includes：0.5~1cm/s first coats at a slow speed 2~4 times at room temperature, then 1~2cm/s
Quickly coating 4~8 times；And/or
Step 3) the vacuum condition：Vacuum degree 50Pa is hereinafter, it is preferred that 30~50Pa of vacuum degree；Reaction temperature is 110-130 DEG C；
And/or
Step 5) the magnetron sputtering condition is d.c. sputtering, 100~150W of power；Time is preferably 20~30s；Preferably,
When magnetron sputtering, device obtained by step 4) is axially horizontally rotated with the speed of 0.5~2r/s.
8. according to the described in any item preparation methods of claim 5-7, which is characterized in that include the following steps：
1) take the titanium silk that diameter is 200~300nm, purity is 99% or more, polished using sand paper, then successively using acetone,
EtOH Sonicate cleans up, and is fixed on Tu Siji, and titanium dioxide dense layer is prepared on its surface in electric heating in situ；It is electrically heated
Temperature is 400~500 DEG C, and heating time is 1~3min；
2) 120~150 DEG C are heated in step 1) obtained device, so that the device is kept 0.5~1r/s of rotation speed, described
Titanium dioxide coating colloid on the titanium dioxide dense layer of device, prepares TiO 2 porous layer；When coating, make the titanium dioxide
Movement speed of the titanium colloid in the titanium dioxide dense layer axial direction is 0.5~3cm/s, and coating number is 2~14 times；It is described
Colloidal tio 2 is by 18NR-T commercial titanium dioxide slurry and solvent in mass ratio 1:4~1:8 are made, and the solvent is second
Alcohol, propyl alcohol or isopropanol；
3) two steps coat PbI on the TiO 2 porous layer of step 2) obtained device at room temperature2-xClxSolution：Make first described
PbI2-xClxMovement speed of the solution in the TiO 2 porous layer axial direction is 0.5~1cm/s, is applied to 2~4 times；It
After adjust the movement speed be 1~2cm/s, be applied to 4~8 times；After the completion of coating, volatilized in 100~120 DEG C of heating molten
PbI is made in agent2-xClxLayer；The PbI2-xClxSolution concentration be 1~1.5mol/L, x=0~0.5, solvent DMF, DMSO or
GBL；
4) step 3) obtained device is placed in vacuum heater, is evacuated to 30~50Pa, being heated to 110~130 DEG C makes
Iodine methylamine distillation and with the PbI on the device2-xClxGas phase reaction (the General reactions time is 3~4 hours) occurs, generates calcium
Titanium ore crystal layer；Later, under inert gas protection in 120 DEG C of temperature heating to remove iodine methylamine remained on surface；
5) step 4) obtained device is immersed in the chlorobenzene solution of hole mobile material spiro-OMeTAD and is taken out after a period of time,
Prepare hole transmission layer；The chlorobenzene solution of the spiro-OMeTAD is by spiro-OMeTAD, LiTFSI, acetonitrile, TBP and solvent
Chlorobenzene is made, and concentration is respectively：70-80mg/ml,8-10mg/ml,10-20μl/ml,20-30μl/ml；
6) step 5) obtained device is placed in magnetic control sputtering device, makes the device with the speed of 0.5~2r/s water in the axial direction
Flat turn is dynamic, and under d.c. sputtering mode, adjustment power is 100~150W, 20~30s of time, and sputtering thin au is used as to electrode；
Alternatively, further winding spun gold in the thin au as to electrode.
9. the fibrous type perovskite solar battery of any one of claim 5-8 the method preparation.
10. any one of claim 1-4,9 the fibrous type perovskite solar battery are in wearable device, building house ornamentation material
The application of material, outdoor power generator field, concrete application include：Clothing, knapsack, wrist strap, the eye of integrated fibers solar battery
Frame；Window, curtain, the barn door of integrated fibers solar battery；Use the photovoltaic tree of fiber solar battery.
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