CN208494762U - The apparatus for coating of perovskite light-absorption layer in a kind of perovskite solar battery - Google Patents
The apparatus for coating of perovskite light-absorption layer in a kind of perovskite solar battery Download PDFInfo
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- CN208494762U CN208494762U CN201821026196.1U CN201821026196U CN208494762U CN 208494762 U CN208494762 U CN 208494762U CN 201821026196 U CN201821026196 U CN 201821026196U CN 208494762 U CN208494762 U CN 208494762U
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- perovskite
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- 239000010408 film Substances 0.000 abstract description 35
- 239000010409 thin film Substances 0.000 abstract description 5
- 238000007761 roller coating Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 230000000903 blocking effect Effects 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- 230000027756 respiratory electron transport chain Effects 0.000 description 10
- 238000007650 screen-printing Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
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- 229910052799 carbon Inorganic materials 0.000 description 5
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- 238000000137 annealing Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Photovoltaic Devices (AREA)
Abstract
The utility model provides a kind of apparatus for coating of perovskite light-absorption layer in perovskite solar battery, has: coating head, the liquid storage device for storing perovskite precursor solution, pedestal and at least one transmission device；Pedestal is fixed with the conductive substrates of solar battery；Transmission device control pedestal or/and coating head move in the coating direction；The upper end of coating head is adjacent with liquid storage device or connects, and is formed with the coating tip contacted with conductive substrates in coating head, can be carried out slidingtype coating or roller coating；The speed of service of transmission device is less than 100m/min；Perovskite precursor solution viscosity is less than 10pa*s.Thus, it is possible to realize that large area coating, film forming homogeneity improves, parameter stability is controllable and can pattern.Particularly, this coating process is particularly suitable for being coated with perovskite thin film on mesoporous layer.
Description
Technical field
The utility model relates to perovskite solar batteries, and in particular to perovskite is inhaled in a kind of perovskite solar battery
The apparatus for coating of photosphere.
Background technique
In past 10 years, perovskite solar battery is quickly grown due to its very prominent advantage, specifically, calcium titanium
The production of mine solar battery is simple, cost is relatively low, can prepare flexible, transparent battery.Meanwhile also there is more suitable band gap
Width can control the color of battery by changing its band gap, prepare colored battery.Furthermore charge diffusion length is up to micro-
Meter level, charge life are longer.In addition, its unique defect characteristics, the property of n-type semiconductor can be presented by making perovskite crystal material both
The property of p-type semiconductor can also be presented in matter, thus its application is more diversified.Therefore, perovskite solar battery and related material
Material has become photovoltaic art research direction, obtains the photoelectric conversion efficiency more than 23% at present, solar-electricity can be greatly reduced
The use cost in pond, application prospect are very wide.
Perovskite solar battery mainly consists of three parts: transparent conductive electrode, perovskite light-absorption layer and to electrode.
In perovskite battery, since perovskite material cavity transmission ability itself is limited, need to be inserted between perovskite and electrode
One layer of hole mobile material is to obtain higher energy conversion efficiency.In ordinary construction, the conductive substrates of transparent conductive electrode and
There are electron transfer layer and hole blocking layer among perovskite light-absorption layer, to having hole transmission layer in electrode and perovskite light-absorption layer.
It is smooth and fine and close directly affect its electronics at present it is believed that perovskite light-absorption layer is the key that entire battery
Mobility, electron lifetime and photoelectric conversion performance, the importance of manufacture craft as one can imagine.However current baby battery preparation
In, the method for spin coating that perovskite light-absorption layer generally uses, spin coating is complete can clearly to see there is gyrate decorative pattern, work as substrate
It is more obvious when bigger.It can be seen that the homogeneity of the film of coating process production is not very ideal, when baby battery, may influence
Less, but as industrialization process in future is accelerated, the demand of large-size substrate thereupon, thus certainly will be badly in need of preferably coating
Technique substitutes.
In contrast, patent document 1 discloses and a kind of prepares calcium titanium in perovskite solar battery using solution degassing method
The method of mine, and patent document 2 disclose it is a kind of based on magnetic field regulation prepare perovskite in perovskite solar battery
Method.Its target is provided to obtain the perovskite of surfacing densification.But the equal complex process of the above method, and equipment at
This is higher, and there are drawbacks when large-scale production.
Existing technical literature:
Patent document:
Patent document 1: Chinese patent discloses CN105702870A；
Patent document 2: Chinese patent discloses CN107482121A.
Utility model content
Utility model will solve the problems, such as:
In view of the problem present on, the technical problem to be solved by the utility model is to provide one kind to be suitable for big
The apparatus for coating for the perovskite light-absorption layer being coated on area perovskite solar cell substrate.
The means solved the problems, such as:
In order to solve the above-mentioned technical problem, perovskite light-absorption layer in a kind of perovskite solar battery of the utility model
Apparatus for coating has:
Coating head, the liquid storage device for storing perovskite precursor solution, pedestal and at least one transmission device；
The pedestal is fixed with the conductive substrates of solar battery；
The transmission device controls the pedestal or/and the coating head moves in the coating direction；
The upper end of the coating head is adjacent with the liquid storage device or connects,
It is formed with the coating tip contacted with the conductive substrates in the coating head, can be carried out slidingtype coating or rolls
Formula coating；
The speed of service of the transmission device is less than 100m/min；
The perovskite precursor solution viscosity is less than 10pa*s.
According to the utility model, coating head is adjacent or is connected on transmission device, in perovskite precursor solution liquid storage device
The continual and steady coating tip for being flowed into coating head of perovskite precursor solution, to perovskite precursor solution complete wetting
After being coated with tip, contact coating head with the solar cell conductive substrate surface being fixed on pedestal, then at the uniform velocity mobile coating
Head and/or pedestal, to form fine and close, smooth liquid film.Also, the speed of service is continuously adjustable and the speed of service is less than 100m/
Thus min can control the thickness of liquid film by adjusting coating speed.And then control gained thickness of dry film.The common rotation of comparison
Transfer film mode, this technique may be implemented large area coating, the raising of film forming homogeneity, parameter stability controllably and can pattern.
Particularly, this coating process is particularly suitable for being coated with perovskite thin film on mesoporous layer.
Also, in the present invention, being also possible to the transmission device and connecting the pedestal, be formed as the coating head
It is fixed and the structure of pedestal movement with the liquid storage device；Alternatively, the transmission device connects the coating head and the storage
Liquid device, be formed as the pedestal fix and structure that the coating head and the liquid storage device move jointly；Alternatively, the transmission dress
It sets and is connect respectively with the pedestal and with the coating head and the liquid storage device, be formed as the pedestal and the coating head is equal
Moveable structure；The pedestal passes through machinery positioning or the fixed conductive substrates of vacuum suction；It can also by transmission device
Adjust the coating head to the conductive substrates distance.By means of this, flexible moving structure can be formed, increases applicability.
In addition, the thickness of liquid film can be controlled by adjusting coating speed by means of transmission device, and then control final gained dry film
Thickness.Also, the distance of transmission device adjusting coating head to conductive substrates can be passed through.As a result, by adjusting this distance, can control
Thickness of liquid film can improve the bad of coating end liquid film drawout by adjustable range and coating speed when being coated with ending
Phenomenon.
Also, in the present invention, when being also possible to roller coating, the coating head is cylindric and can be around
Central axis is freely rotated, and the coating tip is formed in the coating head outer ring, and the liquid storage device separates simultaneously with the coating head
Fixed, relative position remains unchanged, and the perovskite precursor solution flows out to the coating head outer ring from the liquid storage device
The coating tip, by the transmission device, the coating head and the pedestal relative displacement.
Also, in the present invention, when being also possible to slidingtype coating, the coating tip is formed in the painting
Leftover of bolt of cloth lower end is simultaneously directly contacted with the conductive substrates；The perovskite precursor solution flows out to described from the liquid storage device
The coating tip of coating head lower end, by the transmission device, the coating head and the pedestal relative displacement.
Also, in the present invention, being also possible to the coating tip is that porous wicking structure is coated with tip, flexible net
Trellis is coated with tip or flexible linear array arrangement coating tip.
Also, in the present invention, it is also possible to the porous wicking structure coating tip by fiber, foamed plastic, poly-
Vinyl alcohol or polyester are formed；The flexible net trellis coating tip is formed by cotton, fiber crops, silk or chemical fibre；The flexibility line array
Formula arrangement coating tip is formed by hair, palm fibre or plastic wire.
Also, in the present invention, being also possible to the coating head by the burn into of resistance to polar solvent acid and alkali-resistance and Strong oxdiative
The material of reducing agent is formed, and the cross sectional shape of the coating head is continuous or disconnects.Coating head chemical-resistant stability is high as a result,
Avoid precursor solution contaminated.Patterned perovskite thin film, eliminating the later period by laser ablation carries out patterned behaviour
Make, not only reduce cost, but also avoids dust pollution caused by etching.
Also, in the present invention, the material for being also possible to the pedestal is polytetrafluoroethylene (PTFE) or fluoro-containing plastic, stainless
Steel 316, titanium alloy, marble or glass.Since perovskite precursor solution has chemical corrosivity, these materials are selected
It can be to avoid pedestal in operating process by chemical attack.On the other hand, marble or metal resistant to chemical etching these density are selected
Biggish material can increase the quality of pedestal, so that pedestal is more steady, to improve coating homogeneity and quality of forming film.
The coating process of perovskite extinction layer film in a kind of perovskite solar battery, comprising:
1) it is dried up after cleaning conductive substrates with cleaning solution, prepares hole blocking layer in the conductive substrates；
2) on the hole blocking layer, successively sintering prepares electron transfer layer and insulating layer；
3) it after preparing perovskite precursor solution, is transferred in the liquid storage device of perovskite precursor solution, the liquid storage device
In the perovskite precursor solution flow to the coating tip of the coating head, applied to perovskite precursor solution complete wetting
After cloth tip, the coating head contacts with the conductive substrates by coating tip and passes through the transmission device and at the uniform velocity moves,
To form not thermally treated perovskite light-absorption layer, with after annealing；
4) on the perovskite light-absorption layer, it is sequentially prepared hole transmission layer and to electrode.
Calcium titanium according to the utility model, using above-mentioned novel coating process, in perovskite precursor solution liquid storage device
Mine precursor solution, continual and steady is expressed to coating tip, is coated with tip and conductive substrates directly contact, and passes through transmission dress
It sets and at the uniform velocity moves, fine and close, smooth liquid film is formed, so as to improve electron mobility, electron lifetime and photoelectric conversion performance.The painting
Cloth technological parameter is stably and controllable, and can pattern, thus after saving perovskite film forming, then the technique etched, further subtract
Few preparation cost.
Also, in the present invention, being also possible to the cleaning solution includes acetone, alkalis, deionized water, acetone
Ultrasound；The conductive substrates are FTO glass；The hole blocking layer is TiO2Compacted zone, precursor solution solvent be ethyl alcohol and
Water, including tetraisopropyl titanate, acetylacetone,2,4-pentanedione, hydrochloric acid；The electron transfer layer passes through silk-screen printing nano titania slurry
It forms；It is formed as the insulating layer by silk-screen printing nano zirconium dioxide slurry, the hole transmission layer and logical to electrode
Silk-screen printing carbon pastes are crossed to form；The perovskite precursor solution is by lead iodide, CH3NH3I powder and dimethyl sulfoxide are mixed
Enter CH obtained by stirring in N,N-dimethylformamide3NH3PbI3Perovskite precursor solution.
By means of this, the surface blot that can effectively go out, including greasy dirt and fingerprint is used alternatingly in acetone and alkalis
Dirt is cleaned Deng hardly possible.Also, FTO electro-conductive glass has higher heat resistance compared to other transparent conducting glass, such as ITO, AZO
And chemical-resistant stability.Precursor solution is selected, using wet chemistry method at film preparation compacted zone, preparation cost is low, and is conducive to
The amplification of film-forming process, being suitable for film, compacted zone in large-area substrates can stop inside battery hole in electric current collection
It is compound with electronics at electrode, to improve the photoelectric conversion efficiency of battery.Also, the carbon film that carbon pastes are formed both can be used as hole
Transport layer is can be used as again to electrode, and compared to traditional metal to pole, at low cost, stability is good, simple process.Also,
CH3NH3PbI3Perovskite precursor solution is most typical perovskite solution, has the parameter characteristics such as typical viscosity and concentration,
Be conducive to the determination of the utility model coating process parameter.
Utility model effect:
The utility model is capable of providing that a kind of process equipment is simple, easy to operate, and equipment cost is cheap, is conducive to industrialization,
And the apparatus for coating for the perovskite light-absorption layer for being suitable for being coated on large area perovskite solar cell substrate.According to following
Specific embodiment simultaneously refers to attached drawing, is better understood with the above content and other objects, features and advantages of the utility model.
Detailed description of the invention
Fig. 1 is the main view according to the apparatus for coating using continuous slidingtype coating head of one implementation form of the utility model
Figure；
Fig. 2 is the master of the apparatus for coating of the slidingtype coating head disconnected according to the use of another implementation form of the utility model
View；
Fig. 3 is the main view according to the apparatus for coating using roller coating head of the utility model yet another aspect；
Fig. 4 is the top view of the liquid storage device in apparatus for coating shown in FIG. 1；
Fig. 5 is the side view of apparatus for coating shown in Fig. 3；
Fig. 6 is the side view of Fig. 1 and apparatus for coating shown in Fig. 2；
Fig. 7 a, which is shown, is coated with tip according to the porous wicking structure of one implementation form of the utility model；
Fig. 7 b shows the linear array arrangement coating tip of flexibility according to one implementation form of the utility model；
Fig. 8 is the schematic diagram for showing the coating process of the utility model；
Fig. 9 is the cross-sectional view of battery structure obtained by being made by the apparatus for coating and coating process of the utility model；
Figure 10 is the perovskite solar-electricity for showing perovskite solar battery according to the present utility model and prior art
The performance comparison figure in pond；
Symbol description:
1 etched line
2 conductive substrates
3 hole blocking layers (compacted zone)
4 electron transfer layers
5 insulating layers
6 perovskite light-absorption layers
7 hole transmission layers and to electrode
11 coating heads
12 transmission devices
13 pedestals
14 liquid storage devices
15 coating tips
16 connectors
17 intake valves
18 feed inlets
19 coating head isolated areas
Specific embodiment
The utility model is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following implementations
Mode is merely to illustrate the utility model, rather than limits the utility model.Identical in the various figures or corresponding appended drawing reference indicates
The same part, and omit repeated explanation.
Fig. 1 is the main view according to the apparatus for coating using continuous slidingtype coating head of one implementation form of the utility model
Figure；Fig. 2 is the main view of the apparatus for coating of the slidingtype coating head disconnected according to the use of another implementation form of the utility model；
Fig. 3 is the main view according to the apparatus for coating using roller coating head of the utility model yet another aspect；Fig. 4 is Fig. 1
Shown in liquid storage device in apparatus for coating top view；Fig. 5 is the side view of apparatus for coating shown in Fig. 3.As shown in Figure 1, this
Utility model in order to solve the above technical problems, provide a kind of apparatus for coating of perovskite light-absorption layer in perovskite solar battery,
Have: coating head 11, the liquid storage device 14 for storing perovskite precursor solution, transmission device 12 and pedestal 13.Transmission device
12 control pedestals 13 or/and coating head 11 move in the coating direction.Specifically, transmission device 12 can be fixed by connector 16
Coating head 11 and/or pedestal 13.The length of coating head 11 is adjusted according to actually required pattern, continuous or partition, can be such as
It is that continuously, coating head isolated area 19 can also be set on length direction as shown in Figure 2, so as to such as on length direction shown in Fig. 1
Coating shown in Fig. 8 is in the pattern of striated.
As shown in Figure 1, transmission device 12 includes at least stepper motor and conveyer belt, and the speed of service in the utility model
It is continuously adjustable, such as it is smaller than 100m/min, but not limited to this.Coating head 11 is by the burn into of resistance to polar solvent acid and alkali-resistance and strong oxygen
The material for changing reducing agent is formed, and be can connect coating head 11 and/or pedestal 13 on transmission device 12, can be followed the biography of variable speed
Dynamic device 12 at the uniform velocity moves.The material of pedestal 13 is polytetrafluoroethylene (PTFE) or fluoro-containing plastic, Stainless steel 316, titanium alloy, marble
Or glass, solar cell conductive substrate 2 can be fixed by machinery positioning or vacuum suction thereon.Transmission device 12 can be passed through
The distance that coating head 11 arrives conductive substrates 2 is adjusted, which is continuously adjustable, such as 0.1~10mm, it is adjustable to arrive arbitrary value,
After adjusting, the distance immobilizes in coating process.
Also, can be described in detail in this implementation form and aftermentioned implementation form, transmission device 12 controls pedestal 13 or coating head 11 is moved
It is dynamic.And the movement speed on coating direction is continuously adjustable, and adjustable coating head 11 arrives the distance of conductive substrates.Coating head
11 upper end is adjacent with the liquid storage device 14 of perovskite precursor solution or connect, and the relative position of coating head 11 and liquid storage device 14
It is remained in moving process constant.Transmission device 12 connects pedestal 13, be formed as coating head 11 and liquid storage device 14 it is fixed and
The mobile structure of pedestal 13；Alternatively, transmission device 12 connects coating head 11 and liquid storage device 14, is formed as pedestal 13 and fixes and be coated with
First 11 and the structure that moves jointly of liquid storage device 14；Alternatively, transmission device 12 respectively with pedestal 13 and with coating head 11 and liquid storage device
14 connections, are formed as pedestal 13 and the moveable structure of coating head 11.
Also, being formed with the coating tip 15 contacted with conductive substrates 2 in coating head 11, can be carried out slidingtype coating or rolling
Formula coating.Perovskite precursor solution in the liquid storage device 14 of perovskite precursor solution is expressed to coating by gas pressure
Tip, the substrate for being coated with tip 15 and conductive substrates 2 directly contact, and are at the uniform velocity moved by transmission device 12, to be formed not
Thermally treated perovskite light-absorption layer 6, with after annealing.As shown in Fig. 1,2,3,5,6, coating tip 15 is used to form perovskite
The perovskite precursor solution of light-absorption layer 6 is uniformly impregnated with, thus realize even spread, so in coincidence shape in figure.
Specifically, coating head 11 is connected on transmission device 12, the perovskite in perovskite precursor solution liquid storage device 14
The continual and steady coating tip 15 for flowing into coating head 11 of precursor solution, is coated with to perovskite precursor solution complete wetting
After tip 15, contact coating head 11 and the surface for the solar cell conductive substrate 2 being fixed on pedestal 13, then at the uniform velocity move
Coating head 11 is to form fine and close, smooth liquid film.Also, the speed of service of transmission device 2 is continuously adjustable and the speed of service is less than
Thus 100m/min can control the thickness of liquid film by adjusting coating speed, and then control the thickness of gained dry film.Comparison is normal
Spin-coating mode, large area coating may be implemented in this technique, film forming homogeneity improves, parameter stability is controllable and can be with
Patterning.Particularly, this coating process is particularly suitable for being coated with perovskite thin film on mesoporous layer.
Also, as shown in Figure 1, Figure 2, Figure 6 shows, when slidingtype is coated with, the upper end of coating head 11 and perovskite precursor solution are stored up
Liquid device 14 connects, and coating tip 15 is formed in 11 lower end of coating head and directly contacts with conductive substrates 2, perovskite precursor solution
The coating tip 15 that 11 lower end of coating head is flowed out to from liquid storage device 14, by transmission device 12, coating head 11 and 13 phase of pedestal
To displacement, to form not thermally treated perovskite light-absorption layer.
Also, as shown in figs. 3 and 5, when roller is coated with, coating head 11 is cylindric and can be freely rotated around central axis, apply
Cloth tip 15 is formed in 11 outer ring of coating head, and liquid storage device 14 is separated and fixed with coating head 11, and relative position remains unchanged, this reality
It applies in form, liquid storage device 14 connect with coating head 11 and is fixed on connector 16, but not limited to this.Perovskite precursor solution from
The coating tip 15 of 11 outer ring of coating head is flowed out in liquid storage device 14, transmission device 12 connects 11 central axis of coating head and/or bottom
Seat 13, thus when transmission device 12 acts, coating head 11 and 13 relative displacement of pedestal, the perovskite forerunner being coated on tip 15
Liquid solution rolling is coated on the substrate of pedestal 13, to form not thermally treated perovskite light-absorption layer.
Being coated with tip 15 is that porous wicking structure is coated with tip, flexible net trellis is coated with tip, flexible linear array row
Cloth is coated with tip.Wherein, the coating tip 15 of porous wicking structure is formed by fiber, foamed plastic, polyvinyl alcohol or polyester, and
The coating tip 15 of adjustable porosity, flexible net trellis is formed by cotton, fiber crops, silk or chemical fibre, and grid mesh number is adjustable, flexible linear
The coating tip 15 of array arrangement is formed by hair, palm fibre or plastic wire, and gap of arranging is adjustable.But the utility model is not limited to
This, can also use various suitable reasonable materials according to the actual situation, and about hole, gap, number etc., it can freely set,
As long as matching with perovskite precursor solution viscosity, will not leak out under the effect of gravity.
Coating tip 15 can be by wrapping up, bundling, and the modes such as bonding are secured within coating head 11.Perovskite presoma is molten
Fluid viscosity is less than 10pa*s, because perovskite precursor solution concentration and viscosity are excessive, is easy blocking liquid outlet, causes liquid film uneven
It is even.Coating speed is faster, and liquid film is thinner；Grid mesh number is bigger and/or hole is bigger, and it is molten to be more suitable for the small presoma of viscosity
Liquid.Grid mesh number is bigger, and liquid film is thinner；Contact pressure is bigger, and liquid outlet quantity is more, and liquid film is thicker, but pressure further increases
Lead to gap turn narrow, when coating can take away a part of precursor solution, and liquid film is caused to narrow.12 speed of service of transmission device is continuous
The adjustable and speed of service is less than 100m/min, and can adjust the distance that coating head 11 arrives conductive substrates 2 by transmission device 12, into
And easily realize liquid film controlled.
Thus fine and close, smooth liquid film can be formed.The present apparatus is coated with suitable for contact, compares common spin-coating side
Formula, this technique may be implemented large area coating, the raising of film forming homogeneity, parameter stability controllably and can pattern, to save
The technique etched again after perovskite film forming, further reduces the cost.
Fig. 8 is the schematic diagram for showing the coating process of the utility model；Fig. 9 be by the apparatus for coating of the utility model and
The cross-sectional view of battery structure obtained by coating process production.Conductive layer is etched into the quarter of insulation on 2 surface of conductive substrates by laser
Corrosion line 1, for the preparation of subsequent serial module structure, further, the utility model also provides a kind of coating work of perovskite light-absorption layer
Skill, comprising: 1) dried up after cleaning conductive substrates 2 with cleaning solution, hole blocking layer 3 is prepared on the substrate of conductive substrates 2；2) exist
On hole blocking layer 3, successively sintering prepares electron transfer layer 4 and insulating layer 5；3) after preparing perovskite precursor solution, transfer
Into the liquid storage device 14 of perovskite precursor solution, then make perovskite precursor solution it is continual and steady be flowed into coating head 11
Coating tip 15, after perovskite precursor solution complete wetting be coated with tip 15 after, make coating head 11 by coating tip 15
It is contacted with 2 surface of conductive substrates being fixed on pedestal 13, and coating head 11 and/or pedestal is at the uniform velocity moved by transmission device 12
13 so that form fine and close not thermally treated perovskite light-absorption layer 6, with after annealing；4) it on perovskite light-absorption layer 6, successively makes
For hole transmission layer and to electrode 7.
Specifically, the perovskite precursor solution in the liquid storage device 14 of perovskite precursor solution is squeezed by gas pressure
It is pressed onto the coating tip 15 of 11 surface of coating head setting, since liquid capillary acts on, coating tip 15 is sufficiently infiltrated, but calcium
Titanium ore precursor solution will not drip.Coating tip 15 and conductive substrates 2 directly contact, and adjust coating end by transmission device 12
The tip 15 makes its extruding at a distance from pedestal 13, so that the perovskite precursor solution being coated in tip 15 is transferred to conductive base
Bottom 2.Pedestal 13 fixes solar cell conductive substrate 2 by machinery positioning or vacuum suction, and at the uniform velocity by transmission device
Mobile, coating head 11 can be sliding or rolling relative to the mutual displacement of pedestal 13, to form not thermally treated calcium titanium
Mine light-absorption layer, with after annealing.
According to the utility model, using above-mentioned novel coating process, in the liquid storage device 14 of perovskite precursor solution
Perovskite precursor solution, the continual and steady coating tip 15 for being flowed into coating head 11 make the contact of coating head 11 be fixed on bottom
2 surface of conductive substrates on seat 13, then coating head 11 is at the uniform velocity moved, fine and close, smooth liquid film is formed, so as to improve electron transfer
Rate, electron lifetime and photoelectric conversion performance.The coating process parameter stability is controllable, and can pattern, to save calcium titanium
After mine light-absorption layer 6 forms a film, then the technique etched, it is further reduced preparation cost.
It is (following to be also known as the conductive substrates 2 of perovskite solar battery using FTO electro-conductive glass in the utility model
For FTO glass 2), for the SnO2 transparent conducting glass (SnO2:F) of doping fluorine, it is widely used in liquid crystal display, photocatalysis, too
The fields such as positive energy cell substrate, dye-sensitized solar cells, electrochomeric glass.But not limited to this, it can be as the case may be
Change.Also, hole blocking layer 3 is TiO in this implementation form2Compacted zone, can be by the inclusion of tetraisopropyl titanate, levulinic
Ketone, hydrochloric acid, the precursor solution of second alcohol and water are obtained using the wet chemical methods such as spraying, spin coating, slot coated, but are not limited to
This.
The utility model is further described below in conjunction with specific embodiment.
(embodiment 1)
1) respectively with acetone, alkalis, deionized water, 20 points of acetone ultrasonic cleaning FTO glass (i.e., conductive substrates)
Then clock dries up.
2) TiO is prepared on 2 substrate of FTO glass2Compacted zone (i.e., hole blocking layer) 3, precursor solution solvent are ethyl alcohol
And water, including following component: tetraisopropyl titanate (0.3mol/L), acetylacetone,2,4-pentanedione (0.45mol/L), hydrochloric acid
(0.09mol/L).Precursor solution is drawn, is added dropwise on the FTO substrate cleaned up, so that solution is paved with the entire surface FTO, adopt
It is formed a film with spin-coating method, spin speed 3000rpm, time 20s.510 DEG C of sintering 30min in Muffle furnace.
3) on hole blocking layer 3, the mesoporous layer of silk-screen printing nano titania slurry is as electron transfer layer 4, admittedly contain
Amount 10%, solvent terpinol, 510 DEG C of sintering 30min in Muffle furnace.
4) on electron transfer layer 4, silk-screen printing nano zirconium dioxide slurry is as insulating layer 5, solid content 5%, solvent
Terpinol, 510 DEG C of sintering 30min in Muffle furnace.
5) 461 milligrams of lead iodide (PbI are measured2), 159 milligrams of CH3NH3I powder, 78 milligrams of dimethyl sulfoxides are mixed in 600 milligrams
N,N-Dimethylformamide (DMF) stirs 1 hour at room temperature, forms CH3NH3PbI3Perovskite precursor solution.With this calcium titanium
Mine precursor solution prepares not thermally treated perovskite light-absorption layer 6 using equipment shown in Fig. 2 and 6 and technique, uses coating head
11 be PP material, and a length of 200mm is coated with tip 15 and is made of non-woven fabrics, and the dispensing area of coating head 11 is 10.5mm, coating head
Isolated area 19 be 3mm, totally 9.
6) on perovskite light-absorption layer 6, silk-screen printing carbon pastes are as hole transmission layer and to electrode 7, solid content 37%,
Solvent terpinol obtains perovskite solar battery.
(comparative example 1)
1) respectively with acetone, alkalis, deionized water, 20 points of acetone ultrasonic cleaning FTO glass (i.e., conductive substrates)
Then clock dries up.
2) TiO is prepared on 2 substrate of FTO glass2Compacted zone (i.e., hole blocking layer) 3, precursor solution solvent are ethyl alcohol
And water, including following component: tetraisopropyl titanate (0.3mol/L), acetylacetone,2,4-pentanedione (0.45mol/L), hydrochloric acid
(0.09mol/L).Precursor solution is drawn, is added dropwise on the FTO substrate cleaned up, so that solution is paved with the entire surface FTO, adopt
It is formed a film with spin-coating method, spin speed 3000rpm, time 20s.510 DEG C of sintering 30min in Muffle furnace.
3) on hole blocking layer 3, the mesoporous layer of silk-screen printing nano titania slurry is as electron transfer layer 4, admittedly contain
Amount 10%, solvent terpinol, 510 DEG C of sintering 30min in Muffle furnace.
4) on electron transfer layer 4, silk-screen printing nano zirconium dioxide slurry is as insulating layer 5, solid content 5%, solvent
Terpinol, 510 DEG C of sintering 30min in Muffle furnace.
5) 461 milligrams of lead iodide (PbI are measured2), 159 milligrams of CH3NH3I powder, 78 milligrams of dimethyl sulfoxides are mixed in 600 milligrams
N,N-Dimethylformamide (DMF) stirs 1 hour at room temperature, forms CH3NH3PbI3Perovskite precursor solution.With this calcium titanium
Mine precursor solution is spin coating liquid, prepares not thermally treated perovskite light-absorption layer 6 using spin-coating method, spin speed 5000rpm,
Time 20s, 100 DEG C are annealed 5 minutes.
6) on perovskite light-absorption layer 6, silk-screen printing carbon pastes are as hole transmission layer and to electrode 7, solid content 37%,
Solvent terpinol obtains perovskite solar battery.
Figure 10 is the perovskite solar-electricity for showing perovskite solar battery according to the present utility model and prior art
The performance comparison figure in pond, following table further illustrate perovskite light-absorption layer 6 prepared by embodiment 1 according to the present utility model with
The perovskite solar cell properties parameter of perovskite light-absorption layer 6 prepared by the comparative example 1 of prior art.
。
In conjunction with upper table it is found that being made according to the apparatus for coating of the utility model embodiment 1 and corresponding coating process
Battery, transfer efficiency is higher than the solar battery of perovskite thin film prepared by comparative example 1, and is suitable for more large area, is conducive to produce
Industry.After the later period, apparatus for coating was advanced optimized, superior effect can be obtained.
Above specific embodiment has carried out further in detail the purpose of this utility model, technical scheme and beneficial effects
It describes in detail bright, it should be appreciated that the above is only a kind of specific embodiments of the utility model, however it is not limited to which this is practical new
The protection scope of type, under the objective for the essential characteristic for not departing from the utility model, the utility model can be presented as diversified forms,
Therefore the implementation form in the utility model is to be illustrative rather than definitive thereof, since the scope of the utility model is limited by claim
Determine rather than limited by specification, and falls in the institute in the full scope of equivalents of the range that claim defines or the range that it is defined
It changes and is understood to be included in the claims.Within the spirit and principle of the utility model, it is made
Any modification, equivalent substitution, improvement and etc. should be included within the scope of protection of this utility model.
Claims (8)
1. the apparatus for coating of perovskite light-absorption layer in a kind of perovskite solar battery, which is characterized in that have:
Coating head, the liquid storage device for storing perovskite precursor solution, pedestal and at least one transmission device；
The pedestal is fixed with the conductive substrates of solar battery；
The transmission device controls the pedestal or/and the coating head moves in the coating direction；
The upper end of the coating head is adjacent with the liquid storage device or connects,
It is formed with the coating tip contacted with the conductive substrates in the coating head, can be carried out slidingtype coating or roller applies
Cloth；
The speed of service of the transmission device is less than 100m/min；
The perovskite precursor solution viscosity is less than 10pa*s.
2. apparatus for coating according to claim 1, which is characterized in that
The transmission device connects the pedestal, be formed as the coating head and the liquid storage device is fixed and the pedestal is mobile
Structure；
Alternatively, the transmission device connects the coating head and the liquid storage device, is formed as the pedestal and fixes and the coating
The structure that head and the liquid storage device move jointly；
Alternatively, the transmission device is connect with the pedestal and with the coating head and the liquid storage device respectively, be formed as described
The structure that pedestal and the coating head move；
The pedestal passes through machinery positioning or the fixed conductive substrates of vacuum suction；
Also be adjustable by transmission device the coating head to the conductive substrates distance.
3. apparatus for coating according to claim 1, which is characterized in that
When the roller is coated with, the coating head is cylindric and can be freely rotated around central axis that the coating tip is formed
In the coating head outer ring, the liquid storage device is separated and is fixed with the coating head, and relative position remains unchanged, the perovskite
Precursor solution flows out to the coating tip of the coating head outer ring from the liquid storage device, by the transmission device,
The coating head and the pedestal relative displacement.
4. apparatus for coating according to claim 1, which is characterized in that
When the slidingtype is coated with, the coating tip is formed in the coating head lower end and directly connects with the conductive substrates
Touching；The perovskite precursor solution flows out to the coating tip of the coating head lower end from the liquid storage device, passes through
The transmission device, the coating head and the pedestal relative displacement.
5. apparatus for coating according to claim 4, which is characterized in that
The coating tip is that porous wicking structure is coated with tip, flexible net trellis is coated with tip or flexible linear array row
Cloth is coated with tip.
6. apparatus for coating according to claim 5, which is characterized in that
The porous wicking structure coating tip is formed by fiber, foamed plastic, polyvinyl alcohol or polyester；
The flexible net trellis coating tip is formed by cotton, fiber crops, silk or chemical fibre；
The flexible linear array arrangement coating tip is formed by hair, palm fibre or plastic wire.
7. apparatus for coating according to claim 1, which is characterized in that
The coating head is formed by the material of the burn into of resistance to polar solvent acid and alkali-resistance and Strong oxdiative reducing agent, and the coating head is cut
Face shape is continuous or disconnects.
8. apparatus for coating according to claim 1, which is characterized in that
The material of the pedestal is polytetrafluoroethylene (PTFE) or fluoro-containing plastic, Stainless steel 316, titanium alloy, marble or glass.
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| CN108855775A (en) * | 2018-06-30 | 2018-11-23 | 浙江浙能技术研究院有限公司 | The coating process and device of perovskite light-absorption layer in a kind of perovskite solar battery |
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| CN108855775A (en) * | 2018-06-30 | 2018-11-23 | 浙江浙能技术研究院有限公司 | The coating process and device of perovskite light-absorption layer in a kind of perovskite solar battery |
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