CN109742234A - A kind of translucent organic solar batteries and preparation method thereof based on thermochromism - Google Patents
A kind of translucent organic solar batteries and preparation method thereof based on thermochromism Download PDFInfo
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- CN109742234A CN109742234A CN201910051567.4A CN201910051567A CN109742234A CN 109742234 A CN109742234 A CN 109742234A CN 201910051567 A CN201910051567 A CN 201910051567A CN 109742234 A CN109742234 A CN 109742234A
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Classifications
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- 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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Abstract
The present invention relates to a kind of translucent organic solar batteries and preparation method thereof based on thermochromism, its solar battery includes dual functional polymer layer, it is set on flexible thermochromism substrate, first transparency electrode layer, it is set in bifunctional layer, polymer P FN electronics decorative layer, it is set on first transparency electrode layer, polymer active layer, it is set on polymer P FN electronics decorative layer, second transparency electrode layer is set on polymer active layer, wherein, flexible thermochromism substrate is the stepped construction of flexible PET substrate and flexible thermochromic thin film.Solar battery of the invention have the advantages that color, transparency are variable, colour temperature is lower, high conductance, high transmittance and with flexible thermochromism film matches, can large area prepare Grazing condition thermochromic thin film regulation organic solar batteries, have a good application prospect.
Description
Technical field
The present invention relates to organic solar batteries field more particularly to a kind of translucent organic sun based on thermochromism
Energy battery and preparation method thereof.
Background technique
In recent years, with advances in technology and the improvement of people's living standards, solar battery using more and more extensive.
Traditional silicon solar cell cannot achieve translucent since active layer is thicker (2~4 microns), limits it and leads in translucent battery
The application in domain.Polymer solar battery is because active layer thickness generally only has 100nm or so, so that the sun both may be implemented in it
Can generate electricity can transmit sunlight again, therefore receive the extensive concern of researcher.Therefore, different from traditional crystalline silicon sun
The big outstanding advantages that translucentization is it may be implemented in energy battery, polymer solar battery.By reducing translucent polymerization
The thickness of active layer and use transparent conductive cathode and anode in object solar battery, so that translucent polymer solar-electricity
Pond can be used for roof, metope or window etc., further widen its application range.But translucent organic solar batteries
Transparency can not change according to external condition, limit it and be widely used.
Adjusting transparency by thermochromism is a kind of effective ways for changing light transmittance.Thermochromism refer to certain materials because
It is heated that physical change (such as taking off the crystallization water, crystal structure interconversion, steric configuration interconversion) or chemical change (decomposition, change occurs
Close, aoxidize, restore etc.) lead to the variation of molecular structure, molecular conformation, so as to cause the effect of color change in appearance.Have
The material of this effect is known as thermochromic material.
Thermochromism optical texture is introduced in translucent polymer solar battery, thus it is possible to vary translucent organic sun
Active layer completely dispenses with switch or any artificial energy source to the capture ability of photon in a certain wavelength band in energy battery device
The significant advantage that the full-automatic photoelectric conversion and light that can be achieved with response external variation of ambient temperature penetrate, while realizing face
The feature that color is adjustable.For example, University of California Berkeley Yang Peidong professor et al. building is based on CsPbI3-XBrxThe heat of material
Mutagens color perovskite solar battery, this material can switch to dark Perovskite Phase (high-temperature-phase) at 105 DEG C, and transparency is about
It is 35%；At room temperature, when encountering steam, material will automatically switch into transparent non-perovskite phase (low-temperature phase).
However, up to 105 DEG C of transition temperature will affect actual industrial application, while multiple steam intrusion may destroy it
Original structure.In addition, lead-containing materials are resolved as glass coating bring toxicity problem needs.In addition, translucent polymerization
Common transparent conductive electrode is tin indium oxide (ITO) in object solar battery, however, ITO matter is crisp, is only suitable for applying in glass
Etc. hard substrates, be not suitable for the flexible substrates such as PET, can not roll-to-roll continuous printing production.
Summary of the invention
For the technical problems in the prior art, primary and foremost purpose of the invention is to provide a kind of based on thermochromism
Translucent organic solar batteries and preparation method thereof, for the purpose, the present invention is at least provided the following technical solutions:
A kind of translucent organic solar batteries based on thermochromism comprising,
One flexible thermochromism substrate；
One bifunctional layer is set on the flexible thermochromism substrate；
One first transparency electrode layer is set on the dual functional polymer layer；
One polymer P FN electronics decorative layer, is set on the first transparency electrode layer；
One polymer active layer is set on the polymer P FN electronics decorative layer；
One second transparency electrode layer is set on the polymer active layer.
Further, the flexible thermochromism substrate is the stacking knot of flexible PET substrate and flexible thermochromic thin film
Structure, the flexibility thermochromism film in response different temperatures.
Further, the bifunctional layer is dual functional polymer layer or inorganic oxide layer, the thickness of the bifunctional layer
Degree is 40~50nm, and the bifunctional layer uses UV/ozone corona treatment 3~5 minutes.
Further, the dual functional polymer layer is dual functional polymer PFN layers, PVK layers or PFO layers, described inorganic
Oxide skin(coating) is molybdenum trioxide.
Further, the second transparency electrode layer is conducting polymer PEDOT:PSS, the second transparency electrode layer
With a thickness of 50~150nm.
Further, the first transparency electrode layer is super thin metal transparent cathode, the super thin metal transparent cathode
With a thickness of 8~15nm.
Further, the polymer active layer with a thickness of 80~100nm.
A kind of preparation method of the translucent organic solar batteries based on thermochromism comprising following steps:
In the flexible thermochromic thin film of flexible PET substrate side preparation different temperatures response；
In the other side of the PET substrate or the surface spin coating or deposition bifunctional layer of the flexible thermochromic thin film；
First transparency electrode layer is deposited on the bifunctional layer surface；
In the first transparency electrode layer surface spin on polymers PFN electronics decorative layer；
Layer surface spin on polymers active layer is modified in the polymer P FN electronics；
In the polymer active layer surface spin coating second transparency electrode layer.
Further, the flexible PET substrate is in advance through ultraviolet or corona treatment 2~5 minutes, the spin coating or heavy
After product bifunctional layer, the substrate is carried out UV/ozone corona treatment 3~5 minutes；The bifunctional layer is double function
It can FN layers, PVK layers, PFO layers of polymer P or molybdenum trioxide layer.
Further, the preparation of the polymer active layer includes taking PTB7:PCBM [70]: the mixed proportion of ICBA is
1:1~2:0.2~0.3 is dissolved in solvent C B (chlorobenzene) and CN (chlorine added with appropriate additive DIO (1,8- diiodo-octane)
Naphthalene) in form solution, and heat 12 hours on warm table with 60 DEG C and form polymer active layer solution, in the polymer
PFN electronics modifies polymer active layer solution described in layer surface spin coating, is placed under high vacuum environment 3h then to obtain
Dry polymer active layer, wherein the volume ratio of CB:DIO:CN be 92~96:4~2:4~2, PTB7, PCBM [70] and
The concentration of ICBA in the solution is 20~25mg/ml.
Compared with prior art, the present invention at least has the following beneficial effects:
The present invention combines translucent organic solar batteries with thermochromic thin film, realize transparency it is adjustable with
And the adjustable dual function of photoelectric conversion efficiency, both color can spontaneously be changed by the height of sensing external environment temperature
It realizes adjustable visible light transmittance, metastable electric energy can also be generated simultaneously and used for load, there is dual function.And
And solar battery of the invention has that color, transparency are variable, colour temperature is lower, high conductance, high transmittance and and flexible thermal
The advantages of mutagens color film matches, can large area prepare Grazing condition thermochromic thin film regulation organic solar batteries, have
Good application prospect.
Detailed description of the invention
Fig. 1 is that the present invention is based on the translucent organic solar batteries device architecture schematic diagrames of thermochromism.
Fig. 2 be different flexible thermochromic thin films regulations translucent polymer solar battery AM1.5G standard too
J-V the curve in sunlight source.
Fig. 3 is the translucent polymer solar battery of different flexible thermochromic thin film regulations in room temperature (25 DEG C) and adds
The optical transmission spectra of visible wavelength range under hot (40 DEG C) state.
Fig. 4 is the optical transmission spectra of different bifunctional layer electrodes.
Appended drawing reference: 1. flexible thermochromic thin films, 2. flexible PET substrates, 3. bifunctional layers, 4. first transparency electrodes
Layer, 5. polymer P FN electronics decorative layers, 6. polymer active layers, 7. second transparency electrode layers.
Specific embodiment
It is next below that the present invention will be further described in detail.
Translucent organic solar energy cell structure based on thermochromism of the invention is soft as shown in Figure 1, the structure includes
Property thermochromism substrate, bifunctional layer 3 is set to the side of flexible thermochromism substrate, and first transparency electrode layer 4 is set to double
In functional layer 3, polymer P FN electronics decorative layer 5 is set on first transparency electrode layer 4, and polymer active layer 6 is set to polymerization
On object PFN electronics decorative layer 5, second transparency electrode layer 7 is set on polymer active layer 6.In some embodiments, difunctional
Layer 3 can be dual functional polymer layer or inorganic oxide layer, dual functional polymer layer can be PFN layers of dual functional polymer,
PVK layers or PFO layers, which can also use other suitable polymer.Inorganic oxide layer can be molybdenum trioxide or its
Its suitable inorganic oxide.
Flexible thermochromism substrate can be the stepped construction of flexible thermochromic thin film 1 with flexible PET substrate 2, at this
In embodiment, flexible thermochromic thin film 1 is set in the side of flexible PET substrate 2, bifunctional layer 3 is set to PET substrate 2
The other side.In another embodiment, flexible thermochromic thin film 1 is set in the side of flexible PET substrate 2, bifunctional layer 3 is arranged
In flexible thermochromic thin film 1.
The pretreatment of flexible transparent substrate: flexible PET substrate 2 is before laminated flexible thermochromic thin film, by flexible PET
It is sequentially placed in isopropanol and deionized water and is cleaned by ultrasonic respectively 20 minutes, be then dried with nitrogen with dry, finally used
Ultraviolet/corona treatment 5 minutes, to remove surface pollutant that may be present.
Flexible thermochromic thin film 1 is that the organic reversible thermotropic change of light color that mass ratio is 0.5% is mixed in PDMS solution
Obtained by the organic Reversible Thermochromic Materials of dark color that color material and mass ratio are 5%.Organic Reversible Thermochromic Materials are benzene
Phthaleins.In this embodiment, the organic Reversible Thermochromic Materials of light color can be Type-1 (light blue) or Type-2 is (pale red
Color), dark organic Reversible Thermochromic Materials can be Type-3 (navy blue), Type-4 (peony).
By mixing the thermochromic material of different proportion and type in PDMS, construct to different wavelength range high reflection
Flexible thermochromic thin film.Flexible thermochromic thin film 1 is set to flexible PET substrate 2 by the way of spin coating or coining
Surface.So that flexible thermochromism film in response different temperatures.
Bifunctional layer 3 is arranged in the side of flexible thermochromism substrate, bifunctional layer 3 with a thickness of 40~50nm, the reality
It applies in example, bifunctional layer 3 is dual functional polymer PFN layers.Using sol evenning machine the surface of flexible thermochromic thin film 1 or
The another side spin coating polymer solutions of flexible PET substrate 2, the polymer solution are the solution for including PFN.In other embodiments
In, using solwution method on the surface of flexible thermochromic thin film 1 or in the difunctional polymerization of another side spin coating of flexible PET substrate 2
PVK layers of object, with a thickness of 40~50nm.In some embodiments, using vacuum thermal evaporation sedimentation in flexible thermochromic thin film 1
Surface or flexible PET substrate 2 another side deposit molybdenum trioxide, deposition thickness be 40~50nm.
The configuration of polymer solution: PFN is dissolved using anhydrous methanol, and the nothing that volume ratio is 3 ‰ is added in methanol solution
Water acetic acid increases the dissolubility of PFN, and compound concentration is the PFN solution of 1mg/ml.Control the PFN function that spin coating thickness is about 40nm
After layer, ultraviolet/oxygen plasma treatment about 3 that power is 300~500W is carried out to the PET substrate that spin coating is covered with PFN
It~5 minutes, in favor of subsequent preparation first transparency electrode layer 4, forms metal interpenetrating and connects network structure, and then improve film
Conductivity, meanwhile, the plasma enhancing that plasma treatment also can be reduced metallic absorbs, and improves the light transmittance of entire film.
The final flexible substrates for obtaining surface and having dual functional polymer PFN layer, PFN layers of the dual functional polymer with seed layer and
The dual function of optical interval layer.
First transparency electrode layer 4 is arranged on dual functional polymer PFN layer, and first transparency electrode layer can be Ag electrode,
The thickness of first transparency electrode layer 4 is 8~15nm.In the embodiment, which is placed in vacuum coating equipment, true
Reciprocal of duty cycle 5 × 10-5Under conditions of Pa, in the Ag electrode of PFN layers of dual functional polymer of surface deposition about 12nm thickness, to obtain flexibility
Transparent cathode electrode substrate.
Polymer P FN electronics decorative layer 5 is arranged on first transparency electrode layer 4, specifically, being matched using sol evenning machine by above-mentioned
The polymer solution set is spin-coated on the surface of first transparency electrode layer 4, and the thickness of control polymer P FN electronics decorative layer 5 is about
5nm obtains the first transparent flexible electrically-conductive backing plate that surface is covered with polymer P FN electronics decorative layer 5.
Polymer active layer 6 is arranged on polymer P FN electronics decorative layer 5, polymer active layer 6 with a thickness of 80~
100nm.In the embodiment, take PTB7:PCBM [70]: the mass ratio of ICBA is 1:1.5:0.25 mixing, is dissolved in and is added with
Solution is formed in the solvent C B (chlorobenzene) and CN (chloronaphthalene) of 0.3% DIO (1,8- diiodo-octane) additive, wherein CB:DIO:
The volume ratio of CN three is 94:3:3, and the concentration of PTB7, PCBM [70] and ICBA in the above solution is 25mg/ml, and is being added
With 60 DEG C of 12 hours of heating in thermal station.Mixed solution after heating is spin-coated on polymer P FN electronics decorative layer 5.Then
The transparent conductive substrate that surface is covered with polymer active layer 6 is placed on 5 × 10-4Dry 3 under Pa high vacuum environment below
It is~5 hours, preferably 3 hours dry in the embodiment, to obtain the polymer active layer 6 with a thickness of 80~95nm.
Second transparency electrode layer 7 is arranged on polymer active layer 6, second transparency electrode layer 7 with a thickness of 8~15nm,
Second transparency electrode layer 7 is conducting polymer PEDOT:PSS.0.5% surfactant solution is added in PEDOT:PSS solution
(FS -30) and 5% dimethyl sulfoxide (DMSO).And spin coating solution on active layer, then added on warm table with 50 DEG C
Hot 30s evaporates the moisture of film surface remnants, to form second transparency electrode layer 7.
Table 1
Table 1 be translucent polymer solar battery without thermochromic thin film, there is the device of thermochromic thin film to exist
The characteristic parameter of the standard solar source of AM1.5G compares.Wherein, None is the translucent of flexible thermochromic thin film of not arranging in pairs or groups
Polymer solar battery, structure are PET/PFN/Ag/PFN/PTB7:PCBM [70]: ICBA/PEDOT:PSS, Sample1-
4 be the translucent organic solar batteries of the invention based on thermochromism, the temperature of corresponding flexibility thermochromic thin film
Response is different.The structure of Sample1 is Type-1/PET/PFN/Ag/PFN/PTB7:PCBM [70]: ICBA/PEDOT:PSS,
The structure of Sample2 is Type-2/PET/PFN/Ag/PFN/PTB7:PCBM [70]: the knot of ICBA/PEDOT:PSS, Sample3
Structure is Type-3/PET/PFN/Ag/PFN/PTB7:PCBM [70]: the structure of ICBA/PEDOT:PSS, Sample4 are Type-4/
PET/PFN/Ag/PFN/PTB7:PCBM[70]:ICBA/PEDOT:PSS。
Fig. 2 is J-of the translucent polymer solar battery based on Different electrodes under AM1.5G standard analog sunlight
V curve.Fig. 3 is the translucent polymer solar battery of different flexible thermochromic thin film regulations in room temperature (25 DEG C) and heating
The optical transmission spectra of visible wavelength range under (40 DEG C) state.Obtained by J-V curve every photoelectric parameter numerical value (including
JSC、VOC, FF and PCE etc.) enumerated in table 1.Comparison does not use the translucent polymer sun of flexible thermochromic thin film
Energy battery device, in VOCUnder conditions of remaining unchanged with FF, the use of flexible thermochromic thin film is improved inside battery device
Photocell distribution, at room temperature, the J of device Sample 1, Sample 2, Sample 3 and Sample 4SCIt mentions respectively
It is high by 20.8%, 22.1%, 28.0% and 28.2%.Finally, translucent poly- compared to flexible thermochromic thin film of not arranging in pairs or groups
Close the photoelectric conversion efficiency of object solar battery 4.12% and 31.04% visible spectrum mean transmissivity, device
Sample 1, Sample 2, Sample 3 and Sample 4 photoelectric conversion efficiency be respectively increased 4.88%, 4.97%,
5.29% and 5.33%, corresponding transmitance is 21.42%, 19.02%, 10.02% and 4.87%.At 40 DEG C, thermotropic change
The external temperature stimulation of color film in response changes color and transmitance, the J of deviceSCIt is obtained with photoelectric conversion efficiency and transmitance
To different variations, compared to the translucent polymer solar cell device for flexible thermochromic thin film of not arranging in pairs or groups, Sample
1,4.64%, 4.44%, 5.14% and has been respectively increased in the photoelectric efficiency of Sample 2, Sample 3 and Sample 4
5.25%, corresponding transmitance is 28.04%, 29.45%, 14.48% and 11.79%.It can be seen that it is prepared by the present invention too
It is positive can battery have the advantages that high conductance, high transmittance and with flexible thermochromism film matches.Fig. 4 is based on different double function
The optical transmission spectra curve of ergosphere, it is by the optical transmission spectra curve it is found that lower relative to single layer silver electrode visible-range
Average light transmission rate (32.91%), makees bifunctional layer using molybdenum trioxide layer but does not carry out UV/ozone corona treatment,
Its light transmission rate still improves (36.32% vs.32.91%).Further, molybdenum trioxide layer is carried out ultraviolet/smelly
After oxygen plasma treatment, it is 51.53% that light transmission rate, which effectively improves,.There is similar optimization similarly, for polymer P VK
Effect, the transmitance of not plasma-treated PVK/Ag electrode are 37.06%, and treated, and electrode transmitance is increased to
51.53%.UV/ozone corona treatment equally has effect of optimization to the conductivity of electrode, relative to single layer silver electrode
High square resistance, untreated bifunctional layer/Ag bifunctional layer electrode sheet resistance substantially reduces, after further plasma treatment,
MoO3It is 28.36 Ω/ that the sheet resistance of/Ag electrode, which significantly reduces, and it is 28.16 Ω/ that the sheet resistance of PVK/Ag electrode, which significantly reduces,.Cause
This, the bifunctional layer through UV/ozone corona treatment realizes metal electrode and is promoted in optically and electrically both sides.This
Invent provided by preparation method can large area prepare Grazing condition thermochromic thin film regulation organic solar batteries, have very
Good application prospect.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.This
The embodiment of invention is simultaneously not restricted to the described embodiments, and others are any without departing from the spirit and principles of the present invention
Made changes, modifications, substitutions, combinations, simplifications should be equivalent substitute mode, be included in protection scope of the present invention
Within.There is no necessity and possibility to exhaust all the enbodiments (such as replaces different active layer or device directly to make
For in flexible thermochromic thin film), and obvious changes or variations extended from this are still in the invention
Protection scope among.
Claims (10)
1. a kind of translucent organic solar batteries based on thermochromism comprising,
One flexible thermochromism substrate；
One bifunctional layer is set on the flexible thermochromism substrate；
One first transparency electrode layer is set on the dual functional polymer layer；
One polymer P FN electronics decorative layer, is set on the first transparency electrode layer；
One polymer active layer is set on the polymer P FN electronics decorative layer；
One second transparency electrode layer is set on the polymer active layer.
2. the organic solar batteries according to claim 1, which is characterized in that the flexibility thermochromism substrate is flexibility
The stepped construction of PET substrate and flexible thermochromic thin film, the flexibility thermochromism film in response different temperatures.
3. organic solar batteries according to claim 1 or 2, which is characterized in that the bifunctional layer is difunctional poly-
Close nitride layer or inorganic oxide layer, the bifunctional layer with a thickness of 40~50nm, the bifunctional layer is using UV/ozone etc.
Gas ions are handled 3~5 minutes.
4. the organic solar batteries according to claim 3, which is characterized in that the dual functional polymer layer is difunctional
FN layers, PVK layers or PFO layers of polymer P, the inorganic oxide layer is molybdenum trioxide.
5. the organic solar batteries according to claim 1, which is characterized in that the second transparency electrode layer is conductive poly-
Close object PEDOT:PSS, the second transparency electrode layer with a thickness of 50~150nm.
6. -2 or 4 organic solar batteries according to claim 1, which is characterized in that the first transparency electrode layer is
Super thin metal transparent cathode, the super thin metal transparent cathode with a thickness of 8~15nm.
7. -2 or 4 organic solar batteries according to claim 1, which is characterized in that the thickness of the polymer active layer
Degree is 80~100nm.
8. a kind of preparation method of the translucent organic solar batteries based on thermochromism comprising following steps:
In the flexible thermochromic thin film of flexible PET substrate side preparation different temperatures response；
In the other side of the PET substrate or the surface spin coating or deposition bifunctional layer of the flexible thermochromic thin film；
First transparency electrode layer is deposited on the bifunctional layer surface；
In the first transparency electrode layer surface spin on polymers PFN electronics decorative layer；
Layer surface spin on polymers active layer is modified in the polymer P FN electronics；
In the polymer active layer surface spin coating second transparency electrode layer.
9. the preparation method according to claim 8, which is characterized in that it is described flexibility PET substrate in advance through it is ultraviolet or wait from
Daughter is handled 2~5 minutes, after the spin coating or deposition bifunctional layer, is carried out at UV/ozone plasma to the substrate
Reason 3~5 minutes；The bifunctional layer is PFN layers, PVK layers, PFO layers of dual functional polymer or molybdenum trioxide layer.
10. according to the preparation method of claim 8 or 9, which is characterized in that the preparation of the polymer active layer includes,
Take PTB7:PCBM [70]: the mixed proportion of ICBA be 1:1~2:0.2~0.3, be dissolved in added with appropriate additive DIO (1,
8- diiodo-octane) solvent C B (chlorobenzene) and CN (chloronaphthalene) in form solution, and with 60 DEG C of 12 hours of heating on warm table
Polymer active layer solution is formed, the polymer active layer solution described in polymer P FN electronics modification layer surface spin coating, so
It is placed under high vacuum environment 3h afterwards to obtain dry polymer active layer, wherein the volume ratio of CB:DIO:CN is 92
The concentration of~96:4~2:4~2, PTB7, PCBM [70] and ICBA in the solution is 20~25mg/ml.
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