WO2014059802A1

WO2014059802A1 - Photoelectrochromic device

Info

Publication number: WO2014059802A1
Application number: PCT/CN2013/078828
Authority: WO
Inventors: 陈怡�; 武文轩; 孙金礼; 罗多
Original assignee: 珠海兴业绿色建筑科技有限公司; 珠海兴业光电科技有限公司; 珠海兴业新能源科技有限公司; 湖南兴业太阳能科技有限公司; 珠海兴业节能科技有限公司
Priority date: 2012-10-17
Filing date: 2013-07-04
Publication date: 2014-04-24
Also published as: DE212013000019U1; CN103777424A

Abstract

A photoelectrochromic device capable of changing color according to changes in the intensity of solar rays. The present invention mainly comprises a transparent non-conductive substrate (101), an organic solar cell layer, electrochromic layers (401, 403), an electrolyte layer (402) and transparent conductive layers (201, 202, 203). The organic solar cell layer comprises an anode (304), a cathode (301) and an organic photoelectric conversion layer (300). Electricity produced by the photoelectric effect of said organic solar cell can be provided to the electrochromic layers (401, 403) of the device, and by using a photosensitive switch, the change in color of the device can automatically be controlled according to the intensity of solar rays.

Description

Photoelectric color change device

The present invention relates to an electrochromic device, and more particularly to a photochromic device.

Background technique

An electrochromic material refers to a material that changes color due to a change in the polarity and intensity of an applied electric field due to a reversible oxidation or reduction reaction that causes a change in the reflection or transmission intensity of incident light. Electrochromic materials can be classified into two categories: organic materials and inorganic materials. Non-electrochromic materials have received extensive attention due to their stable performance and strong UV resistance, mainly transition metal oxides such as tungsten oxide, nickel oxide, manganese oxide and the like. If the material is sandwiched between two pieces of glass, it can be used on the outer wall of the building. In this way, people can actively control the reflection or transmission intensity of the glass with light as the season and time change, thus saving energy. The purpose of consumption. This color-changing material can also be widely used in other fields, such as: sunglasses, car sunroofs, anti-glare rearview mirrors, etc. If such a color changing material is plated on the inner surface of some flexible organic materials, it can also be used to make a flexible color changing device.

In addition, since the electrochromic device uses only a low DC voltage (generally no more than ±5V), the color of the device can be changed. Thus, if the power generated by the solar cell can be used as the driving voltage of the electrochromic device, energy can be further saved, and the purpose of automatically adjusting the color of the device according to the intensity of external light, that is, the photochromic device can be achieved. For example, U.S. Patent No. 5,377,037 discloses an electrochromic sunglasses powered by a thin film amorphous silicon solar cell. China Patent

CN101673018B discloses a solar photovoltaic electrochromic device based on an inorganic translucent thin film solar cell and an organic electrochromic solution. And Chinese patent CN101930142B discloses an inorganic film based on Photochromic devices for solar cells and electrochromic materials. These technologies use thin-film solar cells made of inorganic semiconductor materials (such as amorphous silicon, CIGS, CdTe, etc.), which rely mainly on the absorption of photons whose energy is greater than the solar spectrum in the range of their semiconductor band gaps (such as the forbidden band of amorphous silicon). A photogenerated current is 1.75 eV, which can only absorb sunlight with a wavelength of less than 765 nm. Therefore, their color is generally deep, and if the overall integrated device structure is adopted, the color variation range of the electrochromic device is reduced. The organic solar cell process is relatively simple, the cost is low, and the absorption spectrum can be adjusted by selecting and adjusting organic materials, and the color can be adjusted in a larger range. In the solar spectrum, visible light (wavelength 400nm-700nm) accounts for only about 44%, ultraviolet light (wavelength 200-400nm) accounts for about 3%, and the remaining 53% (wavelength above 700nm) is near-infrared light and infrared light. If you choose a material that is more transparent to visible light, the material that absorbs near-infrared and infrared light is used to make solar cells, directly supplying electricity to the electrochromic device, not only can save energy to the utmost, but also have the least impact on the color variation range of the device. .

Summary of the invention

In view of the above problems, it is an object of the present invention to provide a photochromic device comprising a layer of organic solar cell material that provides an applied electric field for the device to control color change.

As shown in FIG. 1, the photochromic device of the present invention comprises a transparent non-conductive substrate, an organic solar cell material layer, an electrochromic material layer 1 and an electrochromic material layer 2, which are in two electrochromic material layers. An electrolyte layer between them, and a transparent conductive layer over the electrochromic material layer.

In one embodiment of the invention, the device substrate is at least one transparent non-conductive substrate, which may be an inorganic material such as glass or an organic material such as a PET film or plastic.

In one embodiment of the invention, an organic solar cell material layer is formed on a transparent non-conductive substrate, the organic solar cell material layer comprising an anode, an organic photoelectric conversion material layer, and a cathode. The above anode and cathode include inorganic or organic transparent conductive materials such as: In ₂ 0 ₃ :Sn(IT0), Sn0 ₂ :F(FT0), Ζη0:Α1(ΑΖ0), carbon nanotubes, graphene ( Graphene) and silver nanowires

The organic photoelectric conversion material layer may be a mixed film in which a single layer is formed by mixing one or more organic materials by vacuum co-evaporation, chemical vapor deposition, spin coating or sol-gel; or It is a multilayer film formed by sequentially depositing two or more layers of organic materials; it may also be a dye-sensitized solar cell material composed of a Ti0 ₂ porous nano film, an electrolyte, and a photosensitizing dye. Its main characteristic is transparent to visible light (wavelength between 300nm and 700nm), that is, visible light transmittance is above 50%, mainly generated by absorbing ultraviolet light (wavelength less than 300nm) or near-infrared and infrared light (wavelength greater than 700nm). electric power. Such as: Richard R. Lunt and other organic solar cells made of organic material Chloroaluminum phthalocyanine (ClAlPc) and organic silver electrons, in visible light The average light transmittance in the range was 56%, and the photoelectric conversion efficiency was 1.7%. And the polymer made by Chun-Chao Chen, etc.

Poly (2, 60-4, 8_bis (5-ethylhexylthienyl) benzo- [1, 2_b; 3, 4_b] dithiophene- alt_5_dibutyloctyl_3, 6_bis (5-bromothiophen-2-yl) pyrrolo [3, 4~c] pyrrole -l , 4-dione) (ie PBDTT-DPP) is an electron donor, a polymer solar cell with [6, 6] -phenyl-C61_butyric acid methyl ester (ie PCBM) as an electron acceptor, at a wavelength of 550 nm The light rate is as high as 66%, and its photoelectric conversion efficiency is also 4%.

In one embodiment of the invention, the electrochromic material layer comprises an organic electrochromic material, a transition metal oxide or a Prussian blue, which may be: Vilogen, Pyrazoline Poly (aniline) Tetrathiafulvalene W0 ₃ MoO ₃ , Nb ₂ 0 ₅ Ti0 ₂ , V ₂ 0 ₅ , M0, Ir0 ₂ , Rh ₂ 0 ₃ , Co0 ₂ , Fe ₄ [Fe (CN) ₆ ] ₃ .

In an embodiment of the invention, the electrolyte layer comprises a liquid electrolyte, a solid electrolyte or a polymer electrolyte, and may be: LiNb0 ₃ , LiB0 ₂ , LiF, LiBF ₄ , LiPF ₄ , LiPN0 LiBS0, LiA10 ₂ LiC10 ₄ + Propylenecarbonate Poly (methyl meth-acrylate) (PMMA) Poly (Vinyl Chloride) (PVC), Poly (Ethylene oxide) (PEO), Poly (ethyl eneglycole) (PEG), Poly (vinylbutral) (PVB).

In one embodiment of the invention, there may be a plurality of layers of organic solar cell material, and they are connected in series or in parallel to achieve the voltage and current requirements required to control the electrochromic device.

In one embodiment of the invention, the photochromic device further includes a photosensitive switch that can control the circuitry. The working principle is as follows: When the sunlight is strong, the photosensitive switch directly connects the positive and negative electrodes of the organic solar cell with the positive and negative electrodes of the electrochromic device. The battery is exposed to light due to the photoelectric effect, and the device becomes darker in color. When there is no sunlight or weak light, the photosensitive switch automatically connects the two ends of the electrochromic device directly to form a short circuit, so the color of the device changes from dark to light. Therefore, the device can achieve the purpose of adjusting the color of the device according to the light, that is, the photochromic device.

In one embodiment of the invention, the photochromic device described above further includes a battery to store the amount of electricity produced by the organic solar cell, which can be used to power the photosensitive switch.

DRAWINGS

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

1 is a basic structural view of a photochromic device driven by an organic solar cell. In the figure, 101 and 102 are device substrates, 201, 202 and 203 are transparent conductive layers, 300 is an organic photoelectric conversion material layer, 401 is an electrochromic material layer 1, 402 is an electrolyte layer, and 403 is an electrochromic material layer 2. . 501 and 502 It is a non-conductive adhesive for device packaging.

Fig. 2 is a structural view of a photochromic device of Example 1. 300 is an organic photoelectric conversion material layer including a cathode modification layer 301, an organic electron acceptor layer 302, an organic electron donor layer 303, and an anode modification layer 304.

Fig. 3 is a structural view of a photochromic device of Example 2. In the figure, 300 is an organic photoelectric conversion material layer, an anode modification layer 301, an organic photoelectric conversion active layer 302, and a buffer layer 303. 701 and 702 are fixed height non-conductive spacers.

Specific case I»

Implementation example 1: The specific implementation steps are as follows:

(1) As shown in Fig. 2, a transparent conductive material layer 201 is formed on the transparent non-conductive substrate 101 by magnetron sputtering, such as: IT0 (In ₂ 0 ₃ :Sn), FT0 (Sn0:F) or ΑΖ0 (Ζη0: Α1), the thickness of which is between 100 nm and 200 nm, the sheet resistance is less than 30 Ω/Ο, and the light transmittance is greater than 85%.

(2) The organic photoelectric conversion material layer is formed on the substrate 101 which has been plated with the transparent conductive material 201 by vacuum evaporation, and includes:

a) Cathode modification layer 301, such as: Bathocuproine

(BCP), the thickness of which is between 5nm and 50nm.

b) an organic electron acceptor layer 302, such as: C ₆ . Its thickness is between 10 nm and 100 nm.

c) an organic electron donor layer 303, such as: chloroaluminum phthalocyanine (ClAlPc), having a thickness between 10 nm and 100 nm.

d) An Anode modification layer, such as Mo0 ₃ , having a thickness between 10 nm and 50 nm.

(3) A transparent conductive film 202 is formed by a vacuum evaporation method or a magnetron sputtering method, such as: IT0 (In ₂ 0 ₃ :Sn) , FT0 (SnO:F) or AZ0 (Zn0:Al), the thickness of which is between 100 nm and 200 nm, the sheet resistance is less than 30 Ω/Ο, and the light transmittance is greater than 85%.

(4) The electrochromic material layer 401 is formed by a vacuum evaporation method or a magnetron sputtering method, such as M0, Ir0 ₂ , Rh ₂ 0 ₃ , Co0 ₂ , and has a thickness of between 100 nm and 500 nm.

(5) The electrolyte layer 402 is formed by a vacuum evaporation method or a magnetron sputtering method, such as LiN _b 0 ₃ , LiB0 ₂ , LiF, LiBF ₄ , LiPF ₄ , LiPN0 LiBS0, LiA10 ₂ , and has a thickness of 100 nm to 500 nm.

(6) The electrochromic material layer 403 is formed by a vacuum evaporation method or a magnetron sputtering method, such as: W0 ₃ , Mo0 ₃ , Nb ₂ 0 ₅ Ti0 ₂ , V ₂ 0 ₅ , and the thickness thereof is between 100 nm and 500 nm. .

(7) A transparent conductive film 203 is formed by a vacuum evaporation method or a magnetron sputtering method, such as: IT0 (In ₂ 0 ₃ :Sn), FTO (SnO:F) or ΑΖ0 (Ζη0:Α1), and its thickness is 100 nm to 200 nm. Between, the sheet resistance is less than 30 Ω / □, and the light transmittance is greater than 85%.

(8) Encapsulate another transparent non-conductive substrate 102 with the other layers of the device using non-conductive adhesives 501 and 502 (such as EVA adhesive or epoxy).

(9) Plus external control circuit, including photosensitive switch and wiring. When the illumination is strong, the photosensitive switch 601 is connected to the port 1, and an electric field is generated by the photoelectric effect of the organic solar cell, and Li ⁺ stored in the electrochromic material layer 401 is injected into the electrochromic material layer through the electrolyte layer under the action of the electric field. 403, causing the device to darken. When there is no light or the light intensity is weak (the specific intensity can be controlled by the photosensitive switch), the photosensitive switch 601 is connected to the port 2, and the electrochromic material layers 401 and 403 are directly connected, and the electric field applied to both ends thereof is zero, resulting in the injection. The Li ^{+ of the} electrochromic material layer 403 gradually diffuses back to the electrochromic material layer 401, causing the device color to return to the original light color state. Implementation Example 2: The specific implementation steps are as follows: As shown in Figure 3,

(1) First make 100 parts of the device:

a) forming a transparent conductive material layer 201 on the transparent non-conductive substrate 101 by magnetron sputtering, such as: ITO (In ₂ 0 ₃ :Sn), FTO (SnO:F) or ΑΖ0 (Ζη0:Α1), the thickness thereof Between 100 nm and 200 nm, the sheet resistance is less than 30 Ω/Ο, and the light transmittance is greater than 85%.

b) Making organic photoelectric conversion material layers, including:

i. Anode modification layer 301: using spin-coating

Poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) (艮卩 PED0T: PSS), uniformly deposited on the layer of transparent conductive material 201, and tempered at 120 °C.

ϋ. Organic photoelectric conversion active layer 302: Polymer

Poly (2, 60-4, 8-bis (5-ethylhexylthienyl) benzo- [1, 2_b; 3, 4_b]d ithiophene - alt_5_dibutyloctyl - 3, 6_bis (5_bromothiophen_2_yl )pyrrolo[3, 4- c]pyrrole-1 4- dione) (ie PBDTT-DPP) and

[6,6]-phenyl-C61-butyric acid methyl ester (ie, PCBM) was dissolved in dichlorobenzene solvent at a concentration of 1:2 in a concentration of 0.7%. It was deposited on the PED0T:PSS layer by spin coating to a thickness of between 100 nm and 200 nm.

Iii. Buffer layer 303: A Ti0 ₂ buffer layer was formed by a sol-gel method and subjected to a tempering treatment at 100 ° C, and the thickness thereof was between 100 nm and 200 nm.

c) Making a transparent conductive film 202 by vacuum evaporation or magnetron sputtering, such as: IT0

(In ₂ 0 ₃ :Sn) , FT0 (Sn0:F) or ΑΖ0 (Ζη0:Α1), the thickness is between 100 nm and 200 nm, the sheet resistance is less than 30 Ω/Ο, and the light transmittance is greater than 85%. d) The electrochromic material layer 401 is formed by a vacuum evaporation method or a magnetron sputtering method, such as W0 ₃ , Mo0 ₃ , Nb ₂ 0 ₅ Ti0 ₂ , V ₂ 0 ₅ , and has a thickness of between 100 nm and 500 nm.

(2) Making 200 parts of the device:

a) A transparent conductive film 203 is formed on another non-conductive substrate 102 by vacuum evaporation or magnetron sputtering, such as: ITO (In ₂ 0 ₃ : Sn), FTO (SnO: F) or ΑΖ0 (Ζη0: Α1), the thickness is between 100nm and 200nm, the sheet resistance is less than 30Ω/Ο, and the light transmittance is greater than 85%. b) On the transparent conductive film 203, an electrochromic material layer 403, such as M0, Ir0 ₂ , Rh ₂ 0 ₃ , Co0 ₂ , having a thickness of between 100 nm and 500 nm is formed by vacuum evaporation or magnetron sputtering.

(3) Fixing the fixed height non-conductive spacers 701 and 702 at the edge of the device with a non-conductive adhesive between the 100 and 200 parts of the device, with a height between 10 and 200 microns to ensure The separation distance between the parts is the same.

(4) Pack 100 and 200 parts with non-conductive adhesive 501 and 502 (such as EVA or epoxy).

(5) Inject a liquid electrolyte such as LiC10 ₄ + Propylene Carbonate between the 100 and 200 parts of the device and distribute it evenly throughout the device.

(6) Add external control circuits, including photosensitive switches and wiring. When the illumination is strong, the photosensitive switch 601 is connected to the port 1, and an electric field is generated by the photoelectric effect of the organic solar cell, and the Li ⁺ stored in the electrochromic material layer 403 is injected into the electrochromic material layer through the electrolyte layer under the action of the electric field. 401, causing the device to darken. When there is no light or the light intensity is weak (the specific intensity can be controlled by the photosensitive switch), the photosensitive switch 601 is connected to the port 2, and the electrochromic material layers 401 and 403 are directly connected, and the electric field applied to both ends thereof is zero, resulting in the injection. The Li ^{+ of the} electrochromic material layer 401 gradually diffuses back to the electrochromic material layer 403, causing the device color to return to the original light color state.

Claims

claims

1. A photoelectrochromic device, characterized by including:

Transparent non-conductive substrate;

An organic solar cell material layer formed on the transparent non-conductive substrate;

Electrochromic material layer 1 and electrochromic material layer 2, which are formed on the organic solar cell material layer;

an electrolyte layer formed between two electrochromic material layers;

A transparent conductive layer formed on the electrolyte layer.

2. The photoelectrochromic device according to claim 1, characterized in that the transparent non-conductive substrate includes inorganic materials or organic materials, including: glass, PET film, and plastic.

3. The photoelectrochromic device according to claim 1, wherein the organic solar cell material layer includes an anode, an organic photoelectric conversion material layer and a cathode;

4. The photoelectrochromic device according to claim 3, characterized in that the anode and cathode are mainly composed of inorganic or organic transparent conductive materials, including: In ₂ 0 ₃ : Sn (ITO), Sn0 ₂ : F (FT0), Ζη0:Α1(ΑΖ0), carbon nanotubes, graphene and silver nanowires

(silver nanowires

5. The photoelectrochromic device according to claim 3, wherein the organic photoelectric conversion material layer includes at least one layer of organic polymers, organic small molecule compounds, or a mixture of organic polymers and organic small molecule compounds. Optoelectronic materials composed of.

6. The photoelectrochromic device according to claim 3, wherein the organic photoelectric conversion material layer can be but is not limited to: Poly(3-hexylthiophene) (P3HT), 6, 6-phenyl C61_butyric acid methyl ester (PCBM) Polyl

1, 4_ (2-methoxy5-ethylhexyloxy) phenyl enevi-nylene (MEH-PPV), fullerene (C60) Poly (3, 4-ethylenedioxythiophene) Ploystyrene

sulfonic (PEDOT PSS) Zinc phthalocyanine (ZnPc) Chloroaluminum phthalocyanine (ClAlPc),

Poly (2, 60-4, 8_bis (5-ethylhexylthienyl) benzo- [1, 2_b; 3, 4_b] dithiophene- alt_5_dibutyloctyl_3, 6_bis (5-bromothiophen-2-yl) pyrrolo [3, 4~c] pyrrole -l 4-dione (PBDTT-DPP), carbon nanotubes (Carbon nano_tubes), graphene (Graphene) and silver nanowires (Silver o_wires

7. The photoelectrochromic device according to claim 2, 3, characterized in that the organic photoelectric conversion material layer has a transmittance of visible light (wavelength range between 300nm and 700nm) > 50%, mainly by absorbing ultraviolet light. (wavelength <300nm) or near-infrared light (wavelength>700nm) energy converts light energy into electrical energy, which can be but is not limited to: Chloroaluminum phthalocyanine (ClAlPc)

Poly (2, 60-4, 8_bis (5-ethylhexylthienyl) benzo- [1, 2_b; 3, 4_b] dithiophene- alt_5_dibutyloctyl_3, 6_bis (5-bromothiophen-2-yl) pyrrolo [3, 4~c] pyrrole - 1 4- dione (PBDTT- DPP) poly (3- hexylthiophene) (P3HT), 6 6-phenyl C61-butyric acid methyl ester (PCBM) and fullerene (C60)

8. The photoelectrochromic device according to claim 1, wherein the organic solar cell material layer includes a dye-sensitized solar cell. Wherein, the dye-sensitized solar cell includes an anode, a cathode, a _TiO2 porous nanofilm, an electrolyte and a photosensitive dye.

9. The photoelectrochromic device according to claim 1, wherein the electrochromic material layer includes an organic electrochromic material, a transition metal oxide or Prussian blue (ie: Fe4 [Fe (CN) ₆ ] ₃ )o

10. The photoelectrochromic device according to claim 9, wherein the organic electrochromic material includes Vi logens, Pyrazoline Poly (aniline) or Tetrathiafulvalene.

_11. The photoelectrochromic device according to claim 9, characterized in that the _transition metal oxide includes Ni0, _Ir02 , _Rh203 _, _Co02 _, _W03Mo03 , _Nb205Ti02 , V ₂ 0 ₅ .

12. The photoelectrochromic device according to claim 1, wherein the electrolyte layer includes a liquid electrolyte, a solid film electrolyte or a polymer electrolyte.

13. The photoelectrochromic device according to claim 12, wherein the liquid electrolyte includes a lithium salt and an organic solvent.

14. The photoelectrochromic device according to claim 12, wherein the lithium salt includes LiC10 ₄ , LiBF ₄ , and CF ₃ Li0 ₃ S.

15. The photoelectrochromic device according to claim 12, wherein the organic solvent includes Propylene Carbonate and Dimethylformamide.

16. The photoelectrochromic device according to claim 12, characterized in that the solid film electrolyte includes: LiNb0 ₃ LiB0 ₂ , LiF, LiBF ₄ , LiPF ₄ , LiPON, LiBS0, LiA10 ₂ .

17. The photoelectrochromic device according to claim 12, characterized in that the polymer electrolyte includes: Poly (methyl meth-acrylate (PMMA), Poly (Vinyl Chloride (PVC)), Poly (Ethylene oxide ( PEO) Poly (ethyleneglycole (PEG), Poly (vinylbutral

(PVB).

18. The photoelectrochromic device according to claim 1, wherein the electrochromic device includes one or more organic solar cell material layers and they are connected in series, that is, all of the organic solar cell material layers The anode is connected to the cathode of another organic solar cell material layer to provide the voltage required to change the color of the device.

19. The photoelectrochromic device according to claim 1, the organic solar cell material layer is connected to a photosensitive switch, and the photosensitive switch automatically controls the color depth of the device according to the intensity of light.

20. The photoelectrochromic device according to claim 1, the organic solar cell material layer is connected to a battery, and the battery stores the battery power to provide the power required by the photosensitive switch.