DE102011118902A1 - Printable photovoltaic electrochromic device comprises transparent substrate, thin-film solar cell arranged on transparent substrate and single polarity electrochromic thin film covering and contacting with both the cathode and anode layer - Google Patents

Abstract

Printable photovoltaic electrochromic device comprises: a transparent substrate (100); at least one thin-film solar cell (102), which is arranged on a transparent substrate, where the thin-film solar cell comprises an anode layer (106), a cathode layer (108) and a photoelectric conversion layer between the anode layer and cathode layer, and a portion of the anode layer or a portion of the cathode layer is exposed from the thin-film solar cell; and at least one single polarity electrochromic thin film (104), covering and contacting with both the cathode layer and the anode layer. Printable photovoltaic electrochromic device comprises: a transparent substrate (100); at least one thin-film solar cell (102), which is arranged on a transparent substrate, where the thin-film solar cell comprises an anode layer (106), a cathode layer 108) and a photoelectric conversion layer between the anode layer and cathode layer, and a portion of the anode layer or a portion of the cathode layer is exposed from the thin-film solar cell; and at least one single polarity electrochromic thin film (104), covering and contacting with both the cathode layer and the anode layer, where the single polarity electrochromic thin film comprises a single polarity electrochromic material and a polyelectrolyte.

Description

Technical area

The disclosure relates to a printable photovoltaic electrochromic device having a simple structure.

Background of the invention

An electrochromic device is a device formed by conductive materials and capable of inducing a reversible redox reaction by an applied electric field or current, thereby producing a color change. The preparation of an electrochromic device must have the following properties. Colors exhibited under different tensions must be easily distinguishable, the color change is fast and uniform, over 10,000 reversible color changes of the device color, and the device has high stability. Conventional electrochromic devices include surface-confined electrochromic thin film solid state devices or solution type electrochromic devices.

A surface confined electrochromic thin film solid state device is formed by an upper transparent substrate, a lower transparent substrate and a multilayer electrochromic layer therebetween. The multilayer electrochromic layer is similar to a structure of a battery comprising at least five coated / plated layers having various functions, such as a transparent conductive layer, an electrochromic layer, an electrolyte layer, a tone storage layer and a transparent conductive layer. A solution-type electrochromic device has a simpler structure comprising an upper transparent conductive substrate and a lower transparent conductive substrate. Using epoxy adhesive, the two substrates are adhered to opposite electrode layers and an electrochromic organic solution is interposed therebetween. One component of the solution comprises an electrochromic material with small organic molecules of the oxidizing or reducing type, a polymer electrolyte and a solvent.

Although electrochromic technology has been explored for years, resistance values at outer regions and in the center are significantly different, since electrodes are located in a large area electrochromic device at the edge of the device and electric paths have different lengths at a shallower center and at the edges of the electrochromic device. Oval gradients of color change concentrations from the edges to the central regions occur due to the difference in the resistance values, thereby affecting the uniformity of the color change effects.

In order to broaden the field of application of electrochromic technology, a number of studies concerning the combinations of photoelectric technology and solar cells provide more variable research directions. For example, disclosed U.S. Patent No. 6,369,934 B1 a whole organic multi-layered photoelectrochemical device in which a photosensitive layer and an electrochromic layer are separated on two electrodes of opposite polarity, so as to enable fabrication of the device. Such a device may be described as having an electrochromic material embedded in a dye-sensitized solar cell. An electrochromic material thereof is WO ₃ and the device mainly uses ruthenium dye. The device comprises two transparent conductive substrates and a working electrode layer formed by a photosensitive material, an electrolyte layer and a counter electrode layer formed by an electrochromic material. However, many problems such as the long-term stability of the photosensitive layer and the ability to develop larger-sized devices must be solved in order to apply such a structure to practical applications.

Also revealed U.S. Patent No. 5,377,037 a design of combining a solar cell with an electrochromic device to form a single device, basically by using a stacking method of combining monolithic silicon thin film solar cells with an inorganic electrochromic device on a first conductive glass substrate and then bonding the silicon thin film solar cell to another conductive glass substrate on the other hand, is produced. Between the substrates, a liquid organic electrolyte or a solid inorganic electrolyte layer is disposed. However, the optical contrast before and after the color change achieved by such a technology is relatively low and the color change effect is insignificant. The transparency of the PV-EC device is improved by the incorporation of a semitransparent amorphous silicon-carbon alloy improved with wide band gap. However, as the semi-transparent PV films become very thin, an electrical short circuit easily occurs, making it less attractive to use the device in smart windows.

US Patent Application Publication No. 2010/0000590 A1 and US Pat U.S. Patent No. 7,855,822 provide some liquid type electrochromic photovoltaic devices wherein electrodes are uniformly dispersed on the entire surface of a substrate so that a uniform electric field is formed and an electrochromic solution has the same color change degree in different regions, thereby preventing the iris effect.

Although the above patent applications improve the uniformity of the color change, problems with leaks easily occur due to the electrochromic solution and the liquid electrolyte used.

Summary of the invention

Here, a printable photovoltaic electrochromic device is introduced. The printable photovoltaic electrochromic device comprises at least one transparent substrate, a thin film solar cell on the transparent substrate, and at least one unipolar electrochromic thin film, the unipolar electrochromic thin film comprising a unipolar electrochromic material and a polyelectrolyte. The thin film solar cell includes at least an anode layer, a cathode layer and a photoelectric conversion layer between the anode layer and the cathode layer. A portion of the anode layer or a portion of the cathode layer is exposed by the thin film solar cell. The unipolar electrochromic thin film covers and contacts both the cathode layer and the anode layer.

Due to the above, the unipolar electrochromic thin film according to the disclosure comprises the unipolar electrochromic material and the polyelectrolyte. When used in conjunction with the thin film solar cell having a portion of the anode layer or a portion of the cathode layer exposed, coloration by light irradiation is achieved. Therefore, the printable photovoltaic electrochromic device according to the disclosure does not require additional electrolyte, so that problems of liquid leaks caused by the use of general electrolyte solutions are prevented, and the printable photovoltaic electrochromic device can be integrated into a single-layered structure, thereby reducing the processing time , Additionally, printing methods may be employed to complete the printable photovoltaic electrochromic device according to the disclosure when the thin film solar cell is disposed on a flexible substrate, since according to the disclosure, the device is formed by a coating / printing process.

Some exemplary embodiments accompanied by figures are described in detail below to further describe the disclosure in detail.

Brief description of the drawings

The accompanying drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the disclosure and, together with the description, serve to explain the principles of the disclosure.

1 FIG. 12 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic device according to a first embodiment of the disclosure. FIG.

2 FIG. 12 is a schematic plan view diagram illustrating the printable photovoltaic electrochromic device in FIG 1 shows.

3 FIG. 10 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic device according to a second embodiment of the disclosure. FIG.

4A FIG. 10 is a schematic cross-sectional diagram showing another printable photovoltaic electrochromic device according to the first embodiment of the disclosure. FIG.

4B FIG. 12 is a schematic plan view diagram illustrating the printable photovoltaic electrochromic device in FIG 4a shows.

5 FIG. 12 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic module according to a third embodiment of the disclosure. FIG.

6A FIG. 10 is a schematic perspective diagram showing a printable photovoltaic electrochromic device according to a fourth embodiment of the disclosure. FIG.

6B FIG. 12 is a schematic perspective diagram showing another printable photovoltaic electrochromic device according to the fourth embodiment of the disclosure. FIG.

7 is a TEM photograph of a PANI / PSS unipolar electrochromic thin film of Experiment 1.

8th Figure 13 is a graph showing a curve representing the size of PANI nanospheres.

9 FIG. 12 is a schematic circuit diagram showing an arrangement of a printable photovoltaic electrochromic device and an output switch according to the disclosure. FIG.

10 FIG. 12 is a schematic circuit diagram showing an arrangement of a printable photovoltaic electrochromic device and another output switch according to the disclosure. FIG.

11 FIG. 12 is a schematic circuit diagram showing an arrangement of a printable type photovoltaic electrochromic device and a thin film transistor tube according to the disclosure. FIG.

Description of the embodiments

1 FIG. 12 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic device according to a first embodiment of the disclosure. FIG.

It will open 1 directed. The printable photovoltaic electrochromic device according to a first embodiment of the disclosure is a printable photovoltaic electrochromic device having a substrate structure. A transparent substrate 100 , a thin-film solar cell 102 on the transparent substrate 100 and at least one unipolar electrochromic thin film 104 be for a color change by light irradiation 101 needed. The unipolar electrochromic thin film 104 comprises a unipolar electrochromic material and a polyelectrolyte. The transparent substrate is, for example, glass, a plastic material or a flexible substrate. The above unipolar electrochromic material comprises a positively charged or negatively charged anodic electrochromic material or cathodic electrochromic material and the unipolar electrochromic material may be an electrochromic nanostructure material, such as nanostructured electrochromic material, such as nanostructure metal oxide or nanostructure metal oxide, nanostructured metal complex or nanostructure metal complex a nanostructure metal complex or a nanostructure conductive polymer or nanostructure conductive polymer. The above electrochromic nanostructure material is, for example, nanoparticles, nanorods, nanocables, nanospheres or nanospheres or nanotubes. The above nanostructured metal oxide is, for example, WO ₃ , V ₂ O ₅ , NiO _x or CuO _x . The above nanostructure metal complex is, for example, a Prussian blue analog or InHCF. The above conductive nanostructure polymer is, for example, polyaniline nanospheres, polypyrrole (PPy) nanospheres or PEDOT nanospheres.

The polyelectrolyte, which is in the unipolar electrochromic layer 104 may be a polyanionic electrolyte or a polycationic Eloektrolyt. The polyanionic electrolyte can be classified into three types according to its functional group: phosphate group, carboxyl group or sulfuric acid group. The polycationic electrolyte can be classified into ammonia group and sulfuric acid group. For example, the polyanionic electrolyte is, for example, sodium poly (styrenesulfonate) (PSS), sodium poly (acrylic acid) (NePA), polyacrylic acid (PAA). Polymaleic acid (PMA), poly (Perfluorschwefelsäure (PFSA, trademark as NAFION ^®), and the polycationic electrolyte is, for example, polydiallyldimethylammonium chloride (PDDA), polyallylamine hydrochloride (PAH), poly-L-lysine (PLL) or Polyethyleniamin (PEI).

The anodic or cathodic electrochromic material used in the unipolar electrochromic layer 104 comprises a positively charged anodic or cathodic electrochromic material or a negatively charged anodic or cathodic electrochromic material. For example, for a PEDOT cathodic electrochromic material, a process for polymerizing PEDOT is an oxidative Polymerization, so that after the polymerization positively charged (PEDOT) ^{n + is} obtained (n is a stoichiometric number). A polyanionic electrolyte PSS ^- must also exist to form the unipolar electrochromic material and polyelectrolytes (PEDOT) ^{n +} (PSS) ^n- . For a PANI anodic electrochromic material, a polymerization process is also an oxidative polymerization so that positively charged (PANI) ^{m + is} obtained after the polymerization (m is a stoichiometric number). A polyanionic electrolyte (PSS) ^- must also exist to form the unipolar electrochromic material and polyelectrolytes (PANI) ^{m +} (PSS) ^m- .

Still on 1 based, comprises the thin-film solar cell 102 at least one anode layer 106 , a cathode layer 108 and a photoelectric conversion layer 110 between the anode layer 106 and the cathode layer 108 , A section 106 ' the anode layer 106 is from the thin-film solar cell 102 exposed. A material of the anode layer 106 For example, it is a transparent conductive oxide (TCO) and a material of the cathode layer 108 For example, it is a transparent conductive oxide and a metal (such as silver, aluminum and platinum). The unipolar electrochromic thin film 104 covers both the cathode layer 108 as well as the uncovered section 106 ' the anode layer 106 such that when the printable photovoltaic electrochromic device is exposed to sunlight 101 irradiated, immediately electron-hole pairs are generated in the thin film solar cell and redox reactions in the unipolar electrochromic thin film 104 occur. By ion exchange provided by the polyelectrolyte, a color change occurs in the unipolar electrochromic thin film 104 reached. Therefore, the printable photovoltaic electrochromic device according to the first embodiment achieves by comprising the above printable unipolar electrochromic thin film 104 Effects, such as not requiring an additional electrolyte and a simple manufacturing process and structure.

In addition, if the transparent substrate 100 According to the present embodiment, a flexible substrate, the thin film solar cell may first be disposed on the flexible substrate and the printable photovoltaic electrochromic device in FIG 1 can then be completed by a coating process such as roll-to-roll coating or roll-to-roll coating. Therefore, the printable photovoltaic electrochromic device is suitable for commercial mass production.

In 1 is the anode layer 106 the thin-film solar cell 102 continuous and the circuitry thereof is in 2 shown, wherein the thin film solar cell connected in a parallel manner, and other elements in 1 were omitted. The cathode layer 108 in 2 is individual with an output switch arrangement 200 connected. Such a continuous anode layer 106 can increase the absolute power generation through the thin-film solar cell. However, the disclosure is not limited by this configuration.

The thin-film solar cell 102 According to the first embodiment, a silicon thin film solar cell, a CIGS thin film solar cell, a CdTe thin film solar cell, a CIGS tandem thin film solar cell or a CdTe tandem thin film solar cell among which the most stable type is the silicon thin film solar cell such as an a-Si thin film solar cell may be an a-Si thin film solar cell. Si / mc-Si tandem thin film solar cell or a-Si / a-Si tandem thin film solar cell.

3 FIG. 12 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic device according to a second embodiment of the disclosure, wherein the same reference numerals as those according to the first embodiment represent the same or similar elements. FIG.

It will open 3 directed. The printable photovoltaic electrochromic device according to the present embodiment of the disclosure is a printable photovoltaic electrochromic device having a substrate structure. The thin-film solar cell 102 comprises at least one anode layer 106 , a cathode layer 108 and a photoelectric conversion layer 110 between the anode layer 106 and the cathode layer 108 , A section 108 the cathode layer 108 is from the thin-film solar cell 102 exposed and light 301 falls from the unipolar electrochromic thin film 104 one. Since the printable photovoltaic electrochromic device according to the second embodiment is a device having the substrate structure, the hue of a unipolar electrochromic thin film 104 the energy production of the thin-film solar cell 102 so that the printable photovoltaic electrochromic device according to the second embodiment can be applied to devices which require periodic color change.

In addition are 4A and 4B each is a schematic cross-sectional diagram and a schematic plan view diagram showing another printable photovoltaic electrochromic device according to the first embodiment of the disclosure, wherein the thin-film solar cell is connected in series.

It is going on both 4A as well 4B directed. Different parts of the anode layer 106 the thin-film solar cell 102 are arranged in a striped manner and do not touch each other. The unipolar electrochromic thin film 104 is capable of a color change by light irradiation by both the anode layer 106 as well as the cathode layer 108 the thin-film solar cell 102 are covered. Every part of the anode layer 106 is with the cathode layer 108 another thin-film solar cell and is connected to an output switch arrangement 406 connected.

In addition, after the unipolar electrochromic thin film 104 was formed, an encapsulating or enveloping material 400 the unipolar electrochromic thin film 104 cover (as in 4A shown). Subsequently, a transparent non-conductive substrate 402 such as glass, plastic or a flexible substrate, the encapsulating material 400 cover. A reflective layer 404 , such as a silver or aluminum thin film, may be formed on a surface of the transparent non-conductive substrate 402 are formed so as to form a mirror surface.

5 FIG. 12 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic module according to a third embodiment of the disclosure, wherein the same reference numerals as those according to the first embodiment represent the same or similar elements. FIG.

It will open 5 directed. A printable photovoltaic electrochromic device according to the third embodiment comprises the transparent substrate 100 , a thin-film solar cell 500 on the transparent substrate 100 and at least one unipolar electrochromic thin film 104 , wherein the unipolar electrochromic thin film 104 comprises the unipolar electrochromic material and the polyelectrolyte described in the preceding embodiments. The thin-film solar cell 500 is a monolithic integrated module formed by multiple anode layers 502 on the surface of the transparent substrate 100 , several cathode layers 504 on the anode layers 502 and a photoelectric conversion layer 506 between the anode layers 502 and the cathode layers 504 is formed. The anode layers 506 in each of the thin-film solar cells 500 are with the cathode layers 504 another thin-film solar cell 500 connected, so that a serial connection between the thin-film solar cells 500 is being built. Materials of each of the above layers are described in the preceding embodiments.

When the unipolar electrochromic thin film 104 in 5 is a positively charged anodic or cathodic electrochromic material is used for ion exchange in the regions 508 and 510 requires a polyanionic electrolyte, so that no additional electrolyte or a bipolar electrochromic thin film are needed. The unipolar electrochromic thin film 104 includes only the positively charged anodic or cathodic electrochromic material and the polyanionic electrolyte in a single thin film; in contrast to that of a conventional electrochromic device structure which requires multiple layers of electrolytes, ion storage layers, and bipolar electrochromic thin films to achieve charge neutrality. Therefore, even if several thin-film solar cells 500 in 5 connected in series because the positively charged anodic or cathodic electrochromic material in the unipolar electrochromic thin film 104 is mixed with the polyanionic electrolyte to ion exchange in the regions 508 and 510 provide. Problems of excessive oxidation or excessive reduction caused by charge imbalance in the anodic or cathodic electrochromic material (due to voltage differences in the serially integrated structure) do not occur, so that the printable photovoltaic electrochromic device has no problems of uneven coloration.

6A FIG. 10 is a schematic perspective diagram showing a printable photovoltaic electrochromic device according to a fourth embodiment of the disclosure. FIG. 6b FIG. 12 is a schematic perspective diagram showing another printable photovoltaic electrochromic device according to the fourth embodiment of the disclosure. FIG.

It will open 6A and 6B directed. A printable photovoltaic electrochromic device according to a fourth embodiment comprises a transparent substrate 600 , a thin-film solar cell 602 on the transparent substrate 600 and at least one unipolar electrochromic thin film 604 , wherein the unipolar electrochromic thin film 604 includes the unipolar electrochromic material and the polyelectrolyte described in each of the preceding embodiments. The thin-film solar cell 602 comprises at least one anode 608 , a photoelectric conversion layer 610 and a cathode 612 , A method of forming the patterned thin film solar cell 602 includes laser patterning and laser scribing and sandblasting to form parts of the photoelectric conversion layer 610 and remove the cathode. A type of thin-film solar cell 602 and materials of the transparent substrate 600 , the anode 608 , the photoelectric conversion layer 610 and the cathode 612 are described in the first embodiment.

If the unipolar electrochromic thin film 604 in 6A or 6B is a positively charged anodic or cathodic material with a polyanionic electrolyte and when the anodic electrochromic material is in the unipolar electrochromic thin layer 604 the color changes, provides the polyanionic electrolyte for ion exchange in the unipolar electrochromic thin film 604 over the anode 608 and the cathode 612 ready, so that no additional electrolyte or a bipolar electrochromic thin film are needed.

The following experiments are provided to prove the efficiency described in the disclosure. In the following experiments, a silicon thin film solar cell and a silicon thin film solar cell module are used as examples.

Experiment 1: Preparation of a unipolar electrochromic thin film

0.6 mmol of aminobenzene monomer is added to 20 ml of DI water containing DI water containing 0.5 g of HCl and 1.0 g of poly-sodium styrenesulfate (PSS) to become 20 ml of deionized water. After stirring the above two solutions for two hours, 0.7 mmol of sodium persulfate (APS) as an oxidizing agent is added to the mixed solution and the solution is stirred for 12 hours at 700 rpm at room temperature, thus obtaining a PANI / PSS To obtain a mixture containing positively charged polymeric nanospheres of the anodic material PANI and the polyanionic electrolyte PSS. The following is a chemical equation of the preparation process or the preparation process.

The above method of synthesizing the PANI nanospheres and the polyanionic electrolyte PSS is based on the synthesis method described in U.S. Pat Journal Advanced Materials, 19, 1772-1775 (2007), which is entitled "Fabrication of water-dispersible polyaniline-poly (4-styrenesulfanate) nanoparticles for inkjet printed chemical sensor application" contains.

Subsequently, the PANI / PSS mixture is coated or applied to a glass substrate. After drying, a PANI / PSS unipolar electrochromic thin layer is obtained. By observation with a TEM or an electron tunneling microscope, the PANI / PSS unipolar electrochromic thin film comprises the PANI nanospheres as in 7 shown.

8th Figure 11 is a graph showing a graph representing the sizes of PANI nanospheres measured with a Dynamic Light Scattering Instrument (DLS). The amount of PSS influences the sizes of the nanospheres. According to the measurement results of the present experiment, three peaks of the curve are at approximately 10.7 nm, 51.0 nm and 488.1 nm, so that the sizes of the nanospheres vary from 10 nm to 500 nm.

The following chemical equation demonstrates a mechanism of color change in the polymeric nanospheres of the anodic electrochromic material comprising PANI nanospheres and the polyanionic electrolyte PSS. PANI + m (PSS) ^- ↔ (PANI) ^{m +} (PSS) ^m- + me ^- Leucoemeraldine in the ground state Emeraldin in the salt state Yellow-green, bleached Blue-green, darkened

In the above chemical equation, "m" is a stoichiometric number.

Experiment 2: Preparation and Examination of the Printable Photovoltaic Electrochromic Device

A 5 cm x 6 cm transparent glass substrate is prepared and a silicon thin film solar cell, such as the in 1 is fabricated on the glass substrate with an area of an anode and a cathode of each strip-shaped silicon solar cell measuring 5 cm × 5 cm. An anode layer is a TCO and a cathode layer is a TCO / Ag. An IV curve of such a thin film solar cell is: V _oc 0.93 V, J = 12.3 mA / cm ² , FF = 73.23%, P _max = 20.94 mW, and a power generation efficiency 8.38%.

The PANI / PSS mixture obtained in Experiment 1 is printed on a silicon solar cell module. After drying, a PANI / PSS unipolar electrochromic thin film with a thickness of approximately 100 nm is obtained.

When the above device is irradiated by sunlight, the PANI / PSS unipolar electrochromic thin film on the surface of the transparent anode layer begins to change color in three minutes, gradually changing from yellow-green to blue-green.

Experiment 3: Preparation and investigation of the printable photovoltaic electrochromic module

A 4 cm x 3 cm transparent glass substrate is prepared and a silicon thin film solar cell module, the 5 is fabricated on the glass substrate with an area of an anode and a cathode of each of the silicon solar cells measuring 4 cm x 0.5 cm. The silicon thin film solar cell module includes three sets of silicon thin film solar cells, an anode layer is a TCO, and a cathode layer is a TCO / Ag. An IV curve of such a thin film solar cell module is: V _oc = 3.98 V, I _sc = 26.57 mA, FF% = 64.94%, PwrMax = 69.09 mW, and a power generation efficiency is 5 , 23%.

The PANI / PSS mixture obtained in Experiment 1 is coated on a silicon solar cell module. After drying, a PANI / PSS unipolar electrochromic thin film with a thickness of approximately 100 nm is obtained.

When the above device is irradiated by sunlight, the PANI / PSS unipolar electrochromic thin film on the surface of the transparent anode layer begins to change color in three minutes, gradually changing from yellow-green to blue-green.

In addition, the PANI / PSS unipolar electrochromic thin film remains blue-green if the irradiation time is extended (from three minutes to one hour) and there are no problems with uneven coloration.

Experiment 4: Preparation and investigation of the printable photovoltaic electrochromic module

The silicon thin film solar cell module is manufactured by the method described in Experiment 3, and the silicon thin film solar cell repeatedly undergoes the PANI / PSS spin coating, PANI / PSS spin coating, and dry steps in Experiment 1 to form three printable photovoltaic electrochromic devices be prepared with three, five and ten layers of PANI / PSS unipolar electrochromic thin film.

When the above three devices are irradiated by sunlight, the PANI / PSS unipolar electrochromic thin film on the surface of the transparent anode layer begins to change color in three minutes, gradually changing from yellow-green to blue-green. Therefore, the PANI / PSS unipolar electrochromic thin film, whether with one or up to ten layers, has color change functions by the irradiation of light.

Experiment 5: Preparation of a unipolar electrochromic thin film

100 mg of PSS are added to 50 ml of distilled water containing 1.0 M NaCl and the mixture is stirred for six hours and set aside for subsequent use. 26 μl EDOT monomer is added to a solution of distilled water and 0.2 MH ₂ SO ₄ and the mixture is stirred for two hours. The solutions from the above steps are mixed and stirred for one hour and 56 mg of APS is added thereto. After stirring for two hours at room temperature, the mixture is heated to 80 ° C and stirred for a further six hours. A resulting blue liquid is a PEDOT / PSS mixture.

The method of Experiment 3 is used to prepare the silicon thin film solar cell module, and the above PEDOT / PSS mixture is spin-coated on the silicon thin film solar cell according to the method in Experiment 2. After drying, a PEDOT / PSS unipolar electrochromic thin film with a thickness of approximately 100 nm is obtained.

When the above device is irradiated by sunlight, the PEDOT / PSS unipolar electrochromic thin film on the surface of the cathode layer begins to change color in five minutes, gradually changing from light blue to dark blue.

The following chemical equation shows a color change mechanism in the polymeric nanospheres of the electrochromic material comprising the PEDOT nanospheres and the polyanionic electrolyte PSS. (PEDOT) ^{n +} (PSS) ⁿ + ne ^- ↔ PEDOT + n (PSS) ^- (Transparent light blue, bleached) ↔ (dark blue, darkened) In the above equation, "n" represents a charge number.

According to the above experiment, coloring effects by light irradiation are achieved by following the disclosure.

• 1. Unter Verwendung eines DC/AC-Wandlers 900 bzw. eines Gleichstrom-Wechselstromwandlers 900 wird ein Strom, der durch die Dünnschichtsolarzelle erzeugt wird, in einen AC-Strom, bzw. einen Wechselstrom gewandelt, der als kommerzielle Stromquelle 902 verwendet werden kann, um in allgemeine elektrische Vorrichtungen gespeist zu werden, wie in 9 gezeigt.
• 2. Der Strom, der durch die Dünnschichtsolarzelle erzeugt wird, wird in eine DC-Ladungsspeichervorrichtung 1000 bzw. eine Gleichstromladungsspeichervorrichtung 1000 geleitet (die nachfolgend als eine Batterie verwendet werden kann, um Energie in allgemeine DC-elektrische Vorrichtungen zu speisen), wie in 10 gezeigt.
• 3. Durch Dünnschichttransistorprozesse (TFT-Prozesse) und dergleichen werden Dünnschichttransistoren 1100 an zwei Anschlüssen der Anodenschicht und der Kathodenschicht der Dünnschichtsolarzelle hergestellt, um als Schalter verwendet zu werden, um so jede der Dünnschichtsolarzellen und einen externen Schaltkreis individuell an/aus zuschalten bzw. an/aus zu steuern, wodurch eine aktiv gesteuerte elektrochrome Vorrichtung erreicht wird, wie in 11 gezeigt.

In addition, an output switch assembly may be added to the printable photovoltaic electrochromic device according to the disclosure. The switch of the printable photovoltaic electrochromic device may be formed by the following methods.

• 1. Using a DC / AC converter 900 or a DC-AC converter 900 For example, a current generated by the thin-film solar cell is converted into AC current, that is, as a commercial power source 902 can be used to be fed into general electrical devices, as in 9 shown.
• 2. The current generated by the thin film solar cell is converted into a DC charge storage device 1000 or a DC charge storage device 1000 passed (hereinafter referred to as one Battery can be used to feed power into common DC electrical devices) as in 10 shown.
• 3. Thin film transistor (TFT) processes and the like become thin film transistors 1100 at two terminals of the anode layer and the cathode layer of the thin film solar cell, to be used as switches so as to individually turn on / off each of the thin film solar cells and an external circuit, thereby achieving an actively controlled electrochromic device, as in 11 shown.

In summary, according to the disclosure, the device designs (ie, the thin film solar cell in which a portion of the anode layer or a portion of the cathode layer is exposed from the thin film solar cell) and the use of a unipolar electrochromic thin film comprising the unipolar electrochromic material and the polyelectrolyte, a coloring achieved by light irradiation. Problems with uneven color change do not occur in the monolithically integrated structure thin film solar cell module coated / printed with the unipolar electrochromic material. This is unlike conventional bipolar electrochromic material device structures with electrolytes, which must include designs to balance charges in the bipolar electrochromic layer to achieve a uniform color change. In other words, the printable photovoltaic electrochromic device according to the disclosure is a completely solid state device structure, so that problems of liquid leaks caused by liquid electrolytes are prevented, and the printable photovoltaic electrochromic device can be integrated into single-layered structures, thereby reducing the processing time becomes. In addition, since the device according to the disclosure is formed by a coating process, coating methods can be used to more easily and in larger numbers complete the printable photovoltaic electrochromic device according to the disclosure, if the thin film solar cell is disposed on the flexible substrate.

It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosure without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the disclosure cover modifications and variations of this disclosure, if they come within the scope of the following claims and their equivalents.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 6369934 B1 [0005]
• US 5377037 [0006]
• US 7855822 [0007]

Cited non-patent literature

• Journal Advanced Materials, 19, 1772-1775 (2007), which is entitled "Fabrication of water-dispersible polyaniline-poly (4-styrenesulfanate) nanoparticles for inkjet printed chemical sensor application" [0047]

Claims (20)

A printable photovoltaic electrochromic device, comprising at least a transparent substrate; at least one thin film solar cell disposed on the transparent substrate, the thin film solar cell comprising at least an anode layer, a cathode layer and a photoelectric conversion layer between the anode layer and the cathode layer, and exposing a portion of the anode layer or a portion of the cathode layer from the thin film solar cell; and at least one unipolar electrochromic thin film covering and contacting both the cathode layer and the anode layer, the unipolar electrochromic thin film comprising a unipolar electrochromic material and a polyelectrolyte. The printable photovoltaic electrochromic device of claim 1, wherein the printable photovoltaic electrochromic device comprises a photovoltaic electrochromic superstrate device or a photovoltaic electrochromic substrate device. The printable photovoltaic electrochromic device of claim 1, wherein the unipolar electrochromic material comprises an anodic electrochromic material or a cathodic electrochromic material. The printable photovoltaic electrochromic device of claim 1, wherein the unipolar electrochromic material comprises a nanostructured electrochromic material. The printable photovoltaic electrochromic device of claim 4, wherein the nanostructured electrochromic material comprises a nanostructured metal oxide, a nanostructure metal complex or a nanostructure conductive polymer. A printable photovoltaic electrochromic device according to claim 5, wherein said nanostructured electrochromic material comprises nanoparticles, nanorods, nanowires, nanospheres or nanotubes. A printable photovoltaic electrochromic device according to claim 5, wherein the nanostructured metal oxide comprises WO ₃ , V ₂ O ₅ , NiO _x or CuO _x . A printable photovoltaic electrochromic device according to claim 5, wherein the nanostructured metal complex comprises a Prussian blue analog or InHCF. The printable photovoltaic electrochromic device of claim 5, wherein the nanostructured conductive polymer comprises polyaniline nanospheres, polypyrrole nanospheres or PEDOT nanospheres. A printable photovoltaic electrochromic device according to claim 1, wherein the polyelectrolyte comprises a polyanionic electrolyte or a polycathionic electrolyte. The printable photovoltaic electrochromic device according to claim 10, wherein the polyanionic electrolyte comprises sodium poly (styrylsulfonate), sodium poly (acrylic acid), polyacrylic acid, polymaleic acid or poly (perfluorosulfuric acid). The printable photovoltaic electrochromic device according to claim 10, wherein the polycathionic electrolyte is, for example, polydiallyldimethylammonium chloride, polyallylamine hydrochloride, poly-L-lysine or polyethyleneamine. The printable photovoltaic electrochromic device according to claim 1, wherein the at least one thin film solar cell comprises a plurality of thin film solar cells. A printable photovoltaic electrochromic device according to claim 13, wherein the thin film solar cells are connected in series. A printable photovoltaic electrochromic device according to claim 1, further comprising an encapsulating material covering said thin film solar cell and said unipolar electrochromic material. The printable photovoltaic electrochromic device of claim 15, further comprising a transparent non-conductive substrate covering the encapsulating material. The printable photovoltaic electrochromic device of claim 1, wherein the transparent substrate comprises a flexible substrate. The printable photovoltaic electrochromic device according to claim 1, further comprising a DC-AC converter so as to convert a current provided by the thin-film solar cell into commercial energy. The printable photovoltaic electrochromic device according to claim 1, further comprising a DC charge storage device so as to store a current generated by the thin film solar cell. The printable photovoltaic electrochromic device according to claim 1, further comprising a thin film transistor individually connected to two terminals of the anode layer and the cathode layer of the thin film solar cell so as to individually control an on or off state of the thin film solar cell and an external circuit.

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