DE102011118902B4 - Printable photovoltaic electrochromic device - Google Patents

Abstract

A printable photovoltaic electrochromic device at least comprising: a transparent substrate (100, 600); at least one thin film solar cell (102, 500, 602) disposed on the transparent substrate (100, 600), the thin film solar cell (102, 500, 602 ) at least one anode layer (106, 502, 608), a cathode layer (108, 504, 612) and a photoelectric conversion layer (110, 506, 610) between the anode layer (106, 502, 608) and the cathode layer (108, 504, 612) and a portion of the anode layer or a portion of the cathode layer (108, 504, 612) of the thin film solar cell (102, 500, 602) is exposed; andat least one unipolar electrochromic film (104, 604) covering and contacting both the cathode layer (108, 504, 612) and the anode layer (106, 502, 608), the unipolar electrochromic film (104, 604) being a unipolar electrochromic Comprises 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 manufacture of an electrochromic device must have the following properties. Colors shown under different voltages must be easily distinguishable, the color change is quick and smooth, over 10,000 reversible color changes of the device color, and the device has high stability. Common electrochromic devices include surface-limited solid-state electrochromic devices or solution-type electrochromic devices.

A surface limited, thin film solid state electrochromic device is formed by an upper transparent substrate, a lower transparent substrate and a multilayer electrochromic layer therebetween. The multi-layer 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, an ion 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 bonded with opposing electrode layers and an electrochromic organic solution is placed between them. A component of the solution includes an electrochromic material containing small organic molecules of 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 differ markedly because electrodes in a large area electrochromic device are at the edge of the device and electric field paths are different lengths at a flatter center and at the edges of the electrochromic device. Due to the difference in resistance values, oval gradients of color change concentrations appear from the edges to the central regions, thereby affecting the uniformity of the color change effects.

In order to expand the field of application of electrochromic technology, a number of studies pertaining to the combinations of photoelectric technology and solar cells provide more variable research directions. For example revealed U.S. Patent No. 6,369,934 B1 an entire organic multilayer photo-electrochemical device in which a photosensitive layer and an electrochromic layer are separated at two electrodes of opposite polarity in order to enable the device to be manufactured. Such a device can thus be described as having an electrochromic material which is embedded in a dye 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 devices of larger size must be solved in order to apply such a structure to practical applications.

Also revealed U.S. Patent No. 5,377,037 A 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 made. A liquid organic electrolyte or a solid inorganic electrolyte layer is arranged between the substrates. However, the optical contrast before and after the color change achieved by such technology is relatively small and the color change effect is insignificant. The transparency of the PV-EC device is made possible by the incorporation of a semi-transparent amorphous silicon-carbon alloy improved with wider band gap. However, as the semi-transparent PV thin films become very thin, an electrical short circuit easily occurs, making the device less attractive to use in smart windows.

U.S. Patent Application Publication No. 2010/0000590 A1 and U.S. Patent No. 7,855,822 B2 provide some liquid type electrochromic photovoltaic devices in which electrodes are uniformly scattered over the entire surface of a substrate so that a uniform electric field is formed and an electrochromic solution has the same degree of color change in different regions, thereby preventing the iris effect.

US 2010/0294335 A1 discloses a photovoltaic electrochromic device and method of making the same which changes the color of the electrochromic films upon illumination.

US 7,785,496 B1 discloses an electrochromic device with colorants and a method of forming the colorants. The colorants employ dispersion of colloidal nano-compositions in a carrier liquid.

US 2008/0070062 A1 discloses an electrochromic device with an anionic polyelectrolyte which has been neutralized with lithium and which can be applied from aqueous solutions.

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

Summary of the invention

The present invention is provided by claim 1 appended hereto. Advantageous embodiments are described in the dependent claims. 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, wherein the unipolar electrochromic thin film comprises a unipolar electrochromic material and a polyelectrolyte. The thin-film solar cell comprises at least one anode layer, a cathode layer and a photoelectric conversion layer between the anode layer and the cathode layer. A section or a part of the anode layer or a section or a part 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 in which a portion of the anode layer or a portion of the cathode layer is exposed, coloring by light irradiation is achieved. Therefore, the printable photovoltaic electrochromic device according to the disclosure does not need an additional electrolyte, so that problems of liquid leakage caused by the use of general electrolyte solutions are prevented, and the printable photovoltaic electrochromic device can be integrated into a single-layer structure, thereby reducing the processing time . In addition, printing methods can be used to complete the printable photovoltaic electrochromic device according to the disclosure when the thin film solar cell is arranged 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.

Figure list

• 1 ist ein schematisches Querschnittsdiagramm, das eine druckbare fotovoltaische elektrochrome Vorrichtung gemäß einer ersten Ausführungsform der Offenbarung zeigt.
• 2 ist ein schematisches Draufsichtdiagramm, das die druckbare fotovoltaische elektrochrome Vorrichtung in 1 zeigt.
• 3 ist ein schematisches Querschnittsdiagramm, das eine druckbare fotovoltaische elektrochrome Vorrichtung gemäß einer zweiten Ausführungsform der Offenbarung zeigt.
• 4A ist ein schematisches Querschnittsdiagramm, das eine andere druckbare fotovoltaische elektrochrome Vorrichtung gemäß der ersten Ausführungsform der Offenbarung zeigt.
• 4B ist ein schematisches Draufsichtdiagramm, das die druckbare fotovoltaische elektrochrome Vorrichtung in 4a zeigt.
• 5 ist ein schematisches Querschnittsdiagramm, das ein druckbares fotovoltaisches elektrochromes Modul gemäß einer dritten Ausführungsform der Offenbarung zeigt.
• 6A ist ein schematisches Perspektivdiagramm, das eine druckbare fotovoltaische elektrochrome Vorrichtung gemäß einer vierten Ausführungsform der Offenbarung zeigt.
• 6B ist ein schematisches Perspektivdiagramm, das eine andere druckbare fotovoltaische elektrochrome Vorrichtung gemäß der vierten Ausführungsform der Offenbarung zeigt.
• 7 ist ein TEM-Foto einer PANI/PSS unipolaren elektrochromen Dünnschicht aus Experiment 1.
• 8 ist ein Diagramm, das eine Kurve zeigt, die die Größe von PANI-Nanosphären repräsentiert.
• 9 ist ein schematisches Schaltungsdiagramm, das eine Anordnung einer druckbaren fotovoltaischen elektrochromen Vorrichtung und einen Ausgabeschalter gemäß der Offenbarung zeigt.
• 10 ist ein schematisches Schaltungsdiagramm, das eine Anordnung einer druckbaren fotovoltaischen elektrochromen Vorrichtung und einen anderen Ausgabeschalter gemäß der Offenbarung zeigt.
• 11 ist ein schematisches Schaltungsdiagramm, das eine Anordnung einer druckbaren fotovoltaischen elektrochromen Vorrichtung und einer Dünnschichttransistorröhre gemäß der Offenbarung zeigt.

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 show embodiments of the disclosure and, together with the description, serve to explain the principles of the disclosure.

• 1 Figure 13 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic device according to a first embodiment of the disclosure.
• 2 FIG. 13 is a schematic top plan diagram illustrating the printable photovoltaic electrochromic device in FIG 1 shows.
• 3 Figure 13 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic device according to a second embodiment of the disclosure.
• 4A Fig. 13 is a schematic cross-sectional diagram showing another printable photovoltaic electrochromic device according to the first embodiment of the disclosure.
• 4B FIG. 13 is a schematic top plan diagram illustrating the printable photovoltaic electrochromic device in FIG 4a shows.
• 5 Figure 4 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic module according to a third embodiment of the disclosure.
• 6A Figure 13 is a schematic perspective diagram showing a printable photovoltaic electrochromic device according to a fourth embodiment of the disclosure.
• 6B Fig. 13 is a schematic perspective diagram showing another printable photovoltaic electrochromic device according to the fourth embodiment of the disclosure.
• 7th is a TEM photo of a PANI / PSS unipolar electrochromic thin film from experiment 1 .
• 8th Fig. 13 is a diagram showing a curve representing the size of PANI nanospheres.
• 9 FIG. 13 is a schematic circuit diagram showing an arrangement of a printable photovoltaic electrochromic device and an output switch according to the disclosure.
• 10 FIG. 13 is a schematic circuit diagram showing an arrangement of a printable photovoltaic electrochromic device and another output switch according to the disclosure.
• 11 Figure 13 is a schematic circuit diagram showing an arrangement of a printable photovoltaic electrochromic device and a thin film transistor tube according to the disclosure.

Description of the embodiments

1 Figure 13 is a schematic cross-sectional diagram showing a printable photovoltaic electrochromic device according to a first embodiment of the disclosure.

It will be on 1 referenced. The printable photovoltaic electrochromic device according to a first embodiment of the disclosure is a printable photovoltaic electrochromic device having a superstrate 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 are for a color change due to exposure to light 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 can be an electrochromic nanostructural material or an electrochromic material with nanostructural structure, such as a nanostructural metal oxide or a metal complex or a metal complex with a metal complex with a nanostructure or a conductive nanostructure polymer or a conductive polymer with a nanostructure. The above electrochromic nanostructural material is, for example, nanoparticles, nanorods, nanocables, nanospheres or nanospheres or nanotubes. The above nanostructural 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 analogue or a Prussian blue analogue or InHCF. The above conductive nanostructure polymer is, for example, polyaniline nanospheres, polypyrrole (PPy) nanospheres, or PEDOT nanospheres.

The polyelectrolyte contained in the unipolar electrochromic layer 104 may be a polyanionic electrolyte or a polycationic electrolyte. 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 (styrene sulfonate) (PSS), sodium poly (acrylic acid) (NePA), polyacrylic acid (PAA). Polymaleic acid (PMA), poly (perfluorosulfuric acid Is (PFSA, trademark as NAFION ^®), and the polycationic electrolyte, for example, polydiallyldimethylammonium chloride (PDDA), polyallylamine hydrochloride (PAH), poly-L-lysine (PLL) or polyethyleneimine (PEI).

The anodic or cathodic electrochromic material contained in the unipolar electrochromic layer 104 includes, includes 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 method for polymerizing PEDOT is oxidative polymerisation, so that after polymerisation positively charged (PEDOT) ^{n + is} obtained (n is a stoichiometric number). A polyanionic electrolyte PSS ^- must also exist in order to form the unipolar electrochromic material and polyelectrolytes (PEDOT) ^{n +} (PSS) ^n- . For a PANI anodic electrochromic material, a method of polymerisation is also an oxidative polymerisation, so that after the polymerisation positively charged (PANI) ^{m + is} obtained (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 related, includes 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 is, for example, a transparent conductive oxide (TCO) and a material of the cathode layer 108 is, for example, 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 exposed section 106 ' the anode layer 106 so that when the printable photovoltaic electrochromic device by sunlight 101 is irradiated, electron-hole pairs are immediately generated in the thin-film solar cell and redox reactions in the unipolar electrochromic thin-film 104 occur. Ion exchange provided by the polyelectrolyte causes a color change in the unipolar electrochromic thin film 104 reached. Therefore, the printable photovoltaic electrochromic device according to the first embodiment is achieved by comprising the above printable unipolar electrochromic thin film 104 , Effects such as no need for an additional electrolyte and a simple manufacturing process and structure.

In addition, when the transparent substrate 100 according to the present embodiment is a flexible substrate, the thin film solar cell can first be arranged on the flexible substrate and the printable photovoltaic electrochromic device in 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 throughout and the circuitry thereof is in 2 with the thin film solar cell connected in parallel and other elements in FIG 1 have been 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 by 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, of which the most stable type, a silicon thin-film solar cell, is a-Si-solar cell, Si / mc-Si tandem thin-film solar cell or an a-Si / a-Si tandem thin-film solar cell.

3 Fig. 13 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.

It will be on 3 referenced. 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 can be adjusted 104 the energy production of Thin film solar cell 102 influence, so that the printable photovoltaic electrochromic device according to the second embodiment can be applied to devices that require a periodic color change.

Additionally are 4A and 4B a schematic cross-sectional diagram and a schematic plan view diagram, respectively, 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 gets on both 4A as well 4B referenced. 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 due to light irradiation by both the anode layer 106 as well as the cathode layer 108 the thin-film solar cell 102 are covered. Any 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.

Also, after the unipolar electrochromic thin film 104 was formed, an encapsulating material 400 the unipolar electrochromic thin film 104 cover (as in 4A shown). Then a transparent non-conductive substrate can be used 402 such as glass, plastic, or a flexible substrate is the encapsulating material 400 cover. A reflective layer 404 such as a silver or aluminum thin film can be applied to a surface of the transparent non-conductive substrate 402 can be formed so as to form a mirror surface.

5 Figure 13 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.

It will be on 5 referenced. A printable photovoltaic electrochromic device according to the third embodiment includes the transparent substrate 100 , a thin film solar cell 500 on the transparent substrate 100 and at least one unipolar electrochromic thin film 104 , being the unipolar electrochromic thin film 104 comprises the unipolar electrochromic material and the polyelectrolyte described in the previous embodiments. The thin film solar cell 500 is a monolithic integrated module that consists of several anode layers 502 on the surface of the transparent substrate 100 , multiple 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 series connection between the thin film solar cells 500 is erected. Materials of each of the above layers are described in the previous embodiments.

When the unipolar electrochromic thin film 104 in 5 A positively charged anodic or cathodic electrochromic material is used for ion exchange in the regions 508 and 510 a polyanionic electrolyte is required, so that no additional electrolyte or a bipolar electrochromic thin film are required. 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; as opposed 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 there are 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 intermixed with the polyanionic electrolyte to initiate ion exchange in the regions 508 and 510 to provide. Problems with 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 arise, so that the printable photovoltaic electrochromic device does not have problems with uneven coloring.

6A Figure 13 is a schematic perspective diagram showing a printable photovoltaic electrochromic device according to a fourth embodiment of the disclosure. 6b Fig. 13 is a schematic perspective diagram showing another printable photovoltaic electrochromic device according to the fourth embodiment of the disclosure.

It will be on 6A and 6B referenced. 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 , being the unipolar electrochromic thin film 604 comprises the unipolar electrochromic material and the polyelectrolyte described in each of the previous 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 structuring or laser scribing and sandblasting to create parts of the photoelectric conversion layer 610 and remove the cathode. One 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 version.

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 film 604 When the color changes, the polyanionic electrolyte provides for ion exchange in the unipolar electrochromic thin film 604 above the anode 608 and the cathode 612 ready so that no additional electrolyte or a bipolar electrochromic thin film is required.

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: Manufacture of a unipolar electrochromic thin film

0.6 mmol of aminobenzene monomer is added to 20 ml of deionized water (DIW) containing 0.5M HCl and 1.0 g of poly-sodium styrene sulfate (PSS) and is added to 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 making a PANI / PSS mixture to obtain, the positively charged polymeric nanospheres of the anodic material PANI and the polyanionic electrolyte PSS contains. The following is a chemical equation of the preparation process or the preparation process.

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

The PANI / PSS mixture is then 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 encompasses the PANI nanospheres as in 7th shown.

8th Fig. 13 is a diagram showing a curve representing the sizes of PANI nanospheres measured with a dynamic light scattering instrument (DLS). The amount of PSS affects the sizes of the nanospheres. According to the measurement results of the present experiment, there are three peaks of the curve 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.

Leucoemeraldin im Grundzustand Emeraldin im Salzzustand Gelb-grün, gebleicht Blau-grün, verdunkelt The following chemical equation shows a mechanism of color change in the polymeric nanospheres of the anodic electrochromic material comprising PANI nanospheres and the polyanionic electrolyte PSS. $$\text{PANI}+\text{m}{\left(\text{PSS}\right)}^{-}\leftrightarrow {\left(\text{PANI}\right)}^{\text{m}+}{\left(\text{PSS}\right)}^{\text{m}-}+{\text{me}}^{-}$$

Leucoemeraldin in its basic state Emeraldine in the salt state Yellow-green, bleached Blue-green, darkened

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

Experiment 2: Manufacture and study 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 one in 1 , is fabricated on the glass substrate, with a portion of an anode and a cathode of each strip-shaped silicon solar cell measuring 5 cm x 5 cm. An anode layer is a TCO and a cathode layer is a TCO / Ag. An IV curve or a current-voltage curve of such a thin-film solar cell is: V _oc = 0.93 V, J _sc = 12.3 mA / cm ² , FF = 73.23%, P _max = 20.94 mW and a power generation efficiency is 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 layer 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: Manufacture and study 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 that consists of 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 comprises 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 or a current-voltage curve of such Thin film solar cell module is: V _oc = 3.98 V, I _sc = 26.57 mA, FF% = 64.94%, PwrMax = 69.09mW, and a power generation efficiency is 5.23%.

The PANI / PSS mixture obtained in Experiment 1 is coated or applied to a silicon solar cell module. After drying, a PANI / PSS unipolar electrochromic thin layer 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 layer remains blue-green if the irradiation time is extended (from three minutes to one hour) and there are no problems with uneven coloring.

Experiment 4: Manufacture and study 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 and the PANI / PSS spin coating and the drying steps in Experiment 1, so that three printable photovoltaic electrochromic devices can be produced 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 through the irradiation of light.

Experiment 5: Manufacture of a unipolar electrochromic thin film

100 mg of PSS is added to 50 ml of distilled water containing 1.0M NaCl and the mixture is stirred for six hours and set aside for subsequent use. 26 µl of 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 56mg APS is added to it. 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 fabricate the silicon thin film solar cell module and the above PEDOT / PSS mixture is spin coated onto the silicon thin film solar cell according to the method in Experiment 2. After drying, a PEDOT / PSS unipolar electrochromic thin layer 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.

$$\left(\text{Transparent hellbau},\text{ gebleicht}\right)\leftrightarrow \left(\text{dunkelblau},\text{ verdunkelt}\right)$$

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. $$\begin{array}{c}{\left(\text{PEDOT}\right)}^{\text{n}+}{\left(\text{PSS}\right)}^{\text{n}-}+{\text{no}}^{-}\leftrightarrow \text{PEDOT}+\text{n}{\left(\text{PSS}\right)}^{-}\\ \end{array}$$

$$\left(\text{Transparent light construction},\text{bleached}\right)\leftrightarrow \left(\text{dark blue},\text{darkened}\right)$$

In the above equation, “n” represents a charge number.

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

1. 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. 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. 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.

Additionally, an output switch assembly can be added to the printable photovoltaic electrochromic device according to the disclosure. The switch of the printable photovoltaic electrochromic device can be constituted by the following methods.

1. 1. Using a DC / AC converter 900 or a DC-AC converter 900 a current that is generated by the thin-film solar cell is converted into an AC current or alternating current, which is used as a commercial power source 902 can be used to power general electrical devices, as in 9 shown.
2. 2. The electricity generated by the thin film solar cell is used in a DC charge storage device 1000 and a DC charge storage device, respectively 1000 (which can subsequently be used as a battery to feed power to general DC electrical devices), as in 10 shown.
3. 3. Thin film transistors are made by thin film transistor (TFT) processes and the like 1100 manufactured at two terminals of the anode layer and the cathode layer of the thin-film solar cell to be used as a switch so as to individually switch on / off or control on / off each of the thin-film solar cells and an external circuit, whereby an actively controlled electrochromic device is achieved, 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, coloration achieved by exposure to light. Problems with non-uniform color change do not occur in the thin-film solar cell module with a monolithically integrated structure that has been coated / printed with the unipolar electrochromic material. This is different from conventional device structures made from bipolar electrochromic materials with electrolytes, which must include designs or arrangements to balance charges in the bipolar electrochromic layer in order to achieve a uniform color change. In other words, the printable photovoltaic electrochromic device according to the disclosure is a device structure in a completely solid state, so that problems of liquid leakage caused by liquid electrolytes are prevented, and the printable photovoltaic electrochromic device can be integrated into single-layer 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 complete the printable photovoltaic electrochromic device according to the disclosure in a simpler manner and in greater numbers if the thin film solar cell is arranged on the flexible substrate.

It will be apparent to those skilled in the art that various modifications and variations can be made in 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.

Claims (20)

A printable photovoltaic electrochromic device comprising at least: a transparent substrate (100, 600); at least one thin-film solar cell (102, 500, 602), which is arranged on the transparent substrate (100, 600), the thin-film solar cell (102, 500, 602) having at least one anode layer (106, 502, 608), a cathode layer (108, 504, 612) and a photoelectric conversion layer (110, 506, 610) between the anode layer (106, 502, 608) and the cathode layer (108, 504, 612) and a portion of the anode layer or a portion of the cathode layer (108, 504 , 612) is exposed from the thin film solar cell (102, 500, 602); and at least one unipolar electrochromic thin layer (104, 604) which covers and contacts both the cathode layer (108, 504, 612) and the anode layer (106, 502, 608), the unipolar electrochromic thin layer (104, 604) being a unipolar electrochromic Comprises material and a polyelectrolyte. Printable photovoltaic electrochromic device according to Claim 1 wherein the printable photovoltaic electrochromic device comprises a superstrate photovoltaic electrochromic device or a substrate electrochromic photovoltaic device. Printable photovoltaic electrochromic device according to Claim 1 wherein the unipolar electrochromic material comprises an anodic electrochromic material or a cathodic electrochromic material. Printable photovoltaic electrochromic device according to Claim 1 wherein the unipolar electrochromic material comprises an electrochromic material with a nanostructure. Printable photovoltaic electrochromic device according to Claim 4 wherein the electrochromic material with nanostructure comprises a metal oxide with nanostructure, a metal complex with nanostructure or a conductive polymer with nanostructure. Printable photovoltaic electrochromic device according to Claim 5 , wherein the electrochromic material with a nanostructure comprises nanoparticles, nanorods, nanowires, nanospheres or nanotubes. Printable photovoltaic electrochromic device according to Claim 5 , wherein the metal oxide with nanostructure comprises WO ₃ , V ₂ O ₅ , NiO _x or CuO _x . Printable photovoltaic electrochromic device according to Claim 5 , wherein the metal complex with nanostructure comprises a Prussian blue analog or InHCF. Printable photovoltaic electrochromic device according to Claim 5 wherein the conductive nanostructured polymer comprises polyaniline nanospheres, polypyrrole nanospheres, or PEDOT nanospheres. Printable photovoltaic electrochromic device according to Claim 1 wherein the polyelectrolyte comprises a polyanionic electrolyte or a polycathionic electrolyte. Printable photovoltaic electrochromic device according to Claim 10 wherein the polyanionic electrolyte comprises sodium poly (styryl sulfonate), sodium poly (acrylic acid), polyacrylic acid, polymaleic acid or poly (perfluorosulfuric acid). Printable photovoltaic electrochromic device according to Claim 10 wherein the polycathionic electrolyte is, for example, polydiallyldimethylammonium chloride, polyallylamine hydrochloride, poly-L-lysine or polyethyleneimine. Printable photovoltaic electrochromic device according to Claim 1 wherein the at least one thin-film solar cell (102, 500, 602) comprises a plurality of thin-film solar cells (102, 500, 602). Printable photovoltaic electrochromic device according to Claim 13 , wherein the thin film solar cells (102, 500, 602) are connected in series. Printable photovoltaic electrochromic device according to Claim 1 , further comprising an encapsulating material that covers the thin film solar cell (102, 500, 602) and the unipolar electrochromic material. Printable photovoltaic electrochromic device according to Claim 15 , further comprising a transparent non-conductive substrate covering the encapsulating material. Printable photovoltaic electrochromic device according to Claim 1 wherein the transparent substrate comprises a flexible substrate. 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 (102, 500, 602) into commercial energy. 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 (102, 500, 602). Printable photovoltaic electrochromic device according to Claim 1 , further comprising a thin-film transistor, which is individually connected to two terminals of the anode layer (106, 502, 608) and the cathode layer (108, 504, 612) of the thin-film solar cell (102, 500, 602) so as to enable or disable State of the thin-film solar cell (102, 500, 602) and an external circuit to be controlled individually.

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