Electrochromic organic photovoltaic window system and application thereof in building envelope structure

Abstract

The invention belongs to the technical field of intelligent windows, and particularly relates to an electrochromic organic photovoltaic window system and application thereof in a building envelope. The electrochromic organic photovoltaic window system comprises a window frame and a glass assembly, the window frame is arranged on the periphery of the glass assembly, and the glass assembly comprises a semitransparent organic photovoltaic module and a reversible metal electrodeposition type electrochromic module which are arranged in a stacked mode. And a sealed cavity is formed between the semitransparent organic photovoltaic module and the reversible metal electro-deposition type electrochromic module. The electrochromic organic photovoltaic window system provided by the invention has the advantages of efficient productivity, dynamic energy conservation, visual comfort and environmental friendliness, and can be widely applied to building envelope structures.

Description

Technical Field

[0001] This invention belongs to the field of smart window technology, specifically relating to an electrochromic organic photovoltaic window system and its application in building envelope. Background Technology

[0002] In modern buildings, windows are the weakest link in the building envelope in terms of energy efficiency, with a significant amount of energy lost through them via heat conduction and solar radiation. Therefore, developing "smart window" technology that can dynamically regulate solar radiation is of great significance for reducing building energy consumption for cooling, heating, and lighting.

[0003] Currently, smart window technology for building applications is mainly developing and optimizing along two main directions: semi-transparent photovoltaic technology and electrochromic technology.

[0004] Semi-transparent photovoltaic technologies (such as semi-transparent organic photovoltaics, STOPV) aim to transform windows into energy producers, converting solar radiation (mainly ultraviolet and near-infrared rays) into electricity while allowing some visible light to pass through. Electrochromic technologies (such as reversible metal electrodeposition devices, RME-ECD) can reversibly switch between a transparent and colored state through external stimuli, dynamically controlling solar heat gain and achieving significant energy-saving effects. However, to achieve high light transmittance, semi-transparent organic photovoltaic glass often requires sacrificing the thickness of the active layer or using sparse electrodes, which directly leads to its low photoelectric conversion efficiency. At the same time, its spectral absorption characteristics often result in transmitted light exhibiting undesirable colors (such as highly saturated blue-violet), affecting indoor visual comfort. Furthermore, it lacks dynamic adjustment capabilities and cannot respond to changing weather and sunlight conditions. Summary of the Invention

[0005] The purpose of this invention is to provide an electrochromic organic photovoltaic window system and its application in building envelope. The electrochromic organic photovoltaic window system provided by this invention has the advantages of high energy efficiency, dynamic energy saving, visual comfort and environmental friendliness.

[0006] To achieve the above objectives, the present invention provides the following technical solution: The present invention provides an electrochromic organic photovoltaic window system, including a window frame and a glass assembly. The window frame is disposed on the outer periphery of the glass assembly. The glass assembly includes a semi-transparent organic photovoltaic module and a reversible metal electrodeposition electrochromic module stacked together, and a sealed cavity is provided between the semi-transparent organic photovoltaic module and the reversible metal electrodeposition electrochromic module. The semi-transparent organic photovoltaic module comprises a transparent substrate, a first transparent electrode, a hole transport layer, an active layer, an electron transport layer, a second transparent electrode, and an anti-reflection layer stacked sequentially, with the anti-reflection layer in contact with the sealed cavity. The active layer is made of a donor material, an acceptor material, and additives. The donor material includes PCE10-2F or PCE-10, and the acceptor material includes Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 Any of BM, wherein the additive comprises one or more of diisobutylene (DIB), 1,4-diiodobenzene (DIO), chloronaphthalene (CN), and 1,3,5-trichlorobenzene (TCB).

[0007] Preferably, the reversible metal electrodeposition electrochromic module includes a first conductive transparent substrate and a second conductive transparent substrate stacked together, and a liquid electrolyte disposed between the first conductive transparent substrate and the second conductive transparent substrate; a first transparent conductive layer is disposed on one surface of the first conductive transparent substrate, a second transparent conductive layer is disposed on one surface of the second conductive transparent substrate, the first transparent conductive layer and the second transparent conductive layer are in contact with the liquid electrolyte, and the liquid electrolyte includes soluble silver salt, soluble copper salt, tetrabutylammonium bromide, polyvinylpyrrolidone and organic solvent.

[0008] Preferably, the emissivity of the transparent substrate is ≥0.8, and the emissivity of the antireflective layer is ≤0.3; the mass percentage of the additive in the active layer to the mass of the acceptor material is preferably 40~120%; the mass ratio of the donor material to the acceptor material in the active layer is preferably 1:1~1:3; and the thickness of the active layer is 40~150nm.

[0009] Preferably, the active layer material further includes a dopant component, which differs from the donor material and the acceptor material. The dopant component includes PM6, D18, PTQ10, D18-Cl, PPT-3, Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 One or more of BM; the mass of the doping component preferably accounts for 0.01 to 50% of the donor material.

[0010] Preferably, the material of the hole transport layer includes PEDOT:PSS, 2-PACz, Ph-4PACz, ThCz, MoO3, and NiO. xOne or more of the following: 3-PACz, MeO-2PACz, fullerene materials, BCP, ZnO, and TiO2; the hole transport layer has a thickness of 5-60 nm; the electron transport layer is made of materials including PDINN, PDINO, PDIN, PFN-Br, PFB-Br, PNDIT-F3N, and C. 60 One or more of BCP and PNDIT-F3N-Br; the thickness of the electron transport layer is 5~50nm.

[0011] Preferably, the material of the first transparent electrode includes indium tin oxide (ITO), fluorine-doped tin oxide (FTO), or aluminum-doped zinc oxide (AZO); the thickness of the first transparent electrode is 100-200 nm; the material of the second transparent electrode is a metallic element, including one or more of Ag, Cu, Al, and Au, and the thickness of the second transparent electrode is 10-15 nm; the antireflective layer is a single-layer film structure or a double-layer coupled film structure; the material of the single-layer film structure includes tellurium dioxide, molybdenum trioxide, zinc sulfide, silicon dioxide, titanium dioxide, niobium pentoxide, or tantalum pentoxide; the double-layer coupled film structure includes a first film layer and a second film layer, the first film layer is in contact with the surface of the second transparent electrode, the material of the first film layer includes LiF, MgF2, or ZnSe, and the material of the second film layer includes MoO3, ZnS, or TeO2; the thickness of the antireflective layer is ≤1000 nm.

[0012] Preferably, the materials of the first and second transparent conductive layers include indium tin oxide (ITO), fluorine-doped tin oxide (FTO), or aluminum-doped zinc oxide (AZO); the mass concentration of polyvinylpyrrolidone in the liquid electrolyte is 0.002~0.01 g / mL.

[0013] This invention provides the application of the electrochromic organic photovoltaic window system described above in building envelope.

[0014] Preferably, the building envelope includes building windows, curtain walls, or car sunroofs; When applied, the semi-transparent organic photovoltaic module of the electrochromic organic photovoltaic window system is located on the outdoor side.

[0015] Preferably, the application includes the following steps: The reversible metal electrodeposition electrochromic module switches between a fading state and a colored state according to environmental parameters; the environmental parameters include irradiation intensity and / or ambient temperature. When the reversible metal electrodeposition electrochromic module switches to the colored state, the reflected light enhances the power generation capacity of the semi-transparent organic photovoltaic module.

[0016] This invention provides an electrochromic organic photovoltaic window system, including a window frame and a glass assembly. The window frame is disposed on the outer periphery of the glass assembly. The glass assembly includes a semi-transparent organic photovoltaic module and a reversible metal electrodeposition electrochromic module (hereinafter referred to as the electrochromic module) stacked together, and a sealed cavity is provided between the semi-transparent organic photovoltaic module and the reversible metal electrodeposition electrochromic module. The semi-transparent organic photovoltaic module includes a transparent substrate, a first transparent electrode, a hole transport layer, an active layer, an electron transport layer, a second transparent electrode, and an anti-reflection layer stacked sequentially, and the anti-reflection layer is in contact with the sealed cavity. The active layer is made of a donor material, an acceptor material, and additives. The donor material includes PCE10-2F or PCE-10, and the acceptor material includes Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 The additives include one or more of diisobutylene, 1,4-diiodobenzene, chloronaphthalene, and 1,3,5-trichlorobenzene. Compared with existing single-function energy-saving windows, the electrochromic organic photovoltaic window system provided by this invention integrates a semi-transparent organic photovoltaic module and a reversible metal electrodeposition electrochromic module, enabling both to work synergistically and achieving the following significant beneficial effects: This invention integrates energy "open source" and "energy saving," achieving outstanding overall energy efficiency. The semi-transparent organic photovoltaic (STOPV) module (outdoor side) of this invention continuously converts solar radiation into electrical energy, realizing active energy production within the building envelope. The reversible metal electrodeposition electrochromic (EC) module (indoor side) of this invention dynamically adjusts its light transmittance according to environmental needs. In hot seasons, it effectively blocks solar radiation by switching to a colored state (high reflectivity state), thereby significantly reducing building cooling energy consumption. Simultaneously, this invention achieves synergistic effects between the STOPV module and the EC module: when the EC module is in the colored state, the reflected light can be reabsorbed by the outer STOPV module and used for power generation, resulting in a significant improvement in the overall power generation efficiency of the electrochromic organic photovoltaic window system in the colored state compared to the faded state (from 10.98% to 11.83%). The electrochromic organic photovoltaic window system provided by this invention achieves a synergistic enhancement effect of "energy saving" and "energy generation," which is impossible to achieve with traditional single-technology windows.

[0017] Furthermore, in this invention, the emissivity of the anti-reflective layer is ≤0.3. The electrochromic organic photovoltaic window system provided by this invention possesses excellent thermal performance and intelligent thermal management capabilities. By setting the inner surface of the STOPV module to a low-emissivity surface (the emissivity (ε) of the anti-reflective layer is ≤0.3, for example, 0.20), and combining it with a sealed cavity (which can be filled with smoke or maintained in a vacuum), the electrochromic organic photovoltaic window system provided by this invention can effectively block external heat transfer inward, exhibiting excellent thermal insulation performance. The U-value (heat transfer coefficient, which measures the heat transfer capacity per unit area of ​​the glass component) of the electrochromic organic photovoltaic window system provided by this invention is ≤1.09 W / m². 2 •K, meeting the insulation needs of frigid regions.

[0018] Furthermore, in this invention, the emissivity of the transparent substrate is ≥0.8. The outermost surface of the STOPV module of the electrochromic organic photovoltaic window system provided by this invention is made of a high emissivity material (the emissivity (ε) of the transparent substrate is ≥0.8, for example, it can be 0.85), which is beneficial to quickly dissipate the heat generated by the STOPV module during operation to the external environment in the form of radiation, avoiding the efficiency reduction and additional indoor heat gain caused by its own heating.

[0019] Furthermore, in this invention, the material of the active layer further includes a dopant component, which differs from the donor material and the acceptor material. The dopant component includes PM6, D18, PTQ10, D18-Cl, PPT-3, Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 One or more of BM; the mass of the doping component preferably accounts for 0.01~50% of the donor material. This invention, by adding a doping component to the active layer, using a doping component whose absorption peak position is completely complementary to the original narrow bandgap donor and acceptor, and supplemented with specific additives (additives include one or more of DIB, DIO, CN, and TCB), effectively controls the microstructure of the active layer, broadens the light absorption range, improves exciton separation efficiency and charge mobility, and significantly improves photoelectric conversion efficiency without reducing visible light transmittance, thereby achieving a significant improvement in light utilization efficiency.

[0020] Meanwhile, the electrochromic organic photovoltaic window system provided by this invention effectively solves the problem of light pollution while ensuring high visual comfort. The electrochromic organic photovoltaic window system provided by this invention possesses excellent visual performance: the EC module in this invention can provide neutral-toned transmitted light (correlated color temperature CCT ≈ 6350 K) and an extremely high color rendering index (R²) in the faded state. a(≈ 90%), creating a comfortable and color-accurate indoor lighting environment, fully complying with high-standard building lighting specifications. The electrochromic organic photovoltaic window system provided by this invention can actively suppress light pollution: In the prior art, the high reflectivity of independent reflective electrochromic windows during coloring easily causes light pollution such as glare. In this invention, the EC module and the outer STOPV module work together. The STOPV module actively absorbs most of the visible light reflected by the EC module, successfully suppressing the overall outdoor visible light reflectivity of the electrochromic organic photovoltaic window system provided by this invention to below the building code limit (15%) (the actual measured value in the embodiment of this invention can reach 14.53%), realizing the compatibility of intelligent dimming function and urban environmental protection.

[0021] Furthermore, in this invention, the liquid electrolyte contains polyvinylpyrrolidone (PVP). PVP acts as a polymer inhibitor, inhibiting the intrinsic coloring of the electrolyte through its complexation with metal ions. At the same time, it promotes the formation of a uniform, stable, and highly reflective mirror film layer of metallic silver during the electrodeposition process, thereby achieving a balance between high transparency in the faded state and high reflectivity in the colored state of the electrochromic module.

[0022] The electrochromic organic photovoltaic window system provided by this invention exhibits broad climate adaptability and enormous global energy-saving potential. Building energy consumption simulations based on multiple global climate zones show that the electrochromic organic photovoltaic window system provided by this invention achieves the highest net energy savings in all climate zones (from the hot and dry Zone 0 to the cold and harsh Zone 8).

[0023] Compared to commercial glass windows and stand-alone stop-and-go windows, the electrochromic organic photovoltaic window system provided by this invention achieves optimal annual net energy savings through a dual approach of significantly reducing cooling energy consumption and synergistically increasing power generation. The estimated annual energy savings are 67.51~166.34 kWh / m². 2 .

[0024] In summary, this invention, through the deep coupling and synergistic optimization of a semi-transparent organic photovoltaic module and a reversible metal electrodeposition electrochromic module, successfully solves the long-standing technical challenges in the field of smart windows, such as the difficulty in balancing energy production and energy conservation, and the contradiction between visual comfort and light pollution. It provides a high-performance, high-comfort, and highly adaptable integrated solution for building energy conservation and energy production. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the electrochromic organic photovoltaic window system provided by the present invention; Figure 2 This is a schematic diagram of the spectral management strategy in this invention; Figure 3This is a schematic diagram of the structure of the semi-transparent organic photovoltaic module in this invention; Figure 4 This is a schematic diagram of the reversible metal electrodeposition electrochromic module in this invention; Figure 5 The transmittance curves of the fading and colored states of the reversible metal electrodeposition electrochromic module in this invention are shown. Figure 6 These are the reflectance curves of the faded and colored states of the reversible metal electrodeposition electrochromic module in this invention. Figure 7 This is a visual representation of the actual fading state of the reversible metal electrodeposition electrochromic module in this invention. Figure 8 This is a visual representation of the actual color state of the reversible metal electrodeposition electrochromic module in this invention. Figure 9 This represents the actual visual effect observed through the sample in this invention; Figure 10 The electrochromic organic photovoltaic window system provided by this invention exhibits reflective properties in both the faded and colored states; Figure 11 Comparison of photovoltaic performance improvements achieved through the synergistic effect of the electrochromic organic photovoltaic window system provided by the present invention; Figure 12 Infrared thermal imaging images of the heat gain effects of different window structures visualized in this invention; Figure 13 This provides information on net energy consumption in various climate zones worldwide and the optimal illuminance thresholds corresponding to the state switching of electrochromic modules. In the figure: 1-Window frame, 2-Semi-transparent organic photovoltaic module, 3-Reversible metal electrodeposition electrochromic module, 4-Transparent substrate, 5-Anti-reflective layer, 6-Sealed cavity, 7-First conductive transparent substrate, 8-Second conductive transparent substrate. Detailed Implementation

[0026] The present invention provides an electrochromic organic photovoltaic window system, including a window frame and a glass assembly. The window frame is disposed on the outer periphery of the glass assembly. The glass assembly includes a semi-transparent organic photovoltaic module and a reversible metal electrodeposition electrochromic module stacked together, and a sealed cavity is provided between the semi-transparent organic photovoltaic module and the reversible metal electrodeposition electrochromic module. The semi-transparent organic photovoltaic module comprises a transparent substrate, a first transparent electrode, a hole transport layer, an active layer, an electron transport layer, a second transparent electrode, and an anti-reflection layer stacked sequentially, with the anti-reflection layer in contact with the sealed cavity. The active layer is made of a donor material, an acceptor material, and additives. The donor material includes PCE10-2F or PCE-10, and the acceptor material includes Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 Any of BM, wherein the additive comprises one or more of diisobutylene, 1,4-diiodobenzene, chloronaphthalene, and 1,3,5-trichlorobenzene.

[0027] In this invention, unless otherwise specified, all raw materials / components used in the preparation are commercially available products well known to those skilled in the art.

[0028] A schematic diagram of the electrochromic organic photovoltaic window system provided by this invention is shown below. Figure 1 As shown below, in conjunction with Figure 1 The electrochromic organic photovoltaic window system provided by this invention will be described in detail. The electrochromic organic photovoltaic window system provided by this invention includes a window frame. In this invention, the window frame is disposed on the outer periphery of the glass assembly. The window frame is used to fix the glass assembly and forms a sealed cavity between the semi-transparent organic photovoltaic module and the reversible metal electrodeposition electrochromic module by sealing the semi-transparent organic photovoltaic module and the reversible metal electrodeposition electrochromic module.

[0029] The electrochromic organic photovoltaic window system provided by this invention includes a glass assembly. The glass assembly includes a semi-transparent organic photovoltaic module and a reversible metal electrodeposition electrochromic module stacked together, and a sealed cavity is provided between the semi-transparent organic photovoltaic module and the reversible metal electrodeposition electrochromic module.

[0030] In this invention, the structural schematic diagram of the semi-transparent organic photovoltaic module is shown below. Figure 3 As shown below, in conjunction with Figure 3 This invention provides a detailed description of the semi-transparent organic photovoltaic module. In this invention, the semi-transparent organic photovoltaic module comprises a transparent substrate, a first transparent electrode, a hole transport layer, an active layer, an electron transport layer, a second transparent electrode, and an anti-reflection layer, which are sequentially stacked and contact the sealed cavity. In this invention, the emissivity of the transparent substrate is preferably ≥0.8, and in some embodiments it can be 0.8~0.85. The emissivity of the anti-reflection layer is preferably ≤0.3, and in some embodiments it can be 0.25~0.3. This invention optimizes the emissivity of the anti-reflection layer to ≤0.3, making the anti-reflection layer a low-emissivity surface, thereby effectively blocking external heat gain, reducing the cooling load in summer, and providing insulation in winter.

[0031] The semi-transparent organic photovoltaic module provided by this invention includes a transparent substrate. In this invention, the emissivity of the transparent substrate is preferably ≥0.8. This invention enhances radiative heat dissipation to the external environment during photovoltaic module operation by optimizing the transparent substrate as a high-emissivity surface. In this invention, the material of the transparent substrate preferably includes glass, quartz, polyethylene terephthalate (PET), or polyethylene naphthalate (PEN), and in the embodiments, quartz glass can be used. Preferably, a film is deposited on the outward-facing bottom surface of the transparent substrate to ensure that the emissivity of the transparent substrate is preferably ≥0.8.

[0032] The semi-transparent organic photovoltaic module provided by this invention includes a first transparent electrode disposed on the upper surface of the transparent substrate. In this invention, the material of the first transparent electrode preferably includes one or more of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide (AZO), and in the embodiments, it can be ITO. The thickness of the first transparent electrode is preferably 100~200 nm, and in the embodiments, it can be 140 nm, 145 nm, 120 nm, 170 nm, 145 nm, or 175 nm.

[0033] The semi-transparent organic photovoltaic module provided by this invention includes a hole transport layer disposed on the upper surface of the first transparent electrode. In this invention, the material of the hole transport layer preferably includes PEDOT:PSS, 2-PACz, Ph-4PACz, ThCz, MoO3, and NiO. x One or more of the following: 3-PACz, MeO-2PACz, fullerene materials, BCP, ZnO, and TiO2. In this invention, the fullerene material can be C... 60 In this embodiment of the invention, the hole transport layer can be made of 2-PACz. The thickness of the hole transport layer is preferably 5-60 nm, more preferably 6-30 nm, and even more preferably 10-20 nm.

[0034] The semi-transparent organic photovoltaic module provided by this invention includes an active layer disposed on the upper surface of the hole transport layer. In this invention, the active layer comprises a donor material, an acceptor material, and additives. The donor material includes PCE10-2F or PCE-10. The acceptor material includes Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 Any of BM, in the embodiment it can be Y6, BTP-eC9 or PC. 71 BM. In this invention, the donor material and the acceptor material form a binary system.

[0035] In this invention, the additive includes one or more of diisobutylene (DIB), 1,4-diiodobenzene (DIO), chloronaphthalene (CN), and 1,3,5-trichlorobenzene (TCB), preferably one or two of DIB, DIO, CN, and TCB. In the examples, CN and DIO can be combined, or DIB can be used alone. When the additive is a combination of CN and DIO, the mass ratio of CN to DIO is preferably (1~3):(1~3).

[0036] In this invention, the active layer preferably further includes a dopant component. The dopant component differs from the donor material. The dopant component differs from the acceptor material. In this invention, the dopant component preferably includes PM6, D18, PTQ10, D18-Cl, PPT-3, Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 One or two of BM. The doping components preferably include PM6, D18, PTQ10, D18-Cl, PPT-3, Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 When any of the materials in BM are used, the doping component is referred to as the tertiary component, which together with the donor material and the acceptor material forms a ternary system. The doping component preferably includes PM6, D18, PTQ10, D18-Cl, PPT-3, Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 When any two of the materials in BM are used, the doping components are referred to as the tertiary component and the fourth component, which together with the donor material and the acceptor material form a quaternary system.

[0037] In this invention, the doping component more preferably includes one or more of PM6, D18, PTQ10, D18-Cl and PPT-3, and more preferably any one of PM6, D18, PTQ10, D18-Cl and PPT-3. In the embodiments, it can be PPT-3, PM6 or D18.

[0038] In this invention, the mass of the doped component in the active layer preferably accounts for 0.01 to 50% of the donor material, more preferably 1 to 45%, further preferably 5 to 40%, and even more preferably 10 to 30%.

[0039] In this invention, the percentage of the mass of the additive in the active layer to the mass of the receptor material is preferably 40-120%, more preferably 50-100%, and even more preferably 60-80%.

[0040] In this invention, the mass ratio of donor material to acceptor material in the active layer is preferably 1:1 to 1:3.

[0041] In this invention, the thickness of the active layer is preferably 40-150 nm, more preferably 50-120 nm, and even more preferably 60-110 nm. In the embodiments, it can be 90 nm, 80 nm, 100 nm, 75 nm or 80 nm.

[0042] In this invention, the active layer is mainly composed of narrow bandgap materials, which absorb far-red and near-infrared light for power generation, while allowing most of the visible light to pass through; other functional layers ensure the smooth transport of charge carriers while having high light transmittance, so that the battery has excellent photoelectric conversion efficiency while achieving high visible light transmittance.

[0043] The semi-transparent organic photovoltaic module provided by this invention includes an electron transport layer disposed on the upper surface of the active layer. In this invention, the material of the electron transport layer preferably includes PDINN, PDINO, PDIN, PFN-Br, PFB-Br, PNDIT-F3N, and C. 60 One or more of BCP and PNDIT-F3N-Br, more preferably PDINN, PDINO, PDIN, PFN-Br, PFB-Br, PNDIT-F3N, and C 60 One or two of BCP and PNDIT-F3N-Br, which in the examples can be PDINO or C 60 The combination with BCP, where the material of the electron transport layer is preferably C 60 When combined with BCP, the electron transport layer comprises C stacked from bottom to top. 60 Layer and BCP layer.

[0044] In this invention, the thickness of the electron transport layer is preferably 5-50 nm, and in embodiments it can be 20 nm, 25 nm, 35 nm, 10 nm, or 30 nm. When the electron transport layer comprises C layers stacked from bottom to top... 60 When using the C layer and the BCP layer, 60 The thickness of the layer is preferably 20-25 nm, and the thickness of the BCP layer is preferably 10-15 nm.

[0045] The semi-transparent organic photovoltaic module provided by this invention includes a second transparent electrode disposed on the upper surface of the electron transport layer. In this invention, the material of the second transparent electrode is preferably a metallic element, and the metallic element preferably includes one or more of Ag, Cu, Al, and Au. The thickness of the second transparent electrode is 10-15 nm. In an embodiment of this invention, the second transparent electrode has an Ag elemental layer.

[0046] In this invention, the thickness of the second transparent electrode is preferably 5-30 nm, more preferably 10-25 nm, and even more preferably 12-20 nm. In the embodiments, it can be 16 nm, 13 nm, or 15 nm.

[0047] The semi-transparent organic photovoltaic module provided by this invention includes an anti-reflective layer disposed on the upper surface of the second transparent electrode. In this invention, the anti-reflective layer is preferably a single-layer film structure or a double-layer coupled film structure. The material of the single-layer film structure preferably includes tellurium dioxide (TeO2), molybdenum trioxide (MoO3), zinc sulfide (ZnS), silicon dioxide (SiO2), titanium dioxide (TiO2), niobium pentoxide (Nb2O5), or tantalum pentoxide (Ta2O5), and in this embodiment, it can be MoO3. The double-layer coupled film structure preferably includes a first film layer and a second film layer stacked from bottom to top. The material of the first film layer preferably includes LiF, MgF2, or ZnSe, and the material of the second film layer preferably includes MoO3, ZnS, or TeO2. The material of the double-layer coupled mode structure is more preferably LiF / MoO3, MgF2 / MoO3, LiF / ZnS, MgF2 / ZnS, LiF / TeO2, MgF2 / TeO2 or ZnSe / ZnS, and in the embodiment it can be LiF / MoO3.

[0048] In this embodiment of the invention, the anti-reflective layer is preferably a MoO3 layer or a LiF / MoO3 layer.

[0049] In this invention, the thickness of the antireflective layer is preferably ≤1000nm, more preferably 20~800nm, and even more preferably 30~500nm. In embodiments, it can be 40nm, 30nm, 230nm, or 35nm. In this invention, when the antireflective layer is preferably a single-layer film structure, the thickness of the antireflective layer is preferably 30~60nm. In embodiments, it can be 40nm, 30nm, or 35nm. In this invention, when the antireflective layer is preferably a double-layer coupled film structure, the thickness of the antireflective layer is preferably ≤1000nm, preferably 200~260nm. In embodiments, it can be 230nm. In this invention, when the antireflective layer is a LiF / MoO3 layer, the thickness of the first film layer (LiF layer) is preferably 100~130nm, and the thickness of the second film layer ( / MoO3 layer) is preferably 100~130nm.

[0050] In this invention, the method for preparing the semi-transparent organic photovoltaic module preferably includes the following steps: A transparent substrate with a first transparent electrode on its upper surface is provided; A hole transport layer is prepared on the upper surface of the first transparent electrode; An active layer is prepared on the upper surface of the hole transport layer; An electron transport layer is prepared on the upper surface of the active layer; A second transparent electrode is fabricated on the upper surface of the electron transport layer; An anti-reflective layer is prepared on the upper surface of the second transparent electrode to obtain the semi-transparent organic photovoltaic module.

[0051] This invention provides a transparent substrate with a first transparent electrode on its upper surface. Before fabricating the hole transport layer, the transparent substrate with the first transparent electrode on its upper surface preferably undergoes a pretreatment. In this invention, the pretreatment preferably includes sequentially cleaning and drying the transparent substrate with the first transparent electrode on its upper surface. The cleaning is preferably ultrasonic cleaning, and the ultrasonic cleaning quartz is preferably performed sequentially with detergent, deionized water, and ethanol. This invention removes residual impurities from the surface of the transparent substrate with the first transparent electrode on its upper surface through cleaning. In this invention, the drying is preferably performed using a nitrogen gun.

[0052] This invention prepares a hole transport layer on the upper surface of a first transparent electrode. Preferably, the preparation method of the hole transport layer includes: coating a hole transport layer slurry onto the upper surface of the first transparent electrode, followed by annealing to obtain the hole transport layer. Preferably, the hole transport layer slurry comprises a hole transport layer material and an organic solvent. The organic solvent can be ethanol, and the mass concentration of the hole transport material in the hole transport layer slurry is preferably 0.2~0.3 mg / mL. This invention does not have special requirements for the preparation method of the hole transport layer slurry; the slurry can be prepared using conventional methods according to the hole transport layer material. The coating is performed using a homogenizer. The annealing temperature is preferably 100~150℃, and the annealing time is preferably 5~20 min, which can be 10 min in the example. The annealing is preferably performed on a hot plate.

[0053] After obtaining the hole transport layer, the present invention prepares an active layer on the upper surface of the hole transport layer. In the present invention, the preparation of the active layer is preferably carried out in a protective gas atmosphere, which can be nitrogen. The preparation temperature of the active layer is preferably ≤25℃. The preparation method of the active layer preferably includes: coating an active layer slurry onto the upper surface of the hole transport layer, and then performing an annealing treatment to obtain the active layer. In the present invention, the active layer slurry preferably includes an active layer material and an organic solvent. The organic solvent can be chloroform, and the mass concentration of the active layer material in the active layer slurry is preferably 12~16 mg / mL. The present invention does not have special requirements for the preparation method of the active layer slurry; the active layer slurry can be prepared using conventional preparation methods according to the active layer material. The coating is performed using a homogenizer. The annealing temperature is preferably 60~110℃, and in the example, it can be 100℃; the time is preferably 3~10 min. The annealing treatment is preferably performed on a hot plate.

[0054] After obtaining the active layer, an electron transport layer is prepared on the upper surface of the active layer in this invention. In this invention, the preparation method of the electron transport layer preferably includes spin coating or thermal evaporation. In this invention, when the material of the electron transport layer is preferably PDINO or PNDIT-F3N, the spin coating is performed using PDINO slurry or PNDIT-F3N slurry. The PDINO slurry preferably includes PDINO and an organic solvent, and the mass concentration of PDINO in the PDINO slurry is preferably 1~3 mg / mL, and the organic solvent can be methanol. The PNDIT-F3N slurry preferably includes PNDIT-F3N and an organic solvent, and the mass concentration of PNDIT-F3N in the PNDIT-F3N slurry is preferably 0.1~0.5 mg / mL, and the organic solvent can be methanol. The PNDIT-F3N slurry preferably includes acetic acid, and the volume percentage of the acetic acid contains no impurities (less than 1%). The material of the electron transport layer is preferably C. 60 In the case of / BCP, the present invention uses a thermal evaporation method to prepare the electron transport layer.

[0055] After obtaining the electron transport layer, the present invention fabricates a second transparent electrode on the upper surface of the electron transport layer. In this invention, the second transparent electrode is preferably a metal electrode. The present invention preferably uses a thermal evaporation method to fabricate the second transparent electrode. The thermal evaporation is performed in a vacuum environment.

[0056] An anti-reflective layer is prepared on the upper surface of the second transparent electrode to obtain the semi-transparent organic photovoltaic module. Preferably, the anti-reflective layer is prepared by thermal evaporation. The thermal evaporation is performed in a vacuum environment. In a specific embodiment of the invention, the anti-reflective layer is LiF / MoO3, and a LiF layer and a MoO3 layer are sequentially thermally evaporated onto the surface of the second transparent electrode.

[0057] In this invention, the reversible metal electrodeposition electrochromic module includes a first conductive transparent substrate and a second conductive transparent substrate stacked together, and a liquid electrolyte disposed between the first conductive transparent substrate and the second conductive transparent substrate; a first transparent conductive layer is disposed on one surface of the first conductive transparent substrate, and a second transparent conductive layer is disposed on one surface of the second conductive transparent substrate; the first transparent conductive layer and the second transparent conductive layer are in contact with the liquid electrolyte, and the liquid electrolyte includes soluble silver salt, soluble copper salt, tetrabutylammonium bromide, polyvinylpyrrolidone, and an organic solvent.

[0058] In this invention, the blank substrate of the first conductive transparent substrate is quartz glass. The blank substrate of the second conductive transparent substrate is quartz glass. In this invention, the materials of the first and second transparent conductive layers preferably include indium tin oxide (ITO), fluorine-doped tin oxide (FTO), or aluminum-doped zinc oxide (AZO). The soluble silver salt can be silver nitrate. The soluble copper salt can be copper chloride.

[0059] In this invention, the molar concentration of the soluble silver salt in the liquid electrolyte is preferably 0.07~0.075 mol / L. The molar concentration of the soluble copper salt is preferably 0.005~0.01 mol / L. The molar concentration of tetrabutylammonium bromide is preferably 0.2~0.25 mol / L. In this invention, the mass concentration of polyvinylpyrrolidone in the liquid electrolyte is preferably 0.002~0.01 g / mL, more preferably 0.003~0.008 g / mL, and in the examples, it is 0.006 g / mL. This invention achieves a balance between high transparency in the faded state and high reflectivity in the colored state in the electrochromic module by adding polyvinylpyrrolidone (PVP) to the liquid electrolyte. PVP acts as a polymer inhibitor, suppressing the intrinsic coloring of the electrolyte through its complexation with metal ions. Simultaneously, it promotes the formation of a uniform, stable, and highly reflective mirror film layer of metallic silver during electrodeposition.

[0060] In this invention, the sealed cavity is preferably in a vacuum state or filled with an inert gas, which may be argon.

[0061] This invention provides the application of the electrochromic organic photovoltaic window system described above in building envelope.

[0062] In this invention, the building envelope preferably includes building windows, curtain walls, or car sunroofs.

[0063] In this invention, the semi-transparent organic photovoltaic module of the electrochromic organic photovoltaic window system is located on the outdoor side. The electrochromic organic photovoltaic window system generates electricity through the semi-transparent organic photovoltaic module, and achieves building energy conservation through the dynamic adjustment of the electrochromic module and the synergy of thermal management.

[0064] The electrochromic organic photovoltaic window system provided by this invention can completely block ultraviolet rays and segmentally modulate the spectrum of visible light and near-infrared wavelengths. Specifically, the system allows most visible light to pass through to meet indoor lighting needs, while preferentially allocating solar radiation in specific wavelengths (e.g., 625~1000 nm) to the photovoltaic module for power generation.

[0065] The electrochromic organic photovoltaic window system provided by this invention improves performance through optical synergy between modules: when the electrochromic module is in the colored (reflective) state, it reflects the incident light back to the outer photovoltaic module, realizing secondary absorption of light and power generation, thereby significantly improving the total power generation efficiency of the system in the colored state.

[0066] The electrochromic organic photovoltaic window system provided by this invention achieves the following comprehensive benefits: Optical performance: In the faded state, the system exhibits a neutral hue and a high color rendering index. The ratio of average visible light transmittance to solar heat gain is superior to that of commercial low-emissivity glass, fully complying with building optics codes. Light pollution control: The photovoltaic modules effectively absorb most of the visible light reflected by the electrochromic modules in the tinted state, successfully suppressing the overall outdoor visible light reflectance of the system within building code limits (e.g., 15%). Energy efficiency: This system not only reduces building cooling energy consumption through dynamic dimming, but its built-in photovoltaic modules can also continuously generate electricity. Simulation data shows that it achieves significant net energy savings under various global climatic conditions.

[0067] In the electrochromic organic photovoltaic window system provided by this invention, the semi-transparent organic photovoltaic module and the electrochromic module work together optically and thermally. In this invention, the spectral broadening strategy of the electrochromic organic photovoltaic window system is as follows: Figure 2 As shown, by Figure 2It is understood that the electrochromic organic photovoltaic window system provided by this invention achieves synergistic spectral management: the electrochromic organic photovoltaic window system is configured to segment and manage the solar spectrum. The semi-transparent organic photovoltaic module is optimized to primarily absorb and utilize light in a first preset wavelength band (625~1000 nm) for power generation, while allowing most visible light to pass through; the electrochromic module is configured to have high visible light transmittance in the faded state and to reflect incident light in the colored state. The electrochromic organic photovoltaic window system enhances power generation: when the electrochromic module is in the colored state, it reflects unabsorbed light back to the semi-transparent organic photovoltaic module, realizing secondary absorption of light by the semi-transparent organic photovoltaic module, thereby improving the photoelectric conversion efficiency of the semi-transparent organic photovoltaic module in the colored state. The electrochromic organic photovoltaic window system also achieves synergistic thermal management: the outer surface of the electrochromic organic photovoltaic window system, i.e., the outer surface of the transparent substrate, is set to have high emissivity, preferably greater than 0.8, to enhance radiative heat dissipation to the external environment. The inner surface of the translucent organic photovoltaic module, i.e. the surface of the anti-reflective layer facing the sealed cavity, is configured to have a low emissivity, preferably less than 0.3, to block the transfer of external heat into the room.

[0068] In this invention, when the electrochromic organic photovoltaic window system is applied in a building envelope, the application preferably includes the following steps (i.e., this invention provides a control method for the above-mentioned electrochromic organic photovoltaic window system): The reversible metal electrodeposition electrochromic module switches between a fading state and a coloring state according to environmental parameters, including irradiation intensity and / or ambient temperature.

[0069] When the reversible metal electrodeposition electrochromic module switches to the colored state, the reflected light enhances the power generation capacity of the semi-transparent organic photovoltaic module.

[0070] In this invention, the environmental parameter is preferably irradiance. When the environmental parameter (preferably irradiance) reaches a threshold (i.e., the optimal irradiance for different climate zones in Table 1), the present invention switches the electrochromic module from a fading state to a colored state, using the reflected light to enhance the power generation capacity of the semi-transparent organic photovoltaic module.

[0071] This invention determines the irradiance (i.e., threshold) for different climate zones based on various regions across multiple global climate zones (from the hot and dry Zone 0 to the cold and harsh Zone 8, including Zone 0, Zone 1, Zone 2, Zone 3, Zone 4, Zone 5, Zone 6, Zone 7, and Zone 8). It identifies the threshold values ​​for the corresponding irradiance in each climate zone (220 W / m² for Zone 0).2 Zone 1 is 220W / m 2 Zone 2 is 250W / m 2 Zone 3 is 300W / m 2 Zone 4 is 900W / m 2 Zone 5 is 900W / m 2 Zone 6 is 900W / m 2 Zone 7 has a power consumption of 920W / m 2 Zone 8 is 1000W / m 2 When the electrochromic module is in a fading state, the present invention switches the electrochromic module from the fading state to the tinting state.

[0072] Table 1. Optimal SPEW Irradiance and Net Energy Consumption for Four Window Types Applied in Nine Climate Zones

[0073] Plot the data in Table 1 to obtain... Figure 13 The bar chart shown, Table 1 and Figure 13 In this context, "SPEW" refers to the intelligent electrochromic organic photovoltaic window system (SPEW) prepared in Example 1.

[0074] Table 1 and Figure 13 In this context, "CW", "TMSW", and "PW" represent ordinary commercial glass, electrochromic glass, and ordinary photovoltaic windows, respectively.

[0075] Figure 13 In this context, "NEU" stands for Net Energy Use.

[0076] Based on Table 1 and Figure 13 The results show that, based on building energy consumption simulations in multiple climate zones around the world, the electrochromic organic photovoltaic window system provided by this invention can achieve the highest net energy saving effect in all climate zones (from the hot and dry Zone 0 to the cold and harsh Zone 8).

[0077] In this invention, the fading state and coloring state of the reversible metal electrodeposition electrochromic module can also be controlled by the user.

[0078] In summary, the electrochromic organic photovoltaic window system provided by this invention achieves the following: Improved energy efficiency: The electrochromic organic photovoltaic window system not only reduces building cooling / heating load through dynamic dimming (electrochromic module), but also continuously generates electricity (semi-transparent organic photovoltaic module), and further enhances power generation through optical synergy in the colored state, achieving integration of energy saving and power generation. Photothermal synergy: The unique thermal management surface design (high emissivity on the outer surface and low emissivity on the inner surface) effectively regulates building heat gain and dissipation, significantly improving the system's annual energy efficiency. Visual comfort and environmental compliance: The system's spectral management strategy ensures a high color rendering index and neutral color temperature in the faded state, meeting indoor lighting quality requirements. Simultaneously, the semi-transparent organic photovoltaic module on the outside absorbs most of the visible light reflected by the electrochromic module, successfully suppressing the overall visible light reflectance of the system within building light pollution standards (e.g., 15%). Climate universality: Simulation data shows that this integrated system can achieve significant net energy savings in various climate zones worldwide, from hot to cold, demonstrating broad applicability.

[0079] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0080] Example 1: This embodiment provides a method for preparing a smart electrochromic organic photovoltaic window system (SPEW), which specifically includes the following steps: (1) Fabrication of the semi-transparent organic photovoltaic (STOPV) module. The structural schematic diagram of the semi-transparent organic photovoltaic (STOPV) module provided in this embodiment is shown below. Figure 3 As shown in Table 2, the materials and thicknesses of each layer of the STOPV module are as follows: Table 2. Materials and thicknesses of each layer of the STOPV module

[0081] 1) Use dish soap, deionized water and ethanol to ultrasonically clean the high-transmittance glass with ITO coating in sequence to remove residual impurities on the surface, and then blow it dry with a nitrogen gun for later use. 2) Spin coat the glass surface treated in step 1) with a hole transport layer slurry (ethanol solution, 0.3 mg / mL) using a spin coater, and anneal it on a hot plate at 100°C for 15 min. 3) Place the glass with the hole transport layer prepared in step 2) into a glove box under a nitrogen atmosphere and maintain a constant temperature below 25°C. Spin-coat the active layer slurry (chloroform solvent, mass concentration of 16 mg / mL) using a dynamic spin-coating method to serve as the active layer (also known as the active light-absorbing layer) of the semi-transparent organic photovoltaic module, and anneal it at 100°C for 10 min. In the active layer prepared in this embodiment, the mass of the dopant component accounts for 10% of the mass of the donor material, the mass of the additive accounts for 120% of the mass of the acceptor material, and the mass ratio of the donor material to the acceptor material is 1:3.

[0082] 4) When the electron transport layer material is PDINO or PNDIT-F3N, spin-coating the glass with the active layer prepared in step 3) to prepare the electron transport layer (PDINO uses methanol solvent, with a mass concentration of 3 mg / mL in the slurry; PNDIT-F3N uses methanol solvent, with a mass concentration of 0.5 mg / mL, plus 1% volume fraction of acetic acid); when the electron transport layer material is C 60 / BCP is performed using a thermal evaporation method, C 60 The thickness of the is 15nm, and the thickness of the BCP is 8nm.

[0083] 5) The glass from step 4) with the electron transport layer prepared by spin coating is used to prepare a second transparent electrode in a vacuum environment by thermal evaporation. 6) The glass with the second transparent electrode prepared in step 5) is used to prepare an anti-reflective layer (ε ≈ 0.20) in a vacuum environment using a thermal evaporation method, thus completing the fabrication of the STOPV module. The low emissivity (ε ≈ 0.20) of the anti-reflective layer also serves the system's thermal management function. At this point, the fabrication of the STOPV module is complete.

[0084] (2) Fabrication of a reversible metal electrodeposition electrochromic (EC) module. A schematic diagram of the reversible metal electrodeposition electrochromic (EC) module in this embodiment is shown below. Figure 4 As shown, the specific preparation method is as follows: Two pieces of quartz glass were selected as substrates, and ITO transparent conductive layers were prepared on the two pieces of quartz glass by magnetron sputtering to obtain a first conductive transparent substrate and a second conductive transparent substrate. Preparation of liquid electrolyte: AgNO3, CuCl2, and tetrabutylammonium bromide (TBABr) were dissolved in dimethyl sulfoxide (DMSO) solvent, and polyvinylpyrrolidone (PVP) was added as a polymer inhibitor to obtain a liquid electrolyte. The liquid electrolyte had the following molar concentrations: AgNO3 0.075 mol / L, CuCl2 0.01 mol / L, TBABr 0.25 mol / L, and PVP 0.006 g / mL. In this embodiment, the liquid electrolyte is encapsulated between a first conductive transparent substrate and a second conductive transparent substrate using a filling method, forming a sandwich-structured EC module. The EC module is highly transparent and nearly colorless in its faded state, and can form a highly reflective silver mirror in its colored state. Figure 5 , Figure 6 , Figure 7 and Figure 8 As shown, Figure 5 The transmittance curves for the faded and colored states of the reversible metal electrodeposition electrochromic module are shown. Figure 6 The reflectance curves of the faded and colored states of the reversible metal electrodeposition electrochromic module are shown. Figure 7 The images show the actual visual effects of the faded state of the reversible metal electrodeposition electrochromic electrochromic module in Example 1 and Comparative Example 2. Figure 8 These are actual visual effect images of the colored states of the reversible metal electrodeposition electrochromic modules in Example 1 and Comparative Example 2. Figure 8 The left image shows the silver film breaking after approximately 20 seconds of voltage application without a PVP module in Comparative Example 2. Figure 8 The right-hand figure in Example 1 shows a silver film that remains stable even after 60 seconds of voltage applied by a PVP module. Figure 8 The reversible metal electrodeposition electrochromic module in the left-hand diagram is prepared in the same way as the one in Example 1, i.e., the reversible metal electrodeposition electrochromic module prepared in Comparative Example 1. The difference from Example 1 is that no PVP is added to the liquid electrolyte and the mass concentration of PVP is 0.

[0085] (3) System integration: The prepared STOPV module and EC module are placed opposite each other in the window frame, separated by a spacer frame to form a sealed cavity. The air inside the cavity is replaced with an inert gas (argon) by evacuation and argon backfilling to reduce heat conduction and protect the internal electrodes. The edges of each layer are then sealed, completing the encapsulation of the entire Smart Electrochromic Organic Photovoltaic Window System (SPEW).

[0086] Comparative Example 1 The difference between this and the Smart Electrochromic Organic Photovoltaic Window System (SPEW) provided in Example 1 is that the EC module in Example 1 is replaced with a silver mirror, i.e., the “Organic Photovoltaic Module & Silver Mirror” sample in Table 4.

[0087] Comparative Example 2 The difference between this and the Smart Electrochromic Organic Photovoltaic Window System (SPEW) provided in Example 1 is as follows: Liquid electrolyte is prepared by dissolving AgNO3, CuCl2, and tetrabutylammonium bromide (TBABr) in dimethyl sulfoxide (DMSO) solvent to obtain a liquid electrolyte. In the liquid electrolyte, the molar concentration of AgNO3 is 0.075 mol / L, the molar concentration of CuCl2 is 0.01 mol / L, and the molar concentration of TBABr is 0.25 mol / L.

[0088] Test example: (1) Optical and electrical performance testing of the Smart Electrochromic Organic Photovoltaic Window System (SPEW): The spectral data of the device in both the faded and colored states were measured using a UV-Vis-NIR spectrophotometer. The test results are as follows: Figure 9 As shown in Table 3. Figure 9 The actual visual effect observed through the sample in Example 1 is shown in Table 3. Table 3 shows the color rendering performance of different glass samples. Results: The intelligent electrochromic organic photovoltaic window system (SPEW) prepared in Example 1 has an average visible light transmittance (AVT) of 33.75% and a correlated color temperature (CCT) of 6350 K in the faded state, with a color rendering index (R...). a The value of 90 indicates that it has good visual comfort.

[0089] Table 3. Color development properties of different glass samples.

[0090] In the tinted state, the outdoor visible light reflectance (Ri) of the Smart Electrochromic Organic Photovoltaic Window System (SPEW) is... VIS The light pollution level was successfully suppressed to 14.53%, which is below the building light pollution limit of 15% (e.g., Figure 10 As shown, Figure 10 The reflectance properties of the smart electrochromic organic photovoltaic window system (SPEW) prepared in Example 1 in the faded and colored states.

[0091] (2) Photovoltaic performance was tested using a solar simulator and source table.

[0092] Figure 11 Table 4 shows a comparison of the photovoltaic performance improvements achieved through the synergistic effect of the Smart Electrochromic Organic Photovoltaic Window System (SPEW) prepared in Example 1.

[0093] Table 4 Comparison of photovoltaic performance improvements.

[0094] Depend on Figure 11As shown in Table 4, the initial photoelectric conversion efficiency (PCE) of the STOPV module when operating independently is 10.85%. When integrated with the EC module in its bleached state, the PCE slightly increases to 10.98%. When the EC module switches to its stained state, the PCE significantly increases to 11.83% due to the secondary absorption of its reflected light by the STOPV module. In contrast, when the EC module is replaced by a silver mirror, the PCE reaches 12.43%, demonstrating the enormous potential for reusing reflected light.

[0095] (3) Thermal performance demonstration: The surface temperature distribution of the device was observed using an infrared thermal imager under illumination from a standard solar simulator. Figure 12 Infrared thermal imaging images were used to visualize the heat gain effects of different window structures. Results: Under the same illumination conditions, the SPEW device in the tinted state had a center temperature of only 25.2℃ on its back surface, which is much lower than that of ordinary glass (43.4℃) and independent STOPV or EC modules, directly demonstrating its excellent solar shielding and heat insulation capabilities.

[0096] Its thermal parameters were calculated using Windows software.

[0097] Results: The U value of the argon-filled SPEW was 2.12 W / m 2 The solar heat gain coefficients (SHGC) for the colored and faded states are 0.160 and 0.309, respectively, and the SHGC / AVT ratio (1.09) is better than that of commercial low-emissivity glass (1.26), indicating that it introduces less solar heat radiation while providing the same light transmittance.

[0098] (4) Simulation of building energy-saving benefits The energy-saving potential of the SPEW system in practical applications was evaluated using building energy consumption simulation software. Model establishment: The benchmark model of a large office building developed by the U.S. Department of Energy was adopted, with a window-to-wall ratio of 38.1%; the SPEW spectral data and thermal parameters measured in the example were input into the model; Simulation setup: Comparison of SPEW with commercial glass windows (CW), stand-alone stop-and-see windows (PW), and three-band controlled smart windows (TMSW). The simulation covers multiple global climate zones (Zone 0-8). Control strategy: Set a single-parameter control strategy for SPEW based on the total solar irradiance incident on the outer surface to drive the EC module to switch between bleached and colored states; Simulation results: In hot climate zones (such as Zone 0, representing the city of Abu Dhabi), SPEW can achieve a net energy saving of approximately 137.71 kWh / m² per year compared to CW. 2 This energy-saving effect is superior to PW (124.20 kWh / m³). 2) and TMSW (78.19 kWh / m 2 Its advantages mainly come from two aspects: firstly, its excellent reduction in cooling energy consumption (58.26 kWh / m³). 2 Secondly, there is the power generation from its own operation and the additional power generation gain from the reuse of reflected light in the colored state. Simulation results show that SPEW can achieve significant net energy savings in all climate zones worldwide, demonstrating excellent climate universality (e.g., Figure 13 As shown, Figure 13 This provides the net energy consumption data for various climate zones worldwide and the optimal illuminance thresholds corresponding to the state switching of electrochromic modules.

[0099] Examples 2-4 The preparation methods of Examples 2-4 are basically the same as those of Example 1, except that the structure and materials of the STOPV module described in Table 2 are used.

[0100] As can be seen from the above embodiments, compared with existing single-function energy-saving windows or simple technology superposition solutions, the semi-transparent organic photovoltaic-electrochromic smart window system provided by the present invention, through innovative integrated design and collaborative working mechanism, wherein the integrated design is reflected in the coupling of functions: First, the electrochromic module has high reflectivity in the colored state, and the reflected light is absorbed by the photovoltaic layer to enhance power generation; Second, the electrochromic module has high reflectivity in the colored state, which can shield sunlight and reduce indoor heat gain, but the light reflected from the mirror to the outside is too strong and will cause light pollution. After being absorbed by the organic photovoltaic module, it can ensure that the visible light reflectivity reflected to the outside by the system is below 15%; Third, organic photovoltaics mostly absorb part of red light and therefore often have a high color temperature. After being combined with the electrochromic module, the transmittance curve of the integrated system is smoother and the color temperature returns to neutral. Compared to simple technology stacking, the hollow structure used in this integrated design can achieve better thermal management and bring about higher energy efficiency; since the anti-emission layer is in the middle, it is easier to design the optical performance of the photovoltaic module; separating the two modules with a cavity eliminates the detrimental effect of the photovoltaic thermal effect on the electrochromic electrolyte layer.

[0101] The electrochromic organic photovoltaic window system provided by this invention achieves the following significant beneficial effects: (1) It has achieved the integration of "open source" and "conservation" of energy, with excellent overall energy efficiency. Active Energy Generation: The semi-transparent organic photovoltaic (STOPV) modules on the outside of the system continuously convert solar radiation into electricity, enabling active energy production within the building envelope. Dynamic Energy Saving: The electrochromic (EC) modules on the inside of the system dynamically adjust their transmittance according to environmental needs. During hot seasons, they switch to a colored state (high reflectivity) to effectively block solar radiation, thereby significantly reducing building cooling energy consumption.

[0102] (2) Synergistic effect: Most notably, when the EC module is in the colored state, the light reflected by it can be absorbed again by the outer STOPV module and used for power generation, so that the overall power generation efficiency of the system in the colored state can be significantly improved compared with the bleached state (for example, from 10.98% to 11.83%). This synergistic enhancement effect of "energy saving" and "power generation" cannot be achieved by traditional single technology windows.

[0103] (3) It provides excellent thermal performance and intelligent thermal management capabilities. High-efficiency thermal insulation: By setting the inner surface of the STOPV module to a low emissivity surface (e.g., ε = 0.20) and combining it with argon-filled or vacuum-sealed cavities, the system effectively blocks external heat transfer inward, exhibiting excellent thermal insulation performance with a U-value as low as 1.09 W / m². 2 • K, meeting the insulation needs of frigid regions; Enhanced heat dissipation: The outermost surface of the system is made of a high emissivity material (e.g., ε = 0.85), which helps to quickly dissipate the heat generated by the STOPV module during operation to the external environment in the form of radiation, avoiding the decrease in efficiency and additional indoor heat gain caused by its own heating.

[0104] (4) While ensuring high visual comfort, it effectively solves the problem of light pollution. Superior visual performance: Through precise spectral management, the system provides neutral-toned transmitted light (correlated color temperature CCT ≈ 6350 K) and an extremely high color rendering index (R) even in the faded state. a (≈ 90%), creating a comfortable and color-accurate indoor lighting environment that fully complies with high-standard building lighting codes. Actively suppressing light pollution: Independent reflective electrochromic windows, with their high reflectivity during coloring, can easily cause glare and other light pollution. In this invention, the outer STOPV module actively absorbs most of the visible light reflected by the EC module, successfully suppressing the overall outdoor visible light reflectivity of the system to below building code limits (e.g., 15%) (actually measured at 14.53%), achieving compatibility between intelligent dimming functionality and urban environmental protection.

[0105] (5) It exhibits broad climate adaptability and huge global energy-saving potential. Building energy consumption simulations based on multiple global climate zones show that the intelligent window system provided by this invention can achieve the highest net energy saving effect in all climate zones (from the hot and dry Zone 0 to the cold and harsh Zone 8).

[0106] Compared to commercial glass windows, independent stop-and-go windows, and other advanced dynamic dimming windows, the electrochromic organic photovoltaic window system provided by this invention achieves optimal annual net energy savings through a dual approach of significantly reducing cooling energy consumption and synergistically increasing power generation. The estimated annual energy savings are 67.51-166.34 kWh / m². 2 This demonstrates its significant application value in promoting carbon neutrality in buildings globally.

[0107] In summary, this invention, through the deep coupling and synergistic optimization of organic photovoltaic and electrochromic technologies, successfully solves the long-standing technical challenges in the field of smart windows, such as the difficulty in balancing energy production and energy conservation, and the contradiction between visual comfort and light pollution. It provides a high-performance, high-comfort, and highly adaptable integrated solution for building energy conservation and energy production.

[0108] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An electrochromic organic photovoltaic window system, characterized in that, The device includes a window frame and a glass assembly. The window frame is disposed on the outer periphery of the glass assembly. The glass assembly includes a semi-transparent organic photovoltaic module and a reversible metal electrodeposition electrochromic module stacked together, and a sealed cavity is provided between the semi-transparent organic photovoltaic module and the reversible metal electrodeposition electrochromic module. The semi-transparent organic photovoltaic module comprises a transparent substrate, a first transparent electrode, a hole transport layer, an active layer, an electron transport layer, a second transparent electrode, and an anti-reflection layer stacked sequentially, with the anti-reflection layer in contact with the sealed cavity. The active layer is made of a donor material, an acceptor material, and additives. The donor material includes PCE10-2F or PCE-10, and the acceptor material includes Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 Any of BM, wherein the additive comprises one or more of diisobutylene, 1,4-diiodobenzene, chloronaphthalene, and 1,3,5-trichlorobenzene.

2. The electrochromic organic photovoltaic window system according to claim 1, characterized in that, The reversible metal electrodeposition electrochromic module includes a first conductive transparent substrate and a second conductive transparent substrate stacked together, and a liquid electrolyte disposed between the first conductive transparent substrate and the second conductive transparent substrate; a first transparent conductive layer is disposed on one surface of the first conductive transparent substrate, and a second transparent conductive layer is disposed on one surface of the second conductive transparent substrate; the first transparent conductive layer and the second transparent conductive layer are in contact with the liquid electrolyte, and the liquid electrolyte includes soluble silver salt, soluble copper salt, tetrabutylammonium bromide, polyvinylpyrrolidone, and an organic solvent.

3. The electrochromic organic photovoltaic window system according to claim 1, characterized in that, The emissivity of the transparent substrate is ≥0.8, and the emissivity of the antireflective layer is ≤0.3; the mass percentage of the additive in the active layer to the mass of the acceptor material is preferably 40~120%; the mass ratio of the donor material to the acceptor material in the active layer is preferably 1:1~1:3; and the thickness of the active layer is 40~150nm.

4. The electrochromic organic photovoltaic window system according to claim 1, characterized in that, The active layer material further includes dopant components, which differ from the donor and acceptor materials. These dopant components include PM6, D18, PTQ10, D18-Cl, PPT-3, Y6, BTP-eC9, L8-BO, BO-4Cl, BO-4F, and PC. 71 One or more of BM; the mass of the doping component preferably accounts for 0.01 to 50% of the donor material.

5. The electrochromic organic photovoltaic window system according to claim 1, characterized in that, The hole transport layer is made of materials including PEDOT:PSS, 2-PACz, Ph-4PACz, ThCz, MoO3, and NiO. x One or more of the following: 3-PACz, MeO-2PACz, fullerene materials, BCP, ZnO, and TiO2; the hole transport layer has a thickness of 5-60 nm; the electron transport layer is made of materials including PDINN, PDINO, PDIN, PFN-Br, PFB-Br, PNDIT-F3N, and C. 60 One or more of BCP and PNDIT-F3N-Br; the thickness of the electron transport layer is 5~50nm.

6. The electrochromic organic photovoltaic window system according to claim 1, characterized in that, The first transparent electrode is made of indium tin oxide, fluorine-doped tin oxide, or aluminum-doped zinc oxide; the thickness of the first transparent electrode is 100-200 nm; the second transparent electrode is made of a metallic element, including one or more of Ag, Cu, Al, and Au, and the thickness of the second transparent electrode is 10-15 nm; the antireflective layer is a single-layer film structure or a double-layer coupled film structure; the single-layer film structure is made of tellurium dioxide, molybdenum trioxide, zinc sulfide, silicon dioxide, titanium dioxide, niobium pentoxide, or tantalum pentoxide; the double-layer coupled film structure includes a first film layer and a second film layer, the first film layer being in contact with the surface of the second transparent electrode, the first film layer being made of LiF, MgF2, or ZnSe, and the second film layer being made of MoO3, ZnS, or TeO2; the thickness of the antireflective layer is ≤1000 nm.

7. The electrochromic organic photovoltaic window system according to claim 2, characterized in that, The materials of the first and second transparent conductive layers include indium tin oxide, fluorine-doped tin oxide, or aluminum-doped zinc oxide; the mass concentration of polyvinylpyrrolidone in the liquid electrolyte is 0.002~0.01 g / mL.

8. The application of the electrochromic organic photovoltaic window system according to any one of claims 1 to 7 in the building envelope.

9. The application according to claim 8, characterized in that, The building envelope includes building windows, curtain walls, or car sunroofs; When applied, the semi-transparent organic photovoltaic module of the electrochromic organic photovoltaic window system is located on the outdoor side.

10. The application according to claim 9, characterized in that, The application includes the following steps: The reversible metal electrodeposition electrochromic module switches between a fading state and a colored state according to environmental parameters; the environmental parameters include irradiation intensity and / or ambient temperature. When the reversible metal electrodeposition electrochromic module switches to the colored state, the reflected light enhances the power generation capacity of the semi-transparent organic photovoltaic module.

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