CN117524755A

CN117524755A - Integrated device comprising photovoltaic cell and thin film electrochemical device

Info

Publication number: CN117524755A
Application number: CN202210896042.2A
Authority: CN
Inventors: 刁一凡; 吴兆; 解俊杰; 孙朱行
Original assignee: Longi Green Energy Technology Co Ltd
Current assignee: Longi Green Energy Technology Co Ltd
Priority date: 2022-07-27
Filing date: 2022-07-27
Publication date: 2024-02-06
Also published as: WO2024022402A1

Abstract

The application discloses an integrated device, which comprises a laminated photovoltaic cell and a thin film electrochemical device, wherein the thin film electrochemical device comprises a nanofiber electrode, the thin film electrochemical device is contacted with the photovoltaic cell through the nanofiber electrode, and the nanofiber electrode has a thin film structure; wherein a surface of one side of the thin film structure has a textured structure, and at least a portion of an internal reaction medium of the thin film electrochemical device is disposed on the textured surface to be in contact with the thin film structure; alternatively, the surface of one side of the thin film structure is provided with comb-shaped nanofibers integrally formed with the body of the thin film structure, and at least a part of the internal reaction medium of the thin film electrochemical device is filled in the gaps between the comb-shaped nanofibers on the surface of the thin film structure. The surface structure of the nanofiber electrode can promote contact conduction, increase the internal reaction area of the device and form an anchoring effect on an internal reaction medium.

Description

Integrated device comprising photovoltaic cell and thin film electrochemical device

Technical Field

The present application relates to the field of solar energy, and in particular to an integrated device comprising a photovoltaic cell and a thin film electrochemical device.

Background

The existing photovoltaic integrated device has more problems in practical industrial application. Unlike the common device integration of externally connected photovoltaic cells, the photovoltaic integrated device is an integrated device of photovoltaic cells and thin film devices, which is formed by integrating photovoltaic cells and thin film devices through interlayer electrical connection. The integrated device can reduce a large number of additional equipment and circuits, directly realizes the functional collection of solar energy collection, electric energy conversion and electric device application, and is a great direction of photovoltaic application.

However, the above-described integrated device requires a great deal of attention to the stability of the entire system, in particular the structural stability of the connection site of the photovoltaic cell with the thin-film electrochemical device. When the structure is unstable, the device connection at the interface may be unstable due to the change of external conditions such as climate, temperature, ultraviolet radiation and the like, and further the interlayer electrical connection between the photovoltaic cell and the thin film electrochemical device may be degraded, so that serious carrier recombination may be generated on the surface of the photovoltaic cell, the available effective current of the thin film electrochemical device is reduced, and the life industry of the device is adversely affected. In addition, the practical performance of the thin film electrochemical device is also reduced due to the thinning of the device, and how to ensure the performance of the thin film electrochemical device in the integrated device of the photovoltaic cell and the thin film electrochemical device is also a problem to be solved by the photovoltaic integrated device.

Disclosure of Invention

To the technical problem that exists among the prior art, this application provides an integrated device, the integrated device includes photovoltaic cell and film electrochemical device, film electrochemical device contains nanofiber electrode, nanofiber electrode surface has suede structure or comb structure, can strengthen contact surface and connection in the film electrochemical device, improves the reactivity of inside reaction medium, makes the system resistance decline, and electrochemical reaction's efficiency improves, can form anchor effect in order to improve inner structure's stability to contact structure simultaneously, is favorable to device structural stability and life's promotion.

The specific technical scheme of the application is as follows:

the application provides an integrated device, which comprises a laminated photovoltaic cell and a thin film electrochemical device, wherein the thin film electrochemical device comprises a nanofiber electrode, the thin film electrochemical device is in contact with the photovoltaic cell through the nanofiber electrode, and the nanofiber electrode has a thin film structure;

wherein a surface of one side of the thin film structure has a textured structure, and at least a portion of an internal reaction medium of the thin film electrochemical device is disposed on the textured surface to be in contact with the thin film structure; alternatively, the surface of one side of the thin film structure is provided with comb-shaped nanofibers integrally formed with the body of the thin film structure, and at least a part of the internal reaction medium of the thin film electrochemical device is filled in gaps among the comb-shaped nanofibers on the surface of the thin film structure; the other side surface of the thin film structure is in contact with the surface of the photovoltaic cell and forms interlayer electrical connection.

Preferably, for the integrated device described above, the surface of the other side of the thin film structure has a suede structure or the surface of the other side has comb-like nanofibers integrally formed with the thin film structure.

Preferably, for the integrated device, the thin film structure is a thin film structure formed by tightly stacking nanofibers, and the suede structure or the comb-shaped nanofibers are integrally formed by extending the nanofibers of the thin film structure.

Preferably, for the integrated device described above, wherein the aspect ratio of the individual fibers of the comb structure is > 100 and the diameter of the individual fibers is < 300nm.

Preferably, for the integrated device described above, the maximum dimension of the interlayer direction extension of the nanofiber electrode is 0.05-14 μm.

Preferably, for the integrated device described above, the material of the nanofiber electrode is PEDOT, PPy, PANi or P3HT.

Preferably, for the integrated device described above, the photovoltaic cell includes a light-transmitting layer, a first carrier-transporting functional layer, a photovoltaic absorber layer, and a second carrier-transporting functional layer in this order, and the second carrier-transporting functional layer is in contact with the surface of the other side of the thin film structure.

Or, for the integrated device, the photovoltaic cell includes a light-transmitting layer, a first carrier-transporting functional layer, a photovoltaic absorbing layer, a second carrier-transporting functional layer, and a conductive connecting layer in sequence, the thin film structure is laminated on the conductive connecting layer, and the surface of the other side of the thin film structure is connected with the conductive connecting layer.

Preferably, for the integrated device described above, the interlayer conductivity of the conductive connection layer is > 10S/cm.

Preferably, for the integrated device described above, the conductivity in the in-layer extending direction of the conductive connection layer is 50 times or more of the interlayer conductivity.

ADVANTAGEOUS EFFECTS OF INVENTION

For the integrated device described herein, the nanofiber electrode has a thin film structure due to its presence; wherein a surface of one side of the thin film structure has a textured structure, and at least a portion of an internal reaction medium of the thin film electrochemical device is disposed on the textured surface to be in contact with the thin film structure; alternatively, the surface of one side of the thin film structure is provided with comb-shaped nanofibers integrally formed with the body of the thin film structure, and at least a part of the internal reaction medium of the thin film electrochemical device is filled in gaps among the comb-shaped nanofibers on the surface of the thin film structure; the other side surface of the thin film structure is in contact with the surface of the photovoltaic cell and forms interlayer electrical connection. Therefore, the suede structure or the comb-shaped nanofiber structure of the nanofiber electrode can greatly enhance the contact reaction area of the electrode and the internal reaction medium, has an anchoring effect on the internal reaction medium, and can fully supply the current of the photovoltaic cell to the internal reaction medium directly on the basis of ensuring the stability of the physical structure of the photovoltaic cell so as to promote the internal reaction of the thin film electrochemical device. On the basis, the application further explores the proper comb structure size of the nanofiber electrode, so that the anchoring effect on an internal reaction medium can be further improved, and the conductive contact area and depth of the nanofiber electrode can be enhanced. On the other hand, the nanofiber electrode is connected with the other side surface of the photovoltaic cell and is also arranged to be of a suede of a thin film structure or a comb-shaped structure integrally connected with the nanofiber electrode, carrier export of the photovoltaic cell can be promoted, series resistance of the thin film electrochemical device transmitted to the stacking direction is reduced, an anchoring effect is generated on the carrier transmission layer structure of the photovoltaic cell, physical stability of the photovoltaic cell is improved, recombination of carriers possibly existing at an interface is reduced, and stability and service life of the photovoltaic cell are improved. In addition, the conductive connecting layer is used for reducing surface carrier recombination possibly existing in the direct connection of the nanofiber electrode, and the conductive connecting layer with interlayer conductivity more than 10S/cm or the conductivity of the conductive connecting layer in the in-layer extending direction being more than 50 times of the interlayer conductivity is selected for the current leading-out surface of the photovoltaic cell, so that the transverse conduction between the nanofiber electrode and the dark current recombination between the nanofiber electrode can be ensured in the process of connecting the nanofiber electrode.

Drawings

Fig. 1 is a schematic structural view of a nanofiber electrode, wherein a is a schematic structural view of a film, and c and d are schematic composite structures of a film structure and a comb structure.

Fig. 2 is a schematic diagram of a photovoltaic cell-supercapacitor integrated device according to embodiments of the present application.

Fig. 3A, 3B, 3D, 3E are schematic diagrams of scanning electron microscope of a complex of a thin film structure and a comb structure.

Fig. 3C is a schematic view of a scanning electron microscope having a textured film structure on the surface.

Fig. 4A is a schematic diagram of a photovoltaic cell-supercapacitor integrated device according to embodiments of the present application.

Fig. 4B is a schematic diagram of another photovoltaic cell-supercapacitor integrated device according to embodiments of the present application.

Fig. 5 is a schematic diagram of a scanning electron microscope of a single fiber of comb structure.

Fig. 6 is a schematic diagram of another photovoltaic cell-supercapacitor integrated device according to embodiments of the present application.

Fig. 7 is a schematic diagram of another photovoltaic cell-supercapacitor integrated device according to embodiments of the present application.

FIG. 8 is a schematic diagram of electrochromic phenomena, wherein A is a cyclic voltammogram, B is that the electrochromic electrode turns pale blue at 1.4V, and C is that the electrochromic electrode turns dark purple at-1.8V.

Fig. 9 is a schematic structural view of an electrochromic device, wherein a in fig. 9 is a schematic view of an electrochromic device including a second electrode, and b in fig. 9 is a schematic view of an electrochromic device not including a second electrode.

Fig. 10 is a schematic diagram of a photovoltaic cell-electrochromic device integrated device according to an embodiment of the present application.

Fig. 11 is a schematic view of another photovoltaic cell-electrochromic device integrated device of an embodiment of this application.

Fig. 12 is a schematic view of a photovoltaic cell-chemical reaction apparatus integrated device according to an embodiment of the present application.

FIG. 13 is a schematic view of the structure of a membrane electrode assembly cell.

FIG. 14 is a schematic view showing the structure of an electrolytic cell.

FIG. 15 is a schematic view of the structure of a carbon dioxide reduction cell.

Fig. 16 is a schematic diagram of a nanofiber electrode doubling as an electrode layer.

Fig. 17 is a schematic diagram of a photovoltaic cell-chemical reaction apparatus integrated device with different external circuits in an embodiment of this application.

Fig. 18 is a schematic diagram of another integrated device of a photovoltaic cell-chemical reaction apparatus with a different external circuit in an embodiment of this application.

Fig. 19 is a schematic diagram of another integrated device of a photovoltaic cell-chemical reaction apparatus with a different external circuit in an embodiment of this application.

Fig. 20 is a schematic view of a photovoltaic cell-chemical reaction apparatus integrated device in an embodiment of this application.

Fig. 21 is a schematic view of another photovoltaic cell-chemical reaction apparatus integrated device in an embodiment of this application.

Fig. 22 is a schematic view of another photovoltaic cell-chemical reaction apparatus integrated device in an embodiment of this application.

Fig. 23 is a schematic view of another photovoltaic cell-chemical reaction apparatus integrated device in an embodiment of this application.

Fig. 24 is a schematic view of another photovoltaic cell-chemical reaction apparatus integrated device in an embodiment of this application.

Fig. 25 is a schematic structural view of a photovoltaic cell.

Wherein 1-light-transmitting layers, 2 and 102-first carrier transport functional layers or first carrier transport layers, 3 and 103-photovoltaic cell absorption layers, 41 and 104-second carrier transport functional layers or second carrier transport layers, 5-electrolyte layers, 61-first electrode layers, 7-electrodes, 8-thin film structures, 42 and 200-nanofiber electrodes, 301-second electrodes, 305-first transparent electrodes, 302-electrochromic electrode layers, electrolyte layers of 303-electrochromic reaction devices, 304-ion storage layers, 100-photovoltaic cells, 101-first light-transmitting electrodes, 105-second light-transmitting electrodes, 300-chemical reaction devices, 400-external circuits, 310-membrane electrode type electrolytic cells, 311-first electrode layers, 312-first gas diffusion layer, 313-first catalyst layer, 314-ion exchange membrane, 315-second catalyst layer, 316-second gas diffusion layer, 317-second electrode layer, 318-membrane electrode type cell outlet, 319-membrane electrode type cell inlet, 320-cell type cell, 321-third electrode layer, 322-third catalyst layer, 323-cell, 324-membrane, 325-cell inlet, 327-fourth electrode layer 327, 326-fourth catalyst layer, 328-cell outlet, 329-carbon dioxide inlet, 200& 302-nanofiber electrode doubling as electrochromic electrode layer and second electrode, 401-first wire, 402-second wire, 403-third wire, 404-fourth wire, 405-fifth wire, 10-first external circuit, 11-second external circuit, 12-first switch circuit, 13-second switch circuit, 200& 311-nanofiber electrode doubling as first electrode layer

Detailed Description

The present application is described in detail below with reference to the embodiments depicted in the drawings, wherein like numerals represent like features throughout the several views. While specific embodiments of the present application are shown in the drawings, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.

It should be noted that certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will understand that a person may refer to the same component by different names. The specification and claims do not identify differences in terms of components, but rather differences in terms of the functionality of the components. As referred to throughout the specification and claims, the terms "include" or "comprising" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, as the description proceeds. The scope of the present application is defined by the appended claims.

The prior art electrode for electrochemical reaction has a mode of improving the reaction efficiency mainly comprising improving the conductivity (reducing the resistance) of the electrode and the specific surface area (increasing the contact area) of the electrode, and according to a conductivity formula sigma=nqμ, wherein sigma is the conductivity, n is the carrier concentration, q is the carrier charge, and μ is the carrier mobility. Wherein q is a constant, n depends on doping concentration, mu is related to the morphological characteristics of the material, and the migration rate of carriers in the crystal structure is 0.1-20cm ² /Vs，Whereas the migration rate in amorphous structures<0.1-20cm ² Vs, thus obtaining a heavily doped high crystallinity material is critical to obtaining a high conductivity material.

Based on this, the present application provides an integrated device comprising a stacked photovoltaic cell and a thin film electrochemical device containing a nanofiber electrode, the thin film electrochemical device being in contact with the photovoltaic cell through the nanofiber electrode, the nanofiber electrode having a thin film structure; wherein a surface of one side of the thin film structure has a textured structure, and at least a portion of an internal reaction medium of the thin film electrochemical device is disposed on the textured surface to be in contact with the thin film structure; alternatively, the surface of one side of the thin film structure is provided with comb-shaped nanofibers integrally formed with the body of the thin film structure, and at least a part of the internal reaction medium of the thin film electrochemical device is filled in gaps among the comb-shaped nanofibers on the surface of the thin film structure; the other side surface of the thin film structure is in contact with the surface of the photovoltaic cell and forms interlayer electrical connection.

The thin film electrochemical device refers to a thin film device requiring an internal reaction medium to perform an electrochemical reaction, for example, a chemical reaction device which can perform a chemical reaction or an electrochromic reaction device which performs an electrochromic reaction, or a supercapacitor for storing electric energy, etc.

The nanofiber electrode may be a film structure having a textured structure on one surface, as shown by a in fig. 1, or may be a composite of a film structure and a comb-like nanofiber, which is formed integrally with the body of the film structure, on one surface of the film structure, as shown by b and c in fig. 1. In some embodiments, the photovoltaic cell further comprises a conductive connection layer. The conductive connection layer is in contact with the nanofiber electrode and is connected with the thin film electrochemical device through the nanofiber electrode; preferably, the interlayer conductivity of the conductive connection layer is more than 10S/cm or the conductivity of the conductive connection layer in the in-layer extending direction is more than 50 times of the interlayer conductivity.

In this application, the interlayer conductivity refers to the conductivity in the lamination direction of the photovoltaic cell and the integrated device.

In the present application, the material of the conductive connection layer is not limited as long as it can perform a corresponding function, for example, the conductive connection layer may be an inorganic substance, an organic substance, a carbon material, and/or a metal material, and preferably, the inorganic substance may be a metal oxide (such as zinc oxide, titanium oxide, tin oxide, tunneling silicon oxide, etc.); the organic matter can be small organic molecules (such as PCBM) or organic polymers such as the same material as the nanofiber electrode;

The carbon material can be graphene, fullerene, graphite and other carbon materials;

the metal material may be copper, aluminum, or the like.

The conductive connection layer can enhance current export of the photovoltaic cell, further promote current import to the nanofiber electrode in the application, and in certain structures can reduce cross-sectional recombination of the photovoltaic cell, for example, a common TCO layer or an electron tunneling composite layer is used as the conductive connection layer, has strong interlayer electron conduction capability, and can reduce carrier recombination. In addition, a conductive film layer formed of a metal material or sintered with a metal paste may be used to promote conductive connection between layers. However, the conductive connection layer in the application is not limited to the above materials or structures, and the interlayer conductivity of the conductive connection layer is more than 10S/cm, so that the conductive requirement of the integrated device can be met. On the other hand, the conductivity of the conductive connecting layer in the in-layer extending direction is more than 50 times of the interlayer conductivity, so that better interlayer conductivity can be obtained, and the surface carrier recombination of the photovoltaic cell caused by in-layer conduction is prevented to a certain extent.

In the present application, for the nanofiber electrode formed by the film structure alone, at least one of the two side surfaces has a suede structure (as shown in fig. 3C). Because the film structure is formed by densely stacking nanofibers, the surface is easy to form part of protruding structures with extending and overlapping nanofibers, and the protruding structures have irregular distribution, so that concave-convex rough suede is formed on the surface of the film structure. Firstly, there is a textured surface limited to the surface of the inner side of the thin film electrochemical device, and secondly, a textured structure can be formed at the interface electrically contacting the surface of the photovoltaic cell to make better electrical contact with the carrier conducting material of the photovoltaic cell. The suede structure is a textured surface similar to knitting or a defected surface with widely distributed undulations, hollows and concaves, which can be formed on the surface of a film when the fiber is used for compacting the film structure, and has a certain degree of roughness relative to a defect-free crystal face of a normal solid crystal, so that the contact area of a surface filling material can be enhanced, particularly the reaction area of a filled internal reaction medium is increased, an anchoring effect is formed on the surface filling material, and the structural stability is promoted.

In addition, as shown in fig. 4B, the nanofiber electrode formed by integrating the membrane structure with the comb-shaped nanofibers is similar, and at least one of the two side surfaces of the nanofiber electrode is provided with the comb-shaped nanofibers, firstly, the comb-shaped nanofibers are provided on the inner side surface of the thin film electrochemical device, and secondly, the comb-shaped nanofibers can be formed at the interface electrically contacted with the surface of the photovoltaic cell, so as to make better electrical contact with the carrier conducting material of the photovoltaic cell. The comb-shaped nano-fiber formed on the film structure has the effect similar to the suede structure, and the comb-shaped nano-fiber can also enhance the contact area of the surface filling material, particularly increase the reaction area of the filled internal reaction medium, form an anchoring effect on the surface filling material and promote the structural stability. Moreover, compared with the contact of the suede structure, the comb-shaped nanofiber structure can further increase the contact area and improve the anchoring effect.

In some embodiments, the nanofiber structure electrode is comprised of a film structure having a thickness of 0.05-4 μm and a comb-like nanofiber structure having a length of 0.5-10 μm (as shown in fig. 3A, 3B, 3D, 3E). In this application, the thin film structure must be greater than 50nm to facilitate blocking of the reaction medium within the thin film electrochemical device while improving the stability of the structure, while a thickness below 4 μm may moderately reduce the series resistance, an excessively thick thin film structure is not necessary for the device, and the above thickness range is also applicable to nanofiber electrodes formed by a single layer of a textured film (as shown in fig. 3C), and the size of the textured structure below 0.5 μm does not change particularly greatly the largest dimension extending in the interlayer direction of the thin film relative to the nanofiber structure. In addition, the maximum dimension of the comb-like nanofiber structure extending in the interlayer direction is 0.5-10 μm. The structure of the comb-shaped nano fiber is at least a short comb-shaped fiber structure (shown in figure 3D) with the size more than 0.5 mu m, wherein the height of the short comb-shaped fiber structure extends from the thin film structure substrate and is larger than that of the suede structure, and the short comb-shaped fiber structure can further match the requirements of further expanding the reaction contact surface and stabilizing the internal structure of the partially integrated thin film electrochemical device on the basis of the suede structure. However, in the case of a long comb-like fiber structure, the ends of the fibers are easily bent (as shown in fig. 3E), and the bent comb-like fibers are stacked to form a comb-like fiber structure having numerous voids, but when the maximum dimension length extending in the interlaminar direction of the comb-like fiber structure is more than 10 μm, the bottom voids of the illustrated multi-void comb-like fiber structure will be difficult to be sufficiently filled with a medium, resulting in deterioration of the conductive contact of a partial region of the nanofiber electrode and also deterioration of structural stability. The maximum dimension of the comb-shaped nanofiber structure extending in the interlayer direction is 0.5-10 μm. Thus, the maximum dimension of the nanofiber electrode extending in the interlayer direction may be 0.05-14 μm.

In the present application, the method for producing the film structure is not limited at all, and it can be produced by a method conventional in the art, for example, the following method can be adopted:

for example, take PEDOT: depositing iron oxide (Fe) with thickness of 10-100nm on the second carrier transport functional layer or the conductive connecting layer ₂ O ₃ ) The layer uses a weather polymerization method and an acid-resistant and organic solvent-resistant reactor, the reaction temperature ranges from 110 ℃ to 150 ℃, and the reaction time ranges from 0.5 to 1h; the glass reactor contains the reactants: 5-10. Mu.L of concentrated hydrochloric acid and 100-200. Mu. L1.56M of a hole material (EDOT) to polymerize monomers and organic solutions (benzene, chlorobenzene and toluene). Flushing the empty cells with 6-12M hydrochloric acidFeCl in hole transport layer ₂ Impurity to obtain pure PEDOT film.

In the present application, the method for preparing the composite of the thin film structure and the comb structure is not limited at all, and for example, the thin film structure and the comb structure prepared may be combined by a conventional method to obtain the composite. The preparation method comprises the following steps: taking PEDOT as an example, it is:

depositing a second carrier transport layer or a conductive connection layer with a thickness of>200nm iron oxide (Fe) ₂ O ₃ ) The layer uses a weather polymerization method and an acid-resistant and organic solvent-resistant reactor, the reaction temperature ranges from 120 ℃ to 130 ℃, and the reaction time ranges from 1 hour to 2 hours; the glass reactor contains the reactants: 10-20. Mu.L of concentrated hydrochloric acid and 100-500. Mu. L1.56M of a hole material (EDOT) to polymerize monomers and organic solutions (benzene, chlorobenzene and toluene). Rinsing off FeCl in the hole transport layer using 6-12M hydrochloric acid ₂ Impurity to obtain pure PEDOT film and nanometer fiber composite.

In some embodiments, the aspect ratio of the individual fibers of the comb structure is >100 and the diameter of the individual fibers is < 300nm. In this application, the aspect ratio refers to the ratio of the diameter of an individual fiber to the length of the fiber.

The present application compares the electrical conductivities of the different electrodes, as shown in fig. 1, wherein fig. 1a is a thin film electrode, the electrical conductivity of which is 500S/cm, fig. 1b is a composite of a thin film structure and a comb structure (fiber diameter l1=300 nm, fiber length l2=20 μm) with an aspect ratio of 100, the electrical conductivity of which is 1500S/cm, and fig. 1c is a composite of a thin film structure and a comb structure (fiber diameter l3=100 nm, fiber length l4=100 μm) with an aspect ratio of 1000, the electrical conductivity of which is 3500S/cm, measured by methods conventional in the art.

Therefore, the aspect ratio and the nanofiber diameter of the nanofibers of the nanofiber electrode are limited to the above ranges, and the conductivity S >1000S/cm can be achieved, so that the reaction efficiency can be improved.

In addition, the aspect ratio of the nanofiber electrode is limited in the range, the specific surface, namely the chemical reaction contact surface or the activation area, is greatly increased, the conductivity is greatly increased, the system resistance is reduced, and the efficiency and the yield of the electrochemical reaction are improved.

In some embodiments, the material of the nanofiber electrode is PEDOT (poly 3, 4-ethylenedioxythiophene), PPy (polypyrrole), PANi (polyaniline) or P3HT (poly 3-hexylthiophene).

In some embodiments, the thin film electrochemical device includes an electrode, a first electrode layer in contact with the electrode, a nanofiber electrode, and an electrolyte disposed between the first electrode layer and the nanofiber electrode, the electrolyte disposed between the first electrode layer and the nanofiber electrode having a thickness of less than 10 μm.

The thickness of the electrolyte is controlled within the range, so that the device cannot be short-circuited while the ion diffusion distance is short. In addition, it is to prevent a short circuit of the device caused by the contact of the first electrode layer and the nanofiber electrode.

In some embodiments, the first electrode layer is a nanofiber electrode, and the nanofiber electrode is a thin film structure with a suede or a composite of a thin film structure and a comb structure, preferably, for a thin film structure, the method may be used to prepare: take PEDOT as an example:

depositing iron oxide (Fe) with a thickness of 10-100nm on the electrode ₂ O ₃ ) The layer uses a weather polymerization method and an acid-resistant and organic solvent-resistant reactor, the reaction temperature ranges from 110 ℃ to 150 ℃, and the reaction time ranges from 0.5 to 1h; the glass reactor contains the reactants: 5-10. Mu.L of concentrated hydrochloric acid and 100-200. Mu. L1.56M of a hole material (EDOT) to polymerize monomers and organic solutions (benzene, chlorobenzene and toluene). Rinsing off FeCl in the hole transport layer using 6-12M hydrochloric acid ₂ Impurity to obtain pure PEDOT film.

In this application, as to the preparation method of the composite of the thin film structure and the comb structure, it can be prepared according to the above-described method.

In some embodiments, the first electrode layer is an ion storage layer. In some embodiments, the thin film electrochemical device further comprises an electrochromic reaction electrode layer, with an electrolyte layer disposed between the first electrode layer and the electrochromic electrode layer. In some embodiments, the thin film electrochemical device further comprises a second electrode in contact with the nanofiber electrode; preferably, the nanofiber electrode doubles as the second electrode. In some embodiments, the nanofiber electrode serves as both a second electrode and an electrochromic electrode.

In some embodiments, the thin film electrochemical device is a thin film device or a chemical reaction apparatus, preferably the thin film device is a supercapacitor or an electrochromic reaction apparatus;

preferably, the chemical reaction device is a hydrogen production electrolytic cell or a carbon dioxide reduction electrolytic cell, and further preferably, the hydrogen production electrolytic cell is a membrane electrode type electrolytic cell or an electrolytic tank type electrolytic cell.

Fig. 2 is an integrated device according to an embodiment of the present application, where the thin film device is a supercapacitor (not shown in the figure), and the integrated device includes a photovoltaic cell (not shown in the figure) and a supercapacitor (not shown in the figure), and the supercapacitor includes an electrode 7, a first electrode layer 61 in contact with the electrode 7, a nanofiber electrode 42, and an electrolyte 5 disposed between the first electrode layer 61 and the nanofiber electrode 42, where the first electrode layer 61 is a nanofiber electrode.

In some embodiments, the photovoltaic cell further comprises a conductive connection layer 4-1-2, the conductive connection layer 4-1-2 being in contact with the nanofiber electrode 42 and with a second carrier transport function layer 41 of the photovoltaic cell, such as a photovoltaic cell.

The nanofiber electrodes 42 and 61 may be of a thin film structure, as shown by a in fig. 1, or a composite of a thin film structure and a comb structure, as shown by b and c in fig. 1.

Wherein, the scanning electron microscope image of the film structure is shown in fig. 3C, and the scanning electron microscope image of the composite of the film structure and the comb structure is shown in fig. 3A, 3B, 3D and 3E.

The electrode 7 is not limited in any way as long as it can perform its function, for example, the electrode 7 may be a metal electrode or an inorganic transparent electrode, and in order to reduce the contact resistance between the electrode and the first electrode, it is preferable that the electrode 7 uses a material such as gold (Au), silver (Ag), platinum (Pt), fluorine doped tin oxide (FTO) or the like having a small resistance.

For nanofiber electrodes 61 and 42, they were prepared by the following method:

depositing an oxidizing agent on the electrode of the photovoltaic cell or on the conductive connection layer or on the electrode and electrode 7 of the photovoltaic cell or on the conductive connection layer and electrode 7 near the thin film device;

a solution containing a strongly polar acid and a monomer is contacted with the oxidizing agent to react to obtain a nanofiber structure.

The monomers may be, for example, EDOT (3, 4-ethylenedioxythiophene), 3HT (3-hexylthiophene), py (pyrrole), ani (aniline).

The oxidizing agent is an oxidizing agent having an oxidation potential of 0.7 to 1V, and the oxidizing agent having an oxidation potential of 0.7 to 1V is not limited in any way as long as the corresponding function can be achieved, and for example, the oxidizing agent may be a substance containing iron oxide, silver ion (Ag ⁺ ) Chlorite (OCl) ₂ ^- ) Hypochlorite (OCl) ^- ) Or hypobromous acid (OBr) ^- )。

The thickness of the deposited oxidizing agent is not subject to any limitation as long as it can be operated to achieve the effect.

The highly polar acid is a substance for dissolving the above-mentioned oxidizing agent, for example, a substance containing iron oxide, and may be, for example, concentrated hydrochloric acid, concentrated nitric acid, formic acid, acetic acid, or the like.

Preferably, the volume of the strongly polar acid is 10-40. Mu.L, for example, the volume of the strongly polar acid is 10. Mu.L, 15. Mu.L, 20. Mu.L, 25. Mu.L, 30. Mu.L, 35. Mu.L, 40. Mu.L, or any range therebetween.

Preferably, the volume of the monomer is 100-200. Mu.L, for example, the monomer may be 100. Mu.L, 110. Mu.L, 120. Mu.L, 130. Mu.L, 140. Mu.L, 150. Mu.L, 160. Mu.L, 170. Mu.L, 180. Mu.L, 190. Mu.L, 200. Mu.L, or any range therebetween.

Preferably, the concentration of the monomer is 0.8-2M.

For example, the concentration of the monomer may be 0.8M, 0.9M, 1.0M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, 1.6M, 1.7M, 1.8M, 1.9M, 2.0M, or any range therebetween.

Preferably, the solution containing the strong acid and the monomer is an organic solution containing the strong acid and the monomer, and may be, for example, a benzene solution, a chlorobenzene solution or a toluene solution.

Preferably, the reaction temperature is 110-150 ℃ and the reaction time is 1-2h.

In one embodiment, after contacting the solution containing the strong acid and the monomer with the oxidizing agent to effect the reaction, a step of washing the impurities of the nanofiber structure with a mineral acid is further included.

For example, rinsing with hydrochloric acid, preferably 6-12M hydrochloric acid, to obtain a pure nanofiber structure electrode.

The electrolyte 5 may be a quasi-solid (gel) electrolyte, which may be used in 3 general categories: aqueous phase (H) ₂ SO ₄ /HCl/Na ₂ SO ₄ /NaCl/LiClO ₄ -PVA-H ₂ O), organic phase (Na ₂ SO ₄ /NaCl/LiClO ₄ PVA-acetonitrile, propylene carbonate) and an ionic phase (e.g. 1-butyl-3-methylimidazolium tetrafluoroborate-polyvinylidene difluoride (BMIBF) ₄ -PVDF)) gel. Although the fluidity of the electrolyte is limited by the polymer molecular chains in the solute, it still has some fluidity as the temperature increases. The nano structure of the nanofiber electrode can effectively increase the flow resistance of the gel electrolyte, so that the stability of the gel electrolyte is increased.

In some embodiments, the individual fibers of the comb structure have diameters of 100-1000nm and the nanofiber structure has a roughened surface (electron microscopy image (JEOL 7001LVF FE-SEM) as shown in fig. 5.

The surface roughness suede or comb-shaped contact structure formed on the surface of the film structure can enable the electrolyte 5 to be in contact with the nanofiber structure more fully for conduction, so that the electrode activity in the integrated supercapacitor is further improved; at the same time, the larger surface area may enhance the charge capacity of the supercapacitor.

For single fibers with comb structures, the thinner the diameter of the single fiber is, the larger the specific surface area of the single fiber is, and the more ions can be adsorbed, so that the more energy can be stored.

For example, the individual fibers of the comb structure may have diameters of 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, or any range therebetween.

In some embodiments, as shown in fig. 2, the photovoltaic cell includes a light-transmitting layer 1, a first carrier transport functional layer 2, a photovoltaic cell absorber layer 3, a second carrier transport functional layer 41, and conductive connection layers 4-1-2 in that order.

Preferably, the functional layer refers to one or more layers of structure that may include a passivation layer, a transmission layer, and/or an anti-reflection layer.

The transport layer is used for transporting carriers and may be, for example, a carrier transport layer.

The anti-reflection layer is a conventional structure in the art, and may comprise one or more layers of common anti-reflection structures such as silicon nitride, silicon oxide, silicon oxynitride, aluminum nitride, titanium nitride, aluminum oxide, titanium oxide, and the like, and a part of the anti-reflection layer has a field passivation or chemical passivation function.

Taking the crystalline silicon battery absorption layer as an example, the passivation layer can be doped amorphous silicon, doped polysilicon, aluminum-doped zinc oxide, indium tin oxide and the like, and in addition, a wide-band gap transmission material with low free carrier concentration and high carrier mobility, such as zinc oxide, tin oxide, nickel oxide, titanium nitride, molybdenum oxide and the like, is selected for weakening intrinsic absorption caused by narrow material band gap of the front surface and parasitic absorption caused by free carriers.

For example, when the photovoltaic cell is a silicon crystal cell, the first carrier transport functional layer 2 is a portion of a silicon substrate that implements carrier collection or a portion of a further doped silicon substrate on the surface of the silicon crystal cell substrate, as well as any additional functional layers that implement carrier transport, such as additional tunneling transport layers, transparent conductive layers, and doped or intrinsic amorphous or polycrystalline silicon layers. For example, in a conventional Topcon cell, the first carrier transport functional layer 2 may also be a tunneling composite structure with carrier transport; in a conventional HIT cell, the first carrier transport functional layer 2 may also be a doped amorphous silicon film layer or a transparent conductive material film layer therein. In summary, the film layers capable of realizing the carrier transport function in the prior art belong to the film layers capable of being adopted by the first carrier transport function layer 2. When the first carrier transport functional layer 2 is a transparent conductive film layer, the light-transmitting layer 1 on the surface may be the same film layer as the first carrier transport functional layer 2, or may be a further applied antireflection film layer, such as a silicon nitride film layer.

When the photovoltaic cell is a perovskite cell, the first carrier transport functional layer 2 is a first carrier transport layer, and the second carrier transport functional layer is a second carrier transport layer, as shown in fig. 2.

In the case where the first carrier transport functional layer 2 is the first carrier transport layer 2, it may be an Electron Transport Layer (ETL) or a Hole Transport Layer (HTL).

Here, as for the light-transmitting layer 1, the substance used in the present application is not limited at all as long as it achieves the corresponding function, and for example, indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), or ZnO may be used as the light-transmitting layer 1.

The photovoltaic cell absorber layer 3 is not limited in any way so long as it can perform the corresponding function, and for example, an absorber layer material having an absorption spectrum of 300nm to 1200nm, such as a perovskite absorber layer material, an inorganic absorber layer material, or an organic absorber layer material, may be used, and the perovskite absorber layer material may be MAPbCl ₃ 、MAPbCl _2.4 Br _0.6 Or MAPbBr ₃ The method comprises the steps of carrying out a first treatment on the surface of the The inorganic absorption layer material can be Si, selenium sulfide (CdS), gallium phosphide (GaP) or gallium arsenide (GaAs); the organic absorption layer material is PTB7/PC ₇₀ BM, etc.

In some embodiments, the present application provides a photovoltaic cell of another specific embodiment, as shown in fig. 25, which includes, in order, a first light-transmitting electrode 101, a first carrier-transporting functional layer 102, a photovoltaic absorber layer 103, a second carrier-transporting functional layer 104, and a second light-transmitting electrode 105, where the first carrier-transporting functional layer and the second carrier-transporting functional layer are defined as the photovoltaic cell described above. The material of the first transparent electrode 101 may be Indium Tin Oxide (ITO) or fluorine doped tin oxide (FTO); the second transparent electrode 105 is preferably metal, and may be made of silicon material, aluminum paste sintered, TCO material, or the like.

In some embodiments, when the photovoltaic cell contains a conductive connection layer, the conductive connection layer is in contact with the second light-transmitting electrode 105.

The use temperature of the integrated device is less than 70 ℃ (the operating temperature range of the photovoltaic cell), and the temperature range meets the stable operating temperature of the electrode material and the electrolyte.

The nanofiber structure electrode is used, the specific surface, namely the chemical reaction contact area or the activation area, of the nanofiber structure electrode can be greatly increased, and the nanofiber structure electrode has a large aspect ratio, so that the conductivity is greatly increased, the movement rate of ions in the electrolyte of the supercapacitor is accelerated, and the power density and the rapid cycle efficiency of the supercapacitor are further increased.

In addition, for the nanofiber electrode, when the preparation is performed in the conventional method, for example, taking PEDOT as an example, it is difficult for the conventional PEDOT nanofiber synthesis method to synthesize a uniform and dense nanofiber electrode on the electrode plate, and one important effect of the present application is to improve the light absorption performance of the right electrode layer 61 by replacing the optical film with a film having nanofibers.

The application provides a preparation method of the integrated device, which comprises the following steps:

preparing a photovoltaic cell including the second carrier transport functional layer 41 or the second carrier transport functional layer 41 and the conductive connecting layer 4-1-2;

Preparing a nanofiber electrode 42 on the second carrier transport functional layer 41 or on the conductive connection layer 4-1-2;

a first electrode layer 61 is prepared on the electrode 7, and a photovoltaic cell is connected to the first electrode layer 61 using the electrolyte 5 such that the nanofiber electrode 42, the electrolyte 5, the first electrode layer 61 and the electrode 7 form a supercapacitor and an integrated device, the first electrode layer 61 being a nanofiber electrode.

As for the method of producing the photovoltaic cell, which is a production method commonly used in the art, the present application does not impose any limitation on it.

As shown in fig. 4A, the present application provides an integrated device according to an embodiment, where the integrated device includes a photovoltaic cell (not shown in the figure) and a supercapacitor (not shown in the figure), where the supercapacitor includes an electrode 7, a first electrode layer 6 in contact with the electrode, a nanofiber electrode 42, and an electrolyte 5 disposed between the first electrode layer 61 and the nanofiber electrode 42, where the nanofiber electrode 42 is a composite of a thin film structure and a comb structure, and where the first electrode layer 61 is a nanofiber electrode, and where the nanofiber electrode is a thin film structure.

The method for manufacturing the integrated device is the same as the method for manufacturing the integrated device.

Another photovoltaic cell-supercapacitor integrated device is provided, as shown in fig. 6, the integrated device including a photovoltaic cell (not shown in the figure) and a supercapacitor (not shown in the figure), the supercapacitor including an electrode 7, a first electrode layer 6 in contact with the electrode, a nanofiber electrode 42, and an electrolyte 5 disposed between the first electrode layer 6 and the nanofiber electrode 42, the first electrode layer 6 being a nanofiber electrode, the nanofiber electrode being a composite of a thin film structure and a comb structure.

For the electrode 7, the first electrode layer 6 and the electrolyte 5, see the description above.

For the second carrier transport functional layer 41, the material may be a polymer, a carbon material or a transition metal oxide, wherein the polymer is P3HT or PCBM, the carbon material is graphene oxide, and the transition metal oxide is nickel oxide, molybdenum oxide, tungsten oxide or vanadium oxide.

In some embodiments, the photovoltaic cell includes, in order, a light-transmitting layer 1, a first carrier transport functional layer 2, a photovoltaic cell absorber layer 3, and a second carrier transport functional layer 41.

When the photovoltaic cell is a perovskite cell and the absorption layer 3 is a perovskite absorption layer, the perovskite absorption layer needs to be sealed and then the nanofiber electrode is prepared, so that the perovskite absorption layer is prevented from being corroded in the process of preparing the nanofiber electrode layer (gas phase synthesis process).

In another embodiment of the present application, as shown in fig. 4B, unlike the structure shown in fig. 4A, the other side surface of the thin film structure of the present application is in contact with the surface of the photovoltaic cell and forms an interlayer electrical connection, and the other side surface of the thin film structure also has a suede structure or the other side surface has comb-shaped nanofibers integrally formed with the thin film structure. Taking the PEDOT nanofiber electrode as an example, taking the structure of fig. 4A as a basis, the experimental procedure of nanofiber or film nanofiber composite was repeated on one side of the film plane at 42, resulting in the structure shown in fig. 4B with suede or nanofiber on both sides. Or a substrate with concave-convex suede can be used for growing the nanofiber electrode, so that the surface side and the back side of the nanofiber electrode have corresponding suede structures.

Another integrated device is provided, as shown in fig. 7, and the integrated device includes a photovoltaic cell (not shown in the figure) and a supercapacitor (not shown in the figure), where the supercapacitor includes an electrode 7, a first electrode layer 6 in contact with the electrode, a nanofiber electrode 42, and an electrolyte 5 disposed between the first electrode layer 6 and the nanofiber electrode 42, where the first electrode layer 6 is a nanofiber electrode, where the nanofiber electrode is a composite of a thin film structure and a comb structure, and where the nanofiber electrode 42 is a thin film structure.

In some embodiments, when the thin film device is an electrochromic device, the electrode is a first transparent electrode. In some embodiments, the first electrode layer is an ion storage layer. In some embodiments, the electrochromic device further comprises an electrochromic electrode layer, with an electrolyte layer disposed between the first electrode layer and the electrochromic electrode layer. In some embodiments, the thin film device further comprises a second electrode. In some embodiments, the nanofiber electrode doubles as the second electrode. In some embodiments, the nanofiber electrode serves as both a second electrode and an electrochromic electrode. In some embodiments, the nanofiber electrode has a length of 50-500nm, preferably 50-100nm.

The electrochromic refers to the phenomenon that the electrode material is subjected to stable and reversible color change under the action of an external electric field, and the electrode material is expressed as reversible change of color and transparency in appearance. At the microscopic level, the mechanism of color change is that the electrode material is subjected to stable and reversible oxidation-reduction reaction, and the energy level of the material is changed in the reaction process, so that the color change is represented. Wherein the electrochromic rate is limited by stable and reversible oxidation-reduction reaction rate, and the resistance of the electrode material participating in the reaction is one of determining factors, the reduction of the resistance can effectively increase the reaction rate, so as to accelerate the discoloration, and the electrochromic phenomenon is shown in fig. 8 (the electrode is PEDOT), wherein the graph A is a cyclic voltammogram schematic diagram, and peaks appearing at positive and negative voltages respectively represent oxidation reaction and reduction reaction, and indicate that the PEDOT electrode can stably circulate in the voltage range of +1.4V and-1.8V; panels B and C show the color change of the PEDOT electrode at 1.4V and-1.8V, where panel B is pale blue for the PEDOT electrode at a voltage of 1.4V and panel C is dark purple for the PEDOT electrode at a voltage of-1.8V.

In some embodiments, the material of the ion storage layer may be a metal oxide, such as nickel oxide (NiO), iron oxide (Fe ₂ O ₃ ) Cobalt oxide (Co) ₃ O ₄ ) Etc.; the composite material may be, for example, nickel oxide/reduced graphene oxide (NiO/rGO).

In some embodiments, as shown in fig. 9a, the electrochromic device includes, in order, a nanofiber electrode (not shown in the figure), a second electrode layer 301, an electrochromic electrode layer 302, an electrolyte layer 303, an ion storage layer 304, and a first transparent electrode layer 305, the nanofiber electrode being disposed between a photovoltaic cell and the second electrode layer 301.

In some embodiments, as shown in fig. 9b, the electrochromic device comprises, in order, a nanofiber electrode doubling as a second electrode, an electrochromic electrode layer 302, an electrolyte layer 303, an ion storage layer 304, and a second electrode layer 305, and the photovoltaic cell is connected to the thin film electrochemical device through the nanofiber electrode doubling as a second electrode.

In some embodiments, the electrolyte layer 303 may be an aqueous electrolyte layer or an organic phase electrolyte layer, preferably, the aqueous electrolyte may be H ₂ SO ₄ /HCl/Na ₂ SO ₄ /NaCl/LiClO ₄ –PVA-H ₂ O and the organic phase electrolyte can be Na ₂ SO ₄ /NaCl/LiClO ₄ PVA-acetonitrile, propylene carbonate.

The use of the above described electrolytes is advantageous in that it is relatively environmentally friendly for aqueous electrolytes, but has a low open circuit voltage (< 1.23V), whereas for organic electrolytes, the open circuit voltage is high (1.5-3V), but the organic solvents are not environmentally friendly.

In some embodiments, the working principle is as follows: when the voltage of the electrochromic electrode layer 302 is changed by using the electric energy generated from the photovoltaic cell, as shown in fig. 10 and 11, the electrochromic material is subjected to continuous oxidation-reduction reaction by controlling the sliding rheostat 13 when the first switch circuit 12 and the second switch circuit 13 are connected to the second external circuit 11 and the first external circuit 10, respectively, thereby achieving the continuous color change function.

The rate of change of color generally refers to the rate at which the switch between 2 identical colors is made available by a timer. In addition, the maximum reversible cycling rate determined by Cyclic Voltammetry (CV) can also be characterized, in general, the greater the cycling rate, the faster the rate of discoloration.

For the electrochromic device, when the external circuits are connected, it is necessary to connect the first and second switching circuits 12 and 13 to the second external circuit 11 and 10, respectively, to control the current direction so as to change the state of oxidation or reduction of the electrochromic material to increase the span of its color.

In one embodiment, the electrolyte layer 303 is an organic phase electrolyte layer having a wider open circuit voltage, such that the electrochromic layer undergoes more redox reactions, resulting in more color change.

In one embodiment, the nanofiber electrode serves as both a second electrode and an electrochromic electrode (as shown in FIG. 11), preferably, the nanofiber electrode has a conductivity of 1X 10 or greater ² S/m, namely, in order to fully utilize the heat to enhance the conductivity of the semiconductor, the nanofiber electrode can be closely attached to the electrochromic electrode layer.

When the conductivity of the nanofiber electrode is more than or equal to 1 multiplied by 10 ² At S/m, reversible oxidation-reduction reaction can be stably generated, and the color change before and after the reaction satisfies the color difference value (delta E) of CIE Lab of more than 1.

In some embodiments, the nanofiber electrode has a length of 50-500nm, preferably 50-100nm.

The nanofiber electrode is used as the electrochromic electrode layer, so that the electrochromic material can perform continuous oxidation-reduction reaction, and the continuous color change function is achieved.

The nanofiber electrode structure has a film structure, the surface on one side of the film structure is a suede or a composite of the film structure and a comb-shaped structure, the contact conductive area of the electrode can be further increased, and the contact surface with the electrolyte layer 303 is sufficiently increased, so that the reaction area between the reaction ions and the electrode is larger under the same incident light irradiation and charging voltage, and the electrolyte layer 303 can be more fully contacted and conductive with the nano conductive structure of the electrode layer with the nanofiber structure, so that the electrode activity in an integrated electrochromic device is further improved; meanwhile, the larger surface area can enhance the electrochemical reaction area of the electrochromic device, and is more beneficial to further improving the color changing reaction speed and the color developing uniformity of the electrochromic device.

The application provides a method for preparing the integrated device, which comprises the following steps:

preparing a photovoltaic cell comprising a second carrier transport functional layer or a second carrier transport functional layer and a conductive connecting layer;

preparing a nanofiber electrode on the second carrier transport functional layer or the conductive connecting layer;

a first electrode layer (ion storage layer) is prepared on a first transparent electrode, and a photovoltaic cell is connected to the first electrode layer (ion storage layer) using an electrolyte such that the nanofiber electrode, the electrolyte, the first electrode layer (ion storage layer) and the first transparent electrode form a thin film device and form an integrated device.

In some embodiments, the chemical reaction device has a nanofiber electrode, an electrocatalytic material layer, and a reaction cavity, at least a portion of the electrocatalytic material layer being exposed in the reaction cavity, and the reaction cavity having two or more openings, the photovoltaic cell being in contact with the nanofiber electrode of the chemical reaction device.

As shown in fig. 12, the integrated device includes a photovoltaic cell 100 and a chemical reaction apparatus 300, the chemical reaction apparatus has a nanofiber electrode 200, an electrocatalytic material layer, and a reaction cavity (not shown in the figure), at least a portion of the electrocatalytic material layer is exposed in the reaction cavity, and the reaction cavity has two or more openings, the photovoltaic cell 100 is in contact with the nanofiber electrode 200 of the chemical reaction apparatus 300, and the nanofiber electrode 200 may be a thin film structure or a composite of a thin film structure and a comb structure.

In some embodiments, the chemical reaction apparatus has two symmetrically disposed electrode layers, and the nanofiber electrode is positioned outside of the electrode layer near one side of the photovoltaic cell and in contact with the photovoltaic cell. In one embodiment, the chemical reaction device has two symmetrically arranged electrode layers, and the nanofiber electrode doubles as the electrode layer near one side of the photovoltaic cell and contacts the photovoltaic cell, for example, it can be used as the first electrode layer 311 in a membrane electrode type electrolytic cell.

In some embodiments, the nanofiber electrode of the chemical reaction apparatus has a thickness of 200nm-10 μm, for example, the nanofiber electrode of the chemical reaction apparatus may have a thickness of 200nm, 500nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, etc.

In some embodiments, the reaction chamber is composed of a gas diffusion layer or an electrolytic cell and a film-like substance disposed in the middle of the reaction chamber. In some embodiments, the membranous material is an ion exchange membrane or separator; preferably, the ion exchange membrane is a proton exchange membrane or an anion exchange membrane. In some embodiments, the gas diffusion layer has a porous structure, preferably, the gas diffusion layer is porous carbon or magneli-phase titanium suboxide.

When the reaction chamber is formed of a gas diffusion layer and a membrane-like material, the chemical reaction apparatus is a membrane electrode type electrolytic cell, as shown in 310 of fig. 13, and the membrane-like material is an ion exchange membrane 314, which may be a proton exchange membrane, such as a perfluorosulfonic acid membrane, for example, a Nafion membrane, or an anion exchange membrane, such as a quaternized polystyrene. In some embodiments, as shown at 310 in fig. 13, the gas diffusion layers are symmetrically disposed, namely a first gas diffusion layer 312 and a second gas diffusion layer 316, respectively, and the gas diffusion layers have a porous structure, preferably the gas diffusion layers are porous carbon or magneli phase titanium suboxide.

The electrocatalytic material layer comprises a first catalytic material layer 313 and a second catalytic material layer 315, the first catalytic material layer 313 and the second catalytic material layer 315 are symmetrically arranged inside the reaction cavity and are in contact with a first gas diffusion layer 312 and a second gas diffusion layer 316, and the ion exchange membrane 314 is positioned between the first catalytic material layer 313 and the second catalytic material layer 315.

The material of the first catalytic material layer 313 is selected from one or more of ruthenium, iridium, palladium, platinum, nickel, cobalt, manganese, iron, lithium, tin, lanthanum, and strontium, or an alloy thereof or a composite oxide, hydroxide, hydroperoxide, phosphide, phosphate (phosphorus oxide) phosphorus oxide, nitride, boride, or sulfide thereof.

The material of the second catalytic material layer 315 is one or more selected from platinum, palladium, iridium, rhenium, rhodium, nickel, cobalt, tungsten, copper, silver, gold, bismuth, iron, and zinc, or an alloy thereof or a composite oxide, hydroxide, hydroperoxide, phosphide, phosphate (phosphorus oxide), nitride, boride or sulfide thereof

For the first catalytic material layer 313 and the second catalytic material layer 315, when the first catalytic material layer 313 serves as an anode catalyst layer, the second catalytic material layer 315 is a cathode catalyst layer; when the first catalytic material layer 313 serves as a cathode catalyst layer, the second catalytic material layer 315 is an anode catalyst layer.

In some embodiments, when the chemical reaction apparatus is a membrane electrode type electrolytic cell, the reaction chamber has an air outlet and an air inlet, preferably, an air outlet is disposed at one end of the gas diffusion layer, and an air inlet is disposed at one end of the second catalytic material layer, the air outlet and the air inlet are located at the same end of the reaction chamber, as shown in 310 in fig. 13, air outlets 318 are symmetrically disposed at one ends of the first gas diffusion layer 312 and the second gas diffusion layer 316, and an air inlet 319 is disposed at one end of the second catalytic material layer 315, and the air outlets 318 and the air inlets 319 are located at the same end of the reaction chamber.

In some embodiments, the membrane electrode assembly further comprises a first electrode layer and a second electrode layer, as shown at 310 in fig. 13, the first electrode layer 311 and the second electrode layer 317 are symmetrically disposed outside the first gas diffusion layer 312 and the second gas diffusion layer 316 and are in contact with the first gas diffusion layer 312 and the second gas diffusion layer 316, respectively.

As for the material used for the first electrode layer 311 and the second electrode layer 317, the present application is not limited at all, and for example, a metal such as platinum (Pt) may be used.

In some embodiments, the nanofiber electrode doubles as an electrode layer near one side of the photovoltaic cell, as shown at 200&311 in fig. 16.

In some embodiments, the integrated device further comprises an external circuit 400 (as shown in fig. 12) for providing the electrical energy of the photovoltaic cell to the chemical reaction apparatus, preferably, the external circuit has three connection modes, wherein, in the membrane electrode type electrolytic cell, one connection mode is as shown in fig. 17, the first transparent electrode 101 of the photovoltaic cell is connected with the first electrode layer 311 of the membrane electrode type electrolytic cell through a first electric wire 401, and the second transparent electrode 105 is connected with the second electrode layer 317 of the membrane electrode type electrolytic cell through a second electric wire 402;

In the membrane electrode type electrolytic cell, another connection is shown in fig. 18, in which the first transparent electrode 101 of the photovoltaic cell is connected to the second electrode layer 317 of the membrane electrode type electrolytic cell by a third wire 403, and the second light-transmitting electrode 105 is connected to the first electrode layer 311 of the membrane electrode type electrolytic cell by a fourth wire 404;

in the membrane electrode type electrolytic cell, another connection manner is shown in fig. 19, in which the first transparent electrode 101 of the photovoltaic cell is connected to the second electrode layer of the membrane electrode type electrolytic cell through the fifth wire 405, and for this connection manner, it is necessary to satisfy the energy level matching of the second light-transmitting electrode 105 of the photovoltaic cell, the nanofiber electrode 200, and the first electrode layer 311 of the membrane electrode type electrolytic cell, so as to ensure that carriers can be normally transported.

In some embodiments, when the nanofiber electrode doubles as the first electrode layer 311 of the membrane electrode type electrolytic cell, it is connected in the same manner as described above.

In some embodiments, the principle of operation of the membrane electrode assembly 310: an electrolyte such as water flows in from the membrane electrode assembly type electrolytic cell water inlet 319 through the second catalyst layer 315, and a part of ions flow in to the first catalyst layer 313 through the ion exchange membrane 314. Oxygen and hydrogen are generated at the surface of the catalyst layer by the applied electric field provided by the photovoltaic cells and transported out and collected through the first and second gas diffusion layers 312 and 316 and through the mea outlet 318.

For the membrane electrode type electrolytic cell 310, the preparation method is as follows:

a first catalyst layer 313 and a second catalyst layer 315 are coated on two sides of an ion exchange membrane 314 to form a reaction cavity, and then a first gas diffusion layer 312 and a second gas diffusion layer 316 are symmetrically pressed on two sides of the reaction cavity by a hot pressing method; the first transparent electrode 311 and the nanofiber electrode and the second electrode 317 are then encapsulated.

In some embodiments, when the reaction chamber is composed of an electrolytic cell and a membranous substance, as shown at 320 in fig. 14, the electrode tank 323 is not limited in any way as long as it can perform the corresponding function, for example, the electrolytic tank 323 may be a stainless steel electrolytic tank. The membranous material may be a membrane 324, which is not limited in any way, and may be, for example, an insulating but ion-conductive membrane, such as any one of polypropylene (PP) and Polyethylene (PE), or a double-layer or multi-layer membrane formed by mixing the same, such as a Celgard membrane, preferably Celgard3501, celgard2400 membrane.

In some embodiments, the electrocatalytic material layers include a third catalytic material layer 322 and a fourth catalytic material layer 326, the third catalytic material layer 322 and the fourth catalytic material layer 326 being symmetrically disposed outside the reaction chamber and in contact with an electrolysis cell 323.

As for the material of the third catalytic material layer 322, it is the same as the material of the first catalytic material layer 313;

as for the material of the fourth catalytic material layer 326, it is the same as the material of the second catalytic material layer 315;

for the third catalytic material layer 322 and the fourth catalytic material layer 326, when the third catalytic material layer 322 is used as an anode catalyst layer, the fourth catalytic material layer 326 is used as a cathode catalyst layer; when the third catalytic material layer 322 is used as a cathode catalyst layer, the fourth catalytic material layer 326 is an anode catalyst layer.

In one embodiment, when the chemical reaction apparatus is a membrane electrode type electrolytic cell, the reaction chamber has an air outlet and a water inlet, preferably, an air outlet is provided at one end of the electrolytic cell, and a water inlet is provided at the other end of the electrolytic cell, as shown in 320 of fig. 14, the air outlet 328 is symmetrically provided at one end of the electrolytic cell 323, and the air inlet 325 is provided at the other end of the electrolytic cell 323.

In some embodiments, the electrolytic cell type electrolytic cell further comprises a third electrode layer and a fourth electrode layer, as shown at 320 in fig. 14, the third electrode layer 321 and the fourth electrode layer 327 are symmetrically disposed outside the third catalytic material layer 322 and the fourth catalytic material layer 326, and are respectively connected with the third catalytic material layer 322 and the fourth catalytic material layer 326.

As for the material used for the third electrode layer 321 and the fourth electrode layer 327, the present application is not limited at all, and for example, a metal such as platinum (Pt) may be used.

In some embodiments, when the chemical reaction apparatus is an electrolytic cell, it is connected in the same manner as a membrane electrode type electrolytic cell.

In some embodiments, the cell 320 operates on the principle of: electrolyte, such as water, enters the cell 323 from a cell inlet 325. Oxygen and hydrogen are generated at the surfaces of the first catalyst layer 322 and the second catalyst layer 326 under the applied electric field provided by the photovoltaic cells, and are transported out through a cell outlet 328 and collected.

For the electrolytic cell 320, the preparation method is as follows:

the third catalyst layer 322 and the fourth catalyst layer 326 are coated on both sides of the electrolytic cell 323 to form a reaction chamber, and then the third transparent electrode 321, the nanofiber electrode and the second electrode 327 are encapsulated to form the electrolytic cell 320.

For the carbon dioxide reduction cell, it is the same as the method of manufacturing the electrolytic cell type cell.

For the hydrogen production electrolytic cell described above, a water inlet may be provided at one side of the oxygen-producing electrode in order to collect dry hydrogen.

In some embodiments, when the chemical reaction apparatus is carbon dioxide reduction electrolysis, it includes a third electrode layer 321, a third catalyst layer 322, an electrolytic cell 323, a membrane 324, a fourth catalyst layer 326, and a fourth electrode layer 327, as shown at 300 in fig. 15, an electrolytic cell outlet 328 is provided at one end of the electrolytic cell 323, and a carbon dioxide inlet 329 is provided at the other end of the electrolytic cell 323.

In one embodiment, the nanofiber electrode doubles as an electrode layer near the photovoltaic cell side, i.e., the nanofiber electrode 200 can doubles as the first electrode layer 311 (as shown in fig. 16), the third electrode layer 321, or a third electrode layer (not shown) in the carbon dioxide reduction cell, the nanofiber electrode 200 is electrically conductive, and the nanofiber electrode can be in a thin film structure or a comb structure or a composite of a thin film structure and a comb structure.

In some embodiments, the photovoltaic cell-chemical reaction apparatus integrated device comprises a photovoltaic cell and a chemical reaction apparatus, the chemical reaction apparatus comprises a nanofiber electrode 200, an electrocatalytic material layer and a reaction cavity, at least one part of the electrocatalytic material layer is exposed in the reaction cavity, the reaction cavity is provided with more than two openings, the photovoltaic cell is contacted with the nanofiber electrode 200 of the chemical reaction apparatus, as shown in fig. 20, the photovoltaic cell sequentially comprises a first transparent electrode 101, a first carrier transport layer 102, a photovoltaic absorption layer 103, a second carrier transport layer 104 and a second light-transmitting electrode 105, the chemical reaction apparatus is a membrane electrode type electrolytic cell, the membrane electrode type electrolytic cell sequentially comprises a reaction cavity formed by a first gas diffusion layer 312, a second gas diffusion layer 316 and an ion exchange membrane 314, the electrocatalytic material layer comprises a first catalyst layer 313 and a second catalyst layer 315, the first catalyst layer 313 and the second catalyst layer 315 are disposed in the reaction cavity and are respectively contacted with a first gas diffusion layer 312 and a second gas diffusion layer 316, a first electrode layer 311 and a second electrode layer 317 are symmetrically disposed outside the reaction cavity, the nanofiber electrode 200 is disposed on the first electrode layer 311 near the photovoltaic cell and is respectively provided with a membrane electrode type electrolytic cell air outlet (not shown) at the same end of the first gas diffusion layer 312 and the second gas diffusion layer 316, a membrane electrode type electrolytic cell water inlet (not shown) is disposed at the end of the second catalyst layer 315 and is at the same end as the membrane electrode type electrolytic cell air outlet, the integrated device further comprises an external circuit (not shown), the first transparent electrode 101 of the photovoltaic cell is connected with the first electrode layer 311 in the membrane electrode type electrolytic cell through a first electric wire 401, the second light-transmitting electrode 105 is connected with the second electrode layer 317 through a second electric wire 402, and the nanofiber electrode 200 has a thin film structure.

In one embodiment, the photovoltaic cell-chemical reaction apparatus integrated device comprises a photovoltaic cell and a chemical reaction apparatus, the chemical reaction apparatus comprises a nanofiber electrode 200, an electrocatalytic material layer and a reaction cavity, at least one part of the electrocatalytic material layer is exposed in the reaction cavity, the reaction cavity is provided with more than two openings, the photovoltaic cell is contacted with the nanofiber electrode 200 of the chemical reaction apparatus, as shown in fig. 21, the photovoltaic cell sequentially comprises a first transparent electrode 101, a first carrier transport layer 102, a photovoltaic absorption layer 103, a second carrier transport layer 104 and a second light-transmitting electrode 105, the chemical reaction apparatus is an electrolytic tank type electrolytic tank, the electrolytic tank type electrolytic tank comprises a reaction cavity formed by an electrolytic tank 323 and a diaphragm 324, the third catalyst layer 322 and the fourth catalyst layer 326 are disposed outside the reaction chamber and respectively contact with the electrolytic tank 323, the third electrode layer 321 and the fourth electrode layer 327 are disposed outside the third catalyst layer 322 and the fourth catalyst layer 326 respectively, the nanofiber electrode 200 is disposed on the third electrode layer 321 close to the photovoltaic cell, an electrolytic tank type electrolytic tank air outlet (not shown in the figure) is symmetrically disposed at one end of the electrolytic tank 323, an electrolytic tank type electrolytic tank water inlet (not shown in the figure) is disposed at the other end of the electrolytic tank 323, the integrated device further comprises an external circuit (not shown in the figure), wherein the first transparent electrode 101 of the photovoltaic cell is connected with the third electrode layer 321 through a first electric wire 401, the second transparent electrode 105 is connected with the fourth electrode layer 327 through a second electric wire 402, and the nanofiber electrode 200 is of a thin film structure.

In one embodiment, the integrated device of the photovoltaic cell-chemical reaction apparatus comprises a photovoltaic cell and a chemical reaction apparatus, wherein the chemical reaction apparatus is provided with a nanofiber electrode doubling as a part close to the electrode layer of the photovoltaic cell, an electrocatalytic material layer and a reaction cavity, at least one part of the electrocatalytic material layer is exposed in the reaction cavity, the reaction cavity is provided with more than two openings, the photovoltaic cell is contacted with the nanofiber electrode doubling as a part close to the electrode layer of the photovoltaic cell of the chemical reaction apparatus, as shown in fig. 22, the nanofiber electrode doubling as a part close to the electrode layer of the photovoltaic cell is 200&311 and also serves as a first electrode layer, the photovoltaic cell sequentially comprises a first transparent electrode 101, a first carrier transmission layer 102, a photovoltaic absorption layer 103, a second carrier transmission layer 104 and a second light-transmitting electrode 105, the chemical reaction apparatus is a membrane electrode type electrolytic cell, the membrane electrode type electrolytic cell comprises a reaction cavity formed by a first gas diffusion layer 312, an ion exchange membrane 314 and a second gas diffusion layer 316, a first catalyst layer 313 and a second catalyst layer 315 are arranged in the reaction cavity and respectively contact with the first gas diffusion layer 312 and the second gas diffusion layer 316, nanofiber electrodes 200&311 and a second electrode layer 317 which are also used as a first electrode layer are symmetrically arranged on the outer side of the reaction cavity, a membrane electrode type electrolytic cell air outlet (not shown) is respectively arranged on the same end of the first gas diffusion layer 312 and the second gas diffusion layer 316, a membrane electrode type electrolytic cell water inlet (not shown) is arranged on the end of the second catalyst layer 315 and is positioned on the same end as the membrane electrode type electrolytic cell air outlet, the integrated device further comprises an external circuit (not shown), the first transparent electrode 101 of the photovoltaic cell is connected with the second electrode layer 317 in the membrane electrode type electrolytic cell through the third wire 403, the second light-transmitting electrode 105 is connected with the nanofiber electrode 200&311 which also serves as the first electrode layer through the fourth wire 404, and the nanofiber electrode 200&311 is of a thin film structure.

In one embodiment, the integrated device of the photovoltaic cell-chemical reaction apparatus comprises a photovoltaic cell and a chemical reaction apparatus, wherein the chemical reaction apparatus is provided with a nanofiber electrode doubling as a part close to the electrode layer of the photovoltaic cell, an electrocatalytic material layer and a reaction cavity, at least one part of the electrocatalytic material layer is exposed in the reaction cavity, the reaction cavity is provided with more than two openings, the photovoltaic cell is contacted with the nanofiber electrode doubling as a part close to the electrode layer of the photovoltaic cell of the chemical reaction apparatus, as shown in fig. 23, the nanofiber electrodes 200&311 doubling as a part close to the electrode layer of the photovoltaic cell doubling as a first electrode layer, the photovoltaic cell sequentially comprises a first transparent electrode 101, a first carrier transmission layer 102, a photovoltaic absorption layer 103, a second carrier transmission layer 104 and a second light-transmitting electrode 105, the chemical reaction apparatus is a membrane electrode type electrolytic cell, the membrane electrode type electrolytic cell comprises a reaction cavity formed by a first gas diffusion layer 312, an ion exchange membrane 314 and a second gas diffusion layer 316, a first catalyst layer 313 and a second catalyst layer 315 are arranged in the reaction cavity and respectively contact with the first gas diffusion layer 312 and the second gas diffusion layer 316, nanofiber electrodes 200&311 and a second electrode layer 317 which are also used as a first electrode layer are symmetrically arranged on the outer side of the reaction cavity, a membrane electrode type electrolytic cell air outlet (not shown) is respectively arranged on the same end of the first gas diffusion layer 312 and the second gas diffusion layer 316, a membrane electrode type electrolytic cell water inlet (not shown) is arranged on the end of the second catalyst layer 315 and is positioned on the same end as the membrane electrode type electrolytic cell air outlet, the integrated device further comprises an external circuit (not shown), the first transparent electrode 101 of the photovoltaic cell is connected with the second electrode layer 317 in the membrane electrode type electrolytic cell through the third wire 403, the second transparent electrode 105 is connected with the nanofiber electrode 200&311 which is also used as the first electrode layer through the fourth wire 404, and the nanofiber electrode 200&311 is a composite body of a thin film structure and a comb structure.

In one embodiment, the integrated device of the photovoltaic cell-chemical reaction apparatus comprises a photovoltaic cell and a chemical reaction apparatus, wherein the chemical reaction apparatus is provided with a nanofiber electrode doubling as a part close to the electrode layer of the photovoltaic cell, an electrocatalytic material layer and a reaction cavity, at least one part of the electrocatalytic material layer is exposed in the reaction cavity, the reaction cavity is provided with more than two openings, the photovoltaic cell is contacted with the nanofiber electrode doubling as a part close to the electrode layer of the photovoltaic cell of the chemical reaction apparatus, as shown in fig. 24, the nanofiber electrodes 200 and 311 doubling as a part close to the electrode layer of the photovoltaic cell are doubled as a third electrode layer of a carbon dioxide reduction electrolytic cell, the photovoltaic cell sequentially comprises a first transparent electrode 101, a first carrier transmission layer 102, a photovoltaic absorption layer 103, a second carrier transmission layer 104 and a second light-transmitting electrode 105, the chemical reaction device is a carbon dioxide reduction electrolytic cell, the carbon dioxide reduction electrolytic cell comprises a reaction cavity formed by an electrolytic cell 323 and a diaphragm 324, a third catalyst layer 322 and a fourth catalyst layer 326 are arranged outside the reaction cavity and respectively contacted with the electrolytic cell 323, nanofiber electrodes 200&311 and a fourth electrode layer 327 which are also used as electrode layers are respectively arranged outside the third catalyst layer 322 and the fourth catalyst layer 326, an electrolytic cell air outlet 328 is symmetrically arranged at one end of the electrolytic cell 323, a carbon dioxide air inlet 329 is arranged at the other end of the electrolytic cell 323, the integrated device also comprises an external circuit (not shown in the figure), wherein a first transparent electrode 101 of a photovoltaic cell is connected with the nanofiber electrodes 200&311 which are also used as electrode layers through a first electric wire 401, a second light-transmitting electrode 105 is connected with the fourth electrode layer 327 through a second electric wire 402, the nanofiber electrodes 200 and 311 serving as electrode layers are a composite of a thin film structure and a comb structure.

and preparing a chemical reaction device comprising a nanofiber electrode, an electrocatalytic material layer and a reaction cavity, and connecting the nanofiber electrode of the chemical reaction device with a second electrode of a photovoltaic cell to obtain the integrated device.

In some embodiments, the nanofiber electrode of the chemical reaction apparatus (e.g., membrane electrode type electrolytic cell or electrolytic tank type electrolytic cell or carbon dioxide reduction electrolytic cell) prepared as described above is connected to the second carrier transport layer of the photovoltaic cell to obtain the integrated device.

Examples

The materials used in the test and the test methods are generally and/or specifically described herein, and in the examples which follow,% represents wt%, i.e., weight percent, unless otherwise specified. The reagent or instrument used is not a manufacturer's notice, and is a conventional reagent product which is available in the market, and when the reagent or instrument is a perovskite cell, the first carrier transport function layer 2 is the first carrier transport layer 2, and the second carrier transport function layer 41 is the second carrier transport layer 41.

Example 1 perovskite battery-supercapacitor integrated device

The structure of the perovskite battery-supercapacitor integrated device is shown in fig. 4A, wherein the light-transmitting layer 1 is an ITO transparent electrode, the first carrier transport layer 2 is an HTL, and the photovoltaic cell absorption layer 3 is perovskite MAPbBr ₃ An absorption layer with an absorption spectrum of 300-550nm, a second carrier transport layer 41 of PCBM, a nanofiber electrode 42 of PEDOT nanofiber electrode, which is a composite of a thin film structure (shown in FIG. 3A) and a comb structure, wherein the thickness of the thin film structure is 100nm, the length of individual fibers of the comb structure is 800nm, the diameter of individual PEDOT fibers is 100nm (shown in FIG. 5), and the electrolyte 5 is H ₂ SO ₄ PVA gel, the first electrode layer 61 is a PEDOT thin film structure, and the electrode 7 is an Ag electrode.

A photovoltaic cell comprising the second carrier transport layer 41 is prepared using conventional methods, the first electrode layer 61 is prepared on the electrode 7, and the photovoltaic cell and the first electrode layer 61 are connected using the electrolyte 5 such that the second carrier transport layer 41, the electrolyte 5, the first electrode layer 61 and the electrode 7 form a supercapacitor, thereby forming an integrated device.

The perovskite battery-supercapacitor integrated device and the integrated device obtained without using supercapacitor electrodes having a nanofiber structure described herein were subjected to energy storage efficiency, which refers to an increase in capacitance, which can be obtained by cyclic voltammogram or constant current discharge curve test in an electrochemical workstation according to a conventional method in the art, and then energy density e=1/2 CV according to the following formula ² ,

Power density p=e/t

Where C is capacitance, V is operating voltage, t is discharge time, all parameters are available through constant current charge-discharge test (GCD) to obtain energy density or power density, which is determined to increase by 22.5% and 15% compared to an integrated device obtained without using a supercapacitor electrode with nanofiber electrode.

Example 2 perovskite battery-supercapacitor integrated device

The structure of the perovskite battery-super capacitor integrated device is shown in fig. 6, wherein the light-transmitting layer 1 is a ZnO transparent electrode, the first carrier transmission layer 2 is ETL, and the photovoltaic cell absorption layer 3 is perovskite MAPbBr ₃ An absorption layer with an absorption spectrum ranging from 300 nm to 550nm, a second carrier transport layer 41 of P3HT, a nanofiber electrode 42 of PEDOT nanofiber electrode, which is a composite of a thin film structure with a thickness of 100nm and a comb structure, a single fiber of the comb structure with a length of 800nm, a diameter of 100nm (as shown in FIG. 5), and an electrolyte 5 of H ₂ SO ₄ The first electrode layer 61 is a PPy nanofiber electrode, which is a composite of a PPy thin film structure and a PPy comb structure, the PPy thin film structure has a thickness of 200nm, the length of a single PPy nanofiber is 500nm, the diameter of a single PPy nanofiber is 200nm (as shown in fig. 5), and the electrode 7 is an FTO electrode.

The preparation method is the same as in example 1.

The power density of the prepared perovskite battery-supercapacitor integrated device was increased by 30% and the energy density was increased by 20% as compared to an integrated device obtained without using a supercapacitor electrode having a nanofiber electrode, as determined in the same manner as in example 1.

Example 3 perovskite battery-supercapacitor integrated device

The structure of the perovskite battery-super capacitor integrated device is shown in fig. 7, wherein the light-transmitting layer 1 is an FTO transparent electrode, the first carrier transport layer 2 is ETL, and the photovoltaic cell absorption layer 3 is perovskite mapbecl ₃ An absorption layer with an absorption spectrum of 300-420nm, a second carrier transport layer 41 of P3HT, a second electrode layer 42 of PEDOT film structure, and an electrolyte 5 of H ₂ SO ₄ The first electrode layer 6 is a PEDOT nanofiber electrode, which is a composite of a thin film structure with a thickness of 50nm and a comb structure with individual fibers of 1200nm in length and 100nm in diameter (as shown in fig. 5), and the electrode 7 is a Pt electrode.

The preparation method is the same as in example 1.

The power density of the prepared perovskite battery-supercapacitor integrated device was increased by 30% and the energy density was increased by 20% as compared to an integrated device obtained without using the supercapacitor electrode having the nanofiber structure, as determined in the same manner as in example 1.

Example 4 integration device of perovskite Battery-electrochromic reaction device

The structure of the integrated device of the perovskite battery-electrochromic device is shown in fig. 9b and 11, the light-transmitting layer of the photovoltaic cell 100 is an ITO transparent electrode, the first carrier transport layer is an HTL, and the photovoltaic absorber layer uses MAPbBr ₃ The absorption spectrum range is 300-550nm, the second carrier transmission layer is PCBM, and the electrolyte is BMIBF ₄ PVDF gel, nanofiber electrode (electrochromic layer) 200&302 is a 100nm PEDOT thin film layer; liClO with solid electrolyte as water phase ₄ PVA-acetonitrile gel, ion store 304 is nickel oxide and second electrode 305 is FTO. When the switching circuits 12, 13 are connected 10, 11, respectively, the voltage on the electrochromic electrode and thus the color can be changed by controlling the sliding varistors 13, the rate of change of color of which is increased by 40% compared with devices not using nanofiber electrodes.

Example 5 photovoltaic cell-chemical reaction apparatus Integrated device

The structure is shown in fig. 20, wherein the photovoltaic cell comprises: the photovoltaic absorber layer 103 is perovskite MAPbBr ₃ The absorption spectrum range is 300nm-550nm; the first light-transmitting electrode 101 and the second light-transmitting electrode 105 are ITO; the first carrier transport layer 102 and the second carrier transport layer 104 are PCBM and spira-ome tad, respectively; the chemical reaction device is a membrane electrode type electrolytic cell, which comprises: the reaction cavity is formed by a first gas diffusion layer 312, a second gas diffusion 316 and an ion exchange membrane 314, the electrocatalytic material layer comprises a first catalyst layer 313 and a second catalyst layer 315, and the first gas diffusion layer 312 and the second gas diffusion 316 are porous carbon; the first catalyst layer 313 and the second catalyst layer 315 are disposed in the reaction chamber The integrated device is characterized in that the integrated device is in contact with a first gas diffusion layer 312 and a second gas diffusion layer 316 respectively, a first electrode layer 311 and a second electrode layer 317 are symmetrically arranged on the outer side of a reaction cavity, the nanofiber electrode 200 is arranged on the first electrode layer 311 close to a photovoltaic cell, the nanofiber electrode 200 is of a film structure, a PPy film layer with the thickness of 400nm is arranged on the same end of the first gas diffusion layer 312 and the second gas diffusion layer 316 respectively, a membrane electrode type electrolytic cell air outlet (not shown in the figure) is arranged on the same end of the first gas diffusion layer 312 and the second gas diffusion layer 316 respectively, a membrane electrode type electrolytic cell water inlet (not shown in the figure) is arranged on the end of the second catalyst layer 315 and is positioned on the same end with the membrane electrode type electrolytic cell air outlet, and the integrated device further comprises an external circuit (not shown in the figure), wherein a first light-transmitting electrode 101 of the photovoltaic cell is connected with the first electrode layer 311 in the membrane electrode type electrolytic cell through a first wire 401, and a second light-transmitting electrode 105 is connected with the second electrode layer 317 through a second wire 402, and the first electrode layer 311 and the first electrode layer 317 are Pt; the first catalyst layer 313 and the second catalyst layer 315 are Pt and BiVO4, respectively; ion exchange membrane 314 is Nafion, which has a photovoltaic hydrogen production efficiency (STH) that is improved by 10% compared to devices that do not use nanofiber electrodes.

The STH=electrolytic hydrogen production efficiency and the photovoltaic power generation efficiency are respectively measured to obtain the integrated device, and the electrolytic hydrogen production efficiency and the photovoltaic power generation efficiency are measured by adopting a conventional method in the field.

Example 6 photovoltaic cell-chemical reaction apparatus Integrated device

The structure of which is shown in fig. 21, the photovoltaic cell comprises: the photovoltaic absorber layer 103 is perovskite MAPbCl ₃ The absorption spectrum range is 300nm-760nm, and the first light-transmitting electrode 101 and the second light-transmitting electrode 105 are ITO; the first carrier transport layer 102 and the second carrier transport layer 104 are PCBM and spira-ome tad, respectively; the chemical reaction device is an electrolytic tank type electrolytic cell, which comprises: a reaction chamber formed by an electrolytic bath 323 and a diaphragm 324, a third catalyst layer 322 and a fourth catalyst layer 326 disposed outside the reaction chamber and respectively contacting the electrolytic bath 323, and a second catalyst layer 322 and a fourth catalyst layer 326 disposed outside the third catalyst layer 322 and the fourth catalyst layer 326 respectivelyThe three electrode layers 321 and the fourth electrode layer 327, the nanofiber 200 is arranged on the third electrode layer 321 close to the photovoltaic cell, an electrolytic tank type electrolytic tank air outlet (not shown in the figure) is symmetrically arranged at one end of the electrolytic tank 323, an electrolytic tank type electrolytic tank water inlet (not shown in the figure) is arranged at the other end of the electrolytic tank 323, the integrated device further comprises an external circuit (not shown in the figure), wherein the first transparent electrode 101 of the photovoltaic cell is connected with the third electrode layer 321 in the electrolytic tank type electrolytic tank through a first electric wire 401, the second transparent electrode 105 is connected with the fourth electrode layer 327 through a second electric wire 402, and the third electrode layer 321 and the fourth electrode layer 327 are Pt; the third catalyst layer 322 and the fourth catalyst layer 326 are Pt and BiVO, respectively ₄ The method comprises the steps of carrying out a first treatment on the surface of the The electrolytic tank 323 is a stainless steel electrolytic tank; the separator 324 was Celgard3501, and the nanofiber electrode 200 disposed between the photovoltaic cell and the cell was a thin film structure of 400nm PPy film structure, which was measured as a 10% improvement in hydrogen production efficiency by the same method as in example 1.

Example 7 photovoltaic cell-chemical reaction apparatus Integrated device

The structure of which is shown in fig. 22, the photovoltaic cell comprises: the photovoltaic absorber layer 103 is perovskite MAPbBr ₃ The absorption spectrum range is 300nm-550nm; the first light-transmitting electrode 101 and the second light-transmitting electrode 105 are ITO; the first carrier transport layer 102 and the second carrier transport layer 104 are MoS respectively ₂ And TiO ₂ The method comprises the steps of carrying out a first treatment on the surface of the The chemical reaction device is a membrane electrode type electrolytic cell, which comprises: a reaction chamber composed of a first gas diffusion layer 312, an ion exchange membrane 314 and a second gas diffusion layer 316, a first catalyst layer 313 and a second catalyst layer 315 disposed in the reaction chamber and respectively contacting with the first gas diffusion layer 312 and the second gas diffusion layer 316, and nanofiber electrodes 200 serving as first electrode layers disposed symmetrically outside the reaction chamber&311 and a second electrode layer 317, and are respectively provided at the same ends of the first gas diffusion layer 312 and the second gas diffusion layer 316 A gas outlet (not shown in the figure) of the membrane electrode type electrolytic cell, a water inlet (not shown in the figure) of the membrane electrode type electrolytic cell is arranged at the end of the second catalyst layer 315 and is positioned at the same end with the gas outlet of the membrane electrode type electrolytic cell, the integrated device further comprises an external circuit (not shown in the figure), wherein the first transparent electrode 101 of the photovoltaic cell is connected with the second electrode layer 317 in the membrane electrode type electrolytic cell through a third electric wire 403, and the second light-transmitting electrode 105 is connected with the nanofiber electrode 200 which is also used as the first electrode layer through a fourth electric wire 404&311, the second electrode layer 317 is Au; the first gas diffusion layer 312 and the second gas diffusion layer 316 are Ebonex; the first catalyst layer 313 and the second catalyst layer 315 are Fe respectively ₂ O ₃ And Pd; ion exchange membrane 314 is a quaternized polystyrene; nanofiber electrode 200, which doubles as the first electrode layer, disposed between a photovoltaic cell and a membrane electrode type cell&311 is a film structure, which is a 400nm PEDOT PSS film structure, and the hydrogen production efficiency is improved by 15% as measured by the same method as in example 1.

Example 8 photovoltaic cell-chemical reaction apparatus Integrated device

The structure of which is shown in fig. 23, the photovoltaic cell comprises: the photovoltaic absorption layer 103 is GaAs, and the absorption spectrum range is 300nm-800nm; the first light-transmitting electrode 101 and the second light-transmitting electrode 105 are FTO; the first carrier transport layer 102 and the second carrier transport layer 104 are PCBM and spira-ome tad, respectively; the chemical reaction device is a membrane electrode type electrolytic cell, which comprises: a reaction chamber composed of a first gas diffusion layer 312, an ion exchange membrane 314 and a second gas diffusion layer 316, a first catalyst layer 313 and a second catalyst layer 315 disposed in the reaction chamber and respectively contacting with the first gas diffusion layer 312 and the second gas diffusion layer 316, and nanofiber electrodes 200 serving as first electrode layers disposed symmetrically outside the reaction chamber &311 and a second electrode layer 317, and are respectively provided with a membrane electrode type cell gas outlet (not shown) at the same end of the first gas diffusion layer 312 and the second gas diffusion layer 316, and a membrane electrode type cell water inlet (not shown) at the end of the second catalyst layer 315, which is at the same end as the membrane electrode type cell gas outlet, the collectionThe device further comprises an external circuit (not shown), wherein the first transparent electrode 101 of the photovoltaic cell is connected with the second electrode layer 317 in the membrane electrode type electrolytic cell through the third wire 403, and the second light-transmitting electrode 105 is connected with the nanofiber electrode 200 serving as the first electrode layer through the fourth wire 404&311, the second electrode layer 317 is Au; the first gas diffusion layer 312 and the second gas diffusion layer 316 are porous carbon; the first catalyst layer 313 and the second catalyst layer 315 are respectively IrO ₂ And CuO ₂ The method comprises the steps of carrying out a first treatment on the surface of the Ion exchange membrane 314 is Nafion; nanofiber electrode 200, which doubles as the first electrode layer, disposed between a photovoltaic cell and a membrane electrode type cell&311 is a composite of a film structure and a comb structure, the film structure is a PEDOT film structure with the thickness of 500nm, the diameter of a single PEDOT fiber in the comb structure is 200nm, the length of the single fiber is 10 mu m, and the hydrogen production efficiency is improved by 20 percent according to the measurement method in the same way as in the example 1.

Example 9 photovoltaic cell-chemical reaction apparatus Integrated device

The structure is shown in fig. 24, wherein the photovoltaic cell comprises: the photovoltaic absorber layer 103 is perovskite MAPbCl ₃ The absorption spectrum range is 300nm-760nm, and the first light-transmitting electrode 101 and the second light-transmitting electrode 105 are ITO; the first carrier transport layer 102 and the second carrier transport layer 104 are PCBM and spira-ome tad, respectively; the chemical reaction device is a carbon dioxide reduction electrolytic cell, which comprises: a reaction chamber formed by an electrolytic bath 323 and a diaphragm 324, a third catalyst layer 322 and a fourth catalyst layer 326 disposed outside the reaction chamber and respectively contacting the electrolytic bath 323, and nanofiber electrodes 200 serving as electrode layers disposed outside the third catalyst layer 322 and the fourth catalyst layer 326, respectively&311 and a fourth electrode layer 327, an electrolytic cell outlet 328 is symmetrically arranged at one end of the electrolytic cell 323, a carbon dioxide inlet 329 is arranged at the other end of the electrolytic cell 323, and the integrated device further comprises an external circuit (not shown in the figure), wherein the first transparent electrode 101 of the photovoltaic cell is connected with the nanofiber electrode 200 serving as the electrode layer through a first electric wire 401&311, and the second light-transmitting electrode 105 is connected to the fourth electrode layer 327 via the second wire 402, and also serves as Nanofiber electrode 200 of the first electrode layer&311. The fourth electrode layer 327 is Pt; the third catalyst layer 322 and the fourth catalyst layer 326 are Pt and BiVO, respectively ₄ The method comprises the steps of carrying out a first treatment on the surface of the The electrolytic tank 323 is a stainless steel electrolytic tank; the diaphragm 324 is Celgard3501, and the nanofiber electrode 200, which also serves as the first electrode layer, is disposed between the photovoltaic cell and the electrolyzer type cell&311 is a composite of a film structure of 500nm thick PEDOT film structure, in which the diameter of the individual PEDOT fibers is 200nm and the length of the individual fibers is 15 μm, and a comb structure, in which the carbon dioxide reduction efficiency is improved by 25% as measured by the same method as in example 1.

The above description is only of the preferred embodiments of the present application and is not intended to limit the present application in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present application still fall within the protection scope of the technical solution of the present application.

Claims

1. An integrated device comprising a stacked photovoltaic cell and a thin film electrochemical device, wherein the thin film electrochemical device comprises a nanofiber electrode, the thin film electrochemical device is in contact with the photovoltaic cell through the nanofiber electrode, the nanofiber electrode has a thin film structure;

2. The integrated device of claim 1, wherein the other side surface of the thin film structure has a textured structure or the other side surface has comb-like nanofibers integrally formed with the thin film structure.

3. The integrated device of claim 1 or 2, wherein the thin film structure is a thin film structure formed by tightly stacking nanofibers, and the suede structure or the comb-like nanofibers are integrally formed by extending the nanofibers of the thin film structure.

4. An integrated device according to claim 3, wherein the aspect ratio of the individual fibers of the comb structure is > 100 and the individual fibers have a diameter < 300nm.

5. An integrated device according to claim 3, wherein the maximum dimension of the interlayer direction extension of the nanofiber electrode is 0.05-14 μm.

6. The integrated device of claim 3, wherein the material of the nanofiber electrode is PEDOT, PPy, PANi or P3HT.

7. The integrated device of any one of claims 1-6, wherein the photovoltaic cell comprises, in order, a light transmissive layer, a first carrier transport functional layer, a photovoltaic absorber layer, and a second carrier transport functional layer, the second carrier transport functional layer being in contact with a surface of the other side of the thin film structure.

8. The integrated device of any one of claims 1-6, wherein the photovoltaic cell comprises, in order, a light transmissive layer, a first carrier transport functional layer, a photovoltaic absorber layer, a second carrier transport functional layer, and a conductive connection layer, the thin film structure is laminated on the conductive connection layer, and a surface of the other side of the thin film structure is connected to the conductive connection layer.

9. The integrated device of claim 8, wherein the conductive connection layer has an interlayer conductivity of > 10S/cm.

10. The integrated device of claim 8, wherein an interlayer conductivity of the conductive connection layer is 50 times or more than a conductivity of an in-layer extension direction.