CN111540802A - Novel solar power generation and energy storage dual-function integrated device structure and preparation method thereof - Google Patents
Novel solar power generation and energy storage dual-function integrated device structure and preparation method thereof Download PDFInfo
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- CN111540802A CN111540802A CN202010423921.4A CN202010423921A CN111540802A CN 111540802 A CN111540802 A CN 111540802A CN 202010423921 A CN202010423921 A CN 202010423921A CN 111540802 A CN111540802 A CN 111540802A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/053—Energy storage means directly associated or integrated with the PV cell, e.g. a capacitor integrated with a PV cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention relates to the field of solar cell power generation and energy storage, in particular to a novel solar power generation and energy storage dual-function integrated device structure and a preparation method thereof, wherein the novel solar power generation and energy storage dual-function integrated device structure comprises: a light absorbing layer for generating photo-generated electrons and photo-generated holes; the light absorption layer is arranged between the first energy storage structure layer and the second energy storage structure layer; when the light absorption layer generates the photo-generated electrons and the photo-generated holes, the first energy storage structure layer generates an energy storage chemical reaction by utilizing the photo-generated electrons, and the second energy storage structure layer generates an energy storage chemical reaction by utilizing the photo-generated holes. The invention provides a power generation and energy storage dual-function integrated device structure which has the characteristics of high comprehensive energy utilization efficiency and mutual promotion of charging and discharging processes by simultaneously utilizing the reduction and oxidation capabilities of photogenerated electrons and photogenerated holes to store energy through a first energy storage structure layer and a second energy storage structure layer.
Description
Technical Field
The invention relates to the field of solar cell power generation and energy storage, in particular to a novel solar power generation and energy storage dual-function integrated device structure and a preparation method thereof.
Background
Although solar energy has the advantages of inexhaustible resources and no pollution, the solar energy also has a significant disadvantage: intermittent, i.e., the energy supply is interrupted or fluctuates greatly due to diurnal or climatic changes. The better method for solving the problem is to introduce an energy storage battery, namely, the electric energy generated by the solar battery is stored in the energy storage battery and then is discharged from the energy storage battery when the electricity is needed. The energy storage battery is widely applied under the condition that electronic products in the current society are widely popularized and go deep into daily life of people, and the biggest problem of the energy storage battery is that the capacity of the battery is limited and charging is needed, but the charging in the open air is inconvenient at present. Solar energy is everywhere outdoors, and the resource is very abundant, if can utilize solar energy to come for energy storage battery charging, will greatly alleviate energy storage battery's the problem of charging. Therefore, the solar cell and the energy storage cell have strong complementarity, so that the organic combination of the solar cell and the energy storage cell has been paid attention to by people for a long time. Along with the rapid development of intelligent consumer electronics and electric vehicles, people have increasingly greater demands on mobile energy, and the requirements are also higher and higher: not only requires sufficient energy supply, but also requires portability and portability. Therefore, the solar power generation and energy storage dual-function integrated device is more and more emphasized by people, and a great amount of research is reported in recent years.
The solar power generation and energy storage dual-function integrated device structure disclosed and reported at present is divided according to the number of electrodes of the integrated device and can be divided into the following three types: two-electrode structure, three-electrode structure and four-electrode structure. The integration level of the three-electrode structure and the four-electrode structure is low, the two devices basically work independently, the mutual influence is small, the integration difficulty is low, the mature technology of a single device is convenient to utilize, but the disadvantages are also very obvious: the weight and volume are large, the cost is high, the energy loss is large, and the auxiliary benefit among integrated devices cannot be utilized. The two-electrode structure has the advantages of high integration level, simple structure, low cost, portability, small size and small energy loss, can utilize auxiliary benefits between integrated devices, but has high integration difficulty, can influence each other because the two devices do not work independently, has complex working mechanism, and needs elaborate design to realize the compatibility of the preparation process and the operation process of the two devices. Obviously, the two-electrode structure can embody the meaning of the integrated device, so it is the focus of the research and development at present.
The following three types are currently designed for devices with two-electrode structures: the design of a photosensitive anode-cathode, an anode-photosensitive cathode and a photosensitive anode-photosensitive cathode in series is that a photosensitive material is integrated at the anode or the cathode, and the anode or the cathode stores energy through electron hole pairs generated by the photosensitive material. However, due to the three types of structural designs, the photo-generated electrons and the photo-generated holes are not effectively separated and are easily combined at the interface, so that the photoelectric conversion efficiency is greatly reduced, and meanwhile, in the common energy storage battery, because the internal self-discharge phenomenon of the energy storage battery is prevented through the partition plate, the partition plate prevents the electrons from passing through, the charging current needs to pass through an external circuit, and the energy loss is easily caused. Therefore, a novel solar power generation and energy storage dual-function integrated device structure for improving the photoelectric conversion efficiency and reducing the charging energy loss and a preparation method thereof are urgently needed.
Disclosure of Invention
Based on the above problems, the invention provides a novel solar power generation and energy storage dual-function integrated device structure. The first energy storage structure layer and the second energy storage structure layer simultaneously utilize the photo-generated electrons and the photo-generated holes generated by the light absorption layer to store energy, and compared with the traditional structural design of connecting a photosensitive anode-cathode, an anode-photosensitive cathode and a photosensitive anode-photosensitive cathode in series, the invention simultaneously utilizes the reduction and oxidation capabilities of the photo-generated electrons and the photo-generated holes, and provides a power generation and energy storage dual-function integrated device structure which has the characteristics of high energy comprehensive utilization efficiency and mutual promotion of charging and discharging processes.
According to an embodiment of the present invention, a novel solar power generation and energy storage dual-function integrated device structure is provided, which includes: a light absorbing layer for generating photo-generated electrons and photo-generated holes; the light absorption layer is arranged between the first energy storage structure layer and the second energy storage structure layer; when the light absorption layer generates the photo-generated electrons and the photo-generated holes, the first energy storage structure layer generates an energy storage chemical reaction by utilizing the photo-generated electrons, and the second energy storage structure layer generates an energy storage chemical reaction by utilizing the photo-generated holes.
In some embodiments, the first energy storage structure layer comprises a first electrode and an electron transport layer in contact with each other, the electron transport layer is in contact with the light absorption layer, and the first electrode generates an energy storage chemical reaction by using the photo-generated electrons; the second energy storage structure layer comprises a second electrode and a hole transport layer which are mutually contacted, the hole transport layer is contacted with the light absorption layer, and the second electrode utilizes the photo-generated holes to generate energy storage chemical reaction.
In some embodiments, the electron transport layer and the light absorbing layer achieve electron selective transport properties through energy level matching; the hole transport layer and the light absorption layer realize hole selective transport characteristics through energy level matching.
In some embodiments, the first electrode is TiO2ZnO, graphite, Sn, SiO2、BN、AlN、Al2O3、TiN、MnO2Or V2O5One or more combinations of (a); the second electrode is TiF4、TiF3、CuO、LiMnO2、LiNiO2、LiCoO2、LiFePO4、LiMnPO4、Li2Se、Li2S、Li6C6O6Or Li4C6H4O4One or more combinations thereof.
In some embodiments, the electron transport layer is SnO2、LiFx、KFx、CsFx、CsOx、MgFx、TiOx、ZnO、ZnS、CdS、CdSe、Zn2SO4、BaSnO3、SrTiO4、C60PCBM or PC61One or more combinations of BMs; the hole transport layer is made of Spiro-OMeTAD and Cu2O、CuO、CuGaO2、CuOx:N、Cu2S、CuS、CuI、CuSCN、CuPc、CuInS2、ZnS、MoOx、MoS2、NiO、WOx、VOxOne or a combination of PPS, P3HT, PTAA, FDT, HPDI, or HMDI.
In some embodiments, the novel solar power generation and energy storage dual function integrated device structure further comprises at least one pair of a first conductive layer and a second conductive layer, at least one of the first conductive layer and the second conductive layer having optical transparency; the first conducting layer and the second conducting layer are respectively contacted with the first electrode and the second electrode.
In some embodiments, the first conductive layer is one or more of FTO, ITO, IZO, AZO materials; the second conducting layer is one or a combination of more of aluminum, silver, gold, titanium, palladium, nickel, chromium and copper.
In some embodiments, the first conductive layer is one or more combinations of aluminum, silver, gold, titanium, palladium, nickel, chromium, copper; the second conductive layer is one or a combination of FTO, ITO, IZO and AZO materials.
In some embodiments, the first conductive layer is one or more of FTO, ITO, IZO, AZO materials; the second conductive layer is one or a combination of FTO, ITO, IZO and AZO materials.
In some embodiments, the light absorbing layer is perovskite (ABX)3) Material, gallium arsenide (GaAs), silicon (Si), Copper Indium Gallium Selenide (CIGS), cadmium telluride (CdTe), cadmium sulfide (CdS).
In some embodiments, the light absorbing layer is MAPbI3、(CsxMAyFA1-x-y)Pb(I1-zBrz)3、CsPb(I1- xBrx)3One or more combinations thereof.
According to one embodiment of the invention, a preparation method of a novel solar power generation and energy storage dual-function integrated device is provided, and the method comprises the following steps: preparing a first energy storage structure layer; preparing a second energy storage structure layer; preparing a light absorption layer; and integrating the light absorption layer, the first energy storage structure layer and the second energy storage structure layer on the basis of one of the first energy storage structure layer, the second energy storage structure layer and the light absorption layer as a substrate to prepare the solar power generation and energy storage dual-function integrated device.
In some embodiments, the first energy storage structure layer comprises a first electrode and an electron transport layer, the second energy storage structure layer comprises a second electrode and a hole transport layer, and the preparing the first energy storage structure layer comprises integrating the first electrode and the electron transport layer for a substrate based on one of the first electrode and the electron transport layer; preparing the second energy storage structure layer includes integrating the second electrode and a hole transport layer for a substrate based on one of the second electrode and the hole transport layer.
In some embodiments, the light absorbing layer, the first energy storage structure layer, and the second energy storage structure layer are integrated based on the electron transport layer being in contact with the light absorbing layer and the hole transport layer being in contact with the light absorbing layer.
In some embodiments, the method further comprises: integrating a first conductive layer based on a manner of contacting the first electrode; the second conductive layer is integrated based on being in contact with the second electrode.
In some embodiments, the first electrode is TiO2ZnO, graphite, Sn, SiO2、BN、AlN、Al2O3、TiN、MnO2Or V2O5One or more combinations of (a); the second electrode is TiF4、TiF3、CuO、LiMnO2、LiNiO2、LiCoO2、LiFePO4、LiMnPO4、Li2Se、Li2S、Li6C6O6Or Li4C6H4O4One or more combinations thereof.
In some embodiments, the electron transport layer is SnO2、LiFx、KFx、CsFx、CsOx、MgFx、TiOx、ZnO、ZnS、CdS、CdSe、Zn2SO4、BaSnO3、SrTiO4、C60PCBM or PC61One or more combinations of BMs; the hole transport layer is made of Spiro-OMeTAD and Cu2O、CuO、CuGaO2、CuOx:N、Cu2S、CuS、CuI、CuSCN、CuPc、CuInS2、ZnS、MoOx、MoS2、NiO、WOx、VOxOne or a combination of PPS, P3HT, PTAA, FDT, HPDI, or HMDI.
In some embodiments, the light absorbing layer is perovskite (ABX)3) Materials, gallium arsenide (GaAs), silicon (Si), Copper Indium Gallium Selenide (CIGS), cadmium telluride (CdTe), cadmium sulfide (CdS)) One or more combinations thereof.
In some embodiments, the light absorbing layer is MAPbI3、(CsxMAyFA1-x-y)Pb(I1-zBrz)3、CsPb(I1- xBrx)3One or more combinations thereof.
Compared with the prior art, the invention has the beneficial effects that:
(1) the first energy storage structure layer, the second energy storage structure layer and the light absorption layer form an integrated structure, photo-generated electrons and photo-generated holes generated by the light absorption layer are simultaneously utilized by the first energy storage structure layer and the second energy storage structure layer for energy storage during charging, and energy is released by the first energy storage structure layer and the second energy storage structure layer during discharging, so that the electricity generation and energy storage dual-function integrated device structure has the characteristics of high energy comprehensive utilization efficiency, mutual promotion in the charging and discharging processes and high integration of two electrode structures;
(2) the first energy storage structure layer and the second energy storage structure layer simultaneously utilize the photo-generated electrons and the photo-generated holes generated by the light absorption layer to store energy, and compared with the traditional two-electrode structure design of a photosensitive anode-cathode, an anode-photosensitive cathode and a photosensitive anode-photosensitive cathode in series, the invention simultaneously utilizes the reduction and oxidation capacities of the photo-generated electrons and the photo-generated holes and improves the utilization rate of the photo-generated electrons and the photo-generated holes;
(3) the invention respectively realizes the selective transmission of the photo-generated electrons and the photo-generated holes through the electron transmission layer and the hole transmission layer, avoids the condition that the photo-generated electrons and the photo-generated holes are combined at the interface of the photosensitive material and the electrode material, and improves the photoelectric conversion efficiency;
(4) the integrated structure of charging and discharging is realized through the first energy storage structure layer, the second energy storage structure layer and the light absorption layer, electrons in a conduction band of the light absorption layer and holes in a valence band are selectively transmitted through proper energy level matching respectively, unidirectional flow of electrons in an integrated device is realized, charging current of an energy storage battery can pass through the inside of the integrated device, the phenomenon of internal self-discharging of the integrated device can be prevented, and compared with the traditional energy storage battery, the integrated structure of charging and discharging improves the comprehensive utilization efficiency of energy of the integrated device, wherein the charging current of the energy storage battery needs to pass through an external circuit, and the energy loss of the external circuit is avoided;
(5) the operation processes of charging and discharging of the first energy storage structure layer, the second energy storage structure layer and the light absorption layer can be closely combined, an internal electric consumption field generated by discharging and a photo-generated carrier generated by charging can generate mutual auxiliary benefits in working operation, the generation of the photo-generated carrier is promoted, the internal electric consumption field is offset, the mutual promotion of the charging-discharging process is realized, and the comprehensive energy utilization efficiency and the stability of the integrated device are further improved.
Drawings
Fig. 1 is a schematic structural diagram of a positive type structure of an exemplary solar power generation and energy storage dual function integrated device according to some embodiments of the present invention;
FIG. 2 is a schematic structural diagram of an inversion structure of an exemplary solar power generation and energy storage dual function integrated device, according to some embodiments of the present invention;
FIG. 3 is a schematic structural diagram of another exemplary solar power generation and energy storage dual function integrated device structure, according to some embodiments of the present invention;
FIG. 4 is an exemplary flow chart illustrating a method for fabricating an exemplary integrated solar power generation and energy storage device, according to some embodiments of the present invention;
FIG. 5 is an exemplary flow chart illustrating an integration sequence of an exemplary first energy storage structure layer, a light absorbing layer, and a second energy storage structure layer according to some embodiments of the invention;
FIG. 6 is an exemplary flow chart illustrating an integration sequence of another exemplary first energy storage structure layer, light absorbing layer, and second energy storage structure layer according to some embodiments of the invention;
FIG. 7 is an exemplary flow chart illustrating an integration sequence of a further exemplary first energy storage structure layer, a light absorbing layer, and a second energy storage structure layer according to some embodiments of the invention;
FIG. 8 is an exemplary flow chart illustrating an exemplary first electrode, electron transport layer integration sequence according to some embodiments of the inventions;
FIG. 9 is an exemplary flow chart illustrating yet another exemplary first electrode, electron transport layer, first conductive layer integration sequence according to some embodiments of the inventions;
FIG. 10 is an exemplary flow chart illustrating an exemplary second electrode, hole transport layer integration sequence according to some embodiments of the inventions;
FIG. 11 is an exemplary flow chart illustrating yet another exemplary second electrode, hole transport layer, second conductive layer integration sequence according to some embodiments of the inventions;
fig. 12 is an exemplary flowchart of an integration sequence of materials of layers of the solar power generation and energy storage dual-function integrated device according to the present application.
The solar cell comprises a first conductive layer 11, a first energy storage structure layer 12, a first electrode 121, an electron transport layer 122, a light absorption layer 13, a second energy storage structure layer 14, a hole transport layer 141, a second electrode 142 and a second conductive layer 15.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
It should be noted that all expressions using "first" and "second" in the embodiments of the present invention are used for distinguishing two entities with the same name but different names or different parameters, and it should be noted that "first" and "second" are only used for convenience of description and should not be construed as limitations of the embodiments of the present invention, and they are not described in any more detail in the following embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
FIGS. 1-3 are schematic structural diagrams of exemplary solar power generation and energy storage dual function integrated device structures according to some embodiments of the invention. In some embodiments, the novel solar power generation and energy storage dual function integrated device structure may comprise:
and a light absorbing layer 13 for generating photo-generated electrons and photo-generated holes. Specifically, the light absorbing layer 13 can generate photo-generated electrons and photo-generated holes by the photoelectric effect.
In some embodiments, light-absorbing layer 13 may be a material of a shape that is capable of generating a photoelectric effect, wherein the shape is generally a layered structure so as to absorb more photons to generate more photogenerated electrons and photogenerated holes. In some embodiments, the light absorbing layer 13 may be perovskite (ABX)3) Material, gallium arsenide (GaAs), silicon (Si), Copper Indium Gallium Selenide (CIGS), cadmium telluride (CdTe), cadmium sulfide (CdS). In some embodiments, the light absorbing layer 13 may be one or more combinations of organic lead-based halides, organic-inorganic hybrid lead-based halides, inorganic hybrid lead-based halide perovskite materials, e.g., MAPbI3、(CsxMAyFA1-x-y)Pb(I1-zBrz)3、CsPb(I1-xBrx)3And the like. In some embodiments, the indices (e.g., x, y, z) included in the formula may take on a decimal value between 0-1, e.g., light absorbing layer 13 may be Cs0.05FA0.8MA0.15PbI2.55Br0.45. In some embodiments, the light absorbing layer 13 may have ion conductivity to facilitate an ion transfer process between the first and second energy storage structure layers 12 and 14 for energy storage related charging and discharging processes. In some embodiments, the concentration of non-radiative recombination centers in and at the interface of the light absorbing layer 13 is low in order to improve the lifetime of the non-equilibrium carriers and extend the diffusion length of the non-equilibrium carriers.
And the first energy storage structure layer 12 and the second energy storage structure layer 14 are at least one pair, wherein the first energy storage structure layer 12 and the second energy storage structure layer 14 are respectively in contact with the light absorption layer 13. Specifically, when the light absorption layer 13 generates photo-generated electrons and photo-generated holes, the first energy storage structure layer 12 generates an energy storage chemical reaction by using the photo-generated electrons, and the second energy storage structure layer 14 generates an energy storage chemical reaction by using the photo-generated holes.
In some embodiments, when the light absorption layer 13 generates photo-generated electrons and photo-generated holes, the first energy storage structure layer 12 may perform a reduction reaction using the photo-generated electrons generated by the light absorption layer 13, and the second energy storage structure layer 14 may perform an oxidation reaction using the photo-generated holes generated by the light absorption layer 13, so as to implement an energy storage function. In some embodiments, when the first energy storage structure layer 12 and the second energy storage structure 14 are connected to an external circuit, for example, electrical elements are connected through a wire, because there is a potential difference between the first energy storage structure layer 12 and the second energy storage structure 14, the first energy storage structure layer 12 can automatically perform an oxidation reaction to lose electrons, and the second energy storage structure layer 14 can automatically perform a reduction reaction to obtain electrons, thereby implementing a discharge function.
In some embodiments, for the purpose of performing a reduction reaction and storing energy, the first energy storage structure layer 12 may include a first electrode 121 and an electron transport layer 122 in contact with each other, and the first electrode 121 may generate an energy storage reduction reaction by using photo-generated electrons. In some embodiments, the first electrode 121 may have electrical conductivity so as to achieve electrical conduction of the discharge process. In some embodiments, as shown in fig. 1, when light is irradiated from one side of the first electrode 121, in order to facilitate the light absorption layer 13 to absorb more photons, the first electrode 121 may further have a light-transmitting property. In some embodiments, the first electrode 121 may be TiO2ZnO, graphite, Sn, SiO2、BN、AlN、Al2O3、TiN、MnO2Or V2O5One or more combinations thereof. In some embodiments, in order to facilitate the ability of light absorbing layer 13 to absorb more photons, electron transport layer 122 may be light transmissive. In some embodiments, the electron transport layer 122 may be SnO2、LiFx、KFx、CsFx、CsOx、MgFx、TiOx、ZnO、ZnS、CdS、CdSe、Zn2SO4、BaSnO3、SrTiO4、C60PCBM or PC61One or more combinations of BMs. In some embodimentsThe index (e.g., x) corresponding to the chemical formula of the material of the electron transport layer 122 may take a range of positive values (e.g., 0.5, 1, 1.6, 2, etc.).
In some embodiments, the electron transport layer 122 may implement an electron selective transport characteristic in an energy level matching relationship with the light absorption layer 13, where the electron selective transport characteristic may refer to a characteristic of allowing the photo-generated electrons generated in the light absorption layer 13 to pass through but preventing the photo-generated holes from passing through, so as to effectively separate the photo-generated electrons and avoid a problem that the photo-generated electrons and the photo-generated holes are recombined to reduce the photoelectric conversion efficiency during the energy storage process. In some embodiments, the energy level matching relationship may be achieved by the material selection of the electron transport layer 122 and the light absorption layer 13, for example, the electron transport layer 122 may be selected to be SnO2The thin film, light absorbing layer 13 is perovskite (ABX)3) The material realizes electron selective transport characteristics, and for example, the electron transport layer 122 can be PCBM thin film, and the light absorption layer 13 can be CsPb (I)1-xBrx)3The material realizes the selective electron transport property.
In some embodiments, the material of the first electrode 121 and the material of the electron transport layer 122 may be selected to have an energy level relationship matching, so that the first electrode 121 generates an energy storage reduction reaction by using photo-generated electrons, for example, the first electrode 121 may be selected to be TiO2The thin film, the electron transport layer 122 is SnO2A film; for another example, the first electrode 121 may be a ZnO film, and the electron transport layer 122 may be a PCBM film. The first electrode 121 is made of TiO2The thin film, the electron transport layer 122 is SnO2Thin films as an example, TiO in the process of storing energy by photo-generated electrons2Film and SnO2The film interface may undergo the following chemical reactions:
TiO2+xLi++xe-→LixTiO2(x≤1)
it should be noted that the selection of the specific material for the first energy storage structure layer 12 is only exemplary, and other materials may also be adopted for the specific material for the first energy storage structure layer, for example, the first electrode 121 is a ZnO film, and the electron transport layer 122 is SnO2A film.
In some embodiments, the second energy storage structure layer 14 may include a second electrode 142 and a hole transport layer 141 in contact with each other for the purpose of oxidation reaction and energy storage. In some embodiments, the second electrode 142 may have electrical conductivity to facilitate electrical conduction of the discharge process. In some embodiments, the second electrode 142 may also be light transmissive in order to facilitate the light absorbing layer 13 to absorb more photons when light is irradiated from the second electrode 142. In some embodiments, the second electrode 142 may be TiF4、TiF3、CuO、LiMnO2、LiNiO2、LiCoO2、LiFePO4、LiMnPO4、Li2Se、Li2S、Li6C6O6Or Li4C6H4O4One or more combinations thereof. In some embodiments, hole transport layer 141 may be light transmissive in order to facilitate the ability of the light absorbing layer to absorb more photons. In some embodiments, the hole transport layer 141 may be a pre-prepared hole transport layer precursor solution spin-coated on the light absorption layer by a spin coater, and specifically, the hole transport layer 141 precursor solution may be 72.3mg of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group in 1ml of chlorobenzene]-9,9' -spirobifluorene (Spiro-OMeTAD), 17.5ul of lithium bistrifluoromethylsulfonimide (Li-TFSI) and 28.8ul of 4-tert-butylpyridine (tBP). In some embodiments, the hole transport layer 141 may be Spiro-OMeTAD, Cu2O、CuO、CuGaO2、CuOx:N、Cu2S、CuS、CuI、CuSCN、CuPc、CuInS2、ZnS、MoOx、MoS2、NiO、WOx、VOxPPS, P3HT, PTAA, FDT, HPDI, or HMDI, or a combination thereof. In some embodiments, the index (e.g., x) corresponding to the chemical formula of the hole transport layer 141 material may take a range of positive values (e.g., 0.5, 1, 1.6, 2, etc.).
In some embodiments, the hole transport layer 141 may achieve hole selection in an energy level matching relationship with the light absorbing layer 13The hole selective transport property may be a property of allowing photo-generated holes generated in the light absorbing layer 13 to pass through but preventing photo-generated electrons from passing through, so as to effectively separate the photo-generated holes and avoid the problem that the photo-generated electrons and the photo-generated holes are recombined to reduce the photoelectric conversion efficiency in the energy storage process. In some embodiments, the energy level matching relationship may be achieved by the material selection of the light absorbing layer 13 and the hole transport layer 141, for example, the hole transport layer 141 may be selected to be a Spiro-OMeTAD thin film, and the light absorbing layer 13 may be selected to be perovskite (ABX)3) The material can realize selective electron transport property, and for example, the hole transport layer 141 can be a NiO thin film, and the light absorption layer 13 can be CsPb (I)1-xBrx)3The material realizes the selective electron transport property.
In some embodiments, the material of the second electrode 142 and the material of the hole transport layer 141 are selected to have an energy level relationship matching so that the second electrode 142 generates an energy storage oxidation reaction by using photo-generated holes, for example, the second electrode 142 can be selected to be Li2An S film, wherein the hole transport layer 141 is a Spiro-OMeTAD film; as another example, the second electrode 142 can be selected to be Li6C6O6The thin film, the hole transport layer 141 is a NiO thin film. The second electrode 142 is Li2An S thin film, the hole transport layer 141 is a Spiro-OMeTAD thin film as an example, and Li is used for storing energy by photo-generated holes2The S film and Spiro-OMeTAD film interface can undergo the following chemical reaction:
nLi2S+(2n-2)h+→Li2Sn+(2n-2)Li+(2≤n≤8)
it is noted that the above-mentioned selection of the specific material of the second energy storage structure layer 14 is only exemplary, and other materials can be adopted for the specific material of the second energy storage structure layer 14, for example, the material of the second electrode 142 can be selected to be Li6C6O6Thin film, for example, the material of the second electrode 142 may be selected to be Li4C6H4O4A film.
As an example, when the material of the second electrode 142 is Li6C6O6In the case of thin films, Li6C6O6The film interface with the Spiro-OMeTAD film can undergo the following chemical reaction:
Li6C6O6+2h+→Li4C6O6+2Li+
Li4C6O6+2h+→Li2C6O6+2Li+
as an example, when the material of the second electrode 142 is Li4C6H4O4In the case of thin films, Li4C6H4O4The film interface with the Spiro-OMeTAD film can undergo the following chemical reaction:
Li4C6H4O4+2h+→Li2C6H4O4+2Li+
in some embodiments, the solar power generation and energy storage dual function integrated device structure may further include at least one pair of a first conductive layer 11 and a second conductive layer 15, wherein, in order to facilitate the light absorption layer 13 to absorb more photons, at least one of the first conductive layer 11 and the second conductive layer 15 has light transmittance, for example, as shown in fig. 1, when light is irradiated from the right side, the first conductive layer 11 has light transmittance. In some embodiments, the first conductive layer 11 and the second conductive layer 15 may be in contact with the first electrode 121 and the second electrode 142, respectively, for example, as shown in fig. 1, the first conductive layer 11 having light transmittance is in contact with the first electrode 121 when light is irradiated from the right side, and for example, as shown in fig. 2, the first conductive layer 11 having light transmittance is in contact with the second electrode 142 when light is irradiated from the left side. In some embodiments, a device structure convenient for integration may be formed by the first conductive layer 11 and the second conductive layer 15, and specifically, when integration is performed, each solar power generation and energy storage dual-function integrated device structure may form a circuit structure connected in series or in parallel by the first conductive layer 11 and the second conductive layer 15, so as to achieve the purpose of high power charging and discharging. In some embodiments, in order to facilitate single-sided light transmission, one of the first conductive layer 11 and the second conductive layer 15 may be made of a light-transmitting material, for example, the first conductive layer 11 may be selected to be one or more combinations of FTO, ITO, IZO, AZO materials, and the second conductive layer 15 may be selected to be one or more combinations of aluminum, silver, gold, titanium, palladium, nickel, chromium, and copper; for another example, the second conductive layer 15 may be one or more combinations of FTO, ITO, IZO, and AZO materials, and the first conductive layer 11 may be one or more combinations of aluminum, silver, gold, titanium, palladium, nickel, chromium, and copper. In some embodiments, energy absorption of the double-sided light source may also be achieved by disposing both the first conductive layer 11 and the second conductive layer 15 as light transmissive materials, for example, the first conductive layer 11 may be selected to be one or more combinations of FTO, ITO, IZO, AZO materials, and the second conductive layer 15 may be selected to be one or more combinations of FTO, ITO, IZO, AZO materials.
It should be noted that, in the above structure of the dual-function integrated device for solar power generation and energy storage, the first energy storage structure layer 12 and the second energy storage structure layer 14 are respectively disposed on two sides of the light absorption layer 13, which is only an example, and the specific structure of the dual-function integrated device for solar power generation and energy storage may also have other various manners, for example, as shown in fig. 3, the first energy storage structure layer 12 and the second energy storage structure layer 14 are simultaneously disposed on one side of the light absorption layer 13, and only illumination needs to be irradiated from the other side (for example, the bottom side shown in fig. 3). For another example, a buffer layer or an interface modification layer may be disposed between the main functional layers (e.g., the light absorption layer 13, the first energy storage structure layer 12, the second energy storage structure layer 14, etc.) to achieve better energy level matching or to reduce the concentration of nonradiative recombination centers and the defect density at the interface. For another example, each of the main functional layers (e.g., the light absorbing layer 13, the first energy storage structure layer 12, the second energy storage structure layer 14, etc.) may be doped with an impurity element or an additive to achieve the purpose of energy level matching between the main functional layers, elimination or passivation of defects at the interface, and improvement of crystal quality.
In some embodiments, when the energy storage cell is charged, the photo-generated electrons generated by the light absorption layer 13 flow to the anode of the energy storage cell (for example, the first electrode 121 of the first energy storage structure layer 12), and the first energy storage structure layer 12 performs a reduction reaction by using the photo-generated electrons generated by the light absorption layer 13, so as to implement an anode energy storage function; the photo-generated holes generated by the light absorbing layer 13 flow to the cathode of the energy storage cell (for example, the second electrode 142 of the second energy storage structure layer 14), and the second energy storage structure layer 14 performs an oxidation reaction by using the photo-generated holes generated by the light absorbing layer 13, thereby implementing a cathode energy storage function. Therefore, the first energy storage structure layer 12 and the second energy storage structure layer 14 simultaneously utilize the photo-generated electrons and the photo-generated holes generated by the light absorption layer 13 to store energy, and compared with the traditional structural design of connecting a photosensitive anode-cathode, an anode-photosensitive cathode and a photosensitive anode-photosensitive cathode in series, the invention simultaneously utilizes the reduction and oxidation capacities of the photo-generated electrons and the photo-generated holes, and improves the utilization rate of the photo-generated electrons and the photo-generated holes.
In some embodiments, when the energy storage cell is discharged, electrons flow from the anode (e.g., the first electrode 121 of the first energy storage structure layer 12) to the cathode (e.g., the second electrode 142 of the second energy storage structure layer 14) through an external load circuit, an internal electric field and a corresponding internal voltage inside the cell cause positive ions to migrate from the anode to the cathode, the direction of the internal electric field is directed from the anode to the cathode, and thus, photo-generated electrons and photo-generated holes flow to the anode and the cathode of the energy storage cell, respectively. Therefore, the internal electric field of the energy storage cell in the discharging process is beneficial to the separation of photogenerated electron hole pairs in the solar cell, and the photoproduction current of the solar cell is also beneficial to weakening the internal electric field of the energy storage cell in the discharging process, so that the internal consumption of the energy storage cell in the discharging process is reduced. Therefore, the solar cell and the energy storage device in the integrated device structure provided by the invention can generate mutual auxiliary benefits in the working operation, and the comprehensive energy utilization efficiency and the stability of the integrated device are further improved.
Fig. 4 is an exemplary flow chart of a method for manufacturing a solar power generation and energy storage dual function integrated device according to some embodiments of the invention. The method may include:
step S101, a first energy storage structure layer 12 is prepared. The first energy storage structure layer 12 performs an energy storage chemical reaction by using the photo-generated electrons generated by the light absorption layer 13.
In some embodiments, the first energy storage structure layer 12 may include a first electrode 121 and an electron transport layer 122. In some embodiments, preparing the first energy storage structure layer 12 may include integrating the first electrode 121 and the electron transport layer 122 for a substrate based on one of the first electrode 121 and the electron transport layer 122, for example, as shown in fig. 8, the first energy storage structure layer 12 is formed by integrating the first electrode 121 through step S211 with the electron transport layer 122 as a substrate; for another example, as shown in fig. 9, the first energy storage structure layer 12 is formed through step S212 of integrating the electron transport layer 122 with the first electrode 121 as a substrate. In some embodiments, integrating the first electrode 121 and the electron transport layer 122 may be performed by Physical Vapor Deposition (PVD) (including magnetron sputtering, e-beam evaporation, thermal evaporation, etc.), Atomic Layer Deposition (ALD), Pulsed Laser Deposition (PLD), spray pyrolysis, spray coating, spin coating, blade coating, screen printing, chemical vapor deposition, Plasma Enhanced Chemical Vapor Deposition (PECVD), etc.
In some embodiments, the first electrode 121 may be TiO2ZnO, graphite, Sn, SiO2、BN、AlN、Al2O3、TiN、MnO2Or V2O5One or more combinations thereof. In some embodiments, the first electrode 121 can be prepared by preparing a precursor solution, in TiO2Film is exemplified by TiO2The preparation of the film comprises the preparation of a compact layer and the preparation of a mesoporous structure layer, wherein for the compact layer, a titanium isopropoxide raw solution and an ethanol solution are mixed, a trace amount of concentrated hydrochloric acid solution is added to prepare a compact layer precursor solution, and then the compact layer precursor solution is spin-coated on a clean substrate to prepare TiO after the processes of heating, drying annealing and the like2A dense layer of a thin film; for the mesoporous structure layer, mesoporous titanium dioxide gel (Dyesol 30NR-D) can be diluted by ethanol to prepare a mesoporous structure layer precursor solution, and then the mesoporous structure layer precursor solution is spin-coated on the dense layer and subjected to heating, drying, annealing and other processes to obtain TiO with the dense layer combined with the mesoporous structure layer2A film.
In some embodiments, the electron transport layer 122 may be SnO2、LiFx、KFx、CsFx、CsOx、MgFx、TiOx、ZnO、ZnS、CdS、CdSe、Zn2SO4、BaSnO3、SrTiO4、C60PCBM or PC61One or more combinations of BMs. In some embodiments, the material of the electron transport layer 122 may have a range of positive values (e.g., 0.5, 1, 1.6, 2, etc.) for the corresponding corner mark (e.g., x) of the chemical formula. In some embodiments, the electron transport layer 122 can be prepared by formulating a precursor solution, in SnO2For example, SnO may be used2Mixing the dispersion with ionized water to obtain SnO2Precursor solution, then SnO2The precursor solution is coated on a clean substrate in a spinning way and is subjected to the processes of heating, drying annealing and the like to prepare SnO2A film.
And step S103, preparing a second energy storage structure layer 14. Wherein, the second energy storage structure layer 14 can generate an energy storage chemical reaction by using the photo-generated holes.
In some embodiments, the second energy storage structure layer 14 may include a second electrode 142 and a hole transport layer 141. In some embodiments, preparing the first energy storage structure layer 12 may include integrating the second electrode 142 and the hole transport layer 141 for a substrate based on one of the second electrode 142 and the hole transport layer 141, for example, as shown in fig. 10, forming the second energy storage structure layer 14 by integrating the second electrode 142 with the hole transport layer 141 as a substrate in step S221; for another example, as shown in fig. 11, the second energy storage structure layer 14 is formed through the step S222 of integrating the hole transport layer 141 with the second electrode 142 as a substrate. In some embodiments, integrating the second electrode 142 and the hole transport layer 141 may be performed by Physical Vapor Deposition (PVD) (including magnetron sputtering, e-beam evaporation, thermal evaporation, etc.), Atomic Layer Deposition (ALD), Pulsed Laser Deposition (PLD), spray pyrolysis, spray coating, spin coating, blade coating, screen printing, chemical vapor deposition, Plasma Enhanced Chemical Vapor Deposition (PECVD), etc.
In some embodiments, the second electrode 142 may be TiF4、TiF3、CuO、LiMnO2、LiNiO2、LiCoO2、LiFePO4、LiMnPO4、Li2Se、Li2S、Li6C6O6Or Li4C6H4O4One or more combinations thereof. In some embodiments, the second electrode 142 can be prepared by formulating a precursor solution with Li2S thin film, for example, Li can be added2S is dissolved in isopropanol solution to prepare Li2S precursor solution preparation, then Li2The S precursor solution is coated on a clean substrate in a spinning way and is subjected to the processes of heating, drying annealing and the like to prepare Li2And (S) film.
In some embodiments, the hole transport layer 141 may be Spiro-OMeTAD, Cu2O、CuO、CuGaO2、CuOx:N、Cu2S、CuS、CuI、CuSCN、CuPc、CuInS2、ZnS、MoOx、MoS2、NiO、WOx、VOxPPS, P3HT, PTAA, FDT, HPDI, or HMDI, or a combination thereof. In some embodiments, the index (e.g., x) corresponding to the chemical formula of the hole transport layer 141 material may take a range of positive values (e.g., 0.5, 1, 1.6, 2, etc.). In some embodiments, the hole transport layer 141 can be prepared by preparing a precursor solution, such as a Spiro-OMeTAD thin film, which can be prepared by dissolving chlorobenzene, 2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group]Mixing (9, 9' -spirobifluorene (Spiro-OMeTAD), lithium bistrifluoromethylsulfonimide (Li-TFSI) and 4-tert-butylpyridine (tBP) to prepare a Spiro-OMeTAD precursor solution, then spin-coating the Spiro-OMeTAD precursor solution on a clean substrate, and carrying out heating, drying, annealing and other processes to prepare the Spiro-OMeTAD film.
Step 105 prepares the light absorbing layer 13. The light absorption layer 13 may generate photo-generated electrons and photo-generated holes by a photoelectric effect.
In some embodiments, the light absorbing layer 13 may be perovskite (ABX)3) Material, gallium arsenide (GaAs), silicon (Si), Copper Indium Gallium Selenide (CIGS), cadmium telluride (CdTe), cadmium sulfide (CdS). In some embodiments, the light absorbing layer 13 may be an organolead-based halide, an organic-inorganic hybrid lead-based halide, an inorganic hybrid lead-based halide perovskite materialOne or more combinations of (a), e.g. MAPbI3、(CsxMAyFA1-x-y)Pb(I1-zBrz)3、CsPb(I1-xBrx)3And the like. In some embodiments, the indices (e.g., x, y, z) included in the formula may take on a decimal value between 0-1, e.g., light absorbing layer 13 may be Cs0.05FA0.8MA0.15PbI2.55Br0.45. In some embodiments, light absorbing layer 13 may be prepared by preparing a precursor solution with Cs0.05FA0.8MA0.15PbI2.55Br0.45For example, PbI can be used2、FAI、PbBr2Dissolving MABr and CsI in a mixed solvent of DMF and DMSO to obtain a precursor solution of the light absorption layer 13, and then heating, drying, annealing and the like the precursor solution of the light absorption layer 13 on a clean substrate to obtain the light absorption layer. In some embodiments, an additive may be further doped in the process of preparing the precursor solution of the light absorption layer 13, for example, LiI with a molar percentage of 2% is doped as the additive.
In some embodiments, one of the first energy storage structure layer 12, the second energy storage structure layer 14 and the light absorption layer 13 may be integrated as a substrate, for example, taking fig. 5 as an example, the first energy storage structure layer 12 may be used as a substrate, and then the step S111 of integrating the light absorption layer 13 on the first energy storage structure layer 12 and the step S112 of integrating the second energy storage structure layer 14 on the light absorption layer 13 and the first energy storage structure layer 12 are sequentially performed; for another example, taking fig. 6 as an example, the light absorbing layer 13 may be used as a substrate, and then the step S121 of integrating the first energy storage structure layer 12 on the light absorbing layer 13 and the step S122 of integrating the second energy storage structure layer 14 on the light absorbing layer 13 are performed; for another example, taking fig. 7 as an example, the second energy storage structure layer 14 may be used as a substrate, and then the step S131 of integrating the light absorbing layer 13 on the second energy storage structure layer 14 and the step S132 of integrating the first energy storage structure layer 12 on the light absorbing layer 13 and the second energy storage structure layer 14 are sequentially performed. In some embodiments, the light absorbing layer 13, the first energy storage structure layer 12, and the second energy storage structure layer 14 may be integrated based on the electron transport layer 122 contacting the light absorbing layer 13 and the hole transport layer 141 contacting the light absorbing layer 13. In some embodiments, the integration of the first energy storage structure layer 12, the second energy storage structure layer 14, and the light absorption layer 13 may be achieved by Physical Vapor Deposition (PVD) (including magnetron sputtering, electron beam evaporation, thermal evaporation, etc.), Atomic Layer Deposition (ALD), Pulsed Laser Deposition (PLD), spray pyrolysis, spray coating, spin coating, blade coating, screen printing, chemical vapor deposition, Plasma Enhanced Chemical Vapor Deposition (PECVD), and the like.
In some embodiments, the first conductive layer 11 may be integrated based on being in contact with the first electrode 121, and the second conductive layer 15 may be integrated based on being in contact with the second electrode 142, so that a device structure for facilitating integration may be formed by the first conductive layer 11 and the second conductive layer 15. In some embodiments, in order to facilitate single-sided light transmission, one of the first conductive layer 11 and the second conductive layer 15 may be made of a light-transmitting material, for example, the first conductive layer 11 may be selected to be one or more combinations of FTO, ITO, IZO, AZO materials, and the second conductive layer 15 may be selected to be one or more combinations of aluminum, silver, gold, titanium, palladium, nickel, chromium, and copper; for another example, the second conductive layer 15 may be one or more combinations of FTO, ITO, IZO, and AZO materials, and the first conductive layer 11 may be one or more combinations of aluminum, silver, gold, titanium, palladium, nickel, chromium, and copper. In some embodiments, energy absorption of the double-sided light source may also be achieved by disposing both the first conductive layer 11 and the second conductive layer 15 as light transmissive materials, for example, the first conductive layer 11 may be selected to be one or more combinations of FTO, ITO, IZO, AZO materials, and the second conductive layer 15 may be selected to be one or more combinations of FTO, ITO, IZO, AZO materials. In some embodiments, the integrated first and second conductive layers 11, 15 may be evaporated using Physical Vapor Deposition (PVD) (including magnetron sputtering, electron beam evaporation, thermal evaporation, etc.), Atomic Layer Deposition (ALD), Pulsed Laser Deposition (PLD), spray pyrolysis, spray coating, spin coating, blade coating, screen printing, chemical vapor deposition, Plasma Enhanced Chemical Vapor Deposition (PECVD), or thermal evaporation processes. For example only, the first conductive layer 11 may be provided as an FTO film of a light transmissive material, and the second conductive layer 15 may be provided as a silver film electrode.
It should be noted that the above method is only for clearly illustrating the integration and preparation method of each layer of material, and the sequence steps are not limited, for example, the sequence of step 101, step 103, and step 105 may be interchanged. In addition, the integration order of the materials of the layers is not limited, for example, as shown in fig. 9, the step S312 of integrating the first conductive layer 11 on the first electrode 121 may be completed, and then the mixed-level material composed of the first electrode 121 and the first conductive layer 11 may be integrated with the electron transport layer 122; for another example, as shown in fig. 11, the step S322 of integrating the second conductive layer 15 on the second electrode 142 may be completed first, and then the hole transport layer 141 may be integrated with the mixed-level material composed of the second electrode 142 and the second conductive layer 15. For another example, an integration sequence of steps S401 to S406 shown in fig. 12 may also be employed.
Fig. 12 is an exemplary flowchart of an integration sequence of materials of layers of the solar power generation and energy storage dual-function integrated device according to the present application. By way of example only, the FTO film is used as the first conductive layer 11, and the TiO is used as the first electrode 1212The thin film and the electron transport layer 122 are SnO2The thin film, the light absorbing layer 13 is a perovskite light absorbing layer, the hole transport layer 141 is a Spiro-OMeTAD thin film, and the second electrode 142 is Li2The preparation sequence and the process are explained in detail for the structure of the exemplary novel solar power generation and energy storage dual-function integrated device formed by the S film and the second conductive layer 15 which are made of the metal silver film. The method can comprise the following steps:
s401, a first electrode is integrated on the first conductive layer.
The first conducting layer 11 is made of an FTO conducting glass substrate, the transmittance of visible light of the FTO conducting glass substrate is greater than 80%, the sheet resistance of a thin film is less than 15 omega and greater than 5 omega, the FTO conducting glass substrate is cleaned by a mixed solution of a cleaning agent and deionized water, then is cleaned by the deionized water, and is sequentially cleaned by organic solvents of ethanol, acetone, isopropanol and ethanol, all the solvents are cleaned in an ultrasonic cleaner for 20min, and finally is dried by nitrogen, and then the first conducting layer 11 is pretreated after being treated by ultraviolet ozone for 15 min.
The first electrode 121 is made of TiO2Film, TiO2The film has a two-layer structure, the first layer is a plane compact layer, and the preparation process comprises the following steps: preparing TiO2Dense layer precursor solution: adding the titanium isopropoxide raw solution into the ethanol solution, uniformly stirring, wherein the volume ratio of the titanium isopropoxide raw solution to the ethanol is 1:5, and adding a trace amount of concentrated hydrochloric acid solution (the volume ratio is about 1.5%); absorb TiO2The conductive glass substrate is paved with the dense layer precursor solution FTO, and then spin-coated at 2000 revolutions per minute for 50 seconds; after the spin coating is finished, the substrate is placed on a heating plate and dried for 15 minutes at the temperature of 150 ℃; the substrate was annealed at 500 ℃ for 30 minutes (placed on tin foil paper in a petri dish and placed in a muffle furnace) to complete the integration of the planar compact layer. The second layer is a mesoporous structure layer, and the preparation process comprises the following steps: preparing TiO2Precursor solution of mesoporous structure layer: diluting 30 nm-grain mesoporous titanium dioxide gel (Dyesol 30NR-D) with ethanol (volume ratio is 1: 3); uniformly spin-coating the precursor solution on the substrate after the previous step by using a spin coater, wherein the spin coating speed is 3000 rpm, and the spin coating time is 30 seconds; after the spin coating is finished, the substrate is placed on a heating plate and dried for 10 minutes at the temperature of 100 ℃; and (3) annealing the substrate at 450 ℃ for 30 minutes (putting the substrate on tin foil paper, putting the substrate into a culture dish and putting the culture dish into a muffle furnace) to complete the integration of the mesoporous structure layer. And finally, finishing the process of integrating the first electrode 121 on the first conductive layer 11 after ultraviolet ozone treatment for 15 min.
Step S402, the electron transport layer 122 is integrated on the substrate on which the integration is completed in step S401.
Wherein the electron transport layer 122 is SnO2The preparation process of the film comprises the following steps: configuration SnO2Electron transport layer precursor solution: a uniformly dispersed nano-crystalline tin dioxide solution (hereinafter referred to as SnO)2Stock solution), SnO2The size of the stannic oxide nano crystal grain in the stock solution is between 2nm and 10nm, the dispersion solution is water, and the mass percent of stannic oxide is15 percent; the SnO2SnO reacting the stock solution with deionized water2Stock solution: mixing ionized water in a volume ratio of 1:3, and performing ultrasonic treatment for 20 minutes to obtain planar SnO2Precursor solution; SnO2Uniformly spin-coating the precursor solution on the substrate which is integrated in the step S401 by using a spin coater, wherein the spin coating speed is 4000 revolutions per minute, and the spin coating time is 30 seconds; then the SnO is coated by spin coating at the temperature of 150 DEG C2Annealing the substrate of the precursor solution for 30 minutes to obtain SnO2And the electron transport layer 122 is subjected to ultraviolet ozone treatment for 15min, and then the integration process of the electron transport layer 122 is completed.
In step S403, light absorbing layer 13 is integrated on the substrate on which the integration is completed in step S402.
Wherein the light absorption layer 13 is Cs0.05FA0.8MA0.15PbI2.55Br0.45The preparation process comprises the following steps: preparing a precursor solution: will PbI2(1.2M)、FAI(1.1M)、PbBr2(0.2M), MABr (0.2M), CsI (0.07M) were dissolved in a mixed solvent of DMF and DMSO, with DMSO being 4:1 (volume ratio), and doped with LiI at 2% molar percentage as an additive; uniformly spin-coating the precursor solution on the substrate after the previous step by using a spin coater, wherein the spin speed is 2000 revolutions per minute, the spin coating time is 10 seconds, then 4000 revolutions per minute and the spin coating time is 20 seconds, and 100 mu l of chlorobenzene is dripped on the substrate 5 seconds before the spin coating is finished; then, the substrate spin-coated with the precursor solution is annealed at 100 ℃ for 45min to complete the integration process of the light absorption layer 13 (this step is performed under a nitrogen protection environment).
Step S404, integrating the hole transport layer 141 on the substrate whose integration is completed in step S403.
The hole transport layer 141 is a Spiro-OMeTAD film, and the preparation process thereof is as follows: preparing a precursor solution: the hole transport layer precursor solution may be a mixed solution of 72.3mg of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD), 17.5ul of lithium bistrifluoromethylenesulfonamide (Li-TFSI) and 28.8ul of 4-tert-butylpyridine (tBP) in 1ml of chlorobenzene; uniformly spin-coating the precursor solution on the substrate after the previous step by using a spin coater, wherein the spin-coating speed is 2500 rpm, and the spin-coating time is 30 seconds (the step is carried out under the nitrogen protection environment); then the substrate is placed in a pure oxygen atmosphere at room temperature for 2.5 hours to complete the integration process of the hole transport layer 141.
In step S405, the second electrode 142 is integrated on the substrate whose integration is completed in step S404.
Wherein the second electrode 142 is Li2The preparation process of the S film comprises the following steps: preparing a precursor solution: mixing Li2S (1.5M) is dissolved in isopropanol solution; and uniformly spin-coating the precursor solution on the substrate subjected to the previous step by using a spin coater, wherein the spin-coating speed is 2500 rpm, the spin-coating time is 30 seconds (the step is performed under the nitrogen protection environment), and the integration process of the second electrode 142 is completed after the completion.
In step S406, a second conductive layer 15 is integrated on the substrate on which the integration is completed in step S405.
The second conductive layer 15 is a silver film electrode, and the preparation process thereof is as follows: and (5) putting the substrate obtained in the step (S405) in vacuum evaporation equipment, and evaporating a layer of silver film electrode by a thermal evaporation process, wherein the thickness of the silver film is 100nm-200 nm.
After the sequential integration process with the FTO conductive glass as the substrate is completed, the novel solar power generation and energy storage dual-function integrated device can be prepared.
It should be noted that the above-mentioned method for manufacturing the novel solar power generation and energy storage dual-function integrated device is only an exemplary one to clearly illustrate the process of integrating each layer by spin coating, and does not limit the manufacturing method, the integration method and the integration sequence of the present invention specifically, the method for integrating and manufacturing each layer of material for the novel solar power generation and energy storage dual-function integrated device also has various embodiments, for example, Physical Vapor Deposition (PVD) (including magnetron sputtering, electron beam evaporation, thermal evaporation, etc.), Atomic Layer Deposition (ALD), Pulsed Laser Deposition (PLD), spray pyrolysis, spraying, blade coating, screen printing, chemical vapor deposition, Plasma Enhanced Chemical Vapor Deposition (PECVD), or thermal evaporation process evaporation can be used to integrate and manufacture each main functional layer (for example, the electron transport layer 122, the hole transport layer 141, the hole transport layer, The first electrode 121, the second electrode 142, the light absorbing layer 13, etc.), the integration order may also have various embodiments, such as preparation from step S406 to step S401 in reverse order, or preparation by any permutation and combination forming method of step S401 to step S406.
The above is an embodiment of the present invention. The specific parameters in the above embodiments and examples are only for the purpose of clearly illustrating the invention verification process of the inventor and are not intended to limit the scope of the invention, which is defined by the claims, and all equivalent structural changes made by using the contents of the specification and the drawings of the present invention should be covered by the scope of the present invention.
Claims (19)
1. The utility model provides a novel difunctional integrated device structure of solar energy power generation energy storage which characterized in that includes:
a light absorbing layer for generating photo-generated electrons and photo-generated holes;
the light absorption layer is arranged between the first energy storage structure layer and the second energy storage structure layer;
when the light absorption layer generates the photo-generated electrons and the photo-generated holes, the first energy storage structure layer generates an energy storage chemical reaction by utilizing the photo-generated electrons, and the second energy storage structure layer generates an energy storage chemical reaction by utilizing the photo-generated holes.
2. The novel solar power generation and energy storage dual-function integrated device structure as claimed in claim 1,
the first energy storage structure layer comprises a first electrode and an electron transmission layer which are mutually contacted, the electron transmission layer is contacted with the light absorption layer, and the first electrode utilizes the photo-generated electrons to generate energy storage chemical reaction;
the second energy storage structure layer comprises a second electrode and a hole transport layer which are mutually contacted, the hole transport layer is contacted with the light absorption layer, and the second electrode utilizes the photo-generated holes to generate energy storage chemical reaction.
3. The novel solar power generation and energy storage dual-function integrated device structure as claimed in claim 2,
the electron transmission layer and the light absorption layer realize the selective transmission characteristic of electrons through energy level matching;
the hole transport layer and the light absorption layer realize hole selective transport characteristics through energy level matching.
4. The novel solar power generation and energy storage dual-function integrated device structure as claimed in claim 2,
the first electrode is TiO2ZnO, graphite, Sn, SiO2、BN、AlN、Al2O3、TiN、MnO2Or V2O5One or more combinations of (a);
the second electrode is TiF4、TiF3、CuO、LiMnO2、LiNiO2、LiCoO2、LiFePO4、LiMnPO4、Li2Se、Li2S、Li6C6O6Or Li4C6H4O4One or more combinations thereof.
5. The novel solar power generation and energy storage dual-function integrated device structure as claimed in claim 2,
the electron transport layer is SnO2、LiFx、KFx、CsFx、CsOx、MgFx、TiOx、ZnO、ZnS、CdS、CdSe、Zn2SO4、BaSnO3、SrTiO4、C60PCBM or PC61One or more combinations of BMs;
the hole transport layer is made of Spiro-OMeTAD and Cu2O、CuO、CuGaO2、CuOx:N、Cu2S、CuS、CuI、CuSCN、CuPc、CuInS2、ZnS、MoOx、MoS2、NiO、WOx、VOxOne or a combination of PPS, P3HT, PTAA, FDT, HPDI, or HMDI.
6. The novel solar power generation and energy storage dual function integrated device structure as claimed in claim 1, further comprising at least one pair of a first conductive layer and a second conductive layer, wherein at least one of the first conductive layer and the second conductive layer has optical transparency;
the first conducting layer and the second conducting layer are respectively contacted with the first electrode and the second electrode.
7. The novel solar power generation and energy storage dual-function integrated device structure as claimed in claim 6,
the first conducting layer is one or a combination of FTO, ITO, IZO and AZO materials;
the second conducting layer is one or a combination of more of aluminum, silver, gold, titanium, palladium, nickel, chromium and copper.
8. The novel solar power generation and energy storage dual-function integrated device structure as claimed in claim 6,
the first conducting layer is one or a combination of more of aluminum, silver, gold, titanium, palladium, nickel, chromium and copper;
the second conductive layer is one or a combination of FTO, ITO, IZO and AZO materials.
9. The novel solar power generation and energy storage dual-function integrated device structure as claimed in claim 6,
the first conducting layer is one or a combination of FTO, ITO, IZO and AZO materials;
the second conductive layer is one or a combination of FTO, ITO, IZO and AZO materials.
10. The novel solar power generation and energy storage dual function integrated device structure as claimed in any one of claims 1-9,
the light absorption layer is one or a combination of more of perovskite, gallium arsenide, silicon, copper indium gallium selenide, cadmium telluride and cadmium sulfide.
11. The novel solar power generation and energy storage dual-function integrated device structure as claimed in claim 10,
the light absorbing layer is MAPbI3、(CsxMAyFA1-x-y)Pb(I1-zBrz)3、CsPb(I1-xBrx)3One or more combinations thereof.
12. A preparation method of a novel solar power generation and energy storage dual-function integrated device comprises the following steps:
preparing a first energy storage structure layer;
preparing a second energy storage structure layer;
preparing a light absorption layer;
and integrating the light absorption layer, the first energy storage structure layer and the second energy storage structure layer on the basis of one of the first energy storage structure layer, the second energy storage structure layer and the light absorption layer as a substrate to prepare the solar power generation and energy storage dual-function integrated device.
13. The method for preparing a novel solar power generation and energy storage dual-function integrated device as claimed in claim 12,
the first energy storage structure layer comprises a first electrode and an electron transport layer, and the second energy storage structure layer comprises a second electrode and a hole transport layer;
preparing the first energy storage structure layer comprises integrating the first electrode and the electron transport layer for a substrate based on one of the first electrode and the electron transport layer;
preparing the second energy storage structure layer includes integrating the second electrode and a hole transport layer for a substrate based on one of the second electrode and the hole transport layer.
14. The method for preparing a novel solar power generation and energy storage dual-function integrated device as claimed in claim 13,
and integrating the light absorption layer, the first energy storage structure layer and the second energy storage structure layer based on the mode that the electron transmission layer is in contact with the light absorption layer and the hole transmission layer is in contact with the light absorption layer.
15. The method for preparing a novel solar power generation and energy storage dual-function integrated device as claimed in claim 13, wherein the method further comprises:
integrating a first conductive layer based on a manner of contacting the first electrode;
the second conductive layer is integrated based on being in contact with the second electrode.
16. The method for preparing a novel solar power generation and energy storage dual-function integrated device as claimed in claim 13,
the first electrode is TiO2ZnO, graphite, Sn, SiO2、BN、AlN、Al2O3、TiN、MnO2Or V2O5One or more combinations of (a);
the second electrode is TiF4、TiF3、CuO、LiMnO2、LiNiO2、LiCoO2、LiFePO4、LiMnPO4、Li2Se、Li2S、Li6C6O6Or Li4C6H4O4One or more combinations thereof.
17. The method for preparing a novel solar power generation and energy storage dual-function integrated device as claimed in claim 13,
the electron transport layer is SnO2、LiFx、KFx、CsFx、CsOx、MgFx、TiOx、ZnO、ZnS、CdS、CdSe、Zn2SO4、BaSnO3、SrTiO4、C60PCBM or PC61One or more combinations of BMs;
the hole transport layer is made of Spiro-OMeTAD and Cu2O、CuO、CuGaO2、CuOx:N、Cu2S、CuS、CuI、CuSCN、CuPc、CuInS2、ZnS、MoOx、MoS2、NiO、WOx、VOxOne or a combination of PPS, P3HT, PTAA, FDT, HPDI, or HMDI.
18. The preparation method of the novel solar power generation and energy storage dual-function integrated device as claimed in any one of claims 12 to 17,
the light absorption layer is one or a combination of more of perovskite, gallium arsenide, silicon, copper indium gallium selenide, cadmium telluride and cadmium sulfide.
19. The method for preparing a novel solar power generation and energy storage dual-function integrated device as claimed in claim 18,
the light absorbing layer is MAPbI3、(CsxMAyFA1-x-y)Pb(I1-zBrz)3、CsPb(I1-xBrx)3One or more combinations thereof.
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