CN112260617A - Energy-conserving glass of self-driven integrated type photoelectricity discoloration assembly - Google Patents
Energy-conserving glass of self-driven integrated type photoelectricity discoloration assembly Download PDFInfo
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- 238000002845 discoloration Methods 0.000 title description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
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- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6
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- H—ELECTRICITY
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- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S20/00—Supporting structures for PV modules
- H02S20/20—Supporting structures directly fixed to an immovable object
- H02S20/22—Supporting structures directly fixed to an immovable object specially adapted for buildings
- H02S20/26—Building materials integrated with PV modules, e.g. façade elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1524—Transition metal compounds
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/1533—Constructional details structural features not otherwise provided for
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
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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
- Y02E10/549—Organic PV cells
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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
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A self-driven integrated energy-saving glass of a photoelectric color-changing component relates to an electrochromic device. The self-driven integrated energy-saving glass for the photochromic component comprises a glass substrate layer and two conductive electrode layers; the glass substrate layer is arranged on any outer side of the two conductive electrode layers, the perovskite solar cell part and the electrochromic device part are arranged between the two conductive electrode layers, and the two parts are separated through the laser cutting area; the perovskite solar cell part is sequentially provided with an electron transport layer, a perovskite thin film layer and a hole transport layer; the electrochromic device part is sequentially provided with an electrochromic layer, a lithium ion conductor layer and a lithium storage layer, and the lithium ion conductor layer is arranged between the electrochromic layer and the lithium storage layer. The preparation method is simple, the pattern distribution of the perovskite battery and the electrochromic area can be freely combined and arranged on one plane according to actual needs without mutual influence, the self power generation state and the light penetration regulation and control can be exerted, and the energy and optical regulation and control management is optimized.
Description
Technical Field
The invention relates to an electrochromic device, in particular to self-driven integrated energy-saving glass of a photoelectric electrochromic assembly, which is formed by systematically integrating a perovskite solar cell as an electric driving source and electrochromic energy-saving glass.
Background
In recent years, since non-renewable energy such as petrochemical energy and the like is largely used by human beings, a large amount of carbon dioxide greenhouse gas emission causes a serious greenhouse effect, the annual average temperature of the earth starts to rise continuously after the industrial revolution, extreme climate occurs, the temperature creation history in summer is high, and the temperature creation history in winter is low, so that how to effectively reduce the dependence on the petrochemical energy and improve the power generation ratio of the renewable energy becomes an important development direction of human society. However, in the transition period of gradually replacing the traditional petrochemical energy with renewable energy, how to effectively improve the energy utilization efficiency is another important issue, and therefore, the development of energy-saving technology is a new industry development direction. In particular, since economic activities of human society are mainly in buildings, how to improve energy utilization efficiency of buildings has become a major research topic, for example, industrial development of energy-saving intelligent buildings such as artificial intelligence internet of things (AIOT) and the like. According to the information of the energy bureau of America, if a building introduces energy-saving glass, the energy consumption of air-conditioning energy can be effectively reduced by 20%, so as to achieve the energy-saving effect
et al.MohamedHamdy.Comparison of the energy saving potential of adaptive and controllable smart windows:A state-of-the-art review and simulation studies of thermochromic,photochromic and electrochromic technologies[J].Solar Energy Materials and Solar Cells:2019,200:109828)。
The energy-saving glass is divided into the energy-saving glass with the adjustable light penetration degree and the energy-saving glass with the adjustable light penetration degree, and the energy-saving glass with the adjustable light penetration degree is similar to the automobile heat insulation paper and the like for isolating ultraviolet light and infrared light so as to reduce unnecessary radiant heat in a space and reduce the requirement of the space on an air conditioner. However, since the color of the film such as the heat insulation paper is not adjustable and the transmittance of the film cannot be controlled, the film needs to be heated by external radiation heat such as sunlight in winter to reduce the need of heating in the spaceWhen required, the energy-saving glass with adjustable light transmittance can effectively reduce the requirement of heating in the space and is popular in recent years. This type is called electrochromic energy-saving glass and can be classified into three types according to the working mechanism: the first is the traditional liquid crystal type, and only a power switch can be used for regulating and controlling white atomized glass and transparent glass; the second is a distributed particle compound (SPD) whose mechanism is similar to that of a conventional liquid crystal, which darkens the color of glass to deep blue under application of a bias voltage; the two working mechanisms can control and change the color only by requiring more than 70V of voltage; the third is the color-changing glass based on the inorganic oxide semiconductor, and the working mechanism of the third color-changing glass is as follows: using WO3Or NiO or other inorganic semiconductor material as the working electrode, and the color change is caused by the Li ion entering and exiting in the crystal lattice of the electrode under the oxidation-reduction reaction of the electrode. (HoKuo-Chuan, Chen Hsin-Wei, Hsu Chih-Yu. Photoelectrochromic Materials and Devices, Wiley,2015: 593-. The color-changing glass is widely used in rear-view mirrors of high-grade automobiles (such as BMW, Benz and Audi), and mainly used for reducing glare phenomena caused by front lamps of rear vehicles. In addition, the electrochromic glass is introduced into windows of cabins of boeing airplanes 787 and the like, so that the use frequency of mechanical window curtains can be reduced, and sunlight outside the windows can be controlled to achieve a better visual lighting effect.
However, such oxide inorganic semiconductor type electrochromic glasses have many difficulties and challenges that must be overcome. For example, a Li ion conductive layer in a device generally requires a liquid organic solvent or a gel-like electrolyte layer in which a polymer and an organic solvent are combined, and development of a stable and high-conductivity solid inorganic electrolyte is becoming the direction of development of electrochromic devices. In addition, another difficulty is encountered in engineering design, because the electrochromic component needs to match an external power supply with a central power supply control system in a wiring mode and the like to effectively control the component, and a large amount of manpower and material resources are needed to carry out wiring and connection when the electrochromic component is installed in a building, the installation cost required in the early stage is overhigh, and how to effectively reduce the dependence on the external power supply to reduce the installation cost is also a new research and development subject.
Self-driven systems that integrate solar cells with electrochromic glass have become a new direction of research in the current field. At present, a self-powered electro-optically electrochromic assembly can be obtained by integrating a solar cell and electrochromic glass in a stack manner. However, the management of the optical transmittance of the solar cell directly affects the optical transmittance of the electrochromic system, and it is particularly important to avoid the influence of the solar cell on the optical transmittance of the system and to ensure the photoelectric conversion efficiency of the solar cell.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a unique structure and component design, integrates a perovskite solar cell into the manufacturing process of electrochromic glass, and can realize self-driven integrated energy-saving glass for a photoelectric electrochromic component, which has a simple structure and low cost.
The self-driven integrated energy-saving glass for the photochromic component comprises a glass substrate layer and two conductive electrode layers; the glass substrate layer is arranged on any outer side of the two conductive electrode layers, a perovskite solar cell part and an electrochromic device part are arranged between the two conductive electrode layers, and the perovskite solar cell part and the electrochromic device part are separated through a laser cutting area; the perovskite solar cell part comprises an electron transport layer, a perovskite thin film layer and a hole transport layer, wherein the perovskite thin film layer is arranged between the electron transport layer and the hole transport layer; the electrochromic device part comprises an electrochromic layer, a lithium ion conductor layer and a lithium storage layer, wherein the lithium ion conductor layer is arranged between the electrochromic layer and the lithium storage layer.
The thickness of the conductive electrode layer can be 50-300 nm.
The thickness of the electron transmission layer can be 10-80 nm; the electrochromic layer may have a thickness of 10 to 300 nm.
The thickness of the perovskite thin film layer can be about 400 nm;
the hole transport layer can be made of a spirobifluorene material, nickel oxide or a delafossite material; the thickness of the hole transport layer can be 50-250 nm.
The material of the lithium ion conductor layer is lithium phosphorus oxygen nitrogen (LiPON), and the thickness can be 100-400 nm;
the material of the lithium storage layer can be selected from nickel oxide and cerium oxide (CeO)2) Or tantalum oxide (Ta)2O5) The thickness of the lithium storage layer may be 10 to 300 nm.
The self-driven integrated energy-saving glass for the photoelectric color-changing component can be prepared by the following method:
1) preparing a conductive electrode layer on a transparent glass substrate;
2) preparation of a Li-doped tungsten oxide layer on ITO (Li: WO)3)；
3) In a Li-doped tungsten oxide layer (Li: WO) belonging to a perovskite solar cell portion3) Preparing a perovskite thin film layer and a hole transport layer in sequence;
4) in a layer of Li-doped tungsten oxide (Li: WO) belonging to the electrochromic sector3) Preparing a corresponding functional layer;
5) dividing and cutting the junction area of the perovskite solar cell area and the electrochromic area by adopting a pulse laser scribing mode so as to ensure that the two areas are physically insulated (the areas can be divided again by using laser spots for one circle along the junction area);
6) and depositing a conductive electrode layer on the whole substrate in the perovskite-containing solar cell area and the electrochromic area again.
In step 1), the conductive electrode layer may be a tin-doped indium oxide (ITO) layer or a fluorine-doped tin oxide (FTO) layer, and the preparation may employ a magnetron sputtering process.
In step 2), the preparation of a Li-doped tungsten oxide layer on ITO (Li: WO)3) Magnetron sputtering or wet processing methods can be adopted; what is needed isThe Li-doped tungsten oxide layer (Li: WO)3) The layer is used for both the perovskite solar cell and the electrochromic part;
wherein the part belonging to the perovskite solar cell is used as an electron transport layer with the thickness of 10-80 nm (Li: WO)3) Tin oxide (SnO)2) Layer or titanium oxide layer (TiO)2) Instead); the thickness of the electrochromic layer 3 belonging to the electrochromic part is 10-300 nm, and patterns of the electrochromic layer and the pattern are prepared by adopting a mask plate.
In step 3), the specific method for preparing the perovskite functional layer may be: preparing a perovskite thin film layer in an ink-jet printing mode, wherein the thickness of the perovskite thin film layer is about 400 nm; preparing a hole transport layer by an ink-jet printing mode, wherein the hole transport layer can be a spiral bifluorene material and has the thickness of 150-300 nm; the hole transport layer can also be triphenylamine polymer, and the thickness is about 50-120 nm; the hole transport layer can also be made of nickel oxide or delafossite materials, and the thickness is 50-250 nm.
In the step 4), the corresponding functional layers are a lithium ion conductor layer and a lithium storage layer in sequence; the lithium ion conductor layer can be formed by a magnetron sputtering method, a mask is used for controlling patterns, the solid oxide lithium ion conductor layer is deposited, and a lithium storage layer is deposited on the solid oxide lithium ion conductor layer; the material of the lithium ion conductor layer can be lithium phosphorus oxynitride (LiPON), and the thickness can be 100-400 nm; the thickness of the lithium storage layer can be 10-300 nm, and the material of the lithium storage layer can be nickel oxide or cerium oxide (CeO)2) Or tantalum oxide (Ta)2O5)。
In the step 6), the conductive electrode layer is used as a top electrode layer, ITO or FTO can be adopted, and the thickness of the top electrode layer can be 50-300 nm.
The invention object of the present invention is prepared on a glass substrate by physical deposition, chemical deposition methods. The perovskite solar cell and the electrochromic device share a conductive oxide substrate layer, then have respective functional layers, and finally share a hole transport layer and a top electrode layer at the top. Compared with the prior art, the invention has the advantages that:
1. the preparation process is simple, and large-area large-scale preparation and production can be realized; the conductive substrate layer can be effectively applied to two components at the same time, and the manufacturing process is simple; the self-powered and energy-saving effects can be achieved without an additional external power supply.
2. The perovskite cells and the pattern distribution of the electrochromic regions can be freely combined and arranged on one plane according to actual needs.
3. The invention adopts a unique structure and component design, integrates the solar cell and the electrochromic energy-saving glass which are placed in parallel into a single component, and performs internal electrical connection through a semiconductor process without an external power supply and corresponding wiring. Meanwhile, the solar cell part and the electrochromic part do not influence each other, and the self power generation state and light transmittance regulation and control can be optimally played, so that the effects of optimizing energy and optical regulation and control management are achieved.
Drawings
Fig. 1 is a schematic cross-sectional view (cross-sectional view) of a self-driven integrated photochromic assembly energy-saving glass powered by perovskite solar cells.
Fig. 2 is a schematic front view of a self-driven integrated energy-saving glass for a photochromic device.
Fig. 3 is a physical diagram of a self-driven integrated photochromic component energy-saving glass.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
Fig. 1 is a schematic cross-sectional view of the energy-saving glass of the self-driven integrated photochromic device. A toughened glass substrate 1 is used as a substrate, and the upper and lower parts of the toughened glass substrate are respectively provided with two electrode layers 2 and 9. The glass substrate 1 may be on the electrode layer 2 side or on the electrode layer 9 side. A perovskite solar cell part and an electrochromic device part are arranged between the two electrode layers 2 and 9, the perovskite solar cell part and the electrochromic device part are separated through a laser cutting region 10, and the perovskite solar cell layer surrounds the outer side of the electrochromic device layer, as shown in fig. 2. As shown in fig. 1, the perovskite solar cell layer is sequentially an electron transport layer 4, a perovskite thin film layer 6 and a hole transport layer 8 from bottom to top; the electrochromic device layer sequentially comprises an electrochromic layer 3, a lithium ion conductor layer 5 and a lithium storage layer 7 from bottom to top.
The thicknesses of the two electrode layers 2 and 9 can be both 50-300 nm.
The thickness of the electron transmission layer 4 can be 10-80 nm; the electrochromic layer 3 may have a thickness of 10 to 300 nm.
The thickness of the perovskite thin film layer 6 can be about 400 nm;
the hole transport layer 8 can be made of a spirobifluorene material, nickel oxide or a delafossite material; the thickness of the hole transport layer can be 50-250 nm.
The lithium ion conductor layer 5 is made of lithium phosphorus oxynitride (LiPON) and can be 100-400 nm thick;
the material of the lithium storage layer 7 can be selected from nickel oxide and cerium oxide (CeO)2) Or tantalum oxide (Ta)2O5) The thickness of the lithium storage layer may be 10 to 300 nm.
The preparation method of the self-driven integrated photochromic component energy-saving glass comprises the following steps:
1) preparing a tin-doped indium oxide (ITO) layer or a fluorine-doped tin oxide (FTO) layer on a transparent glass substrate; the preparation can adopt a magnetron sputtering process.
2) Preparation of a Li-doped tungsten oxide layer on ITO (Li: WO)3) (ii) a The preparation of a Li-doped tungsten oxide layer on ITO (Li: WO)3) Magnetron sputtering or wet processing methods can be adopted; the Li-doped tungsten oxide layer (Li: WO)3) The layer is used for both the perovskite solar cell and the electrochromic part; wherein the part belonging to the perovskite solar cell is used as an electron transport layer with the thickness of 10-80 nm (Li: WO)3) Tin oxide (SnO)2) Layer or titanium oxide layer (TiO)2) Instead); the thickness of the electrochromic layer 3 belonging to the electrochromic part is 10 to 300 nm. The patterns of the two are prepared by adopting a mask plate for distinguishing.
3) In a Li-doped tungsten oxide layer (Li: WO) belonging to a perovskite solar cell portion3) Preparing a perovskite thin film layer and a hole transport layer in sequence; the specific method for preparing the perovskite functional layer can be as follows: preparing a perovskite thin film layer in an ink-jet printing mode, wherein the thickness of the perovskite thin film layer is about 400 nm; a hole transport layer is prepared through an ink-jet printing mode (the hole transport layer can be a spiral bifluorene material with the thickness of 150-300 nm, the hole transport layer can also be a triphenylamine polymer with the thickness of about 50-120 nm, and the hole transport layer can also be a nickel oxide or delafossite material with the thickness of 50-250 nm).
4) In a layer of Li-doped tungsten oxide (Li: WO) belonging to the electrochromic sector3) Preparing a corresponding functional layer; the corresponding functional layers are prepared into a lithium ion conductor layer and a lithium storage layer in sequence. The lithium ion conductor layer can be formed by a magnetron sputtering method, a mask is used for controlling patterns, the solid oxide lithium ion conductor layer is deposited, the material is lithium phosphorus oxynitride (LiPON), and the thickness can be 100-400 nm; depositing a nickel oxide lithium storage layer on the solid oxide lithium ion conductor layer, wherein the thickness of the nickel oxide lithium storage layer can be 10-300 nm (the nickel oxide layer can be replaced by cerium oxide (CeO)2) Or tantalum oxide (Ta)2O5))。
5) The junction area of the perovskite solar cell area and the electrochromic area is divided by adopting a pulse laser scribing mode so as to ensure that the two areas are physically insulated (the areas can be divided again by using laser spots to walk for one circle along the junction area).
6) A transparent oxide layer (ITO or FTO) top electrode layer is deposited on the whole substrate (a perovskite-containing solar cell area and an electrochromic area) at one time, and the thickness of the top electrode layer can be 50-300 nm.
Specific preparation method examples are given below.
Example 1:
the preparation method of the self-driven integrated energy-saving glass for the photoelectric color-changing component comprises the following steps:
1) an ITO film is deposited on an ultrathin glass sheet (toughened glass substrate 1) by adopting a magnetron sputtering process, the thickness of the film is 180nm, and the whole size is 10cm multiplied by 10 cm.
2) Depositing tungsten oxide doped with lithium on the ITO by adopting magnetron sputtering, and respectively controlling the thickness of the electrochromic layer 3 to be 100nm by adopting a stainless steel mask plate; also, the thickness of the electron transport layer 4 of the solar cell region was controlled to be 30 nm.
3) Preparing formamidine lead iodine perovskite film layer 6 (Cs) with 5% cesium doping in A site by utilizing ink-jet printing process in perovskite solar region0.05FA0.95PbI3) The crystallization is carried out by combining a high-speed airflow method, and the thickness of the crystal is about 350 nm.
4) And depositing LiPON with the thickness of 200nm in the electrochromic area by utilizing a stainless steel mask plate through a magnetron sputtering process.
5) A stainless steel mask was used to deposit nickel oxide 80nm thick in the electrochromic zones.
6) Depositing nickel oxide with the thickness of 30nm by adopting a magnetron sputtering process in the step 5).
7) And (3) carrying out physical insulation cutting on the perovskite solar cell region and the electrochromic region by adopting pulse laser.
8) The perovskite solar cell obtained in step 7) together with the electrochromic region was deposited with a 150nm thick ITO layer.
9) The perovskite solar cell region is segmented by laser pulse deposition, the interior of the perovskite solar cell is connected in series through electrical connection, and the voltage of two ends connected to the electrochromic region exceeds 3V.
10) The ultra-thin glass is used as an upper cover plate to encapsulate the whole structure, and the device in the working state is shown in fig. 3.
Example 2
Similar to example 1, the difference is that step 2, steps 4-6:
1) an ITO film is deposited on an ultrathin glass sheet (toughened glass substrate 1) by adopting a magnetron sputtering process, the thickness of the film is 180nm, and the whole size is 10cm multiplied by 10 cm.
2) Depositing tungsten oxide doped with lithium on the ITO by adopting magnetron sputtering, and controlling the thickness of the electrochromic layer 3 to be 100nm by adopting a stainless steel mask plate; also, the tin oxide electron transport layer 4 was deposited using an ink jet printing process to a thickness of 30 nm.
3) Preparing formamidine lead iodine perovskite film layer 6 (Cs) with 5% cesium doping in A site by utilizing ink-jet printing process in perovskite solar region0.05FA0.95PbI3) The crystallization is carried out by combining a high-speed airflow method, and the thickness of the crystal is about 350 nm.
4) And depositing LiPON with the thickness of 300nm in the electrochromic area by utilizing a stainless steel mask plate through a magnetron sputtering process.
5) A 130nm thick nickel oxide was deposited in the electrochromic regions using a stainless steel reticle.
6) 150nm thick spirobifluorene was deposited in the solar region using an inkjet printing process.
7) And (3) carrying out physical insulation cutting on the perovskite solar cell region and the electrochromic region by adopting pulse laser.
8) The perovskite solar cell obtained in step 7) together with the electrochromic region was deposited with a 150nm thick ITO layer.
9) The perovskite solar cell region is segmented by laser pulse deposition, the interior of the perovskite solar cell is connected in series through electrical connection, and the voltage of two ends connected to the electrochromic region exceeds 3V.
Example 3
Similar to example 1, the difference is in step 5, step 6:
1) an ITO film is deposited on an ultrathin glass sheet (toughened glass substrate 1) by adopting a magnetron sputtering process, the thickness of the film is 180nm, and the whole size is 10cm multiplied by 10 cm.
2) Depositing tungsten oxide doped with lithium on the ITO by adopting magnetron sputtering, and controlling the thickness of the electrochromic layer 3 to be 100nm by adopting a stainless steel mask plate; also, the tin oxide electron transport layer 4 was deposited using an ink jet printing process to a thickness of 30 nm.
3) Preparing formamidine lead iodine perovskite film layer 6 (Cs) with 5% cesium doping in A site by utilizing ink-jet printing process in perovskite solar region0.05FA0.95PbI3) The crystallization is carried out by combining a high-speed airflow method, and the thickness of the crystal is about 350 nm.
4) And depositing LPON with the thickness of 200nm in the electrochromic area by using a stainless steel mask plate through a magnetron sputtering process.
5) Deposition of 110nm thick Ta in electrochromic regions using stainless steel masks2O5。
6) Depositing CuGaO with thickness of 80nm in solar region by ink-jet printing process2。
7) And (3) carrying out physical insulation cutting on the perovskite solar cell region and the electrochromic region by adopting pulse laser.
8) The perovskite solar cell obtained in step 7) together with the electrochromic region was deposited with a 150nm thick ITO layer.
9) The perovskite solar cell region is segmented by laser pulse deposition, the interior of the perovskite solar cell is connected in series through electrical connection, and the voltage of two ends connected to the electrochromic region exceeds 3V.
The invention object of the present invention is prepared on a glass substrate by physical deposition, chemical deposition methods. The perovskite solar cell and the electrochromic device share a conductive oxide substrate layer and an inorganic oxide layer, then have respective functional layers respectively, and finally share a hole transport layer and a conductive oxide layer at the top.
Claims (9)
1. The energy-saving glass of the self-driven integrated type photoelectric color-changing component is characterized by comprising a glass substrate layer and two conductive electrode layers; the glass substrate layer is arranged on any outer side of the two conductive electrode layers, a perovskite solar cell part and an electrochromic device part are arranged between the two conductive electrode layers, and the perovskite solar cell part and the electrochromic device part are separated through a laser cutting area; the perovskite solar cell part comprises an electron transport layer, a perovskite thin film layer and a hole transport layer, wherein the perovskite thin film layer is arranged between the electron transport layer and the hole transport layer; the electrochromic device part comprises an electrochromic layer, a lithium ion conductor layer and a lithium storage layer, wherein the lithium ion conductor layer is arranged between the electrochromic layer and the lithium storage layer.
2. The self-driven integrated energy-saving glass for a photochromic device according to claim 1, wherein the thickness of the conductive electrode layer is 50 to 300 nm;
the thickness of the electron transmission layer can be 10-80 nm; the thickness of the electrochromic layer can be 10-300 nm;
the thickness of the perovskite thin film layer can be about 400 nm;
the hole transport layer can be made of a spirobifluorene material, nickel oxide or a delafossite material; the thickness of the hole transport layer can be 50-250 nm;
the material of the lithium ion conductor layer is lithium phosphorus oxygen nitrogen (LiPON), and the thickness can be 100-400 nm;
the material of the lithium storage layer can be selected from nickel oxide and cerium oxide (CeO)2) Or tantalum oxide (Ta)2O5) The thickness of the lithium storage layer may be 10 to 300 nm.
3. The method as claimed in claim 1, wherein the method comprises the following steps:
1) preparing a conductive electrode layer on a transparent glass substrate;
2) preparation of a Li-doped tungsten oxide layer on ITO (Li: WO)3)；
3) In a Li-doped tungsten oxide layer (Li: WO) belonging to a perovskite solar cell portion3) Preparing a perovskite thin film layer and a hole transport layer in sequence;
4) in a layer of Li-doped tungsten oxide (Li: WO) belonging to the electrochromic sector3) Preparing a corresponding functional layer;
5) dividing and cutting the boundary area of the perovskite solar cell area and the electrochromic area by adopting a pulse laser scribing mode so as to ensure that the two areas are physically insulated;
6) and depositing a conductive electrode layer on the whole substrate in the perovskite-containing solar cell area and the electrochromic area again.
4. The method according to claim 3, wherein in step 1), the conductive electrode layer is a tin-doped indium oxide (ITO) layer or a fluorine-doped tin oxide (FTO) layer, and the preparation process is performed by a magnetron sputtering process.
5. The method according to claim 3, wherein in step 2), the Li-doped tungsten oxide layer is formed on the ITO (Li: WO)3) Adopting magnetron sputtering or wet processing method; the Li-doped tungsten oxide layer (Li: WO)3) The layer is used for both the perovskite solar cell and the electrochromic part; wherein the part belonging to the perovskite solar cell is used as an electron transmission layer, and the thickness is 10-80 nm; the thickness of an electrochromic layer belonging to an electrochromic part is 10-300 nm, and patterns of the electrochromic layer and the pattern are prepared by adopting a mask plate in a distinguishing way.
6. The method of claim 5, wherein the Li-doped tungsten oxide layer (Li: WO) is formed by a process comprising depositing a layer of Li-doped tungsten oxide on the surface of the glass3) With tin oxide (SnO)2) Layer or titanium oxide layer (TiO)2) Instead of this.
7. The method for preparing the energy-saving glass of the self-driven integrated photochromic component according to claim 3, wherein in the step 3), the specific method for preparing the perovskite functional layer comprises the following steps: preparing a perovskite thin film layer in an ink-jet printing mode, wherein the thickness of the perovskite thin film layer is about 400 nm; preparing a hole transport layer by an ink-jet printing mode, wherein the hole transport layer can be a spiral bifluorene material and has the thickness of 150-300 nm; the hole transport layer can also be triphenylamine polymer, and the thickness is about 50-120 nm; the hole transport layer can also be made of nickel oxide or delafossite materials, and the thickness is 50-250 nm.
8. The method according to claim 3, wherein in step 4), the corresponding functional layers are a lithium ion conductor layer and a lithium storage layer in sequence; magnetic control of the lithium ion conductor layerThe sputtering method is carried out, a mask is utilized to control patterns, a solid oxide lithium ion conductor layer is deposited firstly, and a lithium storage layer is deposited on the solid oxide lithium ion conductor layer; the material of the lithium ion conductor layer can be lithium phosphorus oxynitride (LiPON), and the thickness can be 100-400 nm; the thickness of the lithium storage layer can be 10-300 nm, and the material of the lithium storage layer can be nickel oxide or cerium oxide (CeO)2) Or tantalum oxide (Ta)2O5)。
9. The method according to claim 3, wherein in step 6), the conductive electrode layer is used as a top electrode layer, ITO or FTO is used, and the thickness of the top electrode layer is 50-300 nm.
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| CN104836519A (en) * | 2015-03-24 | 2015-08-12 | 东南大学 | Integrated intelligent glass window based on perovskite solar cell power supply and method for manufacturing same |
| US20180301578A1 (en) * | 2015-10-28 | 2018-10-18 | View, Inc. | Photovoltaic-electrochromic windows |
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