CN112510150A - Hole transport layer, and preparation method and application thereof - Google Patents
Hole transport layer, and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
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- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
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- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
-
- 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
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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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
Abstract
The invention discloses a hole transport layer and a preparation method and application thereof. The preparation method of the hole transport layer comprises the following steps: adopting a nickel salt solution as an electrolyte, and connecting the conductive glass substrate to the cathode of the electrochemical deposition equipment; depositing a first nickel-containing film on a conductive glass substrate at a first current density; depositing a second nickel-containing film on the first nickel-containing film at a second current density, the second current density being less than the first current density; annealing the conductive glass substrate obtained in the step to obtain the NiO with compact structurexMesoporous NiOxA hole transport layer of a two-layer structure. The method has simple process, easy amplification, no change of process equipment, no doping of other materials, and only passing of currentThe density can realize nickel oxide films with two different structures and improve the hole extraction capability of the perovskite solar cell, and a hole transport layer formed after the process is amplified has good large-area uniformity, so that the overall performance of the perovskite solar cell can be obviously improved.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a hole transport layer and a preparation method and application thereof.
Background
In recent years, perovskite solar cells have begun to emerge in the field of view of their excellent cell performance, high photoelectric conversion efficiency, relatively low process manufacturing costs, and relatively simple process steps. The laboratory efficiency of perovskite solar cells has currently exceeded 25%, almost comparable to that of monocrystalline silicon cells, showing great commercial potential. However, most hole transport layers of the currently prepared high-efficiency perovskite solar cells are organic semiconductor materials and the like, the organic semiconductor materials are high in price, and the stability of the prepared devices is poor, so that the method is not suitable for large-area commercial production processes of the perovskite solar cells.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a hole transport layer, a method for preparing the same, and an application thereof, so as to solve at least one of the problems of how to prepare a large-area and uniform hole transport layer, improving the hole extraction capability of a perovskite solar cell from a device structure without doping materials, and improving the overall performance of the perovskite solar cell device.
The present application is primarily based on the following problems:
the inventors have found that the application of metal oxides to perovskite solar cells has good advantages, such as better band matching, better stability, low price, etc., among which nickel oxide (NiO)x) The hole transport layer material is a better hole transport layer material at present, the band gap of the hole transport layer material can be better matched with the energy band of perovskite, generated holes can be better and selectively extracted, the carrier mobility is better, the generated holes can be better extracted, and the transmission loss is reduced. However, at present, the carrier mobility of a pure nickel oxide thin film is not high, the difference between the valence band and the energy band of perovskite is large, partial carrier recombination exists at an interface, certain thin film modification needs to be carried out on nickel oxide, researchers usually realize the treatment of the nickel oxide thin film by doping, but the thin film prepared by the method is very sensitive to the doping proportion of a doping material,is not suitable for commercial production; further, NiO is now usedxThe film preparation process is mostly a spin-coating method and a magnetron sputtering method, the substrate prepared by the former method has small area, the amplification process has great difficulty and challenge, the uneven condition of the film is very easy to generate, most of the solution is thrown away during spin coating, the solution utilization rate is low, the equipment cost of the latter preparation process is high, the film price cost is also high, the prepared nickel oxide film is almost a compact thin-layer structure, the contact area of the perovskite and the hole transmission layer is limited, and the hole extraction capability of the solar cell is limited. Currently, there is an improvement of NiO-based materials by ozone treatmentxA method for performance of thin film perovskite cells, but does not address the problem of effective charge extraction between the NiOx thin film and the perovskite layer interface; the perovskite solar cell based on the nickel oxide mesoporous layer is obtained by doping a core-shell structure of Au into the nickel oxide mesoporous layer, but the technology needs to prepare a hole transmission layer and then prepare the nickel oxide mesoporous layer, has complex process and is not beneficial to large-area industrial production. Therefore, there is a strong need for a simple and controllable preparation process to prepare high quality NiOxA film.
Therefore, a first object of the present invention is to provide a method for preparing a hole transport layer, so as to achieve the effects of realizing the industrial production of a uniform hole transport layer with a large area, improving the carrier mobility of a nickel oxide hole transport layer, and the like. To achieve the above object, according to a first aspect of the present invention, there is provided a method of preparing a hole transport layer, according to an embodiment of the present invention, the method including:
(1) adopting a nickel salt solution as an electrolyte, and connecting the conductive glass substrate to the cathode of the electrochemical deposition equipment;
(2) depositing a first nickel-containing thin film on the conductive glass substrate at a first current density;
(3) depositing a second nickel-containing film on the first nickel-containing film at a second current density, the second current density being less than the first current density;
(4) carrying out the step (3) on the obtained conductive glass substrateAnnealing treatment to obtain NiO with dense structurexMesoporous NiOxA hole transport layer of a two-layer structure.
Further, the step (1) at least satisfies one of the following conditions: the concentration of the nickel salt solution is 0.01-0.05 mol/L; the nickel salt is a nitrate compound and/or a chloride compound of nickel; in the electrochemical deposition equipment, the distance between the conductive glass substrate and the anode is 4-5 cm; in the electrochemical deposition equipment, the positive electrode adopts a nickel sheet which has the same area as the conductive glass substrate and the purity of which is not lower than 99.99 percent; pretreating the conductive glass substrate and then connecting the conductive glass substrate to the electrochemical deposition equipment, wherein the pretreatment comprises the following steps: firstly, removing impurities and oil stains by using a glass cleaning agent or a detergent, then respectively carrying out ultrasonic cleaning by using deionized water, acetone and ethanol, blow-drying by using nitrogen, and finally carrying out ultraviolet ozone cleaning.
Further, the method of preparing the hole transport layer satisfies at least one of the following conditions: in the step (2), the first current density is 0.5-1 mA/cm2The deposition time is 5-60 seconds; in the step (3), the second current density is 0.05-0.1 mA/cm2The deposition time is 120-150 seconds; the first current density and the second current density are each independently a constant value; in the step (4), the annealing treatment is carried out for 1-2 hours at the temperature of 300-500 ℃.
Compared with the prior art, the method for preparing the hole transport layer has at least the following advantages: 1) the method has simple and convenient process and easy amplification, not only solves the problem of holes in the nickel oxide prepared by the spin-coating method, but also can realize the regulation and control of the morphology of the nickel oxide film by regulating and controlling different process parameters of the same equipment/process, improves the performance of a battery device, and a hole transport layer formed after the process is amplified has good large-area uniformity; 2) by adopting an electrochemical deposition method and controlling current density, firstly preparing a compact nickel oxide film on a conductive glass substrate, solving the problem of short circuit caused by direct contact between a perovskite light absorption layer and an electrode, then preparing a mesoporous nickel oxide film, improving the contact area between perovskite and a hole transmission layer, improving the extraction capability of holes under the process condition of not doping other materials, and further improving the overall performance of the perovskite solar cell; 3) the mesoporous nickel oxide film in the hole transport layer prepared by the method can also provide a support for the perovskite film, so that the prepared perovskite film has better crystallinity, the defects are obviously reduced, and the overall performance of the device of the perovskite solar cell can be further improved.
Another object of the present invention is to propose a hole transport layer for a perovskite solar cell to improve the hole extraction capability of the perovskite solar cell and the device performance of the perovskite solar cell. To achieve the above objects, according to a second aspect of the present invention, there is provided a hole transport layer for a perovskite solar cell, the hole transport layer comprising dense NiO according to an embodiment of the present inventionxLayer and mesoporous NiOxLayer of said dense NiOxThe mesoporous NiO is layered on a conductive glass substratexLayered on the dense NiOxOn the layer.
Further, the hole transport layer for the perovskite solar cell is obtained by adopting the preparation method.
Compared with the prior art, the hole transport layer for the perovskite solar cell has at least the following advantages: 1) the hole transport layer has dense NiOxMesoporous NiOxThe compact nickel oxide layer can solve the problem of short circuit caused by direct contact between the perovskite light absorption layer and the electrode, and the mesoporous nickel oxide film can improve the contact area between the perovskite and the hole transmission layer, thereby realizing the improvement of the extraction capability of the hole under the process condition of not doping other materials and further improving the overall performance of the perovskite solar cell; 2) the mesoporous nickel oxide layer can also provide a support for the perovskite thin film, so that the prepared perovskite thin film has better crystallinity, the defects are obviously reduced, and the overall performance of the device of the perovskite solar cell can be further improved.
It is another object of the present invention to propose a perovskite solar cell to improve the overall performance of the perovskite solar cell. To achieve the above object, according to a third aspect of the present invention, the present invention provides a perovskite solar cell, which has the above hole transport layer or the hole transport layer obtained by the above preparation method according to an embodiment of the present invention.
Further, the perovskite solar cell is of a PIN structure.
Further, the perovskite solar cell includes: the light-absorbing material comprises conductive glass, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a barrier layer and electrodes, wherein the conductive glass is provided with a transparent conductive layer; the hole transport layer comprises dense NiO arranged on the transparent conductive layerxLayer and layer disposed between the dense NiOxMesoporous NiO on a layerxA layer; the perovskite light absorption layer is arranged on the mesoporous NiOxOn the layer; the electron transmission layer is arranged on the perovskite light absorption layer; the barrier layer is arranged on the electron transmission layer; the electrode is disposed on the barrier layer.
Further, the perovskite solar cell at least satisfies one of the following conditions: the conductive glass is FTO or ITO; the perovskite light absorption layer is Cs0.05(FA0.83MA0.17)0.95Pb(BrcI1-c) The value range of c is 0.1-0.17; the perovskite light absorption layer is obtained by adopting a slit coating method, a blade coating method, a spin coating method, a vacuum evaporation method or a vacuum evaporation-solution method; the electron transport layer is selected from fullerene, PCBM fullerene derivative, ZnO and SnO2At least one of ITO and AZO; the barrier layer is an organic buffer layer or a metal barrier layer; the electrode is a metal electrode or a transparent electrode; the electrode is at least one selected from gold, silver, aluminum and copper or an ITO transparent electrode.
Compared with the prior art, the perovskite solar cell provided by the invention has at least the following advantages: 1) the perovskite solar cell has a structure different from that of the existing perovskite cell, not only is the hole extraction capacity higher, the carrier mobility is high, the probability of short circuit caused by direct contact of a perovskite light absorption layer and an electrode is lower, but also the perovskite thin film in the cell has good crystallinity and few defects, and has more excellent overall performance; 2) the current density-voltage curve hysteresis phenomenon is small, and the stability is good; 3) is suitable for large-area industrial production and has great development potential.
Another object of the present invention is to provide an energy storage device to improve the overall performance of the energy storage device. To achieve the above object, according to a fourth aspect of the present invention, an energy storage device is proposed, which comprises the above perovskite solar cell according to an embodiment of the present invention. Compared with the prior art, the energy storage device has at least the following advantages: the comprehensive performance is good, the competitive advantage is great, the method is suitable for industrial production, and the user experience is improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a flow chart of a method of preparing a hole transport layer according to one embodiment of the present invention.
FIG. 2 is an electrochemical deposition apparatus constructed in accordance with example 1 of the present invention.
Fig. 3 is a graph showing current densities and electrochemical deposition times controlled when a hole transport layer was prepared according to example 1 of the present invention.
Fig. 4 is a schematic view of laser etching of the conductive glass having a hole transport layer prepared in example 1 of the present invention.
Fig. 5 is a scanning electron micrograph of a hole transport layer prepared in comparative example 1 of the present invention.
Fig. 6 is a scanning electron micrograph of a hole transport layer prepared according to comparative example 2 of the present invention.
FIG. 7 is a scanning electron micrograph of a cell based on a hole transport layer according to the present invention prepared in example 1 of the present invention.
FIG. 8 is a comparison graph of current density-voltage curves of perovskite solar cells prepared in example 1 and comparative examples 1 to 2 of the present invention.
FIG. 9 is a graph comparing the stability of perovskite solar cell devices prepared in example 1 and comparative examples 1 to 2 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to a first aspect of the invention, the invention proposes a method of preparing a hole transport layer, with reference to fig. 1, according to an embodiment of the invention, the method comprising: (1) adopting a nickel salt solution as an electrolyte, and connecting the conductive glass substrate to the cathode of the electrochemical deposition equipment; (2) depositing a first nickel-containing film on a conductive glass substrate at a first current density; (3) depositing a second nickel-containing film on the first nickel-containing film at a second current density, the second current density being less than the first current density; (4) annealing the conductive glass substrate obtained in the step (3) so as to obtain the conductive glass substrate with dense NiOxMesoporous NiOxA hole transport layer of a two-layer structure. The method can realize dense NiO by regulating and controlling different current densities in the same process through electrochemical depositionxMesoporous NiOxThe preparation of the hole transport layer with the double-layer structure is used for the perovskite solar cell, the dense coating of the surface of the conductive glass substrate can be ensured, the increase of the contact area with the perovskite film interface can be ensured through the surface mesoporous structure, and the transmission of interface carriers is facilitated.
The method of manufacturing the hole transport layer according to the above embodiment of the present invention will be described in detail with reference to fig. 1.
According to the embodiment of the invention, the dense NiO is formed by performing two stages of electrochemical deposition under different current densitiesxMesoporous NiOxIn the process of the hole transport layer with the double-layer structure, a nickel salt solution is used as electrolyte, and a conductive glass substrate is connected to a negative electrode of electrochemical deposition equipment. The conductive glass substrate may be pretreated and then connected to the cathode of the electrochemical deposition apparatus, and the pretreatment process may include: firstly, removing impurities and oil stains by using a glass cleaning agent or a detergent, then respectively carrying out ultrasonic cleaning by using deionized water, acetone and ethanol, blow-drying by using nitrogen, and finally carrying out ultraviolet ozone cleaning.
According to an embodiment of the present invention, the types of the nickel salt solution and the conductive glass substrate are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the nickel salt may be various kinds of nitrate compounds containing crystal water or not containing crystal water of nickel, various kinds of water-soluble nickel salts or nickel salt combinations such as chloride compounds containing crystal water or not containing crystal water of nickel, and further, for example, the nickel salt may be nickel nitrate hexahydrate, nickel chloride hexahydrate, anhydrous nickel chloride, or the like; the conductive glass substrate can adopt ITO or FTO conductive glass and the like.
According to another embodiment of the present invention, when the electrochemical deposition apparatus is used for electrochemical deposition in the present invention, the type of the connected positive electrode is not particularly limited, and for example, the positive electrode may be an inert metal positive electrode, and for example, the positive electrode may be a high purity nickel sheet having an area equal to that of the conductive glass substrate and a purity of not less than 99.99%, and the connection of the positive electrode and the negative electrode using the high purity nickel sheet and the conductive glass substrate having the same area, respectively, may further contribute to improving uniformity of electrochemical deposition. Furthermore, the distance between the conductive glass substrate and the anode can be 4-5 cm, and the inventor finds that if the distance between the conductive glass substrate and the anode is too small, the electric field disturbance is easily caused, and if the distance between the conductive glass substrate and the anode is too large, the electrochemical deposition rate can be obviously reduced, and the uniformity and the efficiency of the electrochemical deposition can be further improved by controlling the distance between the conductive glass substrate and the anode to be within the range.
According to another embodiment of the present invention, the concentration of the nickel salt solution may be 0.01 to 0.05mol/L, for example, 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L, or 0.05mol/L, and the inventors found that, if the concentration of the nickel salt solution is too high, it is not easy to control the structure of the nickel oxide thin film and the thickness of the finally formed hole transport layer by adjusting the current density and deposition time of the electrochemical deposition, and the invention is more favorable to control the microstructure and thickness of different nickel oxide thin films in the hole transport layer by selecting the nickel salt solution with the above concentration range.
According to another embodiment of the present invention, the electrochemical deposition apparatus may use a dc regulated power supply as an output device, and preferably a multimeter or an ammeter is connected in series in the circuit as a current display device, so that the current magnitude required in the electrochemical deposition process can be flexibly regulated by controlling the current through voltage, and the change of the current (density) magnitude can be monitored in real time through the multimeter or the ammeter.
According to another embodiment of the present invention, during the electrochemical deposition process, the loop current can be adjusted to reach the desired current by adjusting the voltage, wherein in the step (2), the first current density can be 0.5 to 1mA/cm2For example, it may be 0.5mA/cm2、0.6mA/cm2、0.7mA/cm2、0.8mA/cm2、0.9mA/cm2Or 1mA/cm2The deposition time may be 5 to 60 seconds, for example, 10s, 15s, 20s, 30s, 40s, 50s, or 60s, and the inventors found that if the first current density is too low, it is difficult to form a dense nickel oxide thin film on the conductive glass substrate, and if the current density is too high, it is difficult to control the uniformity of the nickel oxide thin film and the deposition time at the same film thickness; in addition, if the deposition time is too long, the thickness of the nickel oxide film is easy to be too large, and meanwhile, the microstructure of the nickel oxide film is changed to a certain extent, so that the device performance of the perovskite solar cell can be obviously influencedxA film.
According to another embodiment of the present invention, in the step (3), the second current density may be 0.05 to 0.1mA/cm2For example, it may be 0.05mA/cm2、0.06mA/cm2、0.07mA/cm2、0.08mA/cm2、0.09mA/cm2Or 0.1mA/cm2The deposition time may be 120-150 seconds, for example, 120s, 125s, 130s, 135s, 140s, 145s, 150s, etc. the inventors found that if the second current density is too large, it is difficult to form a mesoporous nickel oxide film, and particularly, when the number of deposited charges provided by the potentiometer is the same and constant, the surface roughness of the deposited film becomes smaller and smaller with the increase of the current density, and approaches to a dense morphology; in addition, if the deposition time is too long, not only the deposition thickness of the nickel oxide film is too large, but also a planar nickel oxide film instead of a mesoporous nickel film can be formedxA film.
According to another embodiment of the present invention, the first current density and the second current density may be respectively and independently constant values, and the inventors found that, if the fluctuation range of the first/second current density is large during the electrochemical deposition process, the performance of the cell device is sensitive and the stability of the cell is affected when the prepared hole transport layer is used in the perovskite solar cell, and the uniformity of the finally prepared hole transport layer and the stability of the perovskite solar cell can be further improved by performing two-stage electrochemical deposition at a constant current density.
According to another embodiment of the invention, in the step (4), the annealing treatment can be performed at 300-500 ℃ for 1-2 hours, wherein the annealing treatment temperature can be 300 ℃, 340 ℃, 380 ℃, 420 ℃, 460 ℃ or 500 ℃, and the time can be 1 hour, 1.5 hours or 2 hours, and the like, so that the nickel in the two layers of nickel-containing films can be ensured to be oxidized, and a dense NiO film can be obtainedxMesoporous NiOxHollow of double-layer structureA hole transport layer.
According to another embodiment of the invention, a nickel salt solution with a concentration of 0.01-0.05 mol/L is prepared in advance for standby; manually cleaning a conductive glass substrate by using a glass cleaning agent or a detergent to remove macroscopic impurities, oil stains and the like, then ultrasonically cleaning the conductive glass substrate by using deionized water, acetone and ethanol for 10-20 min respectively, taking out the conductive glass substrate, blow-drying the conductive glass substrate by using nitrogen for later use, and cleaning the conductive glass substrate for 15-20 min by using an ultraviolet ozone cleaning machine before use; the electrochemical deposition equipment uses a direct current stabilized voltage supply as output equipment, a positive electrode adopts a high-purity nickel sheet with the same area as that of a conductive glass substrate, a negative electrode is connected to the conductive glass substrate, current is output in a voltage control current mode to achieve approximate constant current, namely, current corresponding to the area is calculated, voltage is adjusted to enable loop current to reach required current, and the output current density of the compact layer nickel oxide film is 0.5-1 mA/cm2The deposition time is 5-60 seconds, and the output current density of the mesoporous nickel oxide film layer is 0.05-0.1 mA/cm2The deposition time is 120-150 seconds; the electrode spacing is about 4-5 cm, and the deposition time is adjustable within the range; after the two-section electrochemical deposition is finished, washing a sample with deionized water and drying the sample with a nitrogen gun, then placing the sample on a constant-temperature heating table, keeping the temperature constant at 80 ℃, pre-drying the sample for 10 minutes, then raising the temperature to 300-500 ℃ within 30 minutes through temperature programming, then heating and annealing the sample for 1-2 hours at constant temperature, stopping the temperature programming, and naturally cooling the temperature to room temperature to obtain the compact NiOxMesoporous NiOxAnd taking out the sample wafer from the hole transport layer with the double-layer structure and putting the sample wafer into a nitrogen drying cabinet for later use.
In summary, compared with the prior art, the method for preparing the hole transport layer of the present invention has at least the following advantages: 1) the method has simple and convenient process and easy amplification, not only solves the problem of holes in the nickel oxide prepared by the spin-coating method, but also can realize the regulation and control of the morphology of the nickel oxide film by regulating and controlling different process parameters of the same equipment/process, improves the performance of a battery device, and a hole transport layer formed after the process is amplified has good large-area uniformity; 2) by adopting an electrochemical deposition method and controlling current density, firstly preparing a compact nickel oxide film on a conductive glass substrate, solving the problem of short circuit caused by direct contact between a perovskite light absorption layer and an electrode, then preparing a mesoporous nickel oxide film, improving the contact area between perovskite and a hole transmission layer, improving the extraction capability of holes under the process condition of not doping other materials, and further improving the overall performance of the perovskite solar cell; 3) the mesoporous nickel oxide film in the hole transport layer prepared by the method can also provide a support for the perovskite film, so that the prepared perovskite film has better crystallinity, the defects are obviously reduced, and the overall performance of the device of the perovskite solar cell can be further improved.
Based on the same inventive concept, according to a second aspect of the present invention, a hole transport layer for a perovskite solar cell is proposed. According to an embodiment of the present invention, the hole transport layer comprises dense NiOxLayer and mesoporous NiOxLayer, dense NiOxThe mesoporous NiO is layered on the conductive glass substratexLayered on dense NiOxOn the layer. Compared with the prior art, the hole transport layer has at least the following advantages: 1) the hole transport layer has dense NiOxMesoporous NiOxThe compact nickel oxide layer can solve the problem of short circuit caused by direct contact between the perovskite light absorption layer and the electrode, and the mesoporous nickel oxide film can improve the contact area between the perovskite and the hole transmission layer, thereby realizing the improvement of the extraction capability of the hole under the process condition of not doping other materials and further improving the overall performance of the perovskite solar cell; 2) the mesoporous nickel oxide layer can also provide a support for the perovskite thin film, so that the prepared perovskite thin film has better crystallinity, the defects are obviously reduced, and the overall performance of the device of the perovskite solar cell can be further improved.
According to a specific embodiment of the invention, the hole transport layer for the perovskite solar cell can be obtained by adopting the preparation method, the preparation method can ensure that the surface of the conductive glass substrate is densely coated, and can also ensure that the contact area with the perovskite thin film interface is increased through the surface mesoporous structure, so that the interface carrier transport is facilitated, therefore, the problem that holes are generated when the nickel oxide is prepared by a spin-coating method is solved, the shape of the nickel oxide thin film can be regulated and controlled by regulating and controlling different process parameters of the same device, the performance of a battery device is improved, the hole transport layer formed after the process is amplified has good large-area uniformity, and the large-area industrial production of the hole transport layer can be realized. It should be noted that the features and effects described for the method for preparing the hole transport layer are also applicable to the hole transport layer for the perovskite solar cell, and are not described in detail here.
According to a third aspect of the invention, a perovskite solar cell is presented. According to an embodiment of the present invention, the perovskite solar cell has the above hole transport layer or the hole transport layer obtained by the above preparation method. The perovskite solar cell has the advantages of high hole extraction capacity, high carrier mobility, good cell comprehensive performance and the like.
According to an embodiment of the present invention, the perovskite solar cell of the present invention may be a PIN structure, for example, may have a structure of Glass/TCO/dense NiOx/mesoporous NiOx/perovskite/fullerene/BCP/Cu, and the perovskite solar cell mainly includes two structures of NIP and PIN.
According to yet another specific embodiment of the present invention, a perovskite solar cell may comprise: the light-absorbing material comprises conductive glass, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a barrier layer and electrodes, wherein the conductive glass is provided with a transparent conductive layer, and the transparent conductive layer can be a conductive thin film with transparent oxide; the hole transport layer comprises dense NiO arranged on the transparent conductive layerxLayer and layer of dense NiOxMesoporous NiO on a layerxA layer; the perovskite light absorption layer is arranged in the mesoporous NiOxOn the layer; the electron transmission layer is arranged on the perovskite light absorption layer; the barrier layer is arranged on the electron transmission layer; an electrode is disposed on the barrier layer. The efficiency and stability of the perovskite solar cell can be further improved therebyAnd (5) performing qualitative determination.
According to yet another embodiment of the invention, the perovskite solar cell may be a novel solar cell having an organic-inorganic halide with a perovskite crystal structure as light absorbing layer, e.g. the precursor material of the perovskite light absorbing layer may comprise a material selected from MAPbI3、CsFAPbI3、CsFAMAPbI3、CsFAMAPb(IaBr1-a)3、CsFAPb(IbBr1-b)3Wherein a can range from 0.1 to 0.17, and b can range from 0.1 to 0.17; preferably, the perovskite light absorption layer may be Cs0.05(FA0.83MA0.17)0.95Pb(BrcI1-c) And the value range of c is 0.1-0.17, so that the photoelectric property of the perovskite solar cell can be further improved. In addition, the method for forming the perovskite light absorbing layer in the present invention is not particularly limited, and can be selected by those skilled in the art according to actual needs, and can be obtained by, for example, slit coating, knife coating, spin coating, vacuum evaporation, or vacuum evaporation-solution method.
According to another embodiment of the present invention, the conductive glass in the perovskite solar cell may be FTO or ITO, and the electron transport layer may be a transparent transport layer, such as fullerene, PCBM fullerene derivative, ZnO, SnO2At least one of ITO, AZO, and the like. Further, the barrier layer may be an organic buffer layer such as BCP (bathocuproine material) or a metal barrier layer; the electrode may be a metal electrode or a transparent electrode, wherein the metal electrode may be at least one selected from gold, silver, aluminum, copper, and the like, and the transparent electrode may be an ITO transparent electrode or an FTO transparent electrode, and the like.
In summary, the perovskite solar cell of the present invention has at least the following advantages over the prior art: 1) the perovskite solar cell has a structure different from that of the existing perovskite cell, not only is the hole extraction capacity higher, the carrier mobility is high, the probability of short circuit caused by direct contact of a perovskite light absorption layer and an electrode is lower, but also the perovskite thin film in the cell has good crystallinity and few defects, and has more excellent overall performance; 2) the current density-voltage curve hysteresis phenomenon is small, and the stability is good; 3) is suitable for large-area industrial production and has great development potential. It should be noted that the features and effects described in the above aspects of the hole transport layer for the perovskite solar cell and the preparation of the hole transport layer are also applicable to the perovskite solar cell, and are not described in detail here.
According to a fourth aspect of the invention, an energy storage device is presented. According to an embodiment of the invention, the energy storage device comprises the above perovskite solar cell. Compared with the prior art, the energy storage device has at least the following advantages: the comprehensive performance is good, the competitive advantage is great, the method is suitable for industrial production, and the user experience is improved. The type of the energy storage device described in the present invention is not particularly limited, and may be a single perovskite solar cell, or may be a device having a perovskite solar cell, such as a new energy automobile, a storage battery, or the like. In addition, it should be noted that the features and effects described for the above perovskite solar cell are also applicable to the energy storage device, and are not described in detail here.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Step 1, processing of a conductive glass substrate FTO: the method comprises the steps of firstly washing impurities, oil stains and the like visible to naked eyes on an unetched conductive glass substrate by using a glass cleaning agent, then ultrasonically cleaning the unetched conductive glass substrate by using deionized water, acetone and ethanol for 15min respectively, taking out the unetched conductive glass substrate, blow-drying the unetched conductive glass substrate by using nitrogen for later use, and treating the surface of the unetched conductive glass substrate by using an ultraviolet ozone cleaning machine before use.
a) preparing 0.02mol/L nickel nitrate hexahydrate solution: using Ni (NO) with purity more than 97%3)2·6H2Preparing a solution by taking nickel nitrate hexahydrate particles of O as a raw material, dissolving the material in deionized water, stirring or naturally dissolving for 1-2 hours at room temperature to prepare a light green clear solution for later use, and pouring the solution into a square glass jar for later use.
b) Building simple electrochemical deposition equipment; a metal lead is used, a direct-current stabilized voltage power supply is used as output equipment, a multimeter or an ammeter is connected in series in a circuit to serve as current display equipment, the specific circuit connection is shown in figure 2, a high-purity nickel sheet (the purity is 99.99%) with the same area as that of conductive glass is adopted as an anode electrode of electrochemical deposition, and FTO conductive glass is connected to a cathode.
c) The current adopts a voltage control current mode to realize approximately constant current output, and the output current density of the compact layer nickel oxide film is 0.5mA/cm2The deposition time is 30 seconds, and the output current density of the mesoporous nickel oxide film layer is 0.1mA/cm2The deposition time was 150 seconds. The electrode spacing is 4 cm; the whole electrochemical deposition process is shown in figure 3.
d) Washing the sample wafer with deionized water, drying the sample wafer with a nitrogen gun, putting the sample wafer on a constant-temperature heating table, pre-drying for 10 minutes at a constant temperature of 80 ℃, then heating to 300 ℃ within 30 minutes by program heating, then heating and annealing for 1-2 hours at a constant temperature, stopping the program, naturally cooling to room temperature, taking out the sample wafer, and putting the sample wafer into a nitrogen drying cabinet for later use.
The preparation process comprises the steps of blowing clean a cut 25mm multiplied by 25mm substrate by nitrogen, placing the substrate on a spin coater to perform perovskite spin coating, wherein the volume ratio of DMF to DMSO mixed solvent is 4:1, the spin coating process is 4000rpm for 30 seconds, the acceleration is 1000rpm, 300-500 microliter ethyl acetate is dripped at the 25 th second as an anti-solvent, and then the substrate is placed on a constant temperature heating table to be heated and annealed for 45 minutes to prepare the perovskite thin film.
Step 5, preparing an Electron Transport Layer (ETL) and a barrier layer: deposition of fullerenes (C) using a high vacuum deposition apparatus comprising an organic source and a metal source60) As an electron transport layer and as a barrier layer by vapor deposition Bathocuproine (BCP). Wherein the fullerene purity is more than 99%, and the vacuum degree at the beginning of vapor deposition is less than 5 × 10-4And Pa, adopting an organic evaporation source, evaporating to 10 nanometers at the evaporation rate of 0.1 angstrom/second, and then evaporating to 25-30 nanometers at the evaporation rate of 0.3 angstrom/second. And completing the preparation of the electron transmission layer, replacing an evaporation source to evaporate the barrier layer BCP, evaporating at the evaporation rate of 0.1 angstrom/second to 7 nanometers, and completing the evaporation of the barrier layer to obtain the electron transmission layer and the barrier layer film.
Comparative example 1
The difference from the embodiment 1 is that the NiOx film layer is prepared by adopting a compact nickel oxide film prepared by high current density, namely in the step 2, the current of c) is controlled by voltage to realize approximately constant current transmissionThe output current density of the compact layer nickel oxide film is 0.5mA/cm2The thickness of the dense nickel oxide thin film was consistent with that of the hole transport layer in example 1.
Comparative example 2
The difference from the example 1 is that the prepared NiOx film layer adopts the nickel oxide film which is only in the mesoporous structure and is separately prepared at low current density, namely in the step 2, c) the current adopts a voltage control current mode to realize approximately constant current output, and the mesoporous nickel oxide film layer adopts the nickel oxide film layer with the output current density of 0.1mA/cm2The thickness of the mesoporous nickel oxide thin film layer was the same as that of the hole transport layer in example 1.
Example 2
The difference from the example 1 is that in the step 2, the output current density of the c) dense layer nickel oxide film is 1mA/cm2The deposition time is 10 seconds, and the output current density of the mesoporous nickel oxide film layer is 0.05mA/cm2The deposition time was 120 seconds.
And (3) performance testing:
1) scanning electron microscope analysis is respectively carried out on the hole transport layers prepared in the embodiments 1-2 and the comparative examples 1-2, and test results show that the hole transport layer formed by electrochemical deposition with two different current densities in the embodiments of the present invention has a double-layer structure of a compact nickel oxide film and a mesoporous nickel oxide film. FIGS. 5 to 7 are scanning electron micrographs of the hole transport layers formed in comparative example 1, comparative example 2 and example 1 in this order.
2) Respectively carrying out performance tests on the perovskite solar cells prepared in the examples 1-2 and the comparative examples 1-2, wherein before the cell test, a layer of tin is welded at two ends of the cell by ultrasonic welding, and then 1cm of tin is used2The mask plate shields other areas, and only the illumination area is 1cm2Cell area test of (1). Test results show that the perovskite solar cell prepared by the embodiment of the invention has good stability and high photovoltaic conversion efficiency. Wherein, FIG. 8 is a comparison graph of current density-voltage curves of perovskite solar cells prepared in example 1 and comparative examples 1 to 2, and FIG. 9 is a comparison graph of perovskite solar cells prepared in example 1 and comparative examples 1 to 1 ℃ 2, preparing a stability comparison graph of the prepared perovskite solar cell device.
Wherein, in the above embodiment and the attached drawings, c-NiOxRepresenting a compact nickel oxide hole transport layer film; m-NiOxA nickel oxide hole transport layer film with a mesoporous structure is shown; c60Represents a fullerene electron transport layer material; BCP represents bathocuproine material; ECD represents electrochemical deposition.
In summary, in the embodiments of the present invention, by creatively designing the dense NiOx/mesoscopic NiOx double-layer structure for the inorganic hole transport layer of the perovskite solar cell, the perovskite absorption layer can be prevented from directly contacting the electrode, the contact area between the perovskite film layer and the hole transport layer can be greatly increased, and the hole extraction capability can be improved. Furthermore, the design does not change test equipment, other materials are doped, and two nickel oxide films with different structures can be realized only by changing the current density, so that the experimental process is greatly simplified, the function of a support is provided for the perovskite light absorption layer through the mesoporous nickel oxide, the structure of the trans-perovskite solar cell can be improved, the process condition is optimized, the efficiency of the device is improved, the stability of the device is improved, and the process cost is reduced.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of making a hole transport layer, comprising:
(1) adopting a nickel salt solution as an electrolyte, and connecting the conductive glass substrate to the cathode of the electrochemical deposition equipment;
(2) depositing a first nickel-containing thin film on the conductive glass substrate at a first current density;
(3) depositing a second nickel-containing film on the first nickel-containing film at a second current density, the second current density being less than the first current density;
(4) annealing the conductive glass substrate obtained in the step (3) so as to obtain the conductive glass substrate with dense NiOxMesoporous NiOxA hole transport layer of a two-layer structure.
2. The method of claim 1, wherein step (1) satisfies at least one of the following conditions:
the concentration of the nickel salt solution is 0.01-0.05 mol/L;
the nickel salt is a nitrate compound and/or a chloride compound of nickel;
in the electrochemical deposition equipment, the distance between the conductive glass substrate and the anode is 4-5 cm;
in the electrochemical deposition equipment, the positive electrode adopts a nickel sheet which has the same area as the conductive glass substrate and the purity of which is not lower than 99.99 percent;
pretreating the conductive glass substrate and then connecting the conductive glass substrate to the electrochemical deposition equipment, wherein the pretreatment comprises the following steps: firstly, removing impurities and oil stains by using a glass cleaning agent or a detergent, then respectively carrying out ultrasonic cleaning by using deionized water, acetone and ethanol, blow-drying by using nitrogen, and finally carrying out ultraviolet ozone cleaning.
3. A method according to claim 1 or 2, characterized in that at least one of the following conditions is fulfilled:
in the step (2), the first current density is 0.5-1 mA/cm2The deposition time is 5-60 seconds;
in the step (3), the second current density is 0.05-0.1 mA/cm2The deposition time is 120-150 seconds;
the first current density and the second current density are each independently a constant value;
in the step (4), the annealing treatment is carried out for 1-2 hours at the temperature of 300-500 ℃.
4. A hole transport layer for perovskite solar cells, characterized in that the hole transport layer comprises dense NiOxLayer and mesoporous NiOxLayer of said dense NiOxThe mesoporous NiO is layered on a conductive glass substratexLayered on the dense NiOxOn the layer.
5. The hole transport layer according to claim 4, which is prepared by the method according to any one of claims 1 to 3.
6. A perovskite solar cell, characterized by having a hole transport layer as defined in any one of claims 4 to 5 or a hole transport layer produced by the method as defined in any one of claims 1 to 3.
7. The perovskite solar cell according to claim 6, wherein the perovskite solar cell is of a PIN structure.
8. The perovskite solar cell according to claim 6 or 7, comprising:
a conductive glass having a transparent conductive layer;
a hole transport layer comprising dense NiO disposed on the transparent conductive layerxLayer and layer provided on said compactNiOxMesoporous NiO on a layerxA layer;
perovskite light absorption layer, perovskite light absorption layer establishes mesoporous NiOxOn the layer;
the electron transport layer is arranged on the perovskite light absorption layer;
the barrier layer is arranged on the electron transmission layer;
an electrode disposed on the barrier layer.
9. The perovskite solar cell of claim 8, wherein at least one of the following conditions is satisfied:
the conductive glass is FTO or ITO;
the perovskite light absorption layer is Cs0.05(FA0.83MA0.17)0.95Pb(BrcI1-c) The value range of c is 0.1-0.17;
the perovskite light absorption layer is obtained by adopting a slit coating method, a blade coating method, a spin coating method, a vacuum evaporation method or a vacuum evaporation-solution method;
the electron transport layer is selected from fullerene, PCBM fullerene derivative, ZnO and SnO2At least one of ITO and AZO;
the barrier layer is an organic buffer layer or a metal barrier layer;
the electrode is a metal electrode or a transparent electrode;
the electrode is at least one selected from gold, silver, aluminum and copper or an ITO transparent electrode.
10. An energy storage device comprising the perovskite solar cell as defined in any one of claims 6 to 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100033777A (en) * | 2008-09-22 | 2010-03-31 | 서울대학교산학협력단 | The electrode comprising porous nickel oxide thin layer, preparation method and use in electrochromic device and lithium battery therof |
| US20100261067A1 (en) * | 2008-02-25 | 2010-10-14 | Pitts J Roland | Homogeneous, Dual Layer, Solid State, Thin Film Deposition for Structural and/or Electrochemical Characteristics |
| CN109841740A (en) * | 2019-03-22 | 2019-06-04 | 上海交通大学 | A kind of preparation method of the perovskite solar cell based on nickel oxide hole transmission layer |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100261067A1 (en) * | 2008-02-25 | 2010-10-14 | Pitts J Roland | Homogeneous, Dual Layer, Solid State, Thin Film Deposition for Structural and/or Electrochemical Characteristics |
| KR20100033777A (en) * | 2008-09-22 | 2010-03-31 | 서울대학교산학협력단 | The electrode comprising porous nickel oxide thin layer, preparation method and use in electrochromic device and lithium battery therof |
| CN109841740A (en) * | 2019-03-22 | 2019-06-04 | 上海交通大学 | A kind of preparation method of the perovskite solar cell based on nickel oxide hole transmission layer |
Non-Patent Citations (2)
| Title |
|---|
| IK JAE PARK, ET AL.: "Highly Efficient and Uniform 1 cm2 Perovskite Solar Cells with an Electrochemically Deposited NiOx Hole-Extraction Layer", CHEMSUSCHEM, vol. 10, pages 2660 * |
| XINGTIAN YIN, ET AL.: "Nickel Oxide as Efficient Hole Transport Materials for Perovskite Solar Cells", SOL. RRL, vol. 3, pages 1 - 27 * |
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