WO2021258631A1 - 一种提升钙钛矿太阳能电池稳定性的方法 - Google Patents

一种提升钙钛矿太阳能电池稳定性的方法 Download PDF

Info

Publication number
WO2021258631A1
WO2021258631A1 PCT/CN2020/131970 CN2020131970W WO2021258631A1 WO 2021258631 A1 WO2021258631 A1 WO 2021258631A1 CN 2020131970 W CN2020131970 W CN 2020131970W WO 2021258631 A1 WO2021258631 A1 WO 2021258631A1
Authority
WO
WIPO (PCT)
Prior art keywords
perovskite
solar cell
stability
perovskite solar
improving
Prior art date
Application number
PCT/CN2020/131970
Other languages
English (en)
French (fr)
Inventor
唐建新
李艳青
陈力
陈敬德
Original Assignee
苏州大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 苏州大学 filed Critical 苏州大学
Priority to US18/010,154 priority Critical patent/US20230301164A1/en
Publication of WO2021258631A1 publication Critical patent/WO2021258631A1/zh

Links

Classifications

    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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

Definitions

  • the invention belongs to solar technology, and specifically relates to a processing method for improving the stability of a perovskite solar cell.
  • perovskite material solar cells have great development potential.
  • the perovskite light-absorbing layer with a normal-phase crystal structure is the core of this type of solar cell.
  • the light-absorbing layer of this perovskite solar cell has low cost, simple and fast manufacturing process, and large open circuit voltage.
  • the advantages of fast spectral response rate; and the photoelectric conversion efficiency of this perovskite solar cell is higher than that of other solar cells.
  • this material also has drawbacks.
  • the material is highly sensitive to humidity and temperature.
  • perovskite solar cells of a single-phase mixed cation system need to be prepared in an anhydrous and oxygen-free low-temperature environment during the preparation process, and During use, if it is affected by fluctuations in environmental factors, the performance of the battery device will be greatly depleted. At present, the research on this material has made considerable progress, but to achieve industrialization, the stability of the device needs to be effectively guaranteed.
  • the purpose of the present invention is to solve the shortcomings in the existing perovskite mineralization technology, provide a battery that has low requirements on the process environment and convenient preparation method during the preparation of batteries, and can be maintained in a normal environment for a long time. Stable perovskite stability improvement method.
  • the present invention adopts the following technical scheme: a method for improving the stability of the perovskite solar cell, adopting the perovskite precursor for improving the stability of the perovskite solar cell to prepare the perovskite layer of the perovskite solar cell to realize the perovskite Improvement of the stability of solar cells;
  • the perovskite precursor solution for improving the stability of perovskite solar cells includes a perovskite precursor and a solvent for improving the stability of perovskite solar cells;
  • the improving perovskite solar cell Perovskite precursors for stability include bromomethylamine, iodoformamidine, lead iodide, cesium iodide, 3,4-dichloroaniline; the amount of 3,4-dichloroaniline used is bromomethylamine, iodoformamidine, 0.6% to 1.15% of the total weight of lead iodide and cesium iodide.
  • the present invention discloses the composition of a perovskite precursor and a solvent for improving the stability of a perovskite solar cell, and a perovskite precursor solution for improving the stability of a perovskite solar cell; and a perovskite precursor for improving the stability of a perovskite solar cell
  • the body includes bromomethylamine, iodoformamidine, lead iodide, cesium iodide, 3,4-dichloroaniline, of which the amount of 3,4-dichloroaniline is bromomethylamine, iodoformamidine, lead iodide, iodide 0.63 of the weight sum of cesium % ⁇ 1.12%, preferably 0.8% ⁇ 1.05%.
  • the solvent is a mixture of sulfone solvents and amide solvents, such as N,N-dimethylformamide and dimethylsulfoxide; preferably, by volume percentage, N,N-dimethylformamide is 70% to 90% , Dimethyl sulfoxide is 10% to 30%.
  • the present invention further discloses a perovskite solar cell, comprising a perovskite layer prepared from the above-mentioned perovskite precursor for improving the stability of the perovskite solar cell.
  • the perovskite solar cell also includes a conventional substrate, an electron transport layer, a hole transport layer, and an electrode; these are all conventional materials and structures.
  • the weight sum of bromomethylamine, iodoformamidine, lead iodide, and cesium iodide is 100%, wherein bromomethylamine is 1% to 5%, iodoformamidine is 10% to 28%, and lead iodide 50% ⁇ 80%, cesium iodide is the balance, preferably, bromomethylamine is 1.5% ⁇ 2%, iodoformamidine is 17% ⁇ 22%, lead iodide is 65% ⁇ 75%, cesium iodide For the margin.
  • the mass ratio of the perovskite precursor to the solvent for improving the stability of the perovskite solar cell is 1: (0.8-1.5).
  • the weight sum of bromomethylamine, iodoformamidine, lead iodide, and cesium iodide is 100%, and in mass percentage, bromomethylamine It is 1.83%, iodoformamidine is 20.16%, lead iodide is 71.91%, and cesium iodide is the balance; 3,4-dichloroaniline is 1.02%; further, it is used in the above to improve the stability of perovskite solar cells.
  • dimethyl sulfoxide and N,N-dimethylformamide are added to obtain a preferred perovskite precursor solution for improving the stability of the perovskite solar cell.
  • the present invention uses a perovskite precursor solution for improving the stability of the perovskite solar cell to prepare the perovskite solar cell, which can improve the stability of the perovskite solar cell.
  • the preparation method of the above-mentioned perovskite solar cell includes the following steps.
  • the perovskite precursor solution for improving the stability of the perovskite solar cell is spin-coated on the substrate, thermally annealed to obtain the light-absorbing layer of the solar cell, and then the light-absorbing layer
  • a hole transport layer is prepared on the hole transport layer, and an electrode is vapor-deposited on the hole transport layer to obtain a perovskite solar cell
  • spin coating is a two-step process, first spin coating at a speed of 1000 revolutions per second for 10 seconds, and then at 6000 revolutions per second Spin coating at a speed of 30 seconds, and add ether before the end of spin coating.
  • the invention discloses a method for improving the stability of a perovskite solar cell.
  • the perovskite precursor for improving the stability of the perovskite solar cell is used to prepare the perovskite layer of the perovskite solar cell to realize the stability of the perovskite solar cell.
  • the creativity of the present invention is to use a new perovskite precursor to replace the existing perovskite precursor to prepare a perovskite layer for solar cells. Others remain unchanged, which can effectively improve the stability of the perovskite solar cell.
  • the present invention discloses for the first time a perovskite device containing 3,4-dichloroaniline.
  • the photoelectric conversion efficiency is significantly higher than that of an untreated perovskite device, whether it is open circuit voltage, short circuit current density or filling Factors, these conventional parameters for measuring the performance of solar cells, have been greatly improved after the perovskite has been modified. It can be explained that the additives do have an optimization effect on the perovskite, and the result of this optimization is reflected in the morphology of the perovskite crystal.
  • the untreated perovskite crystal is uniform
  • the performance is not good, the size of the grains is different, and the grain size of the processed perovskite is almost similar, and the uniformity is also good; especially the life test results show that after the addition of 3,4-dichloroaniline, The stability of perovskite solar cells has been greatly improved.
  • Figure 1 shows the comparison of the morphology of perovskite that has not been treated with 3,4-dichloroaniline and the crystal morphology of the treated perovskite (scale bar: 200 nm).
  • Figure 2 is a comparison of the photoelectric conversion efficiency of the perovskite solar cell treated with 3,4-dichloroaniline and the photoelectric conversion efficiency of the untreated perovskite solar cell.
  • Figure 3 shows the comparison results of the stability test of the perovskite solar cell without 3,4-dichloroaniline treatment and the stability test of the perovskite solar cell after treatment.
  • the perovskite precursor for improving the stability of the perovskite solar cell of the present invention is composed of bromomethylamine, iodoformamidine, lead iodide, cesium iodide, and 3,4-dichloroaniline; and N,N-dimethyl Base formamide and dimethyl sulfoxide to obtain a perovskite precursor solution for improving the stability of perovskite solar cells.
  • the preparation method of the perovskite precursor solution for improving the stability of the perovskite solar cell of the present invention is to mix bromomethylamine, iodoformamidine, lead iodide, cesium iodide, 3,4-dichloroaniline and a solvent , Obtain the perovskite precursor solution for improving the stability of the perovskite solar cell; further, add iodoformamidine and cesium iodide into the solvent, add bromomethylamine after stirring, and add lead iodide, 3,4 after stirring -Dichloroaniline, stir to obtain a perovskite precursor solution for improving the stability of perovskite solar cells.
  • the perovskite Precursor Solution for Improving the Stability of Perovskite Solar Cells filed by the applicant on the same day.
  • All the raw materials of the present invention are commercially available products, which are conventional solar cell products; the test methods involved are conventional methods in the field.
  • Perovskite solar cell photoelectric conversion efficiency test method put the prepared cell in a solar cell test box, and link the test box with the digital source meter Keithley-2400, open the test software, and fix the open circuit voltage test range at- Between 0.1v ⁇ 1.2V, the test range of short-circuit current is 0mA/cm 2 ⁇ 30 mA/cm 2.
  • the humidity and temperature of the environment are not controlled, and the specific humidity and temperature are changed according to the atmospheric environment.
  • Perovskite solar cell stability test method Put the battery in a solar cell test box without additional protection, expose the perovskite solar cell to the air, and keep the humidity and temperature the same as in the atmospheric environment The same, while the test box is placed under a standard sunlight, every 12 hours, a photoelectric conversion efficiency test on the perovskite solar cell. When the photoelectric conversion efficiency value of the unmodified perovskite solar cell is lower than 1%, the life test is stopped.
  • Example 1 Perovskite precursor solution for improving the stability of perovskite solar cells, the composition is: bromomethylamine is 14.1mg, iodoformamidine is 155.4 mg, lead iodide is 554.3 mg, and cesium iodide is 47 mg , 3,4-Dichloroaniline is 7.86 mg (1.02%), 200mL dimethyl sulfoxide, 800mL N,N-dimethylformamide.
  • the preparation method is as follows: (1) Add N,N-dimethylformamide to dimethyl sulfoxide, and stir the solution evenly.
  • step (1) Weigh iodoformamidine and cesium iodide and add them to the stirred solution in step (1). After stirring for 10 minutes, add bromomethylamine to the solution, raise the temperature of the solution to 50°C, and stir for 10 minutes .
  • step (3) Add lead iodide to the solution prepared in step (2), then add 3,4-dichloroaniline to the solution and stir until it dissolves; keep the solution at a constant temperature of 50°C during the entire adding and stirring process.
  • step (3) The solution prepared in step (3) is continuously stirred at 50° C. for 12 hours to obtain a perovskite precursor solution for improving the stability of the perovskite solar cell.
  • the invention discloses the application of the perovskite precursor for improving the stability of the perovskite solar cell or the perovskite precursor solution for improving the stability of the perovskite solar cell in the preparation of the perovskite solar cell, which can increase calcium Stability of titanium ore solar cells.
  • Example 2 The light-absorbing layer of the solar cell is prepared by spin-coating the perovskite precursor solution for improving the stability of the perovskite solar cell in Example 1 on the substrate and thermally annealing at 150°C for 30 minutes to obtain the solar cell
  • the crystalline morphology of the light-absorbing layer is shown in Figure 1.
  • the spin coating is a two-step process, first spin coating at a speed of 1000 revolutions per second for 10 seconds, then spin coating at a speed of 6000 revolutions per second for 30 seconds, and 15 before the end of the spin coating In seconds, 200 microliters of ether was dropped onto the rotating perovskite membrane.
  • the substrate is FTO glass with TiO 2 or ITO glass with SnO 2 ; the above operations are performed in a glove box with water and oxygen content below 2PPM.
  • Embodiment 3 A perovskite solar cell includes a conventional substrate, an electron transport layer, a hole transport layer, an electrode, and a perovskite layer.
  • the perovskite layer is made of calcium for improving the stability of the perovskite solar cell in the first embodiment. Preparation of titanium ore precursor solution.
  • the preparation method of the above-mentioned solar cell is as follows: spin-coating the perovskite precursor solution for improving the stability of the perovskite solar cell in Example 1 on the substrate, thermally annealing at 150°C for 30 minutes to obtain the light-absorbing layer of the solar cell, and spin-coating It is a two-step process, first spin coating at a speed of 1000 revolutions per second for 10 seconds, and then spin coating at a speed of 6000 revolutions per second for 30 seconds, add ether before the end of the spin coating; then prepare a hole transport layer on the light-absorbing layer, and then The prepared device is placed in a high vacuum electrode evaporation apparatus, and a 110-nanometer-thick silver electrode layer is evaporated on the hole transport layer, and finally a perovskite solar cell is obtained.
  • the perovskite precursor solution spin-coating for improving the stability of the perovskite solar cell is annealed immediately after the spin coating is completed, without the need for prior art vacuum treatment or other steps of volatilizing the solvent before annealing.
  • the substrate is FTO glass with TiO 2 or ITO glass with SnO 2. It is an existing product.
  • the thickness of the electron transport layer TiO 2 or SnO 2 is 100 nm; the above operation is in the glove box and the water and oxygen content is lower than Carried out under 2PPM.
  • the specific preparation method of the above-mentioned solar cell is as follows: (1) The perovskite precursor solution of Example 1 is spin-coated at a speed of 1000 revolutions/sec for 10 seconds and at a speed of 6000 revolutions/sec for 30 seconds. Coat on the FTO glass (or ITO glass) treated in step (1), and add 200 microliters of ether 15 seconds before the end of the spin coating on the rotating perovskite film. The tape after the spin coating is finished FTO glass (ITO glass) with perovskite film is transferred to a flat plate at 150°C and annealed for 30 minutes.
  • Hole transport layer solution preparation 72.3mg Spiro-OMeTAD (2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spiro two Fluorene solution) was dissolved in ultra-dry chlorobenzene, and 28.8 microliters of TBP (4-tert-butylpyridine) was added dropwise to the chlorobenzene solution containing Spiro-OMeTAD, and 17.5 microliters of Li-TFSI solution (520 Mg/ml, acetonitrile as a solvent) was added dropwise to the chlorobenzene solution, mixed and stirred for 8 hours to obtain a hole transport layer solution.
  • TBP 4-tert-butylpyridine
  • Comparative solar cell On the basis of Example 1, 3,4-dichloroaniline was not added, and the rest remained unchanged to obtain a perovskite precursor solution.
  • the perovskite precursor solution for improving the stability of the perovskite solar cell of the first embodiment was replaced with the above-mentioned perovskite precursor solution, and the rest remained unchanged to obtain a comparative solar cell.
  • Figure 1 shows the morphology of the perovskite without 3,4-dichloroaniline treatment and the morphology of the perovskite crystal after treatment (scale bar: 200 nm);
  • the uniformity of the treated perovskite crystals is not good, and the size of the crystal grains is different, and the grain size of the treated perovskite is almost similar, and the uniformity is also good, and the surface of the untreated perovskite film The degree of undulation is also greater than that of the treated perovskite film.
  • Figure 2 shows the photoelectric conversion efficiency of the perovskite solar cell (Example 3, FTO) treated with 3,4-dichloroaniline and the photoelectric conversion efficiency of the untreated perovskite solar cell (comparative solar cell, FTO) Contrast; the photoelectric conversion efficiency of the untreated perovskite device is significantly lower than that of the perovskite device added with 3,4-dichloroaniline.
  • FTO comparative conversion efficiency
  • Figure 3 shows the comparison results of the stability test of the perovskite solar cell (comparative solar cell, FTO) without 3,4-dichloroaniline treatment and the stability test of the perovskite solar cell (Example 3, FTO) after treatment ( 500 hours, humidity: 50%, temperature: 25°C); after adding 3,4-dichloroaniline, the stability of the perovskite solar cell has been greatly improved.
  • the perovskite precursor solution for improving the stability of the perovskite solar cell in Example 3 was replaced with a less perovskite precursor solution, and the rest remained unchanged to obtain an isomer solar cell (FTO), which was subjected to the same stability test , Its photoelectric conversion efficiency dropped from 15.33% of the initial (0h) to 5.68% of 100h.
  • the perovskite precursor solution for improving the stability of the perovskite solar cell in Example 3 was replaced with a multi-perovskite precursor solution, and the rest remained unchanged to obtain an isomer solar cell (FTO), which was subjected to the same stability test , Its photoelectric conversion efficiency dropped from 14.86% of the initial (0h) to 8.37% of 100h.
  • FTO isomer solar cell
  • Example 4 Chloride ions have an influence on the perovskite film-forming performance, and the composition of the perovskite also has a key influence on the perovskite film performance.
  • Perovskite precursor solution for improving the stability of perovskite solar cells.
  • the composition is 14.1 mg bromomethylamine, 155.4 mg iodoformamidine, 554.3 mg lead iodide, 47 mg cesium iodide, 3,4 -Dichloroaniline is 7.32 mg (0.95%), 200 mL dimethyl sulfoxide, 800 mL N,N-dimethylformamide; its preparation method is the same as in Example 1.
  • a solar cell (ITO substrate) was prepared according to the method of Example 3. After the same stability test, its photoelectric conversion efficiency dropped from 17.46% in the initial (0h) to 17.11% in 72h and 16.03% in 100h.
  • Example 5 Chloride ions have an influence on the film-forming properties of the perovskite, and the composition of the perovskite also has a key influence on the performance of the perovskite film.
  • Perovskite precursor solution for improving the stability of perovskite solar cells.
  • the composition is 14.1 mg bromomethylamine, 155.4 mg iodoformamidine, 524.3 mg lead iodide, 77 mg cesium iodide, 3,4 -Dichloroaniline is 7.86 mg (1.02%), 200 mL dimethyl sulfoxide, 800 mL N,N-dimethylformamide; its preparation method is the same as in Example 1.
  • a solar cell (FTO substrate) was prepared according to the method of Example 3. After the same stability test, its photoelectric conversion efficiency dropped from 17.39% at the initial (0h) to 17.02% at 72h and 16.05% at 100h.
  • the untreated perovskite is highly sensitive to the humidity and temperature of the environment. High humidity and high temperature will cause the untreated perovskite to decay and decompose in a very short time, and the calcium with 3,4-dichloroaniline is added. Titanium ore has low sensitivity to humidity and can be stored for a long time in a high-humidity environment, which is also a major advantage of the present invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

一种提升钙钛矿太阳能电池稳定性的方法，将碘甲脒和碘化铯加入溶剂中，搅拌后加入溴甲胺，搅拌后加入碘化铅、3，4-二氯苯胺，搅拌得到提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液；将提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液旋涂于基底上，热退火得到太阳能电池的吸光层。采用该钙钛矿层制备的太阳能电池解决现有钙钛矿技术中存在的缺陷，提供一种用于电池制备过程中对工艺环境要求低、制备方法便捷，且能实现在普通环境中保持很长时间性状稳定的钙钛矿稳定性提升手段。

Description

一种提升钙钛矿太阳能电池稳定性的方法 技术领域
本发明属于太阳能技术，具体涉及一种提升钙钛矿太阳能电池稳定性的处理方法。
 背景技术
太阳能作为清洁能源中的一种稳定的能源供体，已经成为了全球科研和高新技术企业竞相追逐的研究热点。而在如今的太阳能电池应用市面上，硅晶太阳能电池占据了极大地份额，虽历经长时间的探索和发展，以硅晶为核心的太阳能电池拥有良好、稳定的光电转化效率，但因其本身工艺、维护和回收成本高，制备环境要求严苛，回收利用效率低下，回收成本高等缺点，新一代的光电转化材料也顺势而生。其中，基于ABX 3结构的 (A代表阳离子甲胺、甲脒、金属铯等，B代表金属阳离子铅、锡、铋等，X代表卤族元素) 钙钛矿材料类太阳能电池极具开发潜力，拥有正相晶体结构的钙钛矿吸光层是该类太阳能电池的核心，这种钙钛矿太阳能电池的光吸收层相较其他光电材料有着成本低廉，制法工艺简单、快捷，开路电压大，光谱响应速率快等优点；且这种钙钛矿太阳能电池的光电转化效率相比于其他的太阳能电池更高。但这种材料也有弊端，该材料对湿度和温度有较高的敏感性，诸如单一体相的混合阳离子体系的钙钛矿太阳能电池在制备过程中需要在无水无氧低温环境中制备，且使用过程中，如果受到环境因素波动的影响，电池器件的性能会受到极大地损耗。目前，关于这种材料的研究已经有了长足的进展，但实现产业化，器件的稳定性就需要得到有效的保证。
技术问题
本发明的目的是为了解决现有钙钛矿成矿技术中存在的缺陷，提供一种用于电池制备过程中对工艺环境要求低、制备方法便捷，且能实现在普通环境中保持很长时间性状稳定的钙钛矿稳定性提升手段。
 技术解决方案
本发明采用如下技术方案：一种提升钙钛矿太阳能电池稳定性的方法，采用提升钙钛矿太阳能电池稳定性用钙钛矿前驱体制备钙钛矿太阳能电池的钙钛矿层，实现钙钛矿太阳能电池稳定性的提升；所述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液包括提升钙钛矿太阳能电池稳定性用钙钛矿前驱体与溶剂；所述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体包括溴甲胺、碘甲脒、碘化铅、碘化铯、3,4-二氯苯胺；3,4-二氯苯胺用量为溴甲胺、碘甲脒、碘化铅、碘化铯重量和的0.6%～1.15%。
本发明公开的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体与溶剂组成提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液；提升钙钛矿太阳能电池稳定性用钙钛矿前驱体包括溴甲胺、碘甲脒、碘化铅、碘化铯、3,4-二氯苯胺，其中3,4-二氯苯胺用量为溴甲胺、碘甲脒、碘化铅、碘化铯重量和的0.63 %～1.12 %，优选0.8 %～1.05 %。溶剂为砜类溶剂与酰胺类溶剂的混合物，比如N,N-二甲基甲酰胺与二甲亚砜；优选的，按体积百分数，N,N-二甲基甲酰胺为70%～90%，二甲亚砜为10%～30%。
本发明进一步公开了一种钙钛矿太阳能电池，包括钙钛矿层，所述钙钛矿层由上述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体制备。本发明中，钙钛矿太阳能电池还包括常规基底、电子传输层、空穴传输层、电极；这些都为常规材料与结构。
本发明中，以溴甲胺、碘甲脒、碘化铅、碘化铯重量和为100%，其中溴甲胺为1%～5%，碘甲脒为10%～28%，碘化铅为50%～80%，碘化铯为余量，优选的，溴甲胺为1.5%～2%，碘甲脒为17%～22%，碘化铅为65%～75%，碘化铯为余量。
提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液中，提升钙钛矿太阳能电池稳定性用钙钛矿前驱体与溶剂的质量比为1∶（0.8～1.5）。
优选的，本发明提升钙钛矿太阳能电池稳定性用钙钛矿前驱体中，以溴甲胺、碘甲脒、碘化铅、碘化铯重量和为100%，按质量百分数，溴甲胺为1.83%，碘甲脒为20.16%，碘化铅为71.91%，碘化铯为余量；3,4-二氯苯胺为1.02%；进一步的，在上述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体的基础上加入二甲亚砜、N,N-二甲基甲酰胺，得到优选的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液。
本发明公开的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液制备钙钛矿太阳能电池，可以提升钙钛矿太阳能电池稳定性。上述钙钛矿太阳能电池的制备方法，包括以下步骤，将所述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液旋涂于基底上，热退火得到太阳能电池的吸光层，然后在吸光层上制备空穴传输层，在空穴传输层上蒸镀电极，得到钙钛矿太阳能电池；旋涂为两步，先以1000转/秒的速度旋涂10秒，再以6000转/秒的速度旋涂30秒，旋涂结束前滴加乙醚。
本发明公开了提升钙钛矿太阳能电池稳定性的方法，采用上述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体制备钙钛矿太阳能电池的钙钛矿层，实现钙钛矿太阳能电池稳定性的提升；本发明的创造性在于利用新的钙钛矿前驱体替换现有钙钛矿前驱体制备钙钛矿层用于太阳能电池，其他不变，可有效实现钙钛矿太阳能电池稳定性的提升。
 有益效果
本发明首次公开了含有3,4-二氯苯胺的钙钛矿器件，光电转化效率明显高于未经处理的钙钛矿器件的光电转化效率，无论是开路电压还是短路电流密度亦或是填充因子，这些常规衡量太阳能电池性能的参数，在钙钛矿经过修饰后都得到了大幅的提升。由此可以说明，添加剂对钙钛矿确实有优化的作用，而且这种优化结果在钙钛矿晶体形貌有所体现，从两者对比情况来看，未经处理的钙钛矿晶体的均匀性不好，晶粒的尺寸大小不一，而经过处理后的钙钛矿晶粒尺寸几乎相似，均匀性也不错；尤其是寿命测试结果表明，在添加了3,4-二氯苯胺后，钙钛矿太阳能电池的稳定性有了极大地提升。
 附图说明
图1为未经3,4-二氯苯胺处理的钙钛矿形貌和处理后的钙钛矿晶体形貌对比（标尺：200纳米）。
图2为经3,4-二氯苯胺处理后的钙钛矿太阳能电池光电转化效率和未经处理后的钙钛矿太阳能电池光电转化效率对比。
图3为未经3,4-二氯苯胺处理的钙钛矿太阳能电池稳定性测试和处理后钙钛矿太阳能电池稳定性测试对比结果。
 本发明的实施方式
本发明提升钙钛矿太阳能电池稳定性用钙钛矿前驱体由溴甲胺、碘甲脒、碘化铅、碘化铯、3,4-二氯苯胺组成；再加入N,N-二甲基甲酰胺与二甲亚砜，得到提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液。
本发明的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液的制备方法为，将溴甲胺、碘甲脒、碘化铅、碘化铯、3,4-二氯苯胺与溶剂混合，得到提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液；进一步的，将碘甲脒和碘化铯加入溶剂中，搅拌后加入溴甲胺，搅拌后加入碘化铅、3,4-二氯苯胺，搅拌得到提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液。具体参见申请人同日申请的“提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液”。
所有原料都在手套箱中称取，搅拌过程均采用磁力搅拌。
本发明所有原料都是市售产品，为太阳能电池常规产品；涉及的测试方法为本领域常规方法。比如：钙钛矿太阳能电池光电转化效率测试方式：将制备的电池置于太阳能电池测试盒中，并将测试盒同数字源表keithley-2400链接，打开测试软件，将开路电压测试范围固定在-0.1v～1.2V之间，短路电流的测试范围为0mA/cm 2～30 mA/cm 2.打开Newport太阳光模拟器，将光照功率调制AM1.5（等同于一个标准太阳光）。点开相应配套的测试软件，测试钙钛矿太阳能电池的光电转化效率。测试期间对环境的湿度和温度不加以控制，具体湿度和温度依据大气环境氛围而改变。
钙钛矿太阳能电池稳定性测试方法：将电池置于太阳能电池测试盒中，测试盒不加额外保护，让钙钛矿太阳能电池暴露于空气中，保持湿度和温度同大气环境中的湿度和温度一致，同时将测试盒置于一个标准太阳光下，每隔12个小时，对钙钛矿太阳能电池做一次光电转化效率测试。待未经修饰的钙钛矿太阳能电池光电转化效率值低于1%时，停止寿命测试。
实施例一：提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液，组成为：溴甲胺为14.1mg，碘甲脒为155.4 mg，碘化铅为554.3 mg，碘化铯为47 mg，3,4-二氯苯胺为7.86 mg（即1.02%），200mL二甲亚砜、800mL N,N-二甲基甲酰胺。
制备方法如下：（1）将N,N-二甲基甲酰胺加入到二甲亚砜中，将溶液搅拌均匀。
（2）称取碘甲脒和碘化铯，加入到步骤（1）中搅拌好的溶液中，搅拌10min后，再将溴甲胺加入到溶液中，将溶液温度升至50℃，搅拌10min。
（3）将碘化铅加入步骤（2）制备的溶液中，再将3,4-二氯苯胺加入溶液中搅拌至溶解；整个加入搅拌过程中保持溶液50℃恒温。
（4）将步骤（3）中配置好的溶液在50℃下继续搅拌12个小时，得到提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液。
本发明公开了所述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体或者提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液在制备钙钛矿太阳能电池中的应用，可以提升钙钛矿太阳能电池稳定性。
将上述3,4-二氯苯胺更换为3,5-二氯苯胺，其余不变，得到异构体钙钛矿前驱体溶液。
将上述3,4-二氯苯胺的添加量更换为4.62mg（0.6%），其余不变，得到少钙钛矿前驱体溶液。
将上述3,4-二氯苯胺的添加量更换为8.87mg（1.15%），其余不变，得到多钙钛矿前驱体溶液。
实施例二：太阳能电池的吸光层，制备方法为，将实施例一的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液旋涂于基底上，150℃热退火30分钟，得到太阳能电池的吸光层，晶体形貌见图1；旋涂为两步，先以1000转/秒的速度旋涂10秒，再以6000转/秒的速度旋涂30秒，并且在旋涂结束前15秒时将200微升的乙醚滴加在旋转的钙钛矿膜上。
基底为附有TiO 2的FTO玻璃或者附有SnO 2的ITO玻璃；上述操作在手套箱中、水氧含量均低于2PPM下进行。
实施例三：一种钙钛矿太阳能电池包括常规基底、电子传输层、空穴传输层、电极以及钙钛矿层，所述钙钛矿层由实施例一的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液制备。
上述太阳能电池的制备方法如下：将实施例一的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液旋涂于基底上，150℃热退火30分钟，得到太阳能电池的吸光层，旋涂为两步，先以1000转/秒的速度旋涂10秒，再以6000转/秒的速度旋涂30秒，旋涂结束前滴加乙醚；然后在吸光层上制备空穴传输层，再将制备的器件置于高真空电极蒸镀仪中，在空穴传输层上蒸镀上110纳米厚的银电极层，最后得到钙钛矿太阳能电池。本发明的技术方案中，提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液旋涂完成后即刻退火处理，无需现有技术真空处理或者其他退火前挥发溶剂的步骤。
基底为附有TiO 2的FTO玻璃或者附有SnO 2的ITO玻璃，为现有产品，其中电子传输层TiO 2或者SnO 2的厚度为100nm；上述操作在手套箱中、水氧含量均低于2PPM下进行。
具体的，上述太阳能电池具体制备方法如下：（1）将实施例一钙钛矿前驱体溶液依次以1000转/秒的速度旋涂10秒、6000转/秒的速度旋涂30秒的方式旋涂于步骤（1）处理后的FTO玻璃（或ITO玻璃）上，并且在旋涂结束前15秒时将200微升的乙醚滴加在旋转的钙钛矿膜上，旋涂结束后的带有钙钛矿膜的FTO玻璃（ITO玻璃）转移至150℃的平板上退火30分钟。
（2）在步骤（1）处理后的FTO玻璃上旋涂空穴传输层材料（Spiro-oMetad, 2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴溶液）,厚度80nm，旋涂完成后置于饱和氧气环境下放置1min，即得所述太阳能电池半成品，随后，将制备的器件置于高真空电极蒸镀仪中，在空穴传输层上蒸镀上110纳米厚的银电极层，最终可获得钙钛矿太阳能电池完整器件。
空穴传输层溶液配制：72.3mg的Spiro-OMeTAD(2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴溶液)溶于超干氯苯中，取28.8微升的TBP（4-叔丁基吡啶）滴加在含有Spiro-OMeTAD的氯苯溶液中，另外取17.5微升的Li-TFSI溶液（520毫克/毫升，乙腈作为溶剂）滴加在氯苯溶液中，混合搅拌8个小时得到空穴传输层溶液。
对比太阳能电池：在实施例一的基础上，不加入3,4-二氯苯胺，其余不变，得到钙钛矿前体溶液。
在实施例三的基础上，以上述钙钛矿前体溶液替换实施例一的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液，其余不变，得到对比太阳能电池。
性能对比：图1为未经3,4-二氯苯胺处理的钙钛矿形貌和处理后的钙钛矿晶体形貌对比（标尺：200纳米）；从两者对比情况来看，未经处理的钙钛矿晶体的均匀性不好，晶粒的尺寸大小不一，而经过处理后的钙钛矿晶粒尺寸几乎相似，均匀性也不错，并且未经处理的钙钛矿膜表面的起伏度也比处理后的钙钛矿膜的起伏度大。
图2为经3,4-二氯苯胺处理后的钙钛矿太阳能电池（实施例三，FTO）光电转化效率和未经处理后的钙钛矿太阳能电池（对比太阳能电池，FTO）光电转化效率对比；未经处理的钙钛矿器件的光电转化效率明显低于添加了3,4-二氯苯胺的钙钛矿器件的光电转化效率。无论是开路电压还是短路电流密度亦或是填充因子，这些常规衡量太阳能电池性能的参数，在钙钛矿经过修饰后都得到了大幅的提升。由此可以说明，添加剂对钙钛矿确实有优化的作用。
图3为未经3,4-二氯苯胺处理的钙钛矿太阳能电池（对比太阳能电池，FTO）稳定性测试和处理后钙钛矿太阳能电池（实施例三，FTO）稳定性测试对比结果（500小时，湿度：50%，温度：25℃）；在添加了3,4-二氯苯胺后，钙钛矿太阳能电池的稳定性有了极大地提升。
对比例：将实施例三的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液更换为异构体钙钛矿前驱体溶液，其余不变，得到异构体太阳能电池（FTO），经过同样的稳定性测试，其光电转化效率由初始（0h）的15.02%下降到100h的12.58%。
将实施例三的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液更换为少钙钛矿前驱体溶液，其余不变，得到异构体太阳能电池（FTO），经过同样的稳定性测试，其光电转化效率由初始（0h）的15.33%下降到100h的5.68%。
将实施例三的提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液更换为多钙钛矿前驱体溶液，其余不变，得到异构体太阳能电池（FTO），经过同样的稳定性测试，其光电转化效率由初始（0h）的14.86%下降到100h的8.37%。
实施例四：氯离子对钙钛矿成膜性能有影响，同时钙钛矿的组成对钙钛矿膜性能也存在关键影响。
提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液，组成为：溴甲胺为14.1mg，碘甲脒为155.4 mg，碘化铅为554.3 mg，碘化铯为47 mg，3,4-二氯苯胺为7.32 mg（0.95%），200mL二甲亚砜、800mL N,N-二甲基甲酰胺；其制备方法同实施例一。
然后根据实施例三的方法制备太阳能电池（ITO基底），经过同样的稳定性测试，其光电转化效率由初始（0h）的17.46%下降到72h的17.11%、100h的16.03%。
实施例五：氯离子对钙钛矿成膜性能有影响，同时钙钛矿的组成对钙钛矿膜性能也存在关键影响。
提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液，组成为：溴甲胺为14.1mg，碘甲脒为155.4 mg，碘化铅为524.3 mg，碘化铯为77 mg，3,4-二氯苯胺为7.86 mg（1.02%），200mL二甲亚砜、800mL N,N-二甲基甲酰胺；其制备方法同实施例一。
然后根据实施例三的方法制备太阳能电池（FTO基底），经过同样的稳定性测试，其光电转化效率由初始（0h）的17.39%下降到72h的17.02%、100h的16.05%。
在实施例五的基础上，将3,4-二氯苯胺更换为氯甲胺（MACl），其余不变，得到异构体太阳能电池（FTO），经过同样的稳定性测试，其光电转化效率由初始（0h）的16.93%下降到72h的14.39%、100h的13.21%。
另外，未处理的钙钛矿对环境的湿度和温度敏感性高，高湿高温会让未处理的钙钛矿在极短时间内就衰败分解，而添加了3,4-二氯苯胺的钙钛矿对湿度敏感性低，可在高湿环境中保存较长的时间，这也是本发明的一大优势。

Claims (10)

  1. 一种提升钙钛矿太阳能电池稳定性的方法，采用提升钙钛矿太阳能电池稳定性用钙钛矿前驱体制备钙钛矿太阳能电池的钙钛矿层，实现钙钛矿太阳能电池稳定性的提升；所述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液包括提升钙钛矿太阳能电池稳定性用钙钛矿前驱体与溶剂；所述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体包括溴甲胺、碘甲脒、碘化铅、碘化铯、3,4-二氯苯胺。
  2. 根据权利要求1所述提升钙钛矿太阳能电池稳定性的方法，其特征在于，所述3,4-二氯苯胺用量为溴甲胺、碘甲脒、碘化铅、碘化铯重量和的0.60 %～1.15 %。
  3. 根据权利要求1所述提升钙钛矿太阳能电池稳定性的方法，其特征在于，溶剂为砜类溶剂与酰胺类溶剂的混合物。
  4. 根据权利要求1所述提升钙钛矿太阳能电池稳定性的方法，其特征在于，以溴甲胺、碘甲脒、碘化铅、碘化铯重量和为100%，其中溴甲胺为1%～5%，碘甲脒为10%～28%，碘化铅为50%～80%，碘化铯为余量。
  5. 一种钙钛矿太阳能电池，包括钙钛矿层，所述钙钛矿层由提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液制备；提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液包括提升钙钛矿太阳能电池稳定性用钙钛矿前驱体与溶剂；提升钙钛矿太阳能电池稳定性用钙钛矿前驱体包括溴甲胺、碘甲脒、碘化铅、碘化铯、3,4-二氯苯胺。
  6. 根据权利要求5所述钙钛矿太阳能电池，其特征在于，以溴甲胺、碘甲脒、碘化铅、碘化铯重量和为100%，其中溴甲胺为1%～5%，碘甲脒为10%～28%，碘化铅为50%～80%，碘化铯为余量；3,4-二氯苯胺用量为溴甲胺、碘甲脒、碘化铅、碘化铯重量和的0.6 %～1.15 %。
  7. 根据权利要求5所述钙钛矿太阳能电池，其特征在于，钙钛矿太阳能电池还包括常规基底、电子传输层、空穴传输层、电极。
  8. 根据权利要求5所述钙钛矿太阳能电池，其特征在于，3,4-二氯苯胺用量为溴甲胺、碘甲脒、碘化铅、碘化铯重量和的0.63 %～1.12 %。
  9. 权利要求5所述钙钛矿太阳能电池的制备方法，其特征在于，包括以下步骤，将所述提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液旋涂于基底上，热退火得到太阳能电池的吸光层，然后在吸光层上制备空穴传输层，在空穴传输层上蒸镀电极，得到钙钛矿太阳能电池。
  10. 根据权利要求9所述钙钛矿太阳能电池的制备方法，其特征在于，旋涂为两步，先以1000转/秒的速度旋涂10秒，再以6000转/秒的速度旋涂30秒，旋涂结束前滴加乙醚。
PCT/CN2020/131970 2020-06-27 2020-11-26 一种提升钙钛矿太阳能电池稳定性的方法 WO2021258631A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/010,154 US20230301164A1 (en) 2020-06-27 2020-11-26 Method for improving stability of perovskite solar cells

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010593696.9 2020-06-27
CN202010593696.9A CN111740016B (zh) 2020-06-27 2020-06-27 一种提升钙钛矿太阳能电池稳定性的方法

Publications (1)

Publication Number Publication Date
WO2021258631A1 true WO2021258631A1 (zh) 2021-12-30

Family

ID=72651139

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/131970 WO2021258631A1 (zh) 2020-06-27 2020-11-26 一种提升钙钛矿太阳能电池稳定性的方法

Country Status (3)

Country Link
US (1) US20230301164A1 (zh)
CN (1) CN111740016B (zh)
WO (1) WO2021258631A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114628592A (zh) * 2022-03-14 2022-06-14 四川大学 一种掺杂噻吩甲脒氯的高效宽带隙钙钛矿太阳电池及其制备方法
CN114853063A (zh) * 2022-05-30 2022-08-05 天津理工大学 制备钙钛矿/二硫化钼异质结的方法
CN115835659A (zh) * 2023-02-22 2023-03-21 北京科技大学 一种杂化钙钛矿太阳能电池及其制备方法
CN115867054A (zh) * 2022-11-25 2023-03-28 江苏振宁半导体研究院有限公司 一种超适形金属卤化物钙钛矿光电探测器阵列
CN115884611A (zh) * 2023-02-23 2023-03-31 北京科技大学 一种CsPbI3钙钛矿太阳能电池及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111740015B (zh) * 2020-06-27 2022-08-12 苏州大学 提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液
CN111740016B (zh) * 2020-06-27 2021-08-27 苏州大学 一种提升钙钛矿太阳能电池稳定性的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9583724B2 (en) * 2013-12-19 2017-02-28 Nutech Ventures Systems and methods for scalable perovskite device fabrication
CN109888106A (zh) * 2019-03-11 2019-06-14 吉林大学 一种SnO2电子传输层及钙钛矿太阳电池的制备方法
CN109935690A (zh) * 2017-12-15 2019-06-25 北京大学 一种基于硅异质结/钙钛矿二电极的叠层太阳能电池
CN110459680A (zh) * 2019-07-03 2019-11-15 福建师范大学 一种钙钛矿太阳能电池及其制备方法
CN111740015A (zh) * 2020-06-27 2020-10-02 苏州大学 提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液
CN111740016A (zh) * 2020-06-27 2020-10-02 苏州大学 一种提升钙钛矿太阳能电池稳定性的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9583724B2 (en) * 2013-12-19 2017-02-28 Nutech Ventures Systems and methods for scalable perovskite device fabrication
CN109935690A (zh) * 2017-12-15 2019-06-25 北京大学 一种基于硅异质结/钙钛矿二电极的叠层太阳能电池
CN109888106A (zh) * 2019-03-11 2019-06-14 吉林大学 一种SnO2电子传输层及钙钛矿太阳电池的制备方法
CN110459680A (zh) * 2019-07-03 2019-11-15 福建师范大学 一种钙钛矿太阳能电池及其制备方法
CN111740015A (zh) * 2020-06-27 2020-10-02 苏州大学 提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液
CN111740016A (zh) * 2020-06-27 2020-10-02 苏州大学 一种提升钙钛矿太阳能电池稳定性的方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114628592A (zh) * 2022-03-14 2022-06-14 四川大学 一种掺杂噻吩甲脒氯的高效宽带隙钙钛矿太阳电池及其制备方法
CN114628592B (zh) * 2022-03-14 2023-02-28 四川大学 一种掺杂噻吩甲脒氯的高效宽带隙钙钛矿太阳电池及其制备方法
CN114853063A (zh) * 2022-05-30 2022-08-05 天津理工大学 制备钙钛矿/二硫化钼异质结的方法
CN114853063B (zh) * 2022-05-30 2023-05-12 天津理工大学 制备钙钛矿/二硫化钼异质结的方法
CN115867054A (zh) * 2022-11-25 2023-03-28 江苏振宁半导体研究院有限公司 一种超适形金属卤化物钙钛矿光电探测器阵列
CN115835659A (zh) * 2023-02-22 2023-03-21 北京科技大学 一种杂化钙钛矿太阳能电池及其制备方法
CN115884611A (zh) * 2023-02-23 2023-03-31 北京科技大学 一种CsPbI3钙钛矿太阳能电池及其制备方法

Also Published As

Publication number Publication date
US20230301164A1 (en) 2023-09-21
CN111740016A (zh) 2020-10-02
CN111740016B (zh) 2021-08-27

Similar Documents

Publication Publication Date Title
WO2021258631A1 (zh) 一种提升钙钛矿太阳能电池稳定性的方法
WO2021258630A1 (zh) 提升钙钛矿太阳能电池稳定性用钙钛矿前驱体溶液
CN106025085B (zh) 基于Spiro‑OMeTAD/CuXS复合空穴传输层的钙钛矿太阳能电池及其制备方法
CN104993058B (zh) 一种层状钙钛矿结构材料及在甲胺铅碘钙钛矿薄膜太阳能电池中的应用
CN108807694B (zh) 一种超低温稳定的平板钙钛矿太阳能电池及其制备方法
Gao et al. RbCs (MAFA) PbI3 perovskite solar cell with 22.81% efficiency using the precise ions cascade regulation
CN105810831B (zh) 一种铅锡混合钙钛矿薄膜、其制备方法及应用
CN110854273A (zh) 一种有机体异质结掺杂的钙钛矿太阳能电池及其制备方法
CN109742245A (zh) 苯酚取代的富勒烯衍生物在钙钛矿太阳能电池中的应用、钙钛矿太阳能电池及其制备方法
CN108389969A (zh) 一种用于制备钙钛矿太阳能电池钙钛矿层的绿色溶剂体系及混合溶液
CN110429179A (zh) 一种azo/二氧化钛/二氧化锡-氧化石墨烯薄膜及利用其制得的钙钛矿太阳能电池
CN113314672A (zh) 一种钙钛矿太阳能电池及其制备方法
CN113130762A (zh) 太阳能电池的吸光层材料、三元阳离子钙钛矿太阳能电池及其制备方法
CN115188893A (zh) 一种钙钛矿太阳能电池及制备方法
Wang et al. Aniline Sulfonic Acid Induced Uniform Perovskite Film for Large‐Scale Photovoltaics
CN110660914B (zh) 一种低温原位控制合成碘铋铜三元化合物半导体光电薄膜材料的化学方法
Zheng et al. Study of carbon-based hole-conductor-free perovskite solar cells
CN116801652A (zh) 一种晶硅钙钛矿叠层太阳能电池及制备方法
CN111640872A (zh) 一种能调控碘化铅钝化层生长的钙钛矿太阳能电池及制备方法
Hao et al. Improved performance of mesostructured perovskite solar cells via an anti-solvent method
CN109830604A (zh) 一种以聚氧化乙烯薄膜钝化电子传输层与光敏层间界面的钙钛矿光伏电池及其制备方法
CN110993801B (zh) 一种葡萄糖掺杂的有机无机杂化钙钛矿复合膜及其制备和应用
CN113416155A (zh) 一种钙钛矿太阳能电池添加剂的制备方法及其应用
CN110854277B (zh) 一种表面钝化制备硫化锑基薄膜太阳能电池的方法
CN113675347B (zh) 一种制备2d/3d有机-无机杂化钙钛矿太阳能电池的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20942322

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20942322

Country of ref document: EP

Kind code of ref document: A1