全无机钙钛矿太阳电池: 现状与未来

近年来,基于ABX₃结构的有机无机杂化钙钛矿材料因其具有优良的光电特性和廉价的制作成本得到了全世界的广泛关注,但体系中的有机组分容易受到光、热、湿等外界条件的影响而分解,导致器件的PCE发生严重的下降,极大地限制了PSCs(Perovskite solar cells, PSCs)的产业化进程。利用纯无机阳离子完全取代ABX₃结构中的A位有机阳离子制备出全无机钙钛矿材料,因其优异的热稳定性和环境稳定性而得到了快速的发展。现阶段,基于全无机钙钛矿材料的全无机钙钛矿太阳能电池(I-PSCs)的效率已超过19%,应用前景广阔。本文回顾了近年来全无机钙钛矿材料的研究进展,对不同类型的全无机钙钛矿材料进行了综述和讨论,从成膜工艺、掺杂工程、后处理工程等方面论述了如何提升器件的稳定性。最后,对I-PSCs的大面积制备及其柔性应用进行了介绍,揭示了I-PSCs面临的挑战,并对该领域进行了展望。     

无机钙钛矿太阳能电池稳定性研究进展

近年来钙钛矿太阳能电池发展迅速,全无机钙钛矿具有良好的热稳定性、高吸光系数、带隙可调、制备简单等优点备受关注.现今,无机钙钛矿太阳能电池的最高光电转化效率已达19.03%,具有很好的发展潜力.本综述将从无机钙钛矿太阳能电池的制备方法、薄膜掺杂、界面修饰对稳定性影响入手,系统介绍无机钙钛矿太阳能电池的发展并进行分析总结,并着重分析了无机钙钛矿不稳定的原因及其改善方法,最后对于无机钙钛矿太阳能电池的未来进行了展望.     

钙钛矿太阳电池吸光层材料研究进展

近年来,有机-无机卤化铅钙钛矿太阳电池的研究取得了突破性进展,公证记录电池效率22.1%,与CdTe薄膜电池（认证记录电池效率22.1%）和CuInGaSn（CIGS）（认证记录电池效率22.3%）薄膜电池技术相媲美,已经接近于市场上主导地位的晶体硅太阳电池（约25%）。有机卤化铅钙钛矿太阳电池器件的长期效率输出稳定性和含毒性Pb严重制约其实际应用。本文将讨论有机卤化铅钙钛矿太阳电池不稳定性因素和相应的解决方案,并对钙钛矿材料中Pb元素的取代工作和无机非铅钙钛矿材料及其太阳电池的研究进行了阐述与展望。     

湿空气下制备稳定的CsPbI2Br钙钛矿太阳电池

无机钙钛矿太阳能电池由于具有良好的热稳定性,高吸光系数等优点发展迅速。但无机钙钛矿材料对水分极其敏感,一般在惰性环境下中进行制备,操作复杂。本文通过简单的一步旋涂工艺,在无手套箱空气湿度条件下制备CsPbI₂Br无机钙钛矿薄膜,通过介孔TiO₂厚度的优化,对钙钛矿薄膜的结晶、成膜及稳定性进行了分析,发现在较厚基底介孔层上制备的钙钛矿晶粒大、无孔隙;随着基底厚度的减小,其上所形成的CsPbI₂Br薄膜禁带宽度(E_g)增大;电化学阻抗测试表明在较厚基底介孔层上制备的CsPbI₂Br钙钛矿具有更好的载流子提取与传输能力。对不同厚度介孔层上沉积的钙钛矿薄膜稳定性进行测试,发现CsPbI₂Br钙钛矿的稳定性随着介孔层厚度的增加而提高,在空气中做放置144 h后无明显变化。在空气湿度条件下组装成器件,获得到了8.16%的最佳光电转换效率,并且对器件无任何修饰及封装的情况下,在相对湿地低于35%的空气中放置72 h后保持最初效率的73%。     

钙钛矿型太阳电池研究进展

自从2009年钙钛矿材料被应用到太阳电池领域,到现在仅6年的时间里,钙钛矿型太阳电池的光伏转换效率从约3%提高到20.1%,受到全球瞩目。 本文对近年来钙钛矿型太阳电池的发展进行了综述,介绍了钙钛矿吸光材料的性能及其制备,总结了钙钛矿型太阳电池器件结构及其内在机理,探讨了该类型电池待突破的方向和可能的解决途径,阐述了钙钛矿型太阳电池的进展历程,展望了未来发展方向。     

多维CsPbX3无机钙钛矿材料的制备及其在太阳能电池中的应用

近年来全无机CsPbX3(X=Cl、Br、I)型钙钛矿材料由于其高吸光系数、低激子束缚能、长的载流子扩散长度等优点使其在太阳能电池(PSC)器件应用方面备受关注.高效的合成方法和精准的形貌控制对无机钙钛矿的光学性质及其太阳能电池光电性能及稳定性至关重要.本文系统介绍了不同维度无机钙钛矿材料包括零维量子点、一维纳米线/棒...     

锡基钙钛矿太阳电池光吸收材料

钙钛矿太阳电池以其优异的光吸收特性、载流子传输能力以及简单的制备工艺,成为太阳电池领域研究的热点。高效、无污染、低成本一直是太阳电池领域追求的目标。然而,传统钙钛矿太阳电池由于其光吸收材料中含重金属元素铅,对环境有较大影响,从而限制了此类钙钛矿太阳电池的进一步商业化应用。基于此,科学家们都在致力于寻找新的无铅钙钛矿材料。在众多无铅钙钛矿材料中,锡基钙钛矿材料由于其相对较小的毒性、合适的带隙以及相应器件具有较高的能量转换效率等优点,成为最有希望应用于钙钛矿太阳电池的替代材料。然而,锡基钙钛矿太阳电池也存在一些弱点,其能量转换效率和器件稳定性相较于铅基钙钛矿太阳电池仍然存在很大差距,器件制备过程中对空气十分敏感。为了更好地解决这些问题,对锡基钙钛矿材料及器件性能的各种影响因素进行系统地研究势在必行。文章分类介绍了各类锡基钙钛矿材料及其在太阳电池中的应用,包括有机-无机杂化锡基钙钛矿材料,锡铅混合钙钛矿材料和全无机锡基钙钛矿材料,综述了锡基钙钛矿材料及其相应器件性能的最新研究进展,并且讨论了影响器件性能的各项因素,最后对锡基钙钛矿太阳电池未来的发展做出了展望。     

钙钛矿型太阳能电池制备工艺及稳定性研究进展

有机-无机杂化钙钛矿型太阳能电池因其简单的制备工艺,低廉的制造成本,优异的光电转换效率,成为光伏领域的研究热点。钙钛矿光吸收材料具有消光系数高、载流子迁移率高、载流子寿命长、带隙可调控等优点。短短几年内,钙钛矿型太阳能电池的效率从最初的3.8%提高到22.1%。目前,为了获得稳定高效的钙钛矿型太阳能电池,主要有以下几个研究思路：新型器件结构设计;结构功能层的材料形貌设计;结构各功能层间的界面修饰;空穴传输材料的选择;对电极的选择。本文通过文献综述,在回顾了国内外研究者对钙钛矿型太阳能电池的研究历程的基础上,介绍了钙钛矿型太阳能电池的结构和工作原理,重点总结了电子传输层和钙钛矿层的制备工艺及优化,并讨论了钙钛矿型太阳能电池的稳定性以及展望了其商业化的前景。     

钙钛矿型太阳能电池制备工艺及稳定性研究进展

有机-无机杂化钙钛矿型太阳能电池因其简单的制备工艺,低廉的制造成本,优异的光电转换效率,成为光伏领域的研究热点。钙钛矿光吸收材料具有消光系数高、载流子迁移率高、载流子寿命长、带隙可调控等优点。短短几年内,钙钛矿型太阳能电池的效率从最初的3.8%提高到22.1%。目前,为了获得稳定高效的钙钛矿型太阳能电池,主要有以下几个研究思路:新型器件结构设计;结构功能层的材料形貌设计;结构各功能层间的界面修饰;空穴传输材料的选择;对电极的选择。本文通过文献综述,在回顾了国内外研究者对钙钛矿型太阳能电池的研究历程的基础上,介绍了钙钛矿型太阳能电池的结构和工作原理,重点总结了电子传输层和钙钛矿层的制备工艺及优化,并讨论了钙钛矿型太阳能电池的稳定性以及展望了其商业化的前景。     

钙钛矿太阳电池电子传输层与光吸收层的界面工程

钙钛矿太阳电池(PSCs)自2009年出现至今经历了光伏领域前所未有的快速发展,目前经认证的最高光电转换效率已超过23%,极具应用前景。界面工程是提升PSCs性能的有效途径之一,本文回顾了PSCs中电子传输层和钙钛矿光吸收层间界面工程的主要研究工作,根据作用效果将相关研究按照改善钙钛矿光吸收层质量、提高电子传输层与钙钛矿层间的能级匹配度和提升电池稳定性等三类进行了梳理和总结,并对电子传输层和钙钛矿光吸收层间界面工程的前景进行了展望。     

Tailoring Component Interaction for Air-Processed Efficient and Stable All-Inorganic Perovskite Photovoltaic

All-inorganic lead halide perovskites are promising candidates for optoelectronic applications. However, fundamental questions remain over the component interaction in the perovskite precursor solution due to the limitation of the most commonly used solvents of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). Here, we report an interaction tailoring strategy for all-inorganic CsPbI_3−xBr_x perovskites by involving the ionic liquid solvent methylammonium acetate (MAAc). C=O shows strong interaction with lead (Pb²⁺) and N−H⋅⋅⋅I hydrogen bond formation is observed. The interactions stabilize the perovskite precursor solution and allow production of the high-quality perovskite films by retarding the crystallization. Without the necessity for antisolvent treatment, the one-step air-processing approach delivers photovoltaic cells regardless of humidity, with a high efficiency of 17.10 % along with long operation stability over 1500 h under continuous light illumination.     

B-Site Co-Alloying with Germanium Improves the Efficiency and Stability of All-Inorganic Tin-Based Perovskite Nanocrystal Solar Cells

Colloidal lead-free perovskite nanocrystals have recently received extensive attention because of their facile synthesis, the outstanding size-tunable optoelectronic properties, and less or no toxicity in their commercial applications. Tin (Sn) has so far led to the most efficient lead-free solar cells, yet showing highly unstable characteristics in ambient conditions. Here, we propose the synthesis of all-inorganic mixture Sn-Ge perovskite nanocrystals, demonstrating the role of Ge²⁺ in stabilizing Sn²⁺ cation while enhancing the optical and photophysical properties. The partial replacement of Sn atoms by Ge atoms in the nanostructures effectively fills the high density of Sn vacancies, reducing the surface traps and leading to a longer excitonic lifetime and increased photoluminescence quantum yield. The resultant Sn-Ge nanocrystals-based devices show the highest efficiency of 4.9 %, enhanced by nearly 60 % compared to that of pure Sn nanocrystals-based devices.     

High‐Purity Inorganic Perovskite Films for Solar Cells with 9.72 % Efficiency

All‐inorganic perovskite solar cells with high efficiency and improved stability are promising for commercialization. A multistep solution‐processing method was developed to fabricate high‐purity inorganic CsPbBr₃ perovskite films for use in efficient solar cells. By tuning the number of deposition cycles (n) of a CsBr solution, the phase conversion from CsPb₂Br₅ (n ≤3), to CsPbBr₃ (n=4), and Cs₄PbBr₆ (n≥5) was optimized to achieve vertical‐ and monolayer‐aligned grains. Upon interfacial modification with graphene quantum dots, the all‐inorganic perovskite solar cell (without a hole‐transporting layer) achieved a power conversion efficiency (PCE) as high as 9.72 % under standard solar illumination conditions. Under challenging conditions, such as 90 % relative humidity (RH) at 25 °C or 80 °C at zero humidity, the optimized device retained 87 % PCE over 130 days or 95 % over 40 days, compared to the initial efficiency.     

大面积钙钛矿太阳能电池

近年来,钙钛矿太阳能电池因其高效、低成本、可制成柔性器件等突出优点在光伏研究领域备受关注。本文系统综述了大面积钙钛矿电池的最新研究进展,介绍了钙钛矿太阳能电池的结构特点、发展历史、钙钛矿薄膜的主要制备技术及改善的方法等,讨论了大面积钙钛矿太阳能电池目前存在的问题、提高大面积器件效率的方法及大面积钙钛矿太阳能电池的应用研究及工业化。最后,对大面积钙钛矿太阳能电池的应用前景进行了展望。     

界面钝化策略:提高钙钛矿太阳能电池的稳定性

近年来,新兴起的有机无机杂化钙钛矿太阳能电池突飞猛进,在短短十年里其光电转化效率从3.8%迅速发展到目前25.2%的认证效率,被视为最具有应用潜力的新型高效率太阳能电池之一。虽然钙钛矿太阳能电池具有很高的光电转换效率已与多晶硅薄膜电池相媲美,但是电池的长期稳定性仍是阻碍其商业化的一大挑战。钙钛矿表面和晶界存在大量的缺陷,界面钝化来提高钙钛矿太阳能电池的稳定性是非常重要且有效的策略。二维钙钛矿材料是有机胺层与无机层交替的层状钙钛矿,具有体积较大的有机铵阳离子,与传统的三维钙钛矿材料相比对于环境的稳定性较好,并且结构灵活可调,在三维钙钛矿表面修饰二维钙钛矿层钝化缺陷,在提高钙钛矿太阳能电池效率的同时又保证了稳定性,另外,合适的钝化剂分子也能够非常有效地钝化缺陷。本文总结了钙钛矿太阳能电池的不稳定因素,归纳了钙钛矿太阳能电池界面钝化方面的研究进展,指出了二维钙钛矿材料发展的巨大潜力以及寻找合适钝化剂分子的原则,期望能够为获得高性能的钙钛矿太阳能电池进而实现商业化提供有益的指导。     

When Aggregation-Induced Emission Meets Perovskites: Efficient Defect-Passivation and Charge-Transfer for Ambient Fabrication of Perovskite Solar Cells

The intrinsic defects in perovskite film can serve as non-radiative recombination center to limit the performance and stability of metal halide perovskite solar cells (PSCs). The additive engineering in perovskite film is always applied to produce high-efficiency PSCs in recent years. Here, a typical donor-acceptor (D−A) structured aggregation-induced emission (AIE) molecule tetraphenylethene-2-dicyano-methylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TPE-TCF) was introduced into perovskite film. The D−A structure of TPE-TCF molecule provided additional charge transfer channels, contributing to transporting electron of TPE-TCF-based device. The cyano (C≡N) of TPE-TCF can interact with the uncoordinated Pb to from a relatively stable intermediate, PbI₂⋅TPE-TCF, resulting in the slower crystal growth, reduced the defects at the grain boundaries and suppressed carrier recombination. As a consequence, the power conversion efficiency (PCE) of TPE-TCF-modified PSCs achieved a remarkably enhanced from 15.63 to 19.66 % with negligible hysteresis, which was prominent in methylammonium lead iodide-based devices fabricated under ambient condition. Furthermore, the PSCs modified by AIE molecule possessed an outstanding stability and maintain about 86 % of the initial PCE after 300 h storage in air at 25–35 °C with a high relative humidity (RH) of ≈85 %. This work suggests that incorporating AIE molecule into perovskite is a promising strategy for facilitating high-performance PSCs commercialization in ambient environment without glovebox.     

Enhanced Performance of Camphorsulfonic Acid-Doped Perovskite Solar Cells

High-quality perovskite film with large grains and therefore reduced grain boundaries plays a significant role in improving the power conversion efficiency (PCE) and ensuring good long-term stability of the perovskite solar cells. In this work, we found that adding camphorsulfonic acid (CSA), a Lewis base, to the perovskite solution results in the crystallization of larger perovskite grains. By varying the concentration of CSA, we found that the optimal concentration of the additive is 1 mg/mL, which leads to an 20% increase in PCE of the cells compared to the reference CSA-free cell. Interestingly, we observed that the PCE of cells with an excess of CSA was initially poor, but may increase significantly over time, possibly due to CSA migration to the hole-transporting layer, leading to an improvement in its conductivity.     

Stabilization of Highly Efficient and Stable Phase-Pure FAPbI3 Perovskite Solar Cells by Molecularly Tailored 2D-Overlayers

As a result of their attractive optoelectronic properties, metal halide APbI₃ perovskites employing formamidinium (FA⁺) as the A cation are the focus of research. The superior chemical and thermal stability of FA⁺ cations makes α-FAPbI₃ more suitable for solar-cell applications than methylammonium lead iodide (MAPbI₃). However, its spontaneous conversion into the yellow non-perovskite phase (δ-FAPbI₃) under ambient conditions poses a serious challenge for practical applications. Herein, we report on the stabilization of the desired α-FAPbI₃ perovskite phase by protecting it with a two-dimensional (2D) IBA₂FAPb₂I₇ (IBA=iso-butylammonium overlayer, formed via stepwise annealing. The α-FAPbI₃/IBA₂FAPb₂I₇ based perovskite solar cell (PSC) reached a high power conversion efficiency (PCE) of close to 23 %. In addition, it showed excellent operational stability, retaining around 85 % of its initial efficiency under severe combined heat and light stress, that is, simultaneous exposure with maximum power tracking to full simulated sunlight at 80 °C over 500 h.     

高效率钙钛矿型太阳能电池的化学稳定性及其研究进展

近几年来, 钙钛矿太阳能电池器件光电转换效率的最高纪录不断被刷新, 但是关于钙钛矿太阳能电池稳定性的研究报道比较缺乏. 钙钛矿太阳能电池稳定性问题已经成为制约钙钛矿太阳能电池继续发展的瓶颈. 简要讨论了水氧气氛、温度变化、湿法制备、紫外光照等不同敏感环境条件下钙钛矿太阳能电池的化学稳定性问题, 进而对一定环境条件下钙钛矿太阳能电池的化学稳定性及其调控的研究现状进行了综述, 旨在更好地理解钙钛矿太阳能电池稳定性的基础理论问题, 为实现钙钛矿太阳能电池稳定性的调控提供基本依据.