Bulk and surface engineering to improve performance and stability of perovskite solar cells

Human society is craving new and renewable energy sources. Indeed, the need for novel sources is an obligation in order to cope with the exponentially increasing global energy demand. Also, environmentally friendly alternatives to fossil fuels are more crucial than ever in order to limit the effects of global warming. Finally, the current gas and oil crisis underlies the importance for each state to have some alternatives in case of shortage, i.e. to gain some energetic independence. In that regard, solar energy represents the best candidate, given its huge potential and its universal character. In particular, perovskite solar cells (PSCs) show the highest promise amongst emerging technologies. From their first report in 2009, the power conversion efficiency rocketed, to cross 25 % recently. Unfortunately, several important issues remain.Chapter 2. Its lower bandgap makes formamidinium lead iodide (FAPbI3) a more suitable candidate for single-junction solar cells than pure methylammonium lead iodide (MAPbI3). However, its structural and thermodynamic stability is improved by introducing a significant amount of MA and bromide, both of which increase the bandgap and amplify trade-off between the photocurrent and photovoltage. Here, we simultaneously stabilized FAPbI3 into a cubic lattice and minimized the formation of photoinactive phases, such as hexagonal FAPbI3 and PbI2, by introducing 5% MAPbBr3, as revealed by synchrotron X-ray scattering. We were able to stabilize the composition (FA0.95MA0.05Cs0.05)Pb(I0.95Br0.05)3, which exhibits a minimal trade-off between the photocurrent and photovoltage. This material shows low energetic disorder and improved charge-carrier dynamics as revealed by photothermal deflection spectroscopy (PDS) and transient absorption spectroscopy (TAS), respectively. This allowed the fabrication of operationally stable perovskite solar cells yielding reproducible efficiencies approaching 22%.Chapter 3. Herein, we successfully engineered a multi-cation halide composition of perovskite solar cells via the two-step sequential deposition method. Strikingly we find that adding mixtures of 1D polymorphs of orthorhombic d-RbPbI3 and d-CsPbI3 to the PbI2 precursor solution induces the formation of porous mesostructured hexagonal films. This porosity greatly facilitates the heterogeneous nucleation and the penetration of FA/MA cations within the PbI2 film. Thus, the subsequent conversion of PbI2 into the desired multication cubic a-structure by exposing it to a solution of formamidinium methylammonium halides is greatly enhanced. During the conversion step, the d-CsPbI3 also is fully integrated into the 3-D mixed cation perovskite lattice, which exhibits high crystallinity and superior optoelectronic properties. The champion device shows a power conversion efficiency (PCE) over 22%, with an open-circuit voltage of 1.15V, a short-circuit photocurrent of 24.82 mA·cm-2, and a fill factor of 78% at a bandgap of 1.55 eV. Furthermore, these devices exhibit enhanced operational stability, with the best device retaining more than 90% of its initial value of PCE under 1-Sun illumination with maximum power point tracking for 400 h.Chapter 4. A promising approach for the production of highly efficient and stable hybrid perovskite solar cells is employing mixed ion materials. Remarkable performances have been reached by materials comprising a stabilized mixture of methylammonium (MA+) and formamidinium (FA+) as the monovalent cat

Compositional and interfacial optimization for enhancement of perovskite solar cells performance

Essa Awadh R Alharbi

Non-renewable sources are responsible for most of the overall greenhouse gas emissions, the development of sustainable energy sources is of prime importance to mitigate the negative effects of climate change. Among renewable sources, solar energy is one of the most abundant forms of energy available. Perovskite photovoltaics has emerged as one of the promising candidates for harvesting solar energy. However, these perovskite solar cells suffer from instability which is primarily due to the bulk and interface defects. In this thesis, we focus on the passivation of the bulk and interface defects to enable high-performance and stable devices. At the beginning of the thesis, we engineered the composition of mixed-cation and mixed-halide perovskite films by judicious incorporation of guanidinium iodide to suppress the parasitic charge carrier recombination, which enabled the fabrication of >20% efficient and operationally stable PSCs yielding reproducible photovoltage as high as 1.20 V. Thereafter, in our next project, we develop a facile strategy to reduce the level of electronic defects present at the interface between the perovskite film and the hole transport layer by treating the perovskite surface with different types of ammonium salts, namely ethylammonium, imidazolium, and guanidinium iodide. We find that this treatment boosts the power conversion efficiency from 20.5% for the control to 22.3%, 22.1%, and 21.0% for the devices treated with ethylammonium, imidazolium, and guanidinium iodide, respectively. Best performing devices showed a loss in efficiency of only 5% under full sunlight intensity with maximum power tracking for 550 h. We employed 2D-solid-state NMR (1H-1H correlation) spectroscopy to unravel the atomic-level mechanism of this passivation effect. Following that, we applied a facile and very effective method that employs methylammonium triiodide (MAI3) for bulk passivation together with interface passivation developed in the second project for holistic defect mitigation in perovskite solar cells. As a result, the champion device shows a power conversion efficiency (PCE) of 23.46% with a high fill factor (FF) of over 80%. Furthermore, these devices exhibit enhanced operational stability, with the best device retaining ~ 90% of its initial PCE under 1 Sun illumination with maximum power point tracking for 350 h. Finally, in our last project, we reconfigured the design of the alkylammonium halide salts to create a holistic bulk and interface engineering. We show that dimethylammonium head along with octyl chain and iodide counter anion works best in the bulk whereas dimethylammonium head along with octyl chain and fluoride counter anion works best at the interface. With a synergistic combination of both bulk and surface passivation, we achieved a high PCE of 24.91% along with exceptional long-term operational stability. In summary, in this thesis we employed different strategies based on organic ammonium salts to engineer the bulk and interface of the PSCs. We did an in-depth investigation of the optoelectronic properties, local structure, and molecular interactions with a combination of characterization at different length and time scales. Our results show that it is imperative to passivate both bulk and interface defects for obtaining high efficiency and stable solar cells. From our work, one can take inspiration from the design and analysis of new materials for the passivation of the PSCs.

EPFL2022

Evaluation of a Combined Cycle Setup for Solar Tower Power Plants

James Spelling

As our awareness of the dangers of global climate change grows, the development of new renewable energy technologies is of primary importance in the effort to reduce emissions of carbon dioxide and other greenhouse gases. Rapid increases in the price of oil and worries about the stability and security of the extraction of fossil fuels have lead to renewed interest in the development of local energy sources, thereby reducing dependence on foreign sources. Amid the plethora of option available, one of the more promising solutions is the increased use of concentrating solar thermal power. Solar thermal power generation shows great potential for supplying the base electricity needs of numerous countries in the sun-belt regions, stretching from the tropics to the Mediterranean. This has lead to a recent renewal in the development of such systems, most notably with the construction of the PS10 and PS20 central receiver power plants in Spain. However, all currently existing solar thermal power plants have been based around the use of Rankine or steam turbine cycles, which are limited in the efficiencies they can achieve. In order to make better use of the Sun’s energy, higher efficiency cycles should be used. Recent developments in the field of high temperature solar receivers [13] have made it possible to imagine the use of solar thermal energy to drive gas turbine units, potentially allowing the use of combined cycle setups in solar thermal power plants. In order to evaluate the potential improvement in efficiency that can be achieved by using combined cycles in solar thermal power plants, a detailed simulation of such a setup will be performed. By taking into account the requirements of thermal energy storage and the design of the necessary heat exchangers, an objective evaluation of the performance of the combined cycle can be obtained. As a key element in the energy conversion process, particular attention will be given to the modelling and simulation of the high temperature receiver. Due to the highly variable nature of the solar flux, the performance of the receiver will be evaluated over a range of operating points. In order to obtain a detailed breakdown of the sources of losses and irreversibilities within the system, a complete exergy balance will be performed on the power plant. Combined with the standard energy balance, this analysis will allow identification of the key areas for improvement in the design of solar thermal power plants. Finally, in order to determine whether such a setup is economically viable, the construction, operation and maintenance costs will be evaluated in order to predict the levelised energy cost associated with electricity production in a combined cycle plant.

2008

Evaluation of a Combined Cycle Setup for Solar Tower Power Plants

James Spelling

2008

Compositional and interfacial optimization for enhancement of perovskite solar cells performance

Essa Awadh R Alharbi

EPFL2022