Moritz C. Schmidt, Agustin O. Alvarez, Jeroen J. de Boer, Larissa J.M. van de Ven, Bruno Ehrler
{"title":"Consistent Interpretation of Time- and Frequency-Domain Traces of Ion Migration in Perovskite Semiconductors","authors":"Moritz C. Schmidt, Agustin O. Alvarez, Jeroen J. de Boer, Larissa J.M. van de Ven, Bruno Ehrler","doi":"10.1021/acsenergylett.4c02446","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02446","url":null,"abstract":"The migration of mobile ions through the metal halide perovskite layer is still one of the main reasons for the poor stability of perovskite solar cells, LEDs, and photodetectors. To characterize mobile ions in the perovskite layer, time- and frequency-based electrical measurements are promising techniques. However, the presence of transport layers complicates their interpretation, limiting the information about mobile ions that can be extracted, and it is not clear how different features in frequency- and time-domain measurements relate to mobile ions. Here, we characterize a transport-layer-free device with capacitance frequency, capacitance transient, and current transient measurements in the dark, under illumination, and at different temperatures. We extract characteristic ionic signatures from the measurements, which we reproduce with drift-diffusion simulations for each technique. This allows us to explain the origins of the different ionic signatures, advancing our understanding of how electronic characterization techniques can be used to study the properties of mobile ions.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kevin J. Prince, Nicholas P. Irvin, Mirzo Mirzokarimov, Bryan A. Rosales, David T. Moore, Harvey L. Guthrey, Axel F. Palmstrom, Colin A. Wolden, Lance M. Wheeler
{"title":"Holistic Thermo-Optical Design of Laminate Layers for Halide Perovskite Photovoltaic Windows","authors":"Kevin J. Prince, Nicholas P. Irvin, Mirzo Mirzokarimov, Bryan A. Rosales, David T. Moore, Harvey L. Guthrey, Axel F. Palmstrom, Colin A. Wolden, Lance M. Wheeler","doi":"10.1021/acsenergylett.4c02017","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02017","url":null,"abstract":"Though power conversion is an important metric for photovoltaic windows, it must be balanced with visible transmittance, aesthetics (color and haze), and thermal performance. Optical properties are often reported, but thermal performance is typically neglected entirely in photovoltaic window design. Here, we introduce the strategy of using laminate layers to improve the thermo-optical performance of perovskite-based photovoltaic insulating glass units. We design the laminates and insulating glass units by coupling a transfer matrix method optical model to a 1D heat transfer model. We validate our models with experimental fabrication of one-dimensional photonic crystal layers that are deposited on glass and laminated to the perovskite photovoltaic device. The holistic designs neutralize the inherent transmissive red color, and the “red low-e” design dramatically reduce emissivity of the glass surface to significantly improve thermal insulation and boost the photocurrent of the device.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Local Performance Analysis of Perovskite Solar Cells: Implications and Perspectives","authors":"Zexin Yu, Chunlei Zhang, Bo Li, Xin Wu, Xintong Li, Danpeng Gao, Zonglong Zhu","doi":"10.1021/acsenergylett.4c01379","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01379","url":null,"abstract":"Perovskite solar cells (PSCs) have emerged as a leading photovoltaic technology due to their high efficiency and cost-effectiveness, yet long-term stability and consistent performance remain challenges. This perspective discusses how local structural properties, such as grain boundaries and intragrain defects, and optoelectronic properties, including charge transfer and recombination processes, affect PSC performance, emphasizing the role of advanced imaging and mapping techniques in characterizing these properties. Additionally, the perspective extends to the stability of perovskite materials and devices, exploring how imaging and mapping techniques reveal degradation caused by environmental factors such as humidity, temperature, light, and electrical bias. Furthermore, this perspective also discusses the limitations of these local performance analyses, such as characterization scope, resolution, and sensitivity issues, as well as challenges in quantitative analysis. Understanding these constraints is essential for refining local performance analysis methods and advancing perovskite solar cell technology toward more reliable and efficient photovoltaic devices.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dasol Jin, Mihail R. Krumov, Ruth M. Mandel, Phillip J. Milner, Héctor D. Abruña
{"title":"Prussian Blue Analogue Framework Hosts for Li–S Batteries","authors":"Dasol Jin, Mihail R. Krumov, Ruth M. Mandel, Phillip J. Milner, Héctor D. Abruña","doi":"10.1021/acsenergylett.4c02857","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02857","url":null,"abstract":"Lithium–sulfur (Li–S) batteries hold promise for next-generation energy storage due to their high theoretical energy density (∼2600 Wh kg<sup>–1</sup>). However, practical use is hindered by capacity loss from the polysulfide shuttle effect and poor energy efficiency due to slow kinetics. To overcome these challenges, we developed a novel sulfur host material featuring highly porous concave nanocubes derived from a Prussian blue analogue. By controlling the annealing conditions, we achieved a high surface area (up to 248 m<sup>2</sup> g<sup>–1</sup>), which enhances polysulfide adsorption, thereby reducing sulfur dissolution and minimizing the loss of cathode capacity during cycling. <i>Operando</i> Raman spectroscopy revealed that this material also provides a synergistic catalytic effect, lowering polarization/overpotentials within Li–S cells. The optimized material enables an extended battery life with high sulfur loading, a low E/S ratio, and excellent capacity retention over long-term cycles, demonstrating its potential to improve Li–S battery performance.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Exciton Dipole Orientation and Dynamic Reactivity Synergistically Enable Overall Water Splitting in Covalent Organic Frameworks","authors":"Qing Niu, Wenfeng Deng, Yanlei Chen, Qingqing Lin, Liuyi Li, Zheyuan Liu, Jinhong Bi, Yan Yu","doi":"10.1021/acsenergylett.4c02847","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02847","url":null,"abstract":"Covalent organic frameworks (COFs) are promising semiconductor photocatalysts but are still limited in overall water splitting mainly owing to a lack of clear design approaches with which to ameliorate catalytic activities. Here, we demonstrate a synergy of exciton dipole orientation and dynamic reactivity of COFs that enables water splitting for stoichiometric evolution of H<sub>2</sub> and O<sub>2</sub>. The exciton dipole orientation is responsible for driving the spatial separation of photoinduced charges, while the dynamic reactivity of imine bonds of COFs with water and holes is proven for initiating water oxidation. Accordingly, a rationally designed BtS-COF with benzotrithiophene and sulfone units exhibits a much-improved performance in H<sub>2</sub> and O<sub>2</sub> evolution in neutral water under visible light. Its catalytic efficiency is even superior to some photocatalysts with metal-based water oxidation cocatalyst.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Unraveling the Charge Storage Mechanism of β-MnO2 in Aqueous Zinc Electrolytes","authors":"LangYuan Wu, ZhiWei Li, YuXuan Xiang, WenDi Dong, HaiYang Wu, YingHong Xu, ZhenXiao Ling, Munseok S. Chae, Daniel Sharon, Netanel Shpigel, XiaoGang Zhang","doi":"10.1021/acsenergylett.4c02559","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02559","url":null,"abstract":"MnO<sub>2</sub>-based zinc-ion batteries have emerged as a promising candidate for next-generation energy storage systems. Despite extensive research on MnO<sub>2</sub> electrodes, the charging mechanism in mildly acidic electrolytes remains debated. Most studies have focused on α-MnO<sub>2</sub>, and this study aims to shed light on the identity of the charge carrier in β-MnO<sub>2</sub> and the role of the Mn<sup>2+</sup> cations. By employing in situ EQCM-D measurements, along with ssNMR, XRD, TEM, and in situ pH monitoring, we demonstrated that the charging mechanism is primarily governed by proton de/intercalation. Compared to α-MnO<sub>2</sub>, with its larger 2 × 2 tunnels that accommodate hydronium ions, the β-phase has smaller 1 × 1 tunnels, permitting only the insertion of bare protons. During cycling, we observed the formation of new phases on β-MnO<sub>2</sub> originating from the repetitive electrodeposition/dissolution of Mn<sup>2+</sup>. In addition, these phases can reversibly host hydronium ions, resulting in a mixed charging mechanism that involves the insertion of both H<sub>3</sub>O<sup>+</sup> and H<sup>+</sup>.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Logan M. Wilder, Kabirat Balogun, W. Ellis Klein, Prithviraj Chumble, James L. Young
{"title":"Nitrogen Reduction Testing with Real-Time 15NH3 Yield Quantification Using Orbital Multiturn Time-of-Flight Mass Spectrometry","authors":"Logan M. Wilder, Kabirat Balogun, W. Ellis Klein, Prithviraj Chumble, James L. Young","doi":"10.1021/acsenergylett.4c02961","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02961","url":null,"abstract":"Yield validation of dinitrogen reduction reaction (N<sub>2</sub>RR) catalysts with <sup>15</sup>N isotope labeling experiments is frustrated by the high cost of <sup>15</sup>N<sub>2</sub> and the frequent occurrence of <sup>15</sup>NH<sub>3</sub> and <sup>15</sup>NO<sub><i>x</i></sub> impurities in commercial <sup>15</sup>N<sub>2</sub> sources. Also, gas diffusion electrode (GDE) cell architectures are relevant to scaling N<sub>2</sub>RR but underexplored and limited by ex situ product analysis methods. To overcome these obstacles, we develop and demonstrate a protocol for N<sub>2</sub>RR catalyst testing using a scalable GDE cell architecture and specialized test station that facilitates in-line product analysis with multiturn time-of-flight mass spectrometry. This approach provides robust yield measurements through real-time monitoring of <sup>15</sup>NH<sub>3</sub> with ultrahigh mass resolution. The <sup>15</sup>N-containing impurities are also monitored, allowing their influence to be mitigated. A minimum detectable yield of 6 pmol·cm<sup>–2</sup>·s<sup>–1</sup> (at 2.00 sccm and utilizing a 5 cm<sup>2</sup> electrode) for real-time <sup>15</sup>NH<sub>3</sub> yield rate measurements is achieved while using a cost-effective amount of <sup>15</sup>N<sub>2</sub> (<100 mL).","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598001","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Choosing Impactful Perspectives for Energy Research: A Case Study of CO2 Electroreduction","authors":"Phillip Christopher","doi":"10.1021/acsenergylett.4c02907","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02907","url":null,"abstract":"As an editor of a journal that publishes in the area of energy research, I get to see transitions in topical interests of the field. These transitions can be technologically significant. For example, the classes of materials used in photovoltaics, or the use of fuel cells versus batteries in vehicle electrification. These transitions can also be more subtle and highlight shifts in perspectives the field is bringing toward research problems. I joined <i>ACS Energy Letters</i> as an editor in 2018, and in the past few years I started to notice a change in the focus of papers submitted to and published by the journal in the area of CO<sub>2</sub> electroreduction. While there is not agreement on whether CO<sub>2</sub> electroreduction will be broadly deployed, there has been consistent interest from the field of energy researchers. The shift I noticed is not from one chemistry to another (although the specific products of interest have evolved) but a switch in the perspective of researchers. To look into this shift in perspective, I searched all papers published by <i>ACS Energy Letters</i> since 2018 with the keyword “CO<sub>2</sub> reduction” and focused on papers examining electrochemical reactions, processes, and systems. I categorized the papers as focusing on one of the following aspects of CO<sub>2</sub> electroreduction technology: Catalyst: At the active site, often presenting new catalyst materials, new synthetic methods for catalysts, characterization of the active site, surface reaction mechanisms, etc. Environment: The environment where the chemistry occurs, discussing the role of pH, electrolyte, additive layers, flow rates, temperatures, chemical potentials, etc. Process: A process systems perspective focusing on how to assemble electrochemical reactors, flow patterns, bulk resistance losses, scale up viability, overall performance, etc. These classifications fall in the areas of catalyst, reaction, and process or systems science and engineering that are common to the scale up of chemical conversion processes. The compiled group of 167 papers results from the publication of ∼20–30 papers per year in <i>ACS Energy Letters</i> over 7 years, demonstrating consistent interest in the field (see Supporting Information). After categorizing the papers, the shift in perspective I sensed became clear, as seen in Figure 1. From 2018 to 2024, the number of papers focused on studies of the catalyst in CO<sub>2</sub> electroreduction decreased from 18 to 4, or from 75% to 18% of the total papers published on the topic. Alternatively, the number of papers focused on the environment where the chemistry occurs increased from 2 to 9, or from 8 to 40% of the papers. The data in Figure 1 suggests that this change in topical focus occurred steadily over the past 6 years. Papers focused on the CO<sub>2</sub> electroreduction process have remain consistent. Figure 1. % of published papers on CO<sub>2</sub> electroreduction published in <i>ACS Energy Letters","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Scalable Microscale Artificial Synapses of Lead Halide Perovskite with Femtojoule Energy Consumption","authors":"Jeroen J. de Boer, Bruno Ehrler","doi":"10.1021/acsenergylett.4c02360","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02360","url":null,"abstract":"The efficient conduction of mobile ions in halide perovskites is highly promising for artificial synapses (or memristive devices), devices with a conductivity that can be varied by applying a bias voltage. Here we address the challenge of downscaling halide perovskite-based artificial synapses to achieve low energy consumption and allow high-density integration. We fabricate halide perovskite artificial synapses in a back-contacted architecture to achieve microscale devices despite the high solubility of halide perovskites in polar solvents that are commonly used in lithography. The energy consumption of a conductance change of the device is as low as 640 fJ, among the lowest reported for two-terminal halide perovskite artificial synapses so far. Moreover, the high resistance of the device up to hundreds of megaohms, low operating voltage of 100 mV and simple two-terminal architecture enable implementation in highly dense crossbar arrays. These arrays could potentially show orders of magnitude lower energy consumption for computation compared to conventional digital computers.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wenda Wu, Michelle Lehmann, Yuanshun Li, Lei Cheng, Guang Yang
{"title":"Optimizing Nonaqueous Sodium–Polysulfide Redox-Flow Batteries: The Role of Solvation Effects with Glyme Solvents","authors":"Wenda Wu, Michelle Lehmann, Yuanshun Li, Lei Cheng, Guang Yang","doi":"10.1021/acsenergylett.4c02113","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02113","url":null,"abstract":"Nonaqueous redox-flow batteries (NARFBs) that use economical alkali metals and the corresponding metal polysulfides are highly attractive for grid-scale energy storage. Although sodium–sulfur systems have been recognized as promising candidates and have been the focus of many studies due to their high earth abundance and energy density, an understanding of the role of the solvation chemistry of commonly used glyme solvents is missing. Herein, we report a systematic investigation into the solvation effects of glyme-based Na-S electrolytes through comprehensive physiochemical experiments and Density Functional Theory (DFT) simulations. Our findings revealed, on one hand, that an optimal coordination strength between glymes and Na<sup>+</sup> could maintain a relatively smooth Na<sup>+</sup> diffusion. On the other hand, glyme solvents with extended chain lengths shift the reduction potential of S<sub>8</sub><sup>2–</sup> negatively to elevate the formation barrier of undesirable short-chain polysulfides (S<sub><i>n</i></sub><sup>2–</sup>, <i>n</i> ≤ 4) that have high membrane permeability. This solvation phenomenon not only mitigates capacity fading but also extends the operational longevity of the Na-S NARFBs. The results underscore the critical roles of balanced solvent–cation interactions and controlled redox potentials in improving the stability and efficiency of Na-S NARFB systems, marking a significant advancement in the development of sustainable energy storage solutions.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}