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Toney, Michael

Publications and source records attributed to Toney, Michael.

7 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Understanding the Surprising Ionic Conductivity Maximum in Zn(TFSI) 2 Water/Acetonitrile Mixture Electrolytes

Aqueous electrolytes composed of 0.1 M zinc bis-(trifluoromethyl-sulfonyl)-imide (Zn-(TFSI) 2 ) and acetonitrile (ACN) were studied using combined experimental and simulation techniques. The electrolyte was found to be electrochemically stable when the ACN V% is higher than 74.4. In addition, it was found that the ionic conductivity of the mixed solvent electrolytes changes as a function of ACN composition, and a maximum was observed at 91.7 V% of ACN although the salt concentration is the same. This behavior was qualitatively reproduced by molecular dynamics (MD) simulations. Detailed analyses based on experiments and MD simulations show that at high ACN composition the water network existing in the high water composition solutions breaks. As a result, the screening effect of the solvent weakens and the correlation among ions increases, which causes a decrease in ionic conductivity at high ACN V%. Furthermore, this study provides a fundamental understanding of this complex mixed solvent electrolyte system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Sulfur-Donor Additives Preferentially Coordinate Pb 2+ in Perovskite Precursor Solutions

Lewis base solvents, such as dimethylsulfoxide (DMSO), that strongly coordinate with Pb 2+ are commonly added to hybrid organic-inorganic perovskite (HOIP) precursor solutions to improve thin-film morphology and subsequent photovoltaic (PV) performance. Although nearly all previous studies of precursor solution chemistry have focused on oxygen-donor solvents as Lewis base additives, we expect “softer,” sulfur-donor solvents to coordinate more strongly with Pb 2+ , a borderline-soft Lewis acid. To confirm this hypothesis, we performed extended X-ray absorption fine structure (EXAFS) spectroscopy at the Pb LIII absorption edge to probe the coordination environment of Pb 2+ in solutions comprising mixtures of S- and O-donor solvents. Of the S- and O-donor solvent pairs examined, the S-donor solvent consistently outcompetes its O-donor structural analog for coordination sites around Pb 2+ . In the specific comparison between N-methyl-2-pyrrolidone thione (NMPT) and N-methylpyrrolidone (NMP), density-functional theory calculations indicate that NMPT coordination with Pb 2+ is favored by 10 kcal/mol relative to NMP coordination with Pb 2+ . Similar to the addition of DMSO to precursor solutions, the incorporation of NMPT in fractional quantities provides morphological control of the perovskite film. Unlike DMSO, however, we found NMPT to be stable against undesired transmethylation or disproportionation reactions with methylammonium [1]. Consequentially, films processed with NMPT exhibit no sub-gap electronic states near the valence band edge, in contrast with films prepared using DMSO. We thus believe NMPT merits serious consideration as a solution additive for producing stable HOIP precursor solutions and high-quality HOIP thin films. [1] Hamill, J. C.; Sorli, J. C.; Pelczer, I.; Schwartz, J. and Loo, Y. -L. Acid-catalyzed reactions activate DMSO as a reagent in perovskite precursor inks. Chemistry of Materials 2019, 31, 2114-2120.

Hamill, Joseph↗
DOE OSTI2016

In-situ Roll-to-Roll Printing of Highly Efficient Organic Solar Cells

This project focuses on developing a roll-to-roll printing setup for organic solar cells with the capability to follow the film formation in situ with small and wide angle X-ray scattering, and to improve the performance of printed organic solar cells. We demonstrated the use of the printing setup to capture important aspects of existing industrial printing methods, which ensures that the solar cell performance achieved in our printing experiments would be largely retained in an industrial fabrication process. We employed both known and newly synthesized polymers as the donor and acceptor materials, and we studied the morphological changes in real time during the printing process by X-ray scattering. Our experimental efforts are also accompanied by theoretical modeling of both the fluid dynamic aspects of the printing process and the nucleation and crystallization kinetics during the film formation. The combined insight into the printing process gained from the research provides a detailed understanding of the factors governing the printed solar cell’s performance. Finally using the knowledge we gained, we demonstrated large area ( > 10 cm2) printed organic solar cells with more than 5 percent power conversion efficiency, which is best achieved performance for roll-to-roll printed organic solar cells.

14 SOLAR ENERGY↗
DOE OSTI2014

Develop and Test TXM Battery Cells

Summary of the specific research and project accomplishments: The team combined their knowledge and expertise in x-ray science and electrochemistry to quantify lithium concentration gradients for commercially relevant metal oxide cathodes at rates up to 6C. Completion of the project required several significant technical developments including new x-ray experimental methodologies, high-speed and high-accuracy sample multiplexers and a new class of x-ray compatible cells. The results from thin and thick electrodes demonstrated that both spatial heterogeneity and concentration gradients through the thickness of the cathode may be present. The relevance of either phenomena appears to be correlated to aspects of the electrode such as calendaring in addition to the configuration of the experiment (e.g. force between the anode and cathode).

25 ENERGY STORAGE↗