| 1. |
- Agostini, Marco, 1987, et al.
(författare)
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Designing a Safe Electrolyte Enabling Long‐Life Li/S Batteries
- 2019
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 12:18, s. 4176-4184
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Tidskriftsartikel (refereegranskat)abstract
- Lithium–sulfur (Li/S) batteries suffer from “shuttle” reactions in which soluble polysulfide species continuously migrate to and from the Li metal anode. As a consequence, the loss of active material and reactions at the surface of Li limit the practical applications of Li/S batteries. LiNO3 has been proposed as an electrolyte additive to reduce the shuttle reactions by aiding the formation of a stable solid electrolyte interphase (SEI) at the Li metal, limiting polysulfide shuttling. However, LiNO3 is continuously consumed during cycling, especially at low current rates. Therefore, the Li/S battery cycle life is limited by the LiNO3 concentration in the electrolyte. In this work, an ionic liquid (IL) [N-methyl-(n-butyl)pyrrolidinium bis(trifluoromethylsulfonyl)imide] was used as an additive to enable longer cycle life of Li/S batteries. By tuning the IL concentration, an enhanced stability of the SEI and lower flammability of the solutions were demonstrated, that is, higher safety of the battery. The Li/S cell built with a high sulfur mass loading (4 mg cm−2) and containing the IL-based electrolyte demonstrated a stable capacity of 600 mAh g−1 for more than double the number of cycles of a cell containing LiNO3 additive.
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| 2. |
- Jeschke, Steffen, 1986, et al.
(författare)
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Catching TFSI: A Computational–Experimental Approach to β-Cyclodextrin-Based Host–Guest Systems as electrolytes for Li-Ion Batteries
- 2018
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 11:12, s. 1942-1949
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Tidskriftsartikel (refereegranskat)abstract
- Cyclodextrins (CDs) are pyranoside-based macromolecules with a hydrophobic cavity to encapsulate small molecules. They are used as molecular vehicles, for instance in pharmaceutical drug delivery or as solubility enhancer of monomers for their polymerization in aqueous solution. In this context, it was discovered about 10 years ago that the bis(trifluoromethylsulonyl)imide (TFSI) anion forms host–guest complexes with βCD in aqueous media. This sparked interest in using the TFSI anion in lithium-based battery electrolytes open for its encapsulation by βCD as an attractive approach to increase the contribution of the cation to the total ion conductivity. By using semi-empirical quantum mechanical (SQM) methods and the conductor-like screening model for a real solvent (COSMO-RS), a randomly methylated βCD (RMβCD) is here identified as a suitable host for TFSI when using organic solvents often used in battery technology. By combining molecular dynamics (MD) simulations with different NMR and FTIR experiments, the formation of the corresponding RMβCD–TFSI complex was investigated. Finally, the effects of the addition RMβCD to a set of electrolytes on the ion conductivity are measured and explained using three distinct scenarios.
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| 3. |
- Pereira de Carvalho, Rodrigo, et al.
(författare)
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Exploring Metastable Phases During Lithiation of Organic Battery Electrode Materials
- 2022
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Ingår i: ChemSusChem. - : John Wiley & Sons. - 1864-5631 .- 1864-564X. ; :2
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Tidskriftsartikel (refereegranskat)abstract
- In this work, the Li-ion insertion mechanism in organic electrode materials is investigated through the lens of atomic-scale models based on first-principles theory. Starting with a structural analysis, the interplay of density functional theory with evolutionary and potential-mapping algorithms is used to resolve the crystal structure of the different (de)lithiated phases. These methods elucidate different lithiation reaction pathways and help to explore the formation of metastable phases and predict one- or multi-electron reactions, which are still poorly understood for organic intercalation electrodes. The cathode material dilithium 2,5-oxyterephthalate (operating at 2.6 V vs. Li/Li+) is investigated in depth as a case study, owing to its rich redox chemistry. When compared with recent experimental results, it is demonstrated that metastable phases with peculiar ring-ring molecular interactions are more likely to be controlling the redox reactions thermodynamics and consequently the battery voltage.
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| 4. |
- Galkin, Maxim V., et al.
(författare)
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Hydrogen-free catalytic fractionation of woody biomass
- 2016
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 9:23, s. 3280-3287
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Tidskriftsartikel (refereegranskat)abstract
- The pulping industry could become a biorefinery if the lignin and hemicellulose components of the lignocellulose are valorized. Conversion of lignin into well-defined aromatic chemicals is still a major challenge. Lignin depolymerization reactions often occur in parallel with irreversible condensation reactions of the formed fragments. Here, we describe a strategy that markedly suppresses the undesired condensation pathways and allows to selectively transform lignin into a few aromatic compounds. Notably, applying this strategy to woody biomass at organosolv pulping conditions, the hemicellulose, cellulose, and lignin were separated and in parallel the lignin was transformed into aromatic monomers. In addition, we were able to utilize a part of the lignocellulose as an internal source of hydrogen for the reductive lignin transformations. We hope that the presented methodology will inspire researchers in the field of lignin valorization as well as pulp producers to develop more efficient biomass fractionation processes in the future.
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| 5. |
- Messinger, Johannes
(författare)
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Catalysts for solar water splitting
- 2009
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Ingår i: ChemSusChem. - Weinheim : Wiley-VCH Verlagsgesellschaft. - 1864-5631 .- 1864-564X. ; 2:1, s. 47-48
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Tidskriftsartikel (refereegranskat)abstract
- Making H2 while the sun shines: Recently, an inorganic catalyst based on Co2+ and phosphate ions was developed that operates in neutral water under ambient conditions to produce O2 from H2O at low overpotentials. Coupling the setup to a counter electrode at which H2 formation takes place as well as to a solar cell could lead to solar water splitting into H2 and O2.
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| 6. |
- Wu, Hua, et al.
(författare)
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Mixed-Halide Double Perovskite Cs2AgBiX6 (X=Br, I) with Tunable Optical Properties via Anion Exchange
- 2021
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 14:20, s. 4507-4515
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Tidskriftsartikel (refereegranskat)abstract
- Lead-free double perovskites, A2M+M′3+X6, are considered as promising alternatives to lead-halide perovskites, in optoelectronics applications. Although iodide (I) and bromide (Br) mixing is a versatile tool for bandgap tuning in lead perovskites, similar mixed I/Br double perovskite films have not been reported in double perovskites, which may be due to the large activation energy for ion migration. In this work, mixed Br/I double perovskites were realized utilizing an anion exchange method starting from Cs2AgBiBr6 solid thin-films with large grain-size. The optical and structural properties were studied experimentally and theoretically. Importantly, the halide exchange mechanism was investigated. Hydroiodic acid was the key factor to facilitate the halide exchange reaction, through a dissolution–recrystallization process. In addition, the common organic iodide salts could successfully perform halide-exchange while retaining high mixed-halide phase stability and strong light absorption capability.
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| 7. |
- Baggi, Nicolò, et al.
(författare)
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Flow-Integrated Preparation of Norbornadiene Precursors for Solar Thermal Energy Storage
- 2024
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Ingår i: ChemSusChem. - 1864-5631 .- 1864-564X. ; 17:2
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Tidskriftsartikel (refereegranskat)abstract
- Molecular solar thermal (MOST) energy storage systems are getting increased attention related to renewable energy storage applications. Particularly, 2,3-difunctionalized norbornadiene-quadricyclane (NBD-QC) switches bearing a nitrile (CN) group as one of the two substituents are investigated as promising MOST candidates thanks to their high energy storage densities and their red-shifted absorbance. Moreover, such NBD systems can be prepared in large quantities (a requirement for MOST-device applications) in flow through Diels-Alder reaction between cyclopentadiene and appropriately functionalized propynenitriles. However, these acetylene precursors are traditionally prepared in batch from their corresponding acetophenones using reactive chemicals potentially leading to health and physical hazards, especially when working on a several-grams scale. Here, we develop a multistep flow-chemistry route to enhance the production of these crucial precursors. Furthermore, we assess the atom economy (AE) and the E-factor showing improved green metrics compared to classical batch methods. Our results pave the way for a complete flow synthesis of NBDs with a positive impact on green chemistry aspects.
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| 8. |
- Haridas, Anupriya K., et al.
(författare)
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An Electrospun Core–Shell Nanofiber Web as a High-Performance Cathode for Iron Disulfide-Based Rechargeable Lithium Batteries
- 2018
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 11:20, s. 3625-3630
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Tidskriftsartikel (refereegranskat)abstract
- FeS2/C core–shell nanofiber webs were synthesized for the first time by a unique synthesis strategy that couples electrospinning and carbon coating of the nanofibers with sucrose. The design of the one-dimensional core–shell morphology was found to be greatly beneficial for accommodating the volume changes encountered during cycling, to induce shorter lithium ion diffusion pathways in the electrode, and to prevent sulfur dissolution during cycling. A high discharge capacity of 545 mAh g−1 was retained after 500 cycles at 1 C, exhibiting excellent stable cycling performance with 98.8 % capacity retention at the last cycle. High specific capacities of 854 mAh g−1, 518 mAh g−1, and 208 mAh g−1 were obtained at 0.1 C, 1 C, and 10 C rates, respectively, demonstrating the exceptional rate capability of this nanofiber web cathode.
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| 9. |
- Kwong, Wai Ling, et al.
(författare)
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Cationic Vacancy Defects in Iron Phosphide : A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting
- 2017
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Ingår i: ChemSusChem. - : Wiley-Blackwell. - 1864-5631 .- 1864-564X. ; 10:22, s. 4544-4551
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Tidskriftsartikel (refereegranskat)abstract
- Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an approach to modulate the electronic structure of iron phosphide (FeP). The Fe vacancies were produced by chemical leaching of Mg that was introduced into FeP as "sacrificial dopant". The obtained Fe-vacancy-rich FeP nanoparticulate films, which were deposited on Ti foil, show excellent HER activity compared to pristine FeP and Mg-doped FeP, achieving a current density of 10 mAcm(-2) at overpotentials of 108 mV in 1 m KOH and 65 mV in 0.5 m H2SO4, with a near-100% Faradaic efficiency. Our theoretical and experimental analyses reveal that the improved HER activity originates from the presence of Fe vacancies, which lead to a synergistic modulation of the structural and electronic properties that result in a near-optimal hydrogen adsorption free energy and enhanced proton trapping. The success in catalytic improvement through the introduction of cationic vacancy defects has not only demonstrated the potential of Fe-vacancy-rich FeP as highly efficient, earth abundant HER catalyst, but also opens up an exciting pathway for activating other promising catalysts for electrochemical water splitting.
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| 10. |
- Stottmeister, Daniel, et al.
(författare)
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Unraveling Propylene Oxide Formation in Alkali Metal Batteries
- 2024
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Ingår i: ChemSusChem. - 1864-5631 .- 1864-564X. ; 17:3
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Tidskriftsartikel (refereegranskat)abstract
- The increasing need for electrochemical energy storage drives the development of post-lithium battery systems. Among the most promising new battery types are sodium-based battery systems. However, like its lithium predecessor, sodium batteries suffer from various issues like parasitic side reactions, which lead to a loss of active sodium inventory, thus reducing the capacity over time. Some problems in sodium batteries arise from an unstable solid electrolyte interphase (SEI) reducing its protective power e. g., due to increased solubility of SEI components in sodium battery systems. While it is known that the electrolyte affects the SEI structure, the exact formation mechanism of the SEI is not yet fully understood. In this study, we follow the initial SEI formation on a piece of sodium metal submerged in propylene carbonate with and without the electrolyte salt sodium perchlorate. We combine X-ray photoelectron spectroscopy, gas chromatography, and density functional theory to unravel the sudden emergence of propylene oxide after adding sodium perchlorate to the electrolyte solvent. We identify the formation of a sodium chloride layer as a crucial step in forming propylene oxide by enabling precursors formed from propylene carbonate on the sodium metal surface to undergo a ring-closing reaction. Based on our combined theoretical and experimental approach, we identify changes in the electrolyte decomposition process, propose a reaction mechanism to form propylene oxide and discuss alternatives based on known synthesis routes.
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