[{"tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"article_type":"original","publication_status":"published","quality_controlled":"1","citation":{"chicago":"Busato, Matteo, Mariarosaria Tuccillo, Arcangelo Celeste, Alessandro Tofoni, Laura Silvestri, Paola D’Angelo, Stefan Alexander Freunberger, and Sergio Brutti. “Structural Rearrangements of a Cobalt-Free Lithium-Rich Layered Oxide Cathode during Formation.” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2026. <a href=\"https://doi.org/10.1021/acsaem.5c03511\">https://doi.org/10.1021/acsaem.5c03511</a>.","ista":"Busato M, Tuccillo M, Celeste A, Tofoni A, Silvestri L, D’Angelo P, Freunberger SA, Brutti S. 2026. Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation. ACS Applied Energy Materials. 9(1), 686–697.","ieee":"M. Busato <i>et al.</i>, “Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation,” <i>ACS Applied Energy Materials</i>, vol. 9, no. 1. American Chemical Society, pp. 686–697, 2026.","mla":"Busato, Matteo, et al. “Structural Rearrangements of a Cobalt-Free Lithium-Rich Layered Oxide Cathode during Formation.” <i>ACS Applied Energy Materials</i>, vol. 9, no. 1, American Chemical Society, 2026, pp. 686–97, doi:<a href=\"https://doi.org/10.1021/acsaem.5c03511\">10.1021/acsaem.5c03511</a>.","apa":"Busato, M., Tuccillo, M., Celeste, A., Tofoni, A., Silvestri, L., D’Angelo, P., … Brutti, S. (2026). Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsaem.5c03511\">https://doi.org/10.1021/acsaem.5c03511</a>","short":"M. Busato, M. Tuccillo, A. Celeste, A. Tofoni, L. Silvestri, P. D’Angelo, S.A. Freunberger, S. Brutti, ACS Applied Energy Materials 9 (2026) 686–697.","ama":"Busato M, Tuccillo M, Celeste A, et al. Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation. <i>ACS Applied Energy Materials</i>. 2026;9(1):686-697. doi:<a href=\"https://doi.org/10.1021/acsaem.5c03511\">10.1021/acsaem.5c03511</a>"},"corr_author":"1","publication":"ACS Applied Energy Materials","issue":"1","date_created":"2026-01-25T23:01:40Z","scopus_import":"1","file":[{"checksum":"81272c19df41c696c1737168d3ea8c16","content_type":"application/pdf","file_size":5977526,"file_id":"21222","success":1,"creator":"dernst","relation":"main_file","date_updated":"2026-02-12T13:55:28Z","access_level":"open_access","date_created":"2026-02-12T13:55:28Z","file_name":"2026_AppliedEnergyMaterials_Busato.pdf"}],"ddc":["540"],"OA_place":"publisher","publication_identifier":{"eissn":["2574-0962"]},"oa_version":"Published Version","oa":1,"department":[{"_id":"StFr"}],"article_processing_charge":"Yes (via OA deal)","year":"2026","page":"686-697","doi":"10.1021/acsaem.5c03511","month":"01","PlanS_conform":"1","publisher":"American Chemical Society","title":"Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation","_id":"21040","acknowledged_ssus":[{"_id":"M-Shop"},{"_id":"LifeSc"}],"volume":9,"date_published":"2026-01-12T00:00:00Z","intvolume":"         9","acknowledgement":"Elettra-Sincrotrone Trieste S.C.p.A. and its staff are acknowledged for providing synchrotron radiation beamtime and laboratory facilities, in particular the MCX and XAFS beamlines, where the XRD and XAS experiments have been carried out, supported by the projects number: 20217082, 20205109, and 20195014. This study was carried out within the MOST─Sustainable Mobility Center and received funding from the European Union Next-Generation EU (PIANO NAZIONALE DI RIPRESA E RESILIENZA (PNRR)─MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.4─D.D. 1033 17/06/2022, CN00000023). Moreover, the contribution of S.B. and A.C. to this study was carried out within the NEST─Network for Energy Sustainable Transition and received funding from the European Union Next-Generation EU (PNRR─MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.3─D.D. 1561 11/10/2022, B53C22004070006). This manuscript reflects only the authors’ views and opinions, neither the European Union nor the European Commission can be considered responsible for them. Two of us, S.B. and S.A.F., would like to thank the Alistore ERI. L.S. received funds from the Ministry of Ecological Transition in the “Ricerca di Sistema Elettrico” framework. S.A.F. is indebted to ISTA for support. The Scientific Service Units of ISTA supported this research through resources provided by the Lab Support Facility and the Miba Machine Shop.","abstract":[{"text":"Formation during the first cycles of Li-rich layered oxide (LRLO) cathode materials consolidates the interphase and leads to structural changes that are decisive for long-term cyclability. However, the nature and effect of the changes are material-dependent and unknown for the important class of Co-free, Ni-poor LRLOs. Here, we analyze the processes during the tailored formation procedure of a typical class member, Li1.28Ni0.15Mn0.57O2, and demonstrate that it remarkably changes lattice composition and structure as a prerequisite for stable cycling. We combine electrochemistry, operando mass spectrometry, X-ray diffraction, and X-ray absorption spectroscopy with density functional theory simulations. Activation most prominently compresses the layer spacing along the c-axis and increases reversible structural breathing. The large capacity of ∼250 mAh g–1 originates from the Ni2+/Ni4+ and O2–/O– redox couples. Electron exchange during O-redox is smeared over the entire anionic sublattice rather than localized on specific oxygen atomic sites. This redox mechanism is reversible without detrimental oxygen evolution, avoiding continued degradation common in conventional LRLOs. Sequential Ni- and O-redox during activation irreversibly distorts the coordination of the redox-inactive Mn4+ centers. This structural evolution of the MnO6 octahedra appears to enable the superior electrochemical performance of this LRLO phase. These findings define an activation pathway for the important class of Co-free, Ni-poor LRLOs, offering potential guidance for the rational design of high-performance, more sustainable cathode materials.","lang":"eng"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","file_date_updated":"2026-02-12T13:55:28Z","day":"12","date_updated":"2026-02-12T14:04:04Z","type":"journal_article","license":"https://creativecommons.org/licenses/by/4.0/","status":"public","author":[{"last_name":"Busato","first_name":"Matteo","full_name":"Busato, Matteo"},{"full_name":"Tuccillo, Mariarosaria","first_name":"Mariarosaria","last_name":"Tuccillo"},{"last_name":"Celeste","first_name":"Arcangelo","full_name":"Celeste, Arcangelo"},{"last_name":"Tofoni","full_name":"Tofoni, Alessandro","first_name":"Alessandro"},{"full_name":"Silvestri, Laura","first_name":"Laura","last_name":"Silvestri"},{"last_name":"D’Angelo","full_name":"D’Angelo, Paola","first_name":"Paola"},{"first_name":"Stefan Alexander","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","orcid":"0000-0003-2902-5319","last_name":"Freunberger"},{"first_name":"Sergio","full_name":"Brutti, Sergio","last_name":"Brutti"}],"language":[{"iso":"eng"}],"has_accepted_license":"1","OA_type":"hybrid"},{"publisher":"Royal Society of Chemistry","month":"04","date_published":"2026-04-10T00:00:00Z","acknowledged_ssus":[{"_id":"LifeSc"}],"_id":"21730","title":"H2O2 responsive rhodamine-based probe for monitoring early-stage diabetes diagnosis","day":"10","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","abstract":[{"text":"Hydrogen peroxide (H2O2) is a crucial member of the reactive oxygen species (ROS) family, playing roles in cellular signalling and immune responses in human health. Moreover, it is a potential biomarker of diabetes when present in aberrant concentrations. Therefore, monitoring trace levels of H2O2 has become a research hotspot for analytical and sensor chemists. In this context, we report a rhodamine-based fluorescent probe (RN), which shows excellent fluorescent enhancement at 555 nm upon the addition of H2O2 along with a low limit of detection (LOD) of 0.67 ppm and fast response (∼2 min). The probe is highly selective for H2O2, showing no fluorescence enhancement with other ROS. RN is synthesised in a one-pot chemical reaction using rhodamine 6G (R6G) and 4,7,10-trioxa-1,13-tridecanediamine (TTDA). H2O2 detection in pre-treated milk samples proves its real-world viability. We found that RN shows low cytotoxicity, which allowed us to successfully explore its potential to monitor H2O2 generation in a diabetic L929 skin cell line and diabetic mice liver tissue. This result demonstrates promising features for assessing early diabetic progression through fluorescence imaging.","lang":"eng"}],"acknowledgement":"MM acknowledges the Government of India for DST-INSPIRE\r\nfellowship [IF200389] and Federal Ministry of Education, Science and Research (BMBWF) and the OeAD – Austria’s Agency for Education and Internationalisation for an Ernst Mach Grant, weltweit (grant number MPC-2024-01518) for research internship at ISTA. The Scientific Service Units of ISTA supported this research through resources provided by the Lab Support Facility. PG acknowledges the ANRF, India, for his NPDF fellowship (File no. PDF/2022/001960). PB acknowledges ANRF, India, for the SERB-CRG sponsored project GAP-240712 (vide reference no. CRG/2022/001679).","OA_type":"closed access","language":[{"iso":"eng"}],"author":[{"last_name":"Mondal","full_name":"Mondal, Moumita","first_name":"Moumita"},{"last_name":"Ghorai","first_name":"Pravat","full_name":"Ghorai, Pravat"},{"full_name":"Samadder, Asmita","first_name":"Asmita","last_name":"Samadder"},{"id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","first_name":"Stefan Alexander","last_name":"Freunberger","orcid":"0000-0003-2902-5319"},{"full_name":"Banerjee, Priyabrata","first_name":"Priyabrata","last_name":"Banerjee"}],"external_id":{"pmid":["41958432"]},"type":"journal_article","status":"public","pmid":1,"date_updated":"2026-04-16T05:44:49Z","publication":"Journal of Materials Chemistry B","citation":{"ista":"Mondal M, Ghorai P, Samadder A, Freunberger SA, Banerjee P. 2026. H2O2 responsive rhodamine-based probe for monitoring early-stage diabetes diagnosis. Journal of Materials Chemistry B.","ieee":"M. Mondal, P. Ghorai, A. Samadder, S. A. Freunberger, and P. Banerjee, “H2O2 responsive rhodamine-based probe for monitoring early-stage diabetes diagnosis,” <i>Journal of Materials Chemistry B</i>. Royal Society of Chemistry, 2026.","chicago":"Mondal, Moumita, Pravat Ghorai, Asmita Samadder, Stefan Alexander Freunberger, and Priyabrata Banerjee. “H2O2 Responsive Rhodamine-Based Probe for Monitoring Early-Stage Diabetes Diagnosis.” <i>Journal of Materials Chemistry B</i>. Royal Society of Chemistry, 2026. <a href=\"https://doi.org/10.1039/d5tb02687c\">https://doi.org/10.1039/d5tb02687c</a>.","ama":"Mondal M, Ghorai P, Samadder A, Freunberger SA, Banerjee P. H2O2 responsive rhodamine-based probe for monitoring early-stage diabetes diagnosis. <i>Journal of Materials Chemistry B</i>. 2026. doi:<a href=\"https://doi.org/10.1039/d5tb02687c\">10.1039/d5tb02687c</a>","apa":"Mondal, M., Ghorai, P., Samadder, A., Freunberger, S. A., &#38; Banerjee, P. (2026). H2O2 responsive rhodamine-based probe for monitoring early-stage diabetes diagnosis. <i>Journal of Materials Chemistry B</i>. Royal Society of Chemistry. <a href=\"https://doi.org/10.1039/d5tb02687c\">https://doi.org/10.1039/d5tb02687c</a>","short":"M. Mondal, P. Ghorai, A. Samadder, S.A. Freunberger, P. Banerjee, Journal of Materials Chemistry B (2026).","mla":"Mondal, Moumita, et al. “H2O2 Responsive Rhodamine-Based Probe for Monitoring Early-Stage Diabetes Diagnosis.” <i>Journal of Materials Chemistry B</i>, Royal Society of Chemistry, 2026, doi:<a href=\"https://doi.org/10.1039/d5tb02687c\">10.1039/d5tb02687c</a>."},"corr_author":"1","quality_controlled":"1","publication_status":"epub_ahead","article_type":"original","date_created":"2026-04-13T07:45:26Z","department":[{"_id":"StFr"}],"oa_version":"None","publication_identifier":{"eissn":["2050-7518"],"issn":["2050-750X"]},"scopus_import":"1","doi":"10.1039/d5tb02687c","year":"2026","article_processing_charge":"No"},{"file":[{"relation":"main_file","date_updated":"2025-11-04T07:56:19Z","date_created":"2025-11-04T07:56:19Z","file_name":"2025_ACSEnergyLetters_Dutta.pdf","access_level":"open_access","checksum":"368eb041c395a5155218f858947df419","success":1,"creator":"dernst","content_type":"application/pdf","file_id":"20597","file_size":9307654}],"ddc":["540"],"scopus_import":"1","oa_version":"Published Version","department":[{"_id":"StFr"}],"oa":1,"publication_identifier":{"eissn":["2380-8195"]},"OA_place":"publisher","page":"5722-5732","year":"2025","article_processing_charge":"Yes (in subscription journal)","doi":"10.1021/acsenergylett.5c02093","isi":1,"article_type":"letter_note","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"publication_status":"published","publication":"ACS Energy Letters","quality_controlled":"1","citation":{"chicago":"Dutta, Pronoy, Jean Marc Von Mentlen, Soumyadip Mondal, Nikolaos Kostoglou, Bodo D. Wilts, Stefan Alexander Freunberger, Gregor A. Zickler, and Christian Prehal. “Bridging Solution and Solid-State Mechanism: Confined Quasi-Solid-State Conversion in Li–S Batteries.” <i>ACS Energy Letters</i>. American Chemical Society, 2025. <a href=\"https://doi.org/10.1021/acsenergylett.5c02093\">https://doi.org/10.1021/acsenergylett.5c02093</a>.","ista":"Dutta P, Von Mentlen JM, Mondal S, Kostoglou N, Wilts BD, Freunberger SA, Zickler GA, Prehal C. 2025. Bridging solution and solid-state mechanism: Confined quasi-solid-state conversion in Li–S batteries. ACS Energy Letters. 10, 5722–5732.","ieee":"P. Dutta <i>et al.</i>, “Bridging solution and solid-state mechanism: Confined quasi-solid-state conversion in Li–S batteries,” <i>ACS Energy Letters</i>, vol. 10. American Chemical Society, pp. 5722–5732, 2025.","short":"P. Dutta, J.M. Von Mentlen, S. Mondal, N. Kostoglou, B.D. Wilts, S.A. Freunberger, G.A. Zickler, C. Prehal, ACS Energy Letters 10 (2025) 5722–5732.","apa":"Dutta, P., Von Mentlen, J. M., Mondal, S., Kostoglou, N., Wilts, B. D., Freunberger, S. A., … Prehal, C. (2025). Bridging solution and solid-state mechanism: Confined quasi-solid-state conversion in Li–S batteries. <i>ACS Energy Letters</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsenergylett.5c02093\">https://doi.org/10.1021/acsenergylett.5c02093</a>","ama":"Dutta P, Von Mentlen JM, Mondal S, et al. Bridging solution and solid-state mechanism: Confined quasi-solid-state conversion in Li–S batteries. <i>ACS Energy Letters</i>. 2025;10:5722-5732. doi:<a href=\"https://doi.org/10.1021/acsenergylett.5c02093\">10.1021/acsenergylett.5c02093</a>","mla":"Dutta, Pronoy, et al. “Bridging Solution and Solid-State Mechanism: Confined Quasi-Solid-State Conversion in Li–S Batteries.” <i>ACS Energy Letters</i>, vol. 10, American Chemical Society, 2025, pp. 5722–32, doi:<a href=\"https://doi.org/10.1021/acsenergylett.5c02093\">10.1021/acsenergylett.5c02093</a>."},"related_material":{"link":[{"relation":"software","url":" https://doi.org/10.5281/zenodo.17144229"}]},"date_created":"2025-11-02T23:01:35Z","abstract":[{"lang":"eng","text":"“Quasi-solid-state” conversion mechanisms using sparingly solvating electrolytes (SPSEs) bridge the gap between traditional solid–liquid–solid and solid-state sulfur conversion in lithium–sulfur (Li–S) batteries. Although these terms are commonly used, their precise distinctions and impacts on key performance metrics, such as rate capability, energy density, and capacity fading, remain poorly understood. In this work, we employ operando small- and wide-angle X-ray scattering alongside cryogenic transmission electron microscopy (cryo-TEM) to compare Li–S batteries in sparingly solvating and solvating ether-based electrolytes. We find that, unlike solvating electrolytes, SPSEs lead to an extended presence of lithium sulfide during cycling, coexisting with sulfur at a 50% state of charge and beyond. In the charged state, solid sulfur is present in its amorphous form inside the carbon black nanopores. These findings indicate that the limited solubility confines polysulfides in regions near the carbon surface, where these polysulfides enable conversion between the coexisting solid discharge and charge product."}],"intvolume":"        10","acknowledgement":"This work was funded by the European Union (ERC-2022-STG, SOLIDCON, 101078271). Views and opinions expressed are, however, those of the authors only and do not necessarily reflect those of the European Union or the European Research Council Executive Agency. Neither the European Union nor the granting authority can be held responsible for them. TEM measurements were carried out on a JEOL JEM F200 TEM equipped with an energy filter funded by the FFG (grant number 37120633). The authors thank Klara Neumayr, Ayca Senol Güngör, and Lorenz Gruber for valuable discussions and support with lab work. N.K. thanks Oskar Paris from Montanuniversität Leoben for providing access to the gas sorption analyzer.","day":"25","file_date_updated":"2025-11-04T07:56:19Z","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","date_updated":"2025-12-01T15:11:44Z","language":[{"iso":"eng"}],"has_accepted_license":"1","OA_type":"hybrid","status":"public","external_id":{"isi":["001600396000001"]},"type":"journal_article","author":[{"full_name":"Dutta, Pronoy","first_name":"Pronoy","last_name":"Dutta"},{"full_name":"Von Mentlen, Jean Marc","first_name":"Jean Marc","last_name":"Von Mentlen"},{"last_name":"Mondal","first_name":"Soumyadip","full_name":"Mondal, Soumyadip","id":"d25d21ef-dc8d-11ea-abe3-ec4576307f48"},{"last_name":"Kostoglou","full_name":"Kostoglou, Nikolaos","first_name":"Nikolaos"},{"last_name":"Wilts","full_name":"Wilts, Bodo D.","first_name":"Bodo D."},{"id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","first_name":"Stefan Alexander","last_name":"Freunberger","orcid":"0000-0003-2902-5319"},{"last_name":"Zickler","full_name":"Zickler, Gregor A.","first_name":"Gregor A."},{"last_name":"Prehal","full_name":"Prehal, Christian","first_name":"Christian"}],"PlanS_conform":"1","publisher":"American Chemical Society","month":"10","_id":"20593","title":"Bridging solution and solid-state mechanism: Confined quasi-solid-state conversion in Li–S batteries","date_published":"2025-10-25T00:00:00Z","volume":10},{"page":"601–605","year":"2025","article_processing_charge":"Yes (via OA deal)","doi":"10.1038/s41586-025-09587-7","file":[{"success":1,"creator":"dernst","content_type":"application/pdf","file_id":"20500","file_size":3809247,"checksum":"b507ddd23df0388aa65d04dc9b00fe3d","date_created":"2025-10-20T10:26:13Z","file_name":"2025_Nature_Mondal.pdf","access_level":"open_access","relation":"main_file","date_updated":"2025-10-20T10:26:13Z"}],"ddc":["540"],"scopus_import":"1","oa_version":"Published Version","oa":1,"department":[{"_id":"StFr"},{"_id":"Bio"}],"publication_identifier":{"issn":["0028-0836"],"eissn":["1476-4687"]},"OA_place":"publisher","related_material":{"link":[{"description":"News on ISTA website","url":"https://ista.ac.at/en/news/taming-the-bad-oxygen/","relation":"press_release"}]},"issue":"8085","date_created":"2024-08-29T10:40:23Z","isi":1,"article_type":"original","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"publication_status":"published","publication":"Nature","quality_controlled":"1","corr_author":"1","citation":{"apa":"Mondal, S., Nguyen, H. T. K., Hauschild, R., &#38; Freunberger, S. A. (2025). Marcus kinetics control singlet and triplet oxygen evolving from superoxide. <i>Nature</i>. Springer Nature. <a href=\"https://doi.org/10.1038/s41586-025-09587-7\">https://doi.org/10.1038/s41586-025-09587-7</a>","short":"S. Mondal, H.T.K. Nguyen, R. Hauschild, S.A. Freunberger, Nature 646 (2025) 601–605.","ama":"Mondal S, Nguyen HTK, Hauschild R, Freunberger SA. Marcus kinetics control singlet and triplet oxygen evolving from superoxide. <i>Nature</i>. 2025;646(8085):601–605. doi:<a href=\"https://doi.org/10.1038/s41586-025-09587-7\">10.1038/s41586-025-09587-7</a>","mla":"Mondal, Soumyadip, et al. “Marcus Kinetics Control Singlet and Triplet Oxygen Evolving from Superoxide.” <i>Nature</i>, vol. 646, no. 8085, Springer Nature, 2025, pp. 601–605, doi:<a href=\"https://doi.org/10.1038/s41586-025-09587-7\">10.1038/s41586-025-09587-7</a>.","chicago":"Mondal, Soumyadip, Huyen T.K. Nguyen, Robert Hauschild, and Stefan Alexander Freunberger. “Marcus Kinetics Control Singlet and Triplet Oxygen Evolving from Superoxide.” <i>Nature</i>. Springer Nature, 2025. <a href=\"https://doi.org/10.1038/s41586-025-09587-7\">https://doi.org/10.1038/s41586-025-09587-7</a>.","ieee":"S. Mondal, H. T. K. Nguyen, R. Hauschild, and S. A. Freunberger, “Marcus kinetics control singlet and triplet oxygen evolving from superoxide,” <i>Nature</i>, vol. 646, no. 8085. Springer Nature, pp. 601–605, 2025.","ista":"Mondal S, Nguyen HTK, Hauschild R, Freunberger SA. 2025. Marcus kinetics control singlet and triplet oxygen evolving from superoxide. Nature. 646(8085), 601–605."},"date_updated":"2026-04-28T13:18:33Z","pmid":1,"language":[{"iso":"eng"}],"OA_type":"hybrid","has_accepted_license":"1","external_id":{"isi":["001586378900001"],"pmid":["41044415"]},"status":"public","type":"journal_article","author":[{"last_name":"Mondal","first_name":"Soumyadip","full_name":"Mondal, Soumyadip","id":"d25d21ef-dc8d-11ea-abe3-ec4576307f48"},{"first_name":"Huyen T.K.","full_name":"Nguyen, Huyen T.K.","last_name":"Nguyen"},{"orcid":"0000-0001-9843-3522","last_name":"Hauschild","first_name":"Robert","full_name":"Hauschild, Robert","id":"4E01D6B4-F248-11E8-B48F-1D18A9856A87"},{"full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","first_name":"Stefan Alexander","orcid":"0000-0003-2902-5319","last_name":"Freunberger"}],"abstract":[{"lang":"eng","text":"Oxygen redox chemistry is central to life1 and many human-made technologies, such as in energy storage2,3,4. The large energy gain from oxygen redox reactions is often connected with the occurrence of harmful reactive oxygen species3,5,6. Key species are superoxide and the highly reactive singlet oxygen3,4,5,6,7, which may evolve from superoxide. However, the factors determining the formation of singlet oxygen, rather than the relatively unreactive triplet oxygen, are unknown. Here we report that the release of triplet or singlet oxygen is governed by individual Marcus normal and inverted region behaviour. We found that as the driving force for the reaction increases, the initially dominant evolution of triplet oxygen slows down, and singlet oxygen evolution becomes predominant with higher maximum kinetics. This behaviour also applies to the widely observed superoxide disproportionation, in which one superoxide is oxidized by another, in both non-aqueous and aqueous systems, with Lewis and Brønsted acidity controlling the driving forces. Singlet oxygen yields governed by these conditions are relevant, for example, in batteries or cellular organelles in which superoxide forms. Our findings suggest ways to understand and control spin states and kinetics in oxygen redox chemistry, with implications for fields, including life sciences, pure chemistry and energy storage."}],"project":[{"_id":"8df062be-16d5-11f0-9cad-f559b6612c7e","grant_number":"P37169","name":"Singlet oxygen in non-aqueous oxygen redox chemistry"},{"grant_number":"CZI01","name":"Tools for automation and feedback microscopy","_id":"c08e9ad1-5a5b-11eb-8a69-9d1cf3b07473"}],"intvolume":"       646","acknowledgement":"S.A.F. thanks the Institute of Science and Technology Austria (ISTA) for the support. The Scientific Service Units of ISTA supported this research through resources provided by the Imaging and Optics Facility, the Lab Support Facility, the Miba Machine Shop and Scientific Computing. This research was partly funded by the Austrian Science Fund (FWF) (10.55776/P37169 and 10.55776/COE5). For open access purposes, the author has applied for a CC BY public copyright licence to any author-accepted manuscript version arising from this submission. R.H. acknowledges funding through CZI grant DAF2020-225401 (10.37921/120055ratwvi) from the Chan Zuckerberg Initiative DAF, an advised fund of Silicon Valley Community Foundation (10.13039/100014989). H.T.K.N. acknowledges funding by the European Commission Erasmus Mundus Joint Masters programme. We thank M. Sixt and M. Chinon for the discussions about O-redox in life and R. Jethwa for proofreading. Open access funding was provided by ISTA.","day":"16","user_id":"ba8df636-2132-11f1-aed0-ed93e2281fdd","file_date_updated":"2025-10-20T10:26:13Z","title":"Marcus kinetics control singlet and triplet oxygen evolving from superoxide","_id":"17468","date_published":"2025-10-16T00:00:00Z","volume":646,"acknowledged_ssus":[{"_id":"Bio"},{"_id":"LifeSc"},{"_id":"M-Shop"},{"_id":"ScienComp"}],"PlanS_conform":"1","publisher":"Springer Nature","month":"10"},{"scopus_import":"1","oa_version":"None","department":[{"_id":"StFr"}],"publication_identifier":{"issn":["1359-6640"],"eissn":["1364-5498"]},"page":"392-411","year":"2024","article_processing_charge":"No","doi":"10.1039/d3fd90062b","isi":1,"publication_status":"published","article_type":"letter_note","publication":"Faraday Discussions","quality_controlled":"1","citation":{"chicago":"Archer, Lynden A., Peter G. Bruce, Ernesto J. Calvo, Daniel Dewar, James H. J. Ellison, Stefan Alexander Freunberger, Xiangwen Gao, et al. “Towards Practical Metal–Oxygen Batteries: General Discussion.” <i>Faraday Discussions</i>. Royal Society of Chemistry, 2024. <a href=\"https://doi.org/10.1039/d3fd90062b\">https://doi.org/10.1039/d3fd90062b</a>.","ista":"Archer LA, Bruce PG, Calvo EJ, Dewar D, Ellison JHJ, Freunberger SA, Gao X, Hardwick LJ, Horwitz G, Janek J, Johnson LR, Jordan JW, Matsuda S, Menkin S, Mondal S, Qiu Q, Samarakoon T, Temprano I, Uosaki K, Vailaya G, Wachsman ED, Wu Y, Ye S. 2024. Towards practical metal–oxygen batteries: General discussion. Faraday Discussions. 248, 392–411.","ieee":"L. A. Archer <i>et al.</i>, “Towards practical metal–oxygen batteries: General discussion,” <i>Faraday Discussions</i>, vol. 248. Royal Society of Chemistry, pp. 392–411, 2024.","mla":"Archer, Lynden A., et al. “Towards Practical Metal–Oxygen Batteries: General Discussion.” <i>Faraday Discussions</i>, vol. 248, Royal Society of Chemistry, 2024, pp. 392–411, doi:<a href=\"https://doi.org/10.1039/d3fd90062b\">10.1039/d3fd90062b</a>.","apa":"Archer, L. A., Bruce, P. G., Calvo, E. J., Dewar, D., Ellison, J. H. J., Freunberger, S. A., … Ye, S. (2024). Towards practical metal–oxygen batteries: General discussion. <i>Faraday Discussions</i>. Royal Society of Chemistry. <a href=\"https://doi.org/10.1039/d3fd90062b\">https://doi.org/10.1039/d3fd90062b</a>","short":"L.A. Archer, P.G. Bruce, E.J. Calvo, D. Dewar, J.H.J. Ellison, S.A. Freunberger, X. Gao, L.J. Hardwick, G. Horwitz, J. Janek, L.R. Johnson, J.W. Jordan, S. Matsuda, S. Menkin, S. Mondal, Q. Qiu, T. Samarakoon, I. Temprano, K. Uosaki, G. Vailaya, E.D. Wachsman, Y. Wu, S. Ye, Faraday Discussions 248 (2024) 392–411.","ama":"Archer LA, Bruce PG, Calvo EJ, et al. Towards practical metal–oxygen batteries: General discussion. <i>Faraday Discussions</i>. 2024;248:392-411. doi:<a href=\"https://doi.org/10.1039/d3fd90062b\">10.1039/d3fd90062b</a>"},"date_created":"2023-12-20T10:48:09Z","intvolume":"       248","day":"29","user_id":"317138e5-6ab7-11ef-aa6d-ffef3953e345","date_updated":"2025-09-04T11:34:30Z","pmid":1,"language":[{"iso":"eng"}],"external_id":{"pmid":["38112202"],"isi":["001130090400001"]},"status":"public","type":"journal_article","author":[{"full_name":"Archer, Lynden A.","first_name":"Lynden A.","last_name":"Archer"},{"first_name":"Peter G.","full_name":"Bruce, Peter G.","last_name":"Bruce"},{"last_name":"Calvo","first_name":"Ernesto J.","full_name":"Calvo, Ernesto J."},{"last_name":"Dewar","full_name":"Dewar, Daniel","first_name":"Daniel"},{"first_name":"James H. J.","full_name":"Ellison, James H. J.","last_name":"Ellison"},{"full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","first_name":"Stefan Alexander","orcid":"0000-0003-2902-5319","last_name":"Freunberger"},{"first_name":"Xiangwen","full_name":"Gao, Xiangwen","last_name":"Gao"},{"last_name":"Hardwick","full_name":"Hardwick, Laurence J.","first_name":"Laurence J."},{"last_name":"Horwitz","first_name":"Gabriela","full_name":"Horwitz, Gabriela"},{"last_name":"Janek","first_name":"Jürgen","full_name":"Janek, Jürgen"},{"last_name":"Johnson","first_name":"Lee R.","full_name":"Johnson, Lee R."},{"last_name":"Jordan","first_name":"Jack W.","full_name":"Jordan, Jack W."},{"last_name":"Matsuda","full_name":"Matsuda, Shoichi","first_name":"Shoichi"},{"first_name":"Svetlana","full_name":"Menkin, Svetlana","last_name":"Menkin"},{"first_name":"Soumyadip","full_name":"Mondal, Soumyadip","id":"d25d21ef-dc8d-11ea-abe3-ec4576307f48","last_name":"Mondal"},{"last_name":"Qiu","first_name":"Qianyuan","full_name":"Qiu, Qianyuan"},{"last_name":"Samarakoon","full_name":"Samarakoon, Thukshan","first_name":"Thukshan"},{"full_name":"Temprano, Israel","first_name":"Israel","last_name":"Temprano"},{"full_name":"Uosaki, Kohei","first_name":"Kohei","last_name":"Uosaki"},{"first_name":"Ganesh","full_name":"Vailaya, Ganesh","last_name":"Vailaya"},{"last_name":"Wachsman","first_name":"Eric D.","full_name":"Wachsman, Eric D."},{"last_name":"Wu","full_name":"Wu, Yiying","first_name":"Yiying"},{"last_name":"Ye","full_name":"Ye, Shen","first_name":"Shen"}],"publisher":"Royal Society of Chemistry","month":"01","_id":"14701","keyword":["Physical and Theoretical Chemistry"],"title":"Towards practical metal–oxygen batteries: General discussion","date_published":"2024-01-29T00:00:00Z","volume":248},{"date_published":"2024-07-26T00:00:00Z","volume":7,"_id":"17333","title":"Catalysing rate and capacity","publisher":"Springer Nature","month":"07","language":[{"iso":"eng"}],"type":"journal_article","external_id":{"isi":["001278986700012"]},"status":"public","author":[{"first_name":"Soumyadip","id":"d25d21ef-dc8d-11ea-abe3-ec4576307f48","full_name":"Mondal, Soumyadip","last_name":"Mondal"},{"last_name":"Freunberger","orcid":"0000-0003-2902-5319","first_name":"Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander"}],"date_updated":"2025-09-08T08:30:59Z","day":"26","user_id":"317138e5-6ab7-11ef-aa6d-ffef3953e345","abstract":[{"lang":"eng","text":"Aqueous zinc-ion batteries are attractive due to their low cost, environmental friendliness, and exceptional performance, but the latter remains poorly understood. Now, a fast catalytic step involved in oxygen redox catalysis is shown to contribute to capacity at a high rate."}],"intvolume":"         7","date_created":"2024-07-29T07:05:33Z","issue":"7","publication":"Nature Catalysis","quality_controlled":"1","citation":{"short":"S. Mondal, S.A. Freunberger, Nature Catalysis 7 (2024) 759–760.","apa":"Mondal, S., &#38; Freunberger, S. A. (2024). Catalysing rate and capacity. <i>Nature Catalysis</i>. Springer Nature. <a href=\"https://doi.org/10.1038/s41929-024-01184-7\">https://doi.org/10.1038/s41929-024-01184-7</a>","ama":"Mondal S, Freunberger SA. Catalysing rate and capacity. <i>Nature Catalysis</i>. 2024;7(7):759-760. doi:<a href=\"https://doi.org/10.1038/s41929-024-01184-7\">10.1038/s41929-024-01184-7</a>","mla":"Mondal, Soumyadip, and Stefan Alexander Freunberger. “Catalysing Rate and Capacity.” <i>Nature Catalysis</i>, vol. 7, no. 7, Springer Nature, 2024, pp. 759–60, doi:<a href=\"https://doi.org/10.1038/s41929-024-01184-7\">10.1038/s41929-024-01184-7</a>.","chicago":"Mondal, Soumyadip, and Stefan Alexander Freunberger. “Catalysing Rate and Capacity.” <i>Nature Catalysis</i>. Springer Nature, 2024. <a href=\"https://doi.org/10.1038/s41929-024-01184-7\">https://doi.org/10.1038/s41929-024-01184-7</a>.","ieee":"S. Mondal and S. A. Freunberger, “Catalysing rate and capacity,” <i>Nature Catalysis</i>, vol. 7, no. 7. Springer Nature, pp. 759–760, 2024.","ista":"Mondal S, Freunberger SA. 2024. Catalysing rate and capacity. Nature Catalysis. 7(7), 759–760."},"corr_author":"1","isi":1,"publication_status":"published","article_type":"letter_note","doi":"10.1038/s41929-024-01184-7","page":"759-760","year":"2024","article_processing_charge":"No","oa_version":"None","department":[{"_id":"StFr"}],"publication_identifier":{"issn":["2520-1158"]},"scopus_import":"1"},{"doi":"10.1002/anie.202316476","article_processing_charge":"Yes (via OA deal)","year":"2024","publication_identifier":{"issn":["1433-7851"],"eissn":["1521-3773"]},"oa_version":"Published Version","oa":1,"department":[{"_id":"StFr"},{"_id":"GradSch"}],"scopus_import":"1","file":[{"date_updated":"2024-07-16T11:54:46Z","relation":"main_file","access_level":"open_access","file_name":"2024_AngChemieInt_Jethwa.pdf","date_created":"2024-07-16T11:54:46Z","checksum":"fe2c23454279eb9d76ed6ca9970c21c7","file_size":4766445,"file_id":"17261","content_type":"application/pdf","creator":"dernst","success":1}],"ddc":["540"],"ec_funded":1,"date_created":"2023-12-15T16:10:13Z","issue":"28","related_material":{"record":[{"relation":"dissertation_contains","id":"20607","status":"public"}]},"quality_controlled":"1","corr_author":"1","citation":{"short":"R.B. Jethwa, S. Mondal, B. Pant, S.A. Freunberger, Angewandte Chemie International Edition 63 (2024).","apa":"Jethwa, R. B., Mondal, S., Pant, B., &#38; Freunberger, S. A. (2024). To DISP or not? The far‐reaching reaction mechanisms underpinning Lithium‐air batteries. <i>Angewandte Chemie International Edition</i>. Wiley. <a href=\"https://doi.org/10.1002/anie.202316476\">https://doi.org/10.1002/anie.202316476</a>","ama":"Jethwa RB, Mondal S, Pant B, Freunberger SA. To DISP or not? The far‐reaching reaction mechanisms underpinning Lithium‐air batteries. <i>Angewandte Chemie International Edition</i>. 2024;63(28). doi:<a href=\"https://doi.org/10.1002/anie.202316476\">10.1002/anie.202316476</a>","mla":"Jethwa, Rajesh B., et al. “To DISP or Not? The Far‐reaching Reaction Mechanisms Underpinning Lithium‐air Batteries.” <i>Angewandte Chemie International Edition</i>, vol. 63, no. 28, e202316476, Wiley, 2024, doi:<a href=\"https://doi.org/10.1002/anie.202316476\">10.1002/anie.202316476</a>.","chicago":"Jethwa, Rajesh B, Soumyadip Mondal, Bhargavi Pant, and Stefan Alexander Freunberger. “To DISP or Not? The Far‐reaching Reaction Mechanisms Underpinning Lithium‐air Batteries.” <i>Angewandte Chemie International Edition</i>. Wiley, 2024. <a href=\"https://doi.org/10.1002/anie.202316476\">https://doi.org/10.1002/anie.202316476</a>.","ieee":"R. B. Jethwa, S. Mondal, B. Pant, and S. A. Freunberger, “To DISP or not? The far‐reaching reaction mechanisms underpinning Lithium‐air batteries,” <i>Angewandte Chemie International Edition</i>, vol. 63, no. 28. Wiley, 2024.","ista":"Jethwa RB, Mondal S, Pant B, Freunberger SA. 2024. To DISP or not? The far‐reaching reaction mechanisms underpinning Lithium‐air batteries. Angewandte Chemie International Edition. 63(28), e202316476."},"publication":"Angewandte Chemie International Edition","article_type":"review","tmp":{"legal_code_url":"https://creativecommons.org/licenses/by-nc-nd/4.0/legalcode","image":"/images/cc_by_nc_nd.png","short":"CC BY-NC-ND (4.0)","name":"Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)"},"article_number":"e202316476","publication_status":"published","isi":1,"license":"https://creativecommons.org/licenses/by-nc-nd/4.0/","external_id":{"isi":["001241932700001"],"pmid":["38095355"]},"status":"public","type":"journal_article","author":[{"id":"4cc538d5-803f-11ed-ab7e-8139573aad8f","full_name":"Jethwa, Rajesh B","first_name":"Rajesh B","last_name":"Jethwa","orcid":"0000-0002-0404-4356"},{"last_name":"Mondal","first_name":"Soumyadip","full_name":"Mondal, Soumyadip","id":"d25d21ef-dc8d-11ea-abe3-ec4576307f48"},{"last_name":"Pant","first_name":"Bhargavi","id":"50c64d4d-eb97-11eb-a6c2-d33e5e14f112","full_name":"Pant, Bhargavi"},{"first_name":"Stefan Alexander","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","orcid":"0000-0003-2902-5319","last_name":"Freunberger"}],"language":[{"iso":"eng"}],"has_accepted_license":"1","date_updated":"2026-04-07T12:27:23Z","pmid":1,"file_date_updated":"2024-07-16T11:54:46Z","user_id":"317138e5-6ab7-11ef-aa6d-ffef3953e345","day":"08","project":[{"_id":"fc2ed2f7-9c52-11eb-aca3-c01059dda49c","name":"IST-BRIDGE: International postdoctoral program","call_identifier":"H2020","grant_number":"101034413"}],"intvolume":"        63","acknowledgement":"S.A.F. is indebted to ISTA for support. R.B.J. thanks the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 101034413 for funding. B.P. thanks Alistore ERI for providing a PhD scholarship.","abstract":[{"lang":"eng","text":"The short history of research on Li-O2 batteries has seen a remarkable number of mechanistic U-turns over the years. From the initial use of carbonate electrolytes, that were then found to be entirely unsuitable, to the belief that (su)peroxide was solely responsible for degradation, before the more reactive singlet oxygen was found to form, to the hypothesis that capacity depends on a competing surface/solution mechanism before a practically exclusive solution mechanism was identified. Herein, we argue for an ever-fresh look at the reported data without bias towards supposedly established explanations. We explain how the latest findings on rate and capacity limits, as well as the origin of side reactions, are connected via the disproportionation (DISP) step in the (dis)charge mechanism. Therefrom, directions emerge for the design of electrolytes and mediators on how to suppress side reactions and to enable high rate and high reversible capacity."}],"volume":63,"date_published":"2024-07-08T00:00:00Z","_id":"14687","keyword":["General Chemistry","Catalysis"],"title":"To DISP or not? The far‐reaching reaction mechanisms underpinning Lithium‐air batteries","month":"07","publisher":"Wiley"},{"pmid":1,"date_updated":"2026-04-07T12:27:23Z","author":[{"last_name":"Mondal","first_name":"Soumyadip","id":"d25d21ef-dc8d-11ea-abe3-ec4576307f48","full_name":"Mondal, Soumyadip"},{"orcid":"0000-0002-0404-4356","last_name":"Jethwa","first_name":"Rajesh B","full_name":"Jethwa, Rajesh B","id":"4cc538d5-803f-11ed-ab7e-8139573aad8f"},{"last_name":"Pant","full_name":"Pant, Bhargavi","id":"50c64d4d-eb97-11eb-a6c2-d33e5e14f112","first_name":"Bhargavi"},{"first_name":"Robert","full_name":"Hauschild, Robert","id":"4E01D6B4-F248-11E8-B48F-1D18A9856A87","orcid":"0000-0001-9843-3522","last_name":"Hauschild"},{"id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","first_name":"Stefan Alexander","last_name":"Freunberger","orcid":"0000-0003-2902-5319"}],"external_id":{"isi":["001070423500001"],"pmid":["37750344"]},"license":"https://creativecommons.org/licenses/by-nc/3.0/","type":"journal_article","status":"public","has_accepted_license":"1","language":[{"iso":"eng"}],"intvolume":"       248","abstract":[{"lang":"eng","text":"Singlet oxygen (1O2) formation is now recognised as a key aspect of non-aqueous oxygen redox chemistry. For identifying 1O2, chemical trapping via 9,10-dimethylanthracene (DMA) to form the endoperoxide (DMA-O2) has become the mainstay method due to its sensitivity, selectivity, and ease of use. While DMA has been shown to be selective for 1O2, rather than forming DMA-O2 with a wide variety of potentially reactive O-containing species, false positives might hypothetically be obtained in the presence of previously overlooked species. Here, we first give unequivocal direct spectroscopic proof by the 1O2-specific near infrared (NIR) emission at 1270 nm for the previously proposed 1O2 formation pathways, which centre around superoxide disproportionation. We then show that peroxocarbonates, common intermediates in metal-O2 and metal carbonate electrochemistry, do not produce false-positive DMA-O2. Moreover, we identify a previously unreported 1O2-forming pathway through the reaction of CO2 with superoxide. Overall, we give unequivocal proof for 1O2 formation in non-aqueous oxygen redox and show that chemical trapping with DMA is a reliable method to assess 1O2 formation."}],"file_date_updated":"2024-07-16T07:46:39Z","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","day":"01","title":"Singlet oxygen in non-aqueous oxygen redox: Direct spectroscopic evidence for formation pathways and reliability of chemical probes","_id":"13044","keyword":["Physical and Theoretical Chemistry"],"volume":248,"date_published":"2024-01-01T00:00:00Z","month":"01","publisher":"Royal Society of Chemistry","article_processing_charge":"Yes (via OA deal)","year":"2024","page":"175-189","doi":"10.1039/d3fd00088e","scopus_import":"1","file":[{"relation":"main_file","date_updated":"2024-07-16T07:46:39Z","date_created":"2024-07-16T07:46:39Z","file_name":"2024_FaradayDiscussions_Mondal.pdf","access_level":"open_access","checksum":"6515a227ed3e8942496fe6a1feeffd18","success":1,"creator":"dernst","content_type":"application/pdf","file_size":1303733,"file_id":"17249"}],"ddc":["540"],"publication_identifier":{"eissn":["1364-5498"],"issn":["1359-6640"]},"department":[{"_id":"StFr"},{"_id":"Bio"}],"oa":1,"oa_version":"Published Version","related_material":{"record":[{"relation":"dissertation_contains","id":"20607","status":"public"}]},"date_created":"2023-05-22T06:53:34Z","publication_status":"published","tmp":{"name":"Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)","legal_code_url":"https://creativecommons.org/licenses/by-nc/3.0/legalcode","image":"/images/cc_by_nc.png","short":"CC BY-NC (3.0)"},"article_type":"original","isi":1,"citation":{"ama":"Mondal S, Jethwa RB, Pant B, Hauschild R, Freunberger SA. Singlet oxygen in non-aqueous oxygen redox: Direct spectroscopic evidence for formation pathways and reliability of chemical probes. <i>Faraday Discussions</i>. 2024;248:175-189. doi:<a href=\"https://doi.org/10.1039/d3fd00088e\">10.1039/d3fd00088e</a>","apa":"Mondal, S., Jethwa, R. B., Pant, B., Hauschild, R., &#38; Freunberger, S. A. (2024). Singlet oxygen in non-aqueous oxygen redox: Direct spectroscopic evidence for formation pathways and reliability of chemical probes. <i>Faraday Discussions</i>. Royal Society of Chemistry. <a href=\"https://doi.org/10.1039/d3fd00088e\">https://doi.org/10.1039/d3fd00088e</a>","short":"S. Mondal, R.B. Jethwa, B. Pant, R. Hauschild, S.A. Freunberger, Faraday Discussions 248 (2024) 175–189.","mla":"Mondal, Soumyadip, et al. “Singlet Oxygen in Non-Aqueous Oxygen Redox: Direct Spectroscopic Evidence for Formation Pathways and Reliability of Chemical Probes.” <i>Faraday Discussions</i>, vol. 248, Royal Society of Chemistry, 2024, pp. 175–89, doi:<a href=\"https://doi.org/10.1039/d3fd00088e\">10.1039/d3fd00088e</a>.","ista":"Mondal S, Jethwa RB, Pant B, Hauschild R, Freunberger SA. 2024. Singlet oxygen in non-aqueous oxygen redox: Direct spectroscopic evidence for formation pathways and reliability of chemical probes. Faraday Discussions. 248, 175–189.","ieee":"S. Mondal, R. B. Jethwa, B. Pant, R. Hauschild, and S. A. Freunberger, “Singlet oxygen in non-aqueous oxygen redox: Direct spectroscopic evidence for formation pathways and reliability of chemical probes,” <i>Faraday Discussions</i>, vol. 248. Royal Society of Chemistry, pp. 175–189, 2024.","chicago":"Mondal, Soumyadip, Rajesh B Jethwa, Bhargavi Pant, Robert Hauschild, and Stefan Alexander Freunberger. “Singlet Oxygen in Non-Aqueous Oxygen Redox: Direct Spectroscopic Evidence for Formation Pathways and Reliability of Chemical Probes.” <i>Faraday Discussions</i>. Royal Society of Chemistry, 2024. <a href=\"https://doi.org/10.1039/d3fd00088e\">https://doi.org/10.1039/d3fd00088e</a>."},"corr_author":"1","quality_controlled":"1","publication":"Faraday Discussions"},{"date_created":"2023-01-16T09:45:09Z","corr_author":"1","citation":{"short":"C. Prehal, J.-M. von Mentlen, S. Drvarič Talian, A. Vizintin, R. Dominko, H. Amenitsch, L. Porcar, S.A. Freunberger, V. Wood, Nature Communications 13 (2022).","apa":"Prehal, C., von Mentlen, J.-M., Drvarič Talian, S., Vizintin, A., Dominko, R., Amenitsch, H., … Wood, V. (2022). On the nanoscale structural evolution of solid discharge products in lithium-sulfur batteries using operando scattering. <i>Nature Communications</i>. Springer Nature. <a href=\"https://doi.org/10.1038/s41467-022-33931-4\">https://doi.org/10.1038/s41467-022-33931-4</a>","ama":"Prehal C, von Mentlen J-M, Drvarič Talian S, et al. On the nanoscale structural evolution of solid discharge products in lithium-sulfur batteries using operando scattering. <i>Nature Communications</i>. 2022;13. doi:<a href=\"https://doi.org/10.1038/s41467-022-33931-4\">10.1038/s41467-022-33931-4</a>","mla":"Prehal, Christian, et al. “On the Nanoscale Structural Evolution of Solid Discharge Products in Lithium-Sulfur Batteries Using Operando Scattering.” <i>Nature Communications</i>, vol. 13, 6326, Springer Nature, 2022, doi:<a href=\"https://doi.org/10.1038/s41467-022-33931-4\">10.1038/s41467-022-33931-4</a>.","chicago":"Prehal, Christian, Jean-Marc von Mentlen, Sara Drvarič Talian, Alen Vizintin, Robert Dominko, Heinz Amenitsch, Lionel Porcar, Stefan Alexander Freunberger, and Vanessa Wood. “On the Nanoscale Structural Evolution of Solid Discharge Products in Lithium-Sulfur Batteries Using Operando Scattering.” <i>Nature Communications</i>. Springer Nature, 2022. <a href=\"https://doi.org/10.1038/s41467-022-33931-4\">https://doi.org/10.1038/s41467-022-33931-4</a>.","ista":"Prehal C, von Mentlen J-M, Drvarič Talian S, Vizintin A, Dominko R, Amenitsch H, Porcar L, Freunberger SA, Wood V. 2022. On the nanoscale structural evolution of solid discharge products in lithium-sulfur batteries using operando scattering. Nature Communications. 13, 6326.","ieee":"C. Prehal <i>et al.</i>, “On the nanoscale structural evolution of solid discharge products in lithium-sulfur batteries using operando scattering,” <i>Nature Communications</i>, vol. 13. Springer Nature, 2022."},"quality_controlled":"1","publication":"Nature Communications","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"article_type":"original","article_number":"6326","publication_status":"published","isi":1,"doi":"10.1038/s41467-022-33931-4","article_processing_charge":"No","year":"2022","publication_identifier":{"issn":["2041-1723"]},"department":[{"_id":"StFr"}],"oa":1,"oa_version":"Published Version","scopus_import":"1","file":[{"date_updated":"2023-01-27T07:19:11Z","relation":"main_file","file_name":"2022_NatureCommunications_Prehal.pdf","date_created":"2023-01-27T07:19:11Z","access_level":"open_access","checksum":"5034336dbf0f860030ef745c08df9e0e","creator":"dernst","success":1,"file_size":4216931,"file_id":"12411","content_type":"application/pdf"}],"ddc":["540"],"date_published":"2022-10-24T00:00:00Z","volume":13,"keyword":["General Physics and Astronomy","General Biochemistry","Genetics and Molecular Biology","General Chemistry","Multidisciplinary"],"_id":"12208","title":"On the nanoscale structural evolution of solid discharge products in lithium-sulfur batteries using operando scattering","month":"10","publisher":"Springer Nature","author":[{"last_name":"Prehal","full_name":"Prehal, Christian","first_name":"Christian"},{"first_name":"Jean-Marc","full_name":"von Mentlen, Jean-Marc","last_name":"von Mentlen"},{"full_name":"Drvarič Talian, Sara","first_name":"Sara","last_name":"Drvarič Talian"},{"first_name":"Alen","full_name":"Vizintin, Alen","last_name":"Vizintin"},{"full_name":"Dominko, Robert","first_name":"Robert","last_name":"Dominko"},{"full_name":"Amenitsch, Heinz","first_name":"Heinz","last_name":"Amenitsch"},{"full_name":"Porcar, Lionel","first_name":"Lionel","last_name":"Porcar"},{"orcid":"0000-0003-2902-5319","last_name":"Freunberger","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","first_name":"Stefan Alexander"},{"last_name":"Wood","first_name":"Vanessa","full_name":"Wood, Vanessa"}],"status":"public","type":"journal_article","external_id":{"isi":["000871563700006"],"pmid":["36280671"]},"has_accepted_license":"1","language":[{"iso":"eng"}],"pmid":1,"date_updated":"2024-10-09T21:03:47Z","user_id":"4359f0d1-fa6c-11eb-b949-802e58b17ae8","file_date_updated":"2023-01-27T07:19:11Z","day":"24","acknowledgement":"This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant NanoEvolution, grant agreement No 894042. The authors acknowledge the CERIC-ERIC Consortium for the access to the Austrian SAXS beamline and TU Graz for support through the Lead Project LP-03.\r\nLikewise, the use of SOMAPP Lab, a core facility supported by the Austrian Federal Ministry of Education, Science and Research, the Graz University of Technology, the University of Graz, and Anton Paar GmbH is acknowledged. In addition, the authors acknowledge access to the D-22SANS beamline at the ILL neutron source. Electron microscopy measurements were performed at the Scientific Scenter for Optical and Electron Microscopy (ScopeM) of the Swiss Federal Institute of Technology. C.P. and J.M.M. thank A. Senol for her support with the SANS\r\nbeamtime preparation. S.D.T, A.V. and R.D. acknowledge the financial support by the Slovenian Research Agency (ARRS) research core funding P2-0393 and P2-0423. Furthermore, A.V. acknowledge the funding from the Slovenian Research Agency, research project Z2−1863.\r\nS.A.F. is indebted to IST Austria for support. ","intvolume":"        13","abstract":[{"lang":"eng","text":"The inadequate understanding of the mechanisms that reversibly convert molecular sulfur (S) into lithium sulfide (Li<jats:sub>2</jats:sub>S) via soluble polysulfides (PSs) formation impedes the development of high-performance lithium-sulfur (Li-S) batteries with non-aqueous electrolyte solutions. Here, we use operando small and wide angle X-ray scattering and operando small angle neutron scattering (SANS) measurements to track the nucleation, growth and dissolution of solid deposits from atomic to sub-micron scales during real-time Li-S cell operation. In particular, stochastic modelling based on the SANS data allows quantifying the nanoscale phase evolution during battery cycling. We show that next to nano-crystalline Li<jats:sub>2</jats:sub>S the deposit comprises solid short-chain PSs particles. The analysis of the experimental data suggests that initially, Li<jats:sub>2</jats:sub>S<jats:sub>2</jats:sub> precipitates from the solution and then is partially converted via solid-state electroreduction to Li<jats:sub>2</jats:sub>S. We further demonstrate that mass transport, rather than electron transport through a thin passivating film, limits the discharge capacity and rate performance in Li-S cells."}]},{"date_updated":"2024-10-09T21:03:48Z","status":"public","type":"journal_article","external_id":{"isi":["000875635900001"]},"author":[{"full_name":"Kovačič, Sebastijan","first_name":"Sebastijan","last_name":"Kovačič"},{"first_name":"Bettina","full_name":"Schafzahl, Bettina","last_name":"Schafzahl"},{"first_name":"Nadejda B.","full_name":"Matsko, Nadejda B.","last_name":"Matsko"},{"first_name":"Katharina","full_name":"Gruber, Katharina","last_name":"Gruber"},{"first_name":"Martin","full_name":"Schmuck, Martin","last_name":"Schmuck"},{"last_name":"Koller","first_name":"Stefan","full_name":"Koller, Stefan"},{"last_name":"Freunberger","orcid":"0000-0003-2902-5319","first_name":"Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander"},{"last_name":"Slugovc","full_name":"Slugovc, Christian","first_name":"Christian"}],"language":[{"iso":"eng"}],"has_accepted_license":"1","intvolume":"         5","acknowledgement":"S.K. acknowledges the financial support from the Slovenian Research Agency (grants P1-0021, P2-0150). Support by Graz University of Technology (LP-03 – Porous Materials@Work) and from VARTA Innovation GmbH is kindly acknowledged. We thank Umicore for providing the initiator and Matjaž Mazaj (National Institute of Chemistry, Ljubljana) and Karel Jerabek (Czech Academy of Sciences) for measurements and fruitful discussions. S.A.F. is indebted to the Austrian Federal Ministry of Science, Research and Economy; the Austrian Research Promotion Agency (Grant No. 845364); and ISTA for support.","abstract":[{"text":"Polydicyclopentadiene (pDCPD), a thermoset with excellent mechanical properties, has enormous potential as a lightweight, tough, and stable matrix material owing to its highly cross-linked macromolecular network. This work describes generating pDCPD-based foams and hierarchically porous carbons derived therefrom by combining ring-opening metathesis polymerization (ROMP) of DCPD, high internal phase emulsions (HIPEs) as structural templates, and subsequent carbonization. The structure and function of the carbon foams were characterized and discussed in detail using scanning electron, transmission electron, or atomic force microscopy (SEM, TEM, AFM), electron energy-loss spectroscopy (TEM-EELS), N2 sorption, and analyses of electrical conductivity as well as mechanical properties. The resulting materials exhibited uniform, shape-retaining shrinkage of only ∼1/3 after carbonization. No structural failure was observed even when the pDCPD precursor foams were heated to 1400 °C. Instead, the high porosity, void size, and 3D interconnectivity were fully preserved, and the void diameters could be adjusted between 87 and 2.5 μm. Moreover, foams have a carbon content >97%, an electronic conductivity of up to 2800 S·m–1, a Young’s modulus of up to 2.1 GPa, and a specific surface area of up to 1200 m2·g–1. Surprisingly, the pDCPD foams were carbonized into shapes other than monoliths, such as 10’s of micron thick membranes or foamy coatings adhered to a metal foil or grid substrate. The latter coatings even adhere upon bending. Finally, as a use case, carbonized foams were applied as porous cathodes for Li–O2 batteries where the foams show a favorable combination of porosity, active surface area, and pore size for outstanding capacity.","lang":"eng"}],"user_id":"4359f0d1-fa6c-11eb-b949-802e58b17ae8","file_date_updated":"2023-01-27T09:09:15Z","day":"16","title":"Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications","_id":"12227","keyword":["Electrical and Electronic Engineering","Materials Chemistry","Electrochemistry","Energy Engineering and Power Technology","Chemical Engineering (miscellaneous)"],"date_published":"2022-10-16T00:00:00Z","volume":5,"month":"10","publisher":"American Chemical Society","article_processing_charge":"No","page":"14381-14390","year":"2022","doi":"10.1021/acsaem.2c02787","scopus_import":"1","file":[{"relation":"main_file","date_updated":"2023-01-27T09:09:15Z","date_created":"2023-01-27T09:09:15Z","file_name":"2022_AppliedEnergyMaterials_Kovacic.pdf","access_level":"open_access","checksum":"572d15c250ab83d44f4e2c3aeb5f7388","success":1,"creator":"dernst","content_type":"application/pdf","file_size":13105589,"file_id":"12420"}],"ddc":["540"],"publication_identifier":{"issn":["2574-0962"]},"oa_version":"Published Version","oa":1,"department":[{"_id":"StFr"}],"issue":"11","date_created":"2023-01-16T09:48:53Z","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"article_type":"original","publication_status":"published","isi":1,"quality_controlled":"1","citation":{"chicago":"Kovačič, Sebastijan, Bettina Schafzahl, Nadejda B. Matsko, Katharina Gruber, Martin Schmuck, Stefan Koller, Stefan Alexander Freunberger, and Christian Slugovc. “Carbon Foams via Ring-Opening Metathesis Polymerization of Emulsion Templates: A Facile Method to Make Carbon Current Collectors for Battery Applications.” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2022. <a href=\"https://doi.org/10.1021/acsaem.2c02787\">https://doi.org/10.1021/acsaem.2c02787</a>.","ieee":"S. Kovačič <i>et al.</i>, “Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications,” <i>ACS Applied Energy Materials</i>, vol. 5, no. 11. American Chemical Society, pp. 14381–14390, 2022.","ista":"Kovačič S, Schafzahl B, Matsko NB, Gruber K, Schmuck M, Koller S, Freunberger SA, Slugovc C. 2022. Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications. ACS Applied Energy Materials. 5(11), 14381–14390.","mla":"Kovačič, Sebastijan, et al. “Carbon Foams via Ring-Opening Metathesis Polymerization of Emulsion Templates: A Facile Method to Make Carbon Current Collectors for Battery Applications.” <i>ACS Applied Energy Materials</i>, vol. 5, no. 11, American Chemical Society, 2022, pp. 14381–90, doi:<a href=\"https://doi.org/10.1021/acsaem.2c02787\">10.1021/acsaem.2c02787</a>.","short":"S. Kovačič, B. Schafzahl, N.B. Matsko, K. Gruber, M. Schmuck, S. Koller, S.A. Freunberger, C. Slugovc, ACS Applied Energy Materials 5 (2022) 14381–14390.","apa":"Kovačič, S., Schafzahl, B., Matsko, N. B., Gruber, K., Schmuck, M., Koller, S., … Slugovc, C. (2022). Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsaem.2c02787\">https://doi.org/10.1021/acsaem.2c02787</a>","ama":"Kovačič S, Schafzahl B, Matsko NB, et al. Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications. <i>ACS Applied Energy Materials</i>. 2022;5(11):14381-14390. doi:<a href=\"https://doi.org/10.1021/acsaem.2c02787\">10.1021/acsaem.2c02787</a>"},"corr_author":"1","publication":"ACS Applied Energy Materials"},{"oa_version":"Preprint","department":[{"_id":"StFr"}],"oa":1,"publication_identifier":{"issn":["2520-1158"]},"scopus_import":"1","doi":"10.1038/s41929-022-00752-z","year":"2022","page":"193-201","article_processing_charge":"No","publication":"Nature Catalysis","quality_controlled":"1","citation":{"mla":"Cao, Deqing, et al. “Threshold Potentials for Fast Kinetics during Mediated Redox Catalysis of Insulators in Li–O2 and Li–S Batteries.” <i>Nature Catalysis</i>, vol. 5, Springer Nature, 2022, pp. 193–201, doi:<a href=\"https://doi.org/10.1038/s41929-022-00752-z\">10.1038/s41929-022-00752-z</a>.","apa":"Cao, D., Shen, X., Wang, A., Yu, F., Wu, Y., Shi, S., … Chen, Y. (2022). Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries. <i>Nature Catalysis</i>. Springer Nature. <a href=\"https://doi.org/10.1038/s41929-022-00752-z\">https://doi.org/10.1038/s41929-022-00752-z</a>","short":"D. Cao, X. Shen, A. Wang, F. Yu, Y. Wu, S. Shi, S.A. Freunberger, Y. Chen, Nature Catalysis 5 (2022) 193–201.","ama":"Cao D, Shen X, Wang A, et al. Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries. <i>Nature Catalysis</i>. 2022;5:193-201. doi:<a href=\"https://doi.org/10.1038/s41929-022-00752-z\">10.1038/s41929-022-00752-z</a>","chicago":"Cao, Deqing, Xiaoxiao Shen, Aiping Wang, Fengjiao Yu, Yuping Wu, Siqi Shi, Stefan Alexander Freunberger, and Yuhui Chen. “Threshold Potentials for Fast Kinetics during Mediated Redox Catalysis of Insulators in Li–O2 and Li–S Batteries.” <i>Nature Catalysis</i>. Springer Nature, 2022. <a href=\"https://doi.org/10.1038/s41929-022-00752-z\">https://doi.org/10.1038/s41929-022-00752-z</a>.","ieee":"D. Cao <i>et al.</i>, “Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries,” <i>Nature Catalysis</i>, vol. 5. Springer Nature, pp. 193–201, 2022.","ista":"Cao D, Shen X, Wang A, Yu F, Wu Y, Shi S, Freunberger SA, Chen Y. 2022. Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries. Nature Catalysis. 5, 193–201."},"corr_author":"1","isi":1,"publication_status":"published","article_type":"original","date_created":"2022-03-04T07:50:10Z","related_material":{"record":[{"status":"public","id":"9978","relation":"earlier_version"}]},"day":"03","user_id":"4359f0d1-fa6c-11eb-b949-802e58b17ae8","abstract":[{"lang":"eng","text":"Redox mediators could catalyse otherwise slow and energy-inefficient cycling of Li–S and Li–O2 batteries by shuttling electrons or holes between the electrode and the solid insulating storage materials. For mediators to work efficiently they need to oxidize the solid with fast kinetics but with the lowest possible overpotential. However, the dependence of kinetics and overpotential is unclear, which hinders informed improvement. Here, we find that when the redox potentials of mediators are tuned via, for example, Li+ concentration in the electrolyte, they exhibit distinct threshold potentials, where the kinetics accelerate several-fold within a range as small as 10 mV. This phenomenon is independent of types of mediator and electrolyte. The acceleration originates from the overpotentials required to activate fast Li+/e− extraction and the following chemical step at specific abundant surface facets. Efficient redox catalysis at insulating solids therefore requires careful consideration of the surface conditions of the storage materials and electrolyte-dependent redox potentials, which may be tuned by salt concentrations or solvents."}],"intvolume":"         5","acknowledgement":"This work was financially supported by the National Natural Science Foundation of China (grant nos. 51773092, 21975124, 11874254, 51802187 and U2030206). It was further supported by Fujian science & technology innovation laboratory for energy devices of China (21C-LAB), Key Research Project of Zhejiang Laboratory (grant no. 2021PE0AC02) and the Cultivation Program for the Excellent Doctoral Dissertation of Nanjing Tech University. S.A.F. is indebted to IST Austria for support.","language":[{"iso":"eng"}],"type":"journal_article","external_id":{"isi":["000763879400001"]},"status":"public","author":[{"full_name":"Cao, Deqing","first_name":"Deqing","last_name":"Cao"},{"first_name":"Xiaoxiao","full_name":"Shen, Xiaoxiao","last_name":"Shen"},{"last_name":"Wang","first_name":"Aiping","full_name":"Wang, Aiping"},{"last_name":"Yu","full_name":"Yu, Fengjiao","first_name":"Fengjiao"},{"last_name":"Wu","full_name":"Wu, Yuping","first_name":"Yuping"},{"last_name":"Shi","first_name":"Siqi","full_name":"Shi, Siqi"},{"first_name":"Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","last_name":"Freunberger","orcid":"0000-0003-2902-5319"},{"first_name":"Yuhui","full_name":"Chen, Yuhui","last_name":"Chen"}],"date_updated":"2024-10-09T21:01:46Z","main_file_link":[{"url":"https://doi.org/10.21203/rs.3.rs-750965/v1","open_access":"1"}],"publisher":"Springer Nature","month":"03","volume":5,"date_published":"2022-03-03T00:00:00Z","_id":"10813","keyword":["Process Chemistry and Technology","Biochemistry","Bioengineering","Catalysis"],"title":"Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries"},{"file":[{"creator":"dernst","success":1,"file_size":3827583,"file_id":"12319","content_type":"application/pdf","checksum":"cf0bed3a2535c11d27244cd029dbc1d0","file_name":"2022_ACSEnergyLetters_Prehal.pdf","date_created":"2023-01-20T08:43:51Z","access_level":"open_access","date_updated":"2023-01-20T08:43:51Z","relation":"main_file"}],"ddc":["540"],"scopus_import":"1","oa":1,"department":[{"_id":"StFr"},{"_id":"EM-Fac"}],"oa_version":"Published Version","publication_identifier":{"eissn":["2380-8195"]},"page":"3112-3119","year":"2022","article_processing_charge":"Yes (via OA deal)","doi":"10.1021/acsenergylett.2c01711","isi":1,"tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"article_type":"original","publication_status":"published","publication":"ACS Energy Letters","citation":{"mla":"Prehal, Christian, et al. “Exclusive Solution Discharge in Li-O₂ Batteries?” <i>ACS Energy Letters</i>, vol. 7, no. 9, American Chemical Society, 2022, pp. 3112–19, doi:<a href=\"https://doi.org/10.1021/acsenergylett.2c01711\">10.1021/acsenergylett.2c01711</a>.","short":"C. Prehal, S. Mondal, L. Lovicar, S.A. Freunberger, ACS Energy Letters 7 (2022) 3112–3119.","apa":"Prehal, C., Mondal, S., Lovicar, L., &#38; Freunberger, S. A. (2022). Exclusive solution discharge in Li-O₂ batteries? <i>ACS Energy Letters</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsenergylett.2c01711\">https://doi.org/10.1021/acsenergylett.2c01711</a>","ama":"Prehal C, Mondal S, Lovicar L, Freunberger SA. Exclusive solution discharge in Li-O₂ batteries? <i>ACS Energy Letters</i>. 2022;7(9):3112-3119. doi:<a href=\"https://doi.org/10.1021/acsenergylett.2c01711\">10.1021/acsenergylett.2c01711</a>","chicago":"Prehal, Christian, Soumyadip Mondal, Ludek Lovicar, and Stefan Alexander Freunberger. “Exclusive Solution Discharge in Li-O₂ Batteries?” <i>ACS Energy Letters</i>. American Chemical Society, 2022. <a href=\"https://doi.org/10.1021/acsenergylett.2c01711\">https://doi.org/10.1021/acsenergylett.2c01711</a>.","ista":"Prehal C, Mondal S, Lovicar L, Freunberger SA. 2022. Exclusive solution discharge in Li-O₂ batteries? ACS Energy Letters. 7(9), 3112–3119.","ieee":"C. Prehal, S. Mondal, L. Lovicar, and S. A. Freunberger, “Exclusive solution discharge in Li-O₂ batteries?,” <i>ACS Energy Letters</i>, vol. 7, no. 9. American Chemical Society, pp. 3112–3119, 2022."},"corr_author":"1","quality_controlled":"1","related_material":{"record":[{"relation":"dissertation_contains","id":"20607","status":"public"}]},"issue":"9","date_created":"2022-09-08T09:51:09Z","abstract":[{"text":"Capacity, rate performance, and cycle life of aprotic Li–O2 batteries critically depend on reversible electrodeposition of Li2O2. Current understanding states surface-adsorbed versus solvated LiO2 controls Li2O2 growth as surface film or as large particles. Herein, we show that Li2O2 forms across a wide range of electrolytes, carbons, and current densities as particles via solution-mediated LiO2 disproportionation, bringing into question the prevalence of any surface growth under practical conditions. We describe a unified O2 reduction mechanism, which can explain all found capacity relations and Li2O2 morphologies with exclusive solution discharge. Determining particle morphology and achievable capacities are species mobilities, true areal rate, and the degree of LiO2 association in solution. Capacity is conclusively limited by mass transport through the tortuous Li2O2 rather than electron transport through a passivating Li2O2 film. Provided that species mobilities and surface growth are high, high capacities are also achieved with weakly solvating electrolytes, which were previously considered prototypical for low capacity via surface growth.","lang":"eng"}],"acknowledgement":"S.A.F. and C.P. are indebted to the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant Agreement No. 636069). This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie Grant NanoEvolution, Grant Agreement No. 894042. S.A.F. and S.M. are indebted to Institute of Science and Technology Austria (ISTA) for support. This research was supported by the Scientific Service Units of ISTA through resources provided by the Electron Microscopy Facility and the Miba Machine Shop. C.P. thanks Vanessa Wood (ETH Zürich) for her continuing support.","intvolume":"         7","day":"29","file_date_updated":"2023-01-20T08:43:51Z","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","pmid":1,"date_updated":"2026-04-07T12:27:23Z","has_accepted_license":"1","language":[{"iso":"eng"}],"author":[{"full_name":"Prehal, Christian","first_name":"Christian","last_name":"Prehal"},{"last_name":"Mondal","first_name":"Soumyadip","id":"d25d21ef-dc8d-11ea-abe3-ec4576307f48","full_name":"Mondal, Soumyadip"},{"orcid":"0000-0001-6206-4200","last_name":"Lovicar","full_name":"Lovicar, Ludek","id":"36DB3A20-F248-11E8-B48F-1D18A9856A87","first_name":"Ludek"},{"last_name":"Freunberger","orcid":"0000-0003-2902-5319","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","first_name":"Stefan Alexander"}],"status":"public","external_id":{"isi":["000860787000001"],"pmid":["36120663"]},"type":"journal_article","publisher":"American Chemical Society","month":"08","_id":"12065","title":"Exclusive solution discharge in Li-O₂ batteries?","volume":7,"date_published":"2022-08-29T00:00:00Z","acknowledged_ssus":[{"_id":"EM-Fac"},{"_id":"M-Shop"}]},{"user_id":"4359f0d1-fa6c-11eb-b949-802e58b17ae8","day":"11","intvolume":"         9","acknowledgement":"M.O.T. acknowledges DST/TMD/HFC/2 K18/58, DST-SERB, MHRD fast track, and DST Nanomission forfinancialassistance. Z.M.B. acknowledges CSIR-SRF fellowship fromMHRD, India. S.A.F. acknowledges support from IST Austria.","abstract":[{"lang":"eng","text":"“Hydrogen economy” could enable a carbon-neutral sustainable energy chain. However, issues with safety, storage, and transport of molecular hydrogen impede its realization. Alcohols as liquid H2 carriers could be enablers, but state-of-the-art reforming is difficult, requiring high temperatures >200 °C and pressures >25 bar, and the resulting H2 is carbonized beyond tolerance levels for direct use in fuel cells. Here, we demonstrate ambient temperature and pressure alcohol reforming in a fuel cell (ARFC) with a simultaneous electrical power output. The alcohol is oxidized at the alkaline anode, where the resulting CO2 is sequestrated as carbonate. Carbon-free H2 is liberated at the acidic cathode. The neutralization energy between the alkaline anode and the acidic cathode drives the process, particularly the unusually high entropy gain (1.27-fold ΔH). The significantly positive temperature coefficient of the resulting electromotive force allows us to harvest a large fraction of the output energy from the surrounding, achieving a thermodynamic efficiency as high as 2.27. MoS2 as the cathode catalyst allows alcohol reforming even under open-air conditions, a challenge that state-of-the-art alcohol reforming failed to overcome. We further show reforming of a wide range of alcohols. The ARFC offers an unprecedented route toward hydrogen economy as CO2 is simultaneously captured and pure H2 produced at mild conditions."}],"external_id":{"isi":["000625460400010"]},"type":"journal_article","status":"public","author":[{"full_name":"Manzoor Bhat, Zahid Manzoor","first_name":"Zahid Manzoor","last_name":"Manzoor Bhat"},{"last_name":"Thimmappa","full_name":"Thimmappa, Ravikumar","first_name":"Ravikumar"},{"full_name":"Dargily, Neethu Christudas ","first_name":"Neethu Christudas ","last_name":"Dargily"},{"first_name":"Abdul ","full_name":"Raafik, Abdul ","last_name":"Raafik"},{"last_name":"Kottaichamy","full_name":"Kottaichamy, Alagar Raja ","first_name":"Alagar Raja "},{"first_name":"Mruthyunjayachari Chattanahalli ","full_name":"Devendrachari, Mruthyunjayachari Chattanahalli ","last_name":"Devendrachari"},{"full_name":"Itagi, Mahesh","first_name":"Mahesh","last_name":"Itagi"},{"last_name":" Makri Nimbegondi Kotresh","first_name":"Harish","full_name":" Makri Nimbegondi Kotresh, Harish"},{"orcid":"0000-0003-2902-5319","last_name":"Freunberger","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","first_name":"Stefan Alexander"},{"first_name":"Musthafa ","full_name":"Ottakam Thotiyl, Musthafa ","last_name":"Ottakam Thotiyl"}],"language":[{"iso":"eng"}],"date_updated":"2024-10-09T21:00:24Z","month":"02","publisher":"American Chemical Society","date_published":"2021-02-11T00:00:00Z","volume":9,"_id":"9113","title":"Ambient condition alcohol reforming to hydrogen with electricity output","publication_identifier":{"eissn":["2168-0485"]},"oa_version":"None","department":[{"_id":"StFr"}],"scopus_import":"1","doi":"10.1021/acssuschemeng.0c07547","article_processing_charge":"No","page":"3104-3111","year":"2021","quality_controlled":"1","corr_author":"1","citation":{"ista":"Manzoor Bhat ZM, Thimmappa R, Dargily NC, Raafik A, Kottaichamy AR, Devendrachari MC, Itagi M,  Makri Nimbegondi Kotresh H, Freunberger SA, Ottakam Thotiyl M. 2021. Ambient condition alcohol reforming to hydrogen with electricity output. ACS Sustainable Chemistry and Engineering. 9(8), 3104–3111.","ieee":"Z. M. Manzoor Bhat <i>et al.</i>, “Ambient condition alcohol reforming to hydrogen with electricity output,” <i>ACS Sustainable Chemistry and Engineering</i>, vol. 9, no. 8. American Chemical Society, pp. 3104–3111, 2021.","chicago":"Manzoor Bhat, Zahid Manzoor, Ravikumar Thimmappa, Neethu Christudas  Dargily, Abdul  Raafik, Alagar Raja  Kottaichamy, Mruthyunjayachari Chattanahalli  Devendrachari, Mahesh Itagi, Harish  Makri Nimbegondi Kotresh, Stefan Alexander Freunberger, and Musthafa  Ottakam Thotiyl. “Ambient Condition Alcohol Reforming to Hydrogen with Electricity Output.” <i>ACS Sustainable Chemistry and Engineering</i>. American Chemical Society, 2021. <a href=\"https://doi.org/10.1021/acssuschemeng.0c07547\">https://doi.org/10.1021/acssuschemeng.0c07547</a>.","ama":"Manzoor Bhat ZM, Thimmappa R, Dargily NC, et al. Ambient condition alcohol reforming to hydrogen with electricity output. <i>ACS Sustainable Chemistry and Engineering</i>. 2021;9(8):3104-3111. doi:<a href=\"https://doi.org/10.1021/acssuschemeng.0c07547\">10.1021/acssuschemeng.0c07547</a>","apa":"Manzoor Bhat, Z. M., Thimmappa, R., Dargily, N. C., Raafik, A., Kottaichamy, A. R., Devendrachari, M. C., … Ottakam Thotiyl, M. (2021). Ambient condition alcohol reforming to hydrogen with electricity output. <i>ACS Sustainable Chemistry and Engineering</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acssuschemeng.0c07547\">https://doi.org/10.1021/acssuschemeng.0c07547</a>","short":"Z.M. Manzoor Bhat, R. Thimmappa, N.C. Dargily, A. Raafik, A.R. Kottaichamy, M.C. Devendrachari, M. Itagi, H.  Makri Nimbegondi Kotresh, S.A. Freunberger, M. Ottakam Thotiyl, ACS Sustainable Chemistry and Engineering 9 (2021) 3104–3111.","mla":"Manzoor Bhat, Zahid Manzoor, et al. “Ambient Condition Alcohol Reforming to Hydrogen with Electricity Output.” <i>ACS Sustainable Chemistry and Engineering</i>, vol. 9, no. 8, American Chemical Society, 2021, pp. 3104–11, doi:<a href=\"https://doi.org/10.1021/acssuschemeng.0c07547\">10.1021/acssuschemeng.0c07547</a>."},"publication":"ACS Sustainable Chemistry and Engineering","publication_status":"published","article_type":"original","isi":1,"date_created":"2021-02-12T09:20:18Z","issue":"8"},{"main_file_link":[{"url":"https://doi.org/10.26434/chemrxiv.11447775","open_access":"1"}],"publisher":"National Academy of Sciences","month":"04","volume":118,"date_published":"2021-04-06T00:00:00Z","acknowledged_ssus":[{"_id":"EM-Fac"}],"title":"In situ small-angle X-ray scattering reveals solution phase discharge of Li–O2 batteries with weakly solvating electrolytes","_id":"9301","keyword":["small-angle X-ray scattering","oxygen reduction","disproportionation","Li-air battery"],"day":"06","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","abstract":[{"lang":"eng","text":"Electrodepositing insulating lithium peroxide (Li2O2) is the key process during discharge of aprotic Li–O2 batteries and determines rate, capacity, and reversibility. Current understanding states that the partition between surface adsorbed and dissolved lithium superoxide governs whether Li2O2 grows as a conformal surface film or larger particles, leading to low or high capacities, respectively. However, better understanding governing factors for Li2O2 packing density and capacity requires structural sensitive in situ metrologies. Here, we establish in situ small- and wide-angle X-ray scattering (SAXS/WAXS) as a suitable method to record the Li2O2 phase evolution with atomic to submicrometer resolution during cycling a custom-built in situ Li–O2 cell. Combined with sophisticated data analysis, SAXS allows retrieving rich quantitative structural information from complex multiphase systems. Surprisingly, we find that features are absent that would point at a Li2O2 surface film formed via two consecutive electron transfers, even in poorly solvating electrolytes thought to be prototypical for surface growth. All scattering data can be modeled by stacks of thin Li2O2 platelets potentially forming large toroidal particles. Li2O2 solution growth is further justified by rotating ring-disk electrode measurements and electron microscopy. Higher discharge overpotentials lead to smaller Li2O2 particles, but there is no transition to an electronically passivating, conformal Li2O2 coating. Hence, mass transport of reactive species rather than electronic transport through a Li2O2 film limits the discharge capacity. Provided that species mobilities and carbon surface areas are high, this allows for high discharge capacities even in weakly solvating electrolytes. The currently accepted Li–O2 reaction mechanism ought to be reconsidered."}],"intvolume":"       118","acknowledgement":"S.A.F. and C.P. are indebted to the European Research Council under the European Union's Horizon 2020 research and innovation program (Grant Agreement No. 636069), the Austrian Federal Ministry of Science, Research and Economy, and the Austrian Research Promotion Agency (Grant No. 845364). We acknowledge A. Zankel and H. Schroettner for support with SEM measurements. C.P. thanks N. Kostoglou, C. Koczwara, M. Hartmann, and M. Burian for discussions on gas sorption analysis, C++ programming, Monte Carlo modeling, and in situ SAXS experiments, respectively. We thank S. Stadlbauer for help with Karl Fischer titration, R. Riccò for gas sorption measurements, and acknowledge Graz University of Technology for support through the Lead Project LP-03. Likewise, the use of SOMAPP Lab, a core facility supported by the Austrian Federal Ministry of Education, Science and Research, the Graz University of Technology, the University of Graz, and Anton Paar GmbH is acknowledged. S.A.F. is indebted to Institute of Science and Technology Austria (IST Austria) for support. This research was supported by the Scientific Service Units of IST Austria through resources provided by the Electron Microscopy Facility.","language":[{"iso":"eng"}],"status":"public","type":"journal_article","external_id":{"pmid":["33785597"],"isi":["000637398300050"]},"author":[{"first_name":"Christian","full_name":"Prehal, Christian","last_name":"Prehal"},{"full_name":"Samojlov, Aleksej","first_name":"Aleksej","last_name":"Samojlov"},{"last_name":"Nachtnebel","first_name":"Manfred","full_name":"Nachtnebel, Manfred"},{"orcid":"0000-0001-6206-4200","last_name":"Lovicar","full_name":"Lovicar, Ludek","id":"36DB3A20-F248-11E8-B48F-1D18A9856A87","first_name":"Ludek"},{"last_name":"Kriechbaum","full_name":"Kriechbaum, Manfred","first_name":"Manfred"},{"full_name":"Amenitsch, Heinz","first_name":"Heinz","last_name":"Amenitsch"},{"orcid":"0000-0003-2902-5319","last_name":"Freunberger","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","first_name":"Stefan Alexander"}],"date_updated":"2025-06-12T06:56:39Z","pmid":1,"publication":"Proceedings of the National Academy of Sciences of the United States of America","quality_controlled":"1","citation":{"ieee":"C. Prehal <i>et al.</i>, “In situ small-angle X-ray scattering reveals solution phase discharge of Li–O2 batteries with weakly solvating electrolytes,” <i>Proceedings of the National Academy of Sciences of the United States of America</i>, vol. 118, no. 14. National Academy of Sciences, 2021.","ista":"Prehal C, Samojlov A, Nachtnebel M, Lovicar L, Kriechbaum M, Amenitsch H, Freunberger SA. 2021. In situ small-angle X-ray scattering reveals solution phase discharge of Li–O2 batteries with weakly solvating electrolytes. Proceedings of the National Academy of Sciences of the United States of America. 118(14), e2021893118.","chicago":"Prehal, Christian, Aleksej Samojlov, Manfred Nachtnebel, Ludek Lovicar, Manfred Kriechbaum, Heinz Amenitsch, and Stefan Alexander Freunberger. “In Situ Small-Angle X-Ray Scattering Reveals Solution Phase Discharge of Li–O2 Batteries with Weakly Solvating Electrolytes.” <i>Proceedings of the National Academy of Sciences of the United States of America</i>. National Academy of Sciences, 2021. <a href=\"https://doi.org/10.1073/pnas.2021893118\">https://doi.org/10.1073/pnas.2021893118</a>.","ama":"Prehal C, Samojlov A, Nachtnebel M, et al. In situ small-angle X-ray scattering reveals solution phase discharge of Li–O2 batteries with weakly solvating electrolytes. <i>Proceedings of the National Academy of Sciences of the United States of America</i>. 2021;118(14). doi:<a href=\"https://doi.org/10.1073/pnas.2021893118\">10.1073/pnas.2021893118</a>","short":"C. Prehal, A. Samojlov, M. Nachtnebel, L. Lovicar, M. Kriechbaum, H. Amenitsch, S.A. Freunberger, Proceedings of the National Academy of Sciences of the United States of America 118 (2021).","apa":"Prehal, C., Samojlov, A., Nachtnebel, M., Lovicar, L., Kriechbaum, M., Amenitsch, H., &#38; Freunberger, S. A. (2021). In situ small-angle X-ray scattering reveals solution phase discharge of Li–O2 batteries with weakly solvating electrolytes. <i>Proceedings of the National Academy of Sciences of the United States of America</i>. National Academy of Sciences. <a href=\"https://doi.org/10.1073/pnas.2021893118\">https://doi.org/10.1073/pnas.2021893118</a>","mla":"Prehal, Christian, et al. “In Situ Small-Angle X-Ray Scattering Reveals Solution Phase Discharge of Li–O2 Batteries with Weakly Solvating Electrolytes.” <i>Proceedings of the National Academy of Sciences of the United States of America</i>, vol. 118, no. 14, e2021893118, National Academy of Sciences, 2021, doi:<a href=\"https://doi.org/10.1073/pnas.2021893118\">10.1073/pnas.2021893118</a>."},"isi":1,"article_type":"original","publication_status":"published","article_number":"e2021893118","date_created":"2021-03-31T07:00:01Z","issue":"14","oa_version":"Preprint","department":[{"_id":"StFr"},{"_id":"EM-Fac"}],"oa":1,"publication_identifier":{"eissn":["1091-6490"],"issn":["0027-8424"]},"scopus_import":"1","doi":"10.1073/pnas.2021893118","year":"2021","article_processing_charge":"No"},{"isi":1,"article_number":"050550","publication_status":"published","publication":"Journal of The Electrochemical Society","citation":{"ama":"Maffre M, Bouchal R, Freunberger SA, et al. Investigation of electrochemical and chemical processes occurring at positive potentials in “Water-in-Salt” electrolytes. <i>Journal of The Electrochemical Society</i>. 2021;168(5). doi:<a href=\"https://doi.org/10.1149/1945-7111/ac0300\">10.1149/1945-7111/ac0300</a>","apa":"Maffre, M., Bouchal, R., Freunberger, S. A., Lindahl, N., Johansson, P., Favier, F., … Bélanger, D. (2021). Investigation of electrochemical and chemical processes occurring at positive potentials in “Water-in-Salt” electrolytes. <i>Journal of The Electrochemical Society</i>. IOP Publishing. <a href=\"https://doi.org/10.1149/1945-7111/ac0300\">https://doi.org/10.1149/1945-7111/ac0300</a>","short":"M. Maffre, R. Bouchal, S.A. Freunberger, N. Lindahl, P. Johansson, F. Favier, O. Fontaine, D. Bélanger, Journal of The Electrochemical Society 168 (2021).","mla":"Maffre, Marion, et al. “Investigation of Electrochemical and Chemical Processes Occurring at Positive Potentials in ‘Water-in-Salt’ Electrolytes.” <i>Journal of The Electrochemical Society</i>, vol. 168, no. 5, 050550, IOP Publishing, 2021, doi:<a href=\"https://doi.org/10.1149/1945-7111/ac0300\">10.1149/1945-7111/ac0300</a>.","ista":"Maffre M, Bouchal R, Freunberger SA, Lindahl N, Johansson P, Favier F, Fontaine O, Bélanger D. 2021. Investigation of electrochemical and chemical processes occurring at positive potentials in “Water-in-Salt” electrolytes. Journal of The Electrochemical Society. 168(5), 050550.","ieee":"M. Maffre <i>et al.</i>, “Investigation of electrochemical and chemical processes occurring at positive potentials in ‘Water-in-Salt’ electrolytes,” <i>Journal of The Electrochemical Society</i>, vol. 168, no. 5. IOP Publishing, 2021.","chicago":"Maffre, Marion, Roza Bouchal, Stefan Alexander Freunberger, Niklas Lindahl, Patrik Johansson, Frédéric Favier, Olivier Fontaine, and Daniel Bélanger. “Investigation of Electrochemical and Chemical Processes Occurring at Positive Potentials in ‘Water-in-Salt’ Electrolytes.” <i>Journal of The Electrochemical Society</i>. IOP Publishing, 2021. <a href=\"https://doi.org/10.1149/1945-7111/ac0300\">https://doi.org/10.1149/1945-7111/ac0300</a>."},"quality_controlled":"1","issue":"5","date_created":"2021-06-03T09:58:38Z","scopus_import":"1","department":[{"_id":"StFr"}],"oa_version":"None","publication_identifier":{"eissn":["1945-7111"],"issn":["0013-4651"]},"year":"2021","article_processing_charge":"No","doi":"10.1149/1945-7111/ac0300","publisher":"IOP Publishing","month":"05","_id":"9447","keyword":["Renewable Energy","Sustainability and the Environment","Electrochemistry","Materials Chemistry","Electronic","Optical and Magnetic Materials","Surfaces","Coatings and Films","Condensed Matter Physics"],"title":"Investigation of electrochemical and chemical processes occurring at positive potentials in “Water-in-Salt” electrolytes","volume":168,"date_published":"2021-05-01T00:00:00Z","abstract":[{"lang":"eng","text":"Lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) based water-in-salt electrolytes (WiSEs) has recently emerged as a new promising class of electrolytes, primarily owing to their wide electrochemical stability windows (~3–4 V), that by far exceed the thermodynamic stability window of water (1.23 V). Upon increasing the salt concentration towards superconcentration the onset of the oxygen evolution reaction (OER) shifts more significantly than the hydrogen evolution reaction (HER) does. The OER shift has been explained by the accumulation of hydrophobic anions blocking water access to the electrode surface, hence by double layer theory. Here we demonstrate that the processes during oxidation are much more complex, involving OER, carbon and salt decomposition by OER intermediates, and salt precipitation upon local oversaturation. The positive shift in the onset potential of oxidation currents was elucidated by combining several advanced analysis techniques: rotating ring-disk electrode voltammetry, online electrochemical mass spectrometry, and X-ray photoelectron spectroscopy, using both dilute and superconcentrated electrolytes. The results demonstrate the importance of reactive OER intermediates and surface films for electrolyte and electrode stability and motivate further studies of the nature of the electrode."}],"intvolume":"       168","day":"01","user_id":"c635000d-4b10-11ee-a964-aac5a93f6ac1","date_updated":"2024-10-21T06:02:10Z","language":[{"iso":"eng"}],"author":[{"last_name":"Maffre","first_name":"Marion","full_name":"Maffre, Marion"},{"full_name":"Bouchal, Roza","first_name":"Roza","last_name":"Bouchal"},{"first_name":"Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","last_name":"Freunberger","orcid":"0000-0003-2902-5319"},{"last_name":"Lindahl","first_name":"Niklas","full_name":"Lindahl, Niklas"},{"full_name":"Johansson, Patrik","first_name":"Patrik","last_name":"Johansson"},{"full_name":"Favier, Frédéric","first_name":"Frédéric","last_name":"Favier"},{"last_name":"Fontaine","first_name":"Olivier","full_name":"Fontaine, Olivier"},{"last_name":"Bélanger","full_name":"Bélanger, Daniel","first_name":"Daniel"}],"status":"public","external_id":{"isi":["000657724200001"]},"type":"journal_article"},{"date_created":"2021-08-31T12:54:16Z","related_material":{"record":[{"relation":"later_version","status":"public","id":"10813"}]},"citation":{"ama":"Cao D, Shen X, Wang A, et al. Sharp kinetic acceleration potentials during mediated redox catalysis of insulators. <i>Research Square</i>. doi:<a href=\"https://doi.org/10.21203/rs.3.rs-750965/v1\">10.21203/rs.3.rs-750965/v1</a>","apa":"Cao, D., Shen, X., Wang, A., Yu, F., Wu, Y., Shi, S., … Chen, Y. (n.d.). Sharp kinetic acceleration potentials during mediated redox catalysis of insulators. <i>Research Square</i>. Research Square. <a href=\"https://doi.org/10.21203/rs.3.rs-750965/v1\">https://doi.org/10.21203/rs.3.rs-750965/v1</a>","short":"D. Cao, X. Shen, A. Wang, F. Yu, Y. Wu, S. Shi, S.A. Freunberger, Y. Chen, Research Square (n.d.).","mla":"Cao, Deqing, et al. “Sharp Kinetic Acceleration Potentials during Mediated Redox Catalysis of Insulators.” <i>Research Square</i>, Research Square, doi:<a href=\"https://doi.org/10.21203/rs.3.rs-750965/v1\">10.21203/rs.3.rs-750965/v1</a>.","ista":"Cao D, Shen X, Wang A, Yu F, Wu Y, Shi S, Freunberger SA, Chen Y. Sharp kinetic acceleration potentials during mediated redox catalysis of insulators. Research Square, <a href=\"https://doi.org/10.21203/rs.3.rs-750965/v1\">10.21203/rs.3.rs-750965/v1</a>.","ieee":"D. Cao <i>et al.</i>, “Sharp kinetic acceleration potentials during mediated redox catalysis of insulators,” <i>Research Square</i>. Research Square.","chicago":"Cao, Deqing, Xiaoxiao Shen, Aiping Wang, Fengjiao Yu, Yuping Wu, Siqi Shi, Stefan Alexander Freunberger, and Yuhui Chen. “Sharp Kinetic Acceleration Potentials during Mediated Redox Catalysis of Insulators.” <i>Research Square</i>. Research Square, n.d. <a href=\"https://doi.org/10.21203/rs.3.rs-750965/v1\">https://doi.org/10.21203/rs.3.rs-750965/v1</a>."},"corr_author":"1","publication":"Research Square","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"publication_status":"submitted","doi":"10.21203/rs.3.rs-750965/v1","article_processing_charge":"No","page":"21","year":"2021","publication_identifier":{"eissn":["2693-5015"]},"department":[{"_id":"StFr"}],"oa":1,"oa_version":"Preprint","file":[{"creator":"cchlebak","success":1,"file_id":"9979","file_size":1019662,"content_type":"application/pdf","checksum":"1878e91c29d5769ed5a827b0b7addf00","file_name":"2021_ResearchSquare_Cao.pdf","date_created":"2021-08-31T14:02:19Z","access_level":"open_access","date_updated":"2021-08-31T14:02:19Z","relation":"main_file"}],"ddc":["541"],"date_published":"2021-08-18T00:00:00Z","_id":"9978","keyword":["Catalysis","Energy engineering","Materials theory and modeling"],"title":"Sharp kinetic acceleration potentials during mediated redox catalysis of insulators","month":"08","publisher":"Research Square","author":[{"full_name":"Cao, Deqing","first_name":"Deqing","last_name":"Cao"},{"last_name":"Shen","first_name":"Xiaoxiao","full_name":"Shen, Xiaoxiao"},{"last_name":"Wang","first_name":"Aiping","full_name":"Wang, Aiping"},{"first_name":"Fengjiao","full_name":"Yu, Fengjiao","last_name":"Yu"},{"last_name":"Wu","full_name":"Wu, Yuping","first_name":"Yuping"},{"full_name":"Shi, Siqi","first_name":"Siqi","last_name":"Shi"},{"orcid":"0000-0003-2902-5319","last_name":"Freunberger","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","first_name":"Stefan Alexander"},{"full_name":"Chen, Yuhui","first_name":"Yuhui","last_name":"Chen"}],"type":"preprint","status":"public","has_accepted_license":"1","language":[{"iso":"eng"}],"date_updated":"2024-10-09T21:01:46Z","file_date_updated":"2021-08-31T14:02:19Z","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","day":"18","acknowledgement":"This work was financially supported by the National Natural Science Foundation of China (51773092, 21975124, 11874254, 51802187, U2030206). S.A.F. is indebted to IST Austria for support. ","abstract":[{"lang":"eng","text":"Redox mediators could catalyse otherwise slow and energy-inefficient cycling of Li-S and Li-O 2 batteries by shuttling electrons/holes between the electrode and the solid insulating storage materials. For mediators to work efficiently they need to oxidize the solid with fast kinetics yet the lowest possible overpotential. Here, we found that when the redox potentials of mediators are tuned via, e.g., Li + concentration in the electrolyte, they exhibit distinct threshold potentials, where the kinetics accelerate several-fold within a range as small as 10 mV. This phenomenon is independent of types of mediators and electrolyte. The acceleration originates from the overpotentials required to activate fast Li + /e – extraction and the following chemical step at specific abundant surface facets. Efficient redox catalysis at insulating solids requires therefore carefully considering the surface conditions of the storage materials and electrolyte-dependent redox potentials, which may be tuned by salt concentrations or solvents."}]},{"page":"21","year":"2021","article_processing_charge":"No","date_updated":"2021-12-03T10:35:42Z","doi":"10.21203/rs.3.rs-818607/v1","language":[{"iso":"eng"}],"author":[{"last_name":"Prehal","first_name":"Christian","full_name":"Prehal, Christian"},{"first_name":"Sara Drvarič","full_name":"Talian, Sara Drvarič","last_name":"Talian"},{"last_name":"Vizintin","first_name":"Alen","full_name":"Vizintin, Alen"},{"first_name":"Heinz","full_name":"Amenitsch, Heinz","last_name":"Amenitsch"},{"last_name":"Dominko","first_name":"Robert","full_name":"Dominko, Robert"},{"last_name":"Freunberger","orcid":"0000-0003-2902-5319","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","first_name":"Stefan Alexander"},{"last_name":"Wood","full_name":"Wood, Vanessa","first_name":"Vanessa"}],"status":"public","type":"preprint","abstract":[{"lang":"eng","text":"Insufficient understanding of the mechanism that reversibly converts sulphur into lithium sulphide (Li2S) via soluble polysulphides (PS) hampers the realization of high performance lithium-sulphur cells. Typically Li2S formation is explained by direct electroreduction of a PS to Li2S; however, this is not consistent with the size of the insulating Li2S deposits. Here, we use in situ small and wide angle X-ray scattering (SAXS/WAXS) to track the growth and dissolution of crystalline and amorphous deposits from atomic to sub-micron scales during charge and discharge. Stochastic modelling based on the SAXS data allows quantification of the chemical phase evolution during discharge and charge. We show that Li2S deposits predominantly via disproportionation of transient, solid Li2S2 to form primary Li2S crystallites and solid Li2S4 particles. We further demonstrate that this process happens in reverse during charge. These findings show that the discharge capacity and rate capability in Li-S battery cathodes are therefore limited by mass transport through the increasingly tortuous network of Li2S / Li2S4 / carbon pores rather than electron transport through a passivating surface film."}],"ddc":["621"],"acknowledgement":"This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant NanoEvolution, grant agreement No 894042. The authors acknowledge TU Graz for support through the Lead Project LP-03. Likewise, the use of SOMAPP Lab, a core facility supported by the Austrian Federal Ministry of Education, Science and Research, the Graz University\r\n6 of Technology, the University of Graz, and Anton Paar GmbH is acknowledged. S.D.T, A.V. and R.D. acknowledge the financial support by the Slovenian Research Agency (ARRS) research core funding P2-0393. Furthermore, A.V. acknowledge the funding from the Slovenian Research Agency, research project Z2-1863. S.A.F. is indebted to IST Austria for support. ","department":[{"_id":"StFr"}],"oa":1,"day":"16","oa_version":"Preprint","user_id":"8b945eb4-e2f2-11eb-945a-df72226e66a9","_id":"9980","keyword":["Li2S","Lithium Sulphur Batteries","SAXS","WAXS"],"title":"Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries","date_published":"2021-08-16T00:00:00Z","date_created":"2021-09-02T08:45:00Z","main_file_link":[{"open_access":"1","url":"https://www.researchsquare.com/article/rs-818607/v1"}],"tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"publication_status":"submitted","month":"08","publication":"Research Square","citation":{"short":"C. Prehal, S.D. Talian, A. Vizintin, H. Amenitsch, R. Dominko, S.A. Freunberger, V. Wood, Research Square (n.d.).","apa":"Prehal, C., Talian, S. D., Vizintin, A., Amenitsch, H., Dominko, R., Freunberger, S. A., &#38; Wood, V. (n.d.). Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries. <i>Research Square</i>. <a href=\"https://doi.org/10.21203/rs.3.rs-818607/v1\">https://doi.org/10.21203/rs.3.rs-818607/v1</a>","ama":"Prehal C, Talian SD, Vizintin A, et al. Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries. <i>Research Square</i>. doi:<a href=\"https://doi.org/10.21203/rs.3.rs-818607/v1\">10.21203/rs.3.rs-818607/v1</a>","mla":"Prehal, Christian, et al. “Mechanism of Li2S Formation and Dissolution in Lithium-Sulphur Batteries.” <i>Research Square</i>, doi:<a href=\"https://doi.org/10.21203/rs.3.rs-818607/v1\">10.21203/rs.3.rs-818607/v1</a>.","chicago":"Prehal, Christian, Sara Drvarič Talian, Alen Vizintin, Heinz Amenitsch, Robert Dominko, Stefan Alexander Freunberger, and Vanessa Wood. “Mechanism of Li2S Formation and Dissolution in Lithium-Sulphur Batteries.” <i>Research Square</i>, n.d. <a href=\"https://doi.org/10.21203/rs.3.rs-818607/v1\">https://doi.org/10.21203/rs.3.rs-818607/v1</a>.","ieee":"C. Prehal <i>et al.</i>, “Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries,” <i>Research Square</i>. .","ista":"Prehal C, Talian SD, Vizintin A, Amenitsch H, Dominko R, Freunberger SA, Wood V. Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries. Research Square, <a href=\"https://doi.org/10.21203/rs.3.rs-818607/v1\">10.21203/rs.3.rs-818607/v1</a>."}},{"doi":"10.1038/s41557-021-00643-z","article_processing_charge":"No","year":"2021","page":"465-471","publication_identifier":{"issn":["1755-4330"],"eissn":["1755-4349"]},"oa":1,"department":[{"_id":"StFr"}],"oa_version":"Submitted Version","scopus_import":"1","file":[{"date_updated":"2021-09-16T22:30:03Z","relation":"main_file","file_name":"2021_NatureChem_Petit_acceptedVersion.pdf","date_created":"2021-03-22T11:46:00Z","access_level":"open_access","checksum":"3ee3f8dd79ed1b7bb0929fce184c8012","creator":"dernst","file_size":1811448,"file_id":"9276","content_type":"application/pdf","embargo":"2021-09-15"}],"ddc":["540"],"date_created":"2021-03-16T11:12:20Z","issue":"5","corr_author":"1","citation":{"mla":"Petit, Yann K., et al. “Mechanism of Mediated Alkali Peroxide Oxidation and Triplet versus Singlet Oxygen Formation.” <i>Nature Chemistry</i>, vol. 13, no. 5, Springer Nature, 2021, pp. 465–71, doi:<a href=\"https://doi.org/10.1038/s41557-021-00643-z\">10.1038/s41557-021-00643-z</a>.","ama":"Petit YK, Mourad E, Prehal C, et al. Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation. <i>Nature Chemistry</i>. 2021;13(5):465-471. doi:<a href=\"https://doi.org/10.1038/s41557-021-00643-z\">10.1038/s41557-021-00643-z</a>","apa":"Petit, Y. K., Mourad, E., Prehal, C., Leypold, C., Windischbacher, A., Mijailovic, D., … Freunberger, S. A. (2021). Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation. <i>Nature Chemistry</i>. Springer Nature. <a href=\"https://doi.org/10.1038/s41557-021-00643-z\">https://doi.org/10.1038/s41557-021-00643-z</a>","short":"Y.K. Petit, E. Mourad, C. Prehal, C. Leypold, A. Windischbacher, D. Mijailovic, C. Slugovc, S.M. Borisov, E. Zojer, S. Brutti, O. Fontaine, S.A. Freunberger, Nature Chemistry 13 (2021) 465–471.","ista":"Petit YK, Mourad E, Prehal C, Leypold C, Windischbacher A, Mijailovic D, Slugovc C, Borisov SM, Zojer E, Brutti S, Fontaine O, Freunberger SA. 2021. Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation. Nature Chemistry. 13(5), 465–471.","ieee":"Y. K. Petit <i>et al.</i>, “Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation,” <i>Nature Chemistry</i>, vol. 13, no. 5. Springer Nature, pp. 465–471, 2021.","chicago":"Petit, Yann K., Eléonore Mourad, Christian Prehal, Christian Leypold, Andreas Windischbacher, Daniel Mijailovic, Christian Slugovc, et al. “Mechanism of Mediated Alkali Peroxide Oxidation and Triplet versus Singlet Oxygen Formation.” <i>Nature Chemistry</i>. Springer Nature, 2021. <a href=\"https://doi.org/10.1038/s41557-021-00643-z\">https://doi.org/10.1038/s41557-021-00643-z</a>."},"quality_controlled":"1","publication":"Nature Chemistry","article_type":"original","publication_status":"published","isi":1,"author":[{"last_name":"Petit","full_name":"Petit, Yann K.","first_name":"Yann K."},{"last_name":"Mourad","full_name":"Mourad, Eléonore","first_name":"Eléonore"},{"first_name":"Christian","full_name":"Prehal, Christian","last_name":"Prehal"},{"last_name":"Leypold","full_name":"Leypold, Christian","first_name":"Christian"},{"last_name":"Windischbacher","first_name":"Andreas","full_name":"Windischbacher, Andreas"},{"last_name":"Mijailovic","full_name":"Mijailovic, Daniel","first_name":"Daniel"},{"last_name":"Slugovc","first_name":"Christian","full_name":"Slugovc, Christian"},{"full_name":"Borisov, Sergey M.","first_name":"Sergey M.","last_name":"Borisov"},{"full_name":"Zojer, Egbert","first_name":"Egbert","last_name":"Zojer"},{"first_name":"Sergio","full_name":"Brutti, Sergio","last_name":"Brutti"},{"first_name":"Olivier","full_name":"Fontaine, Olivier","last_name":"Fontaine"},{"last_name":"Freunberger","orcid":"0000-0003-2902-5319","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","first_name":"Stefan Alexander"}],"external_id":{"pmid":["33723377"],"isi":["000629296400001"]},"status":"public","type":"journal_article","has_accepted_license":"1","language":[{"iso":"eng"}],"pmid":1,"date_updated":"2024-10-09T21:00:28Z","file_date_updated":"2021-09-16T22:30:03Z","user_id":"c635000d-4b10-11ee-a964-aac5a93f6ac1","day":"15","acknowledgement":"S.A.F. is indebted to the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 636069) as well as IST Austria. O.F thanks the French National Research Agency (STORE-EX Labex Project ANR-10-LABX-76-01). We thank EL-Cell GmbH (Hamburg, Germany) for the pressure test cell. We thank R. Saf for help with the mass spectrometry, J. Schlegl for manufacturing instrumentation, M. Winkler of Acib GmbH, G. Strohmeier and R. Fürst for HPLC measurements and S. Mondal and S. Stadlbauer for kinetic measurements.","intvolume":"        13","abstract":[{"text":"Aprotic alkali metal–O2 batteries face two major obstacles to their chemistry occurring efficiently, the insulating nature of the formed alkali superoxides/peroxides and parasitic reactions that are caused by the highly reactive singlet oxygen (1O2). Redox mediators are recognized to be key for improving rechargeability. However, it is unclear how they affect 1O2 formation, which hinders strategies for their improvement. Here we clarify the mechanism of mediated peroxide and superoxide oxidation and thus explain how redox mediators either enhance or suppress 1O2 formation. We show that charging commences with peroxide oxidation to a superoxide intermediate and that redox potentials above ~3.5 V versus Li/Li+ drive 1O2 evolution from superoxide oxidation, while disproportionation always generates some 1O2. We find that 1O2 suppression requires oxidation to be faster than the generation of 1O2 from disproportionation. Oxidation rates decrease with growing driving force following Marcus inverted-region behaviour, establishing a region of maximum rate.","lang":"eng"}],"acknowledged_ssus":[{"_id":"M-Shop"}],"volume":13,"date_published":"2021-03-15T00:00:00Z","title":"Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation","_id":"9250","keyword":["General Chemistry","General Chemical Engineering"],"month":"03","publisher":"Springer Nature"},{"issue":"12","date_created":"2020-04-20T19:29:31Z","isi":1,"tmp":{"legal_code_url":"https://creativecommons.org/licenses/by-nc-nd/4.0/legalcode","image":"/images/cc_by_nc_nd.png","short":"CC BY-NC-ND (4.0)","name":"Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)"},"article_type":"original","publication_status":"published","article_number":"137175","publication":"Electrochimica Acta","corr_author":"1","citation":{"ieee":"A. Samojlov, D. Schuster, J. Kahr, and S. A. Freunberger, “Surface and catalyst driven singlet oxygen formation in Li-O2 cells,” <i>Electrochimica Acta</i>, vol. 362, no. 12. Elsevier, 2020.","ista":"Samojlov A, Schuster D, Kahr J, Freunberger SA. 2020. Surface and catalyst driven singlet oxygen formation in Li-O2 cells. Electrochimica Acta. 362(12), 137175.","chicago":"Samojlov, Aleksej, David Schuster, Jürgen Kahr, and Stefan Alexander Freunberger. “Surface and Catalyst Driven Singlet Oxygen Formation in Li-O2 Cells.” <i>Electrochimica Acta</i>. Elsevier, 2020. <a href=\"https://doi.org/10.1016/j.electacta.2020.137175\">https://doi.org/10.1016/j.electacta.2020.137175</a>.","ama":"Samojlov A, Schuster D, Kahr J, Freunberger SA. Surface and catalyst driven singlet oxygen formation in Li-O2 cells. <i>Electrochimica Acta</i>. 2020;362(12). doi:<a href=\"https://doi.org/10.1016/j.electacta.2020.137175\">10.1016/j.electacta.2020.137175</a>","short":"A. Samojlov, D. Schuster, J. Kahr, S.A. Freunberger, Electrochimica Acta 362 (2020).","apa":"Samojlov, A., Schuster, D., Kahr, J., &#38; Freunberger, S. A. (2020). Surface and catalyst driven singlet oxygen formation in Li-O2 cells. <i>Electrochimica Acta</i>. Elsevier. <a href=\"https://doi.org/10.1016/j.electacta.2020.137175\">https://doi.org/10.1016/j.electacta.2020.137175</a>","mla":"Samojlov, Aleksej, et al. “Surface and Catalyst Driven Singlet Oxygen Formation in Li-O2 Cells.” <i>Electrochimica Acta</i>, vol. 362, no. 12, 137175, Elsevier, 2020, doi:<a href=\"https://doi.org/10.1016/j.electacta.2020.137175\">10.1016/j.electacta.2020.137175</a>."},"quality_controlled":"1","year":"2020","article_processing_charge":"Yes (via OA deal)","doi":"10.1016/j.electacta.2020.137175","ddc":["540"],"file":[{"checksum":"1ab1aa2024d431e2a089ea336bc08298","content_type":"application/pdf","file_id":"8593","file_size":1404030,"success":1,"creator":"dernst","relation":"main_file","date_updated":"2020-10-01T13:20:45Z","access_level":"open_access","date_created":"2020-10-01T13:20:45Z","file_name":"2020_ElectrochimicaActa_Samojlov.pdf"}],"scopus_import":"1","department":[{"_id":"StFr"}],"oa":1,"oa_version":"Published Version","_id":"7672","title":"Surface and catalyst driven singlet oxygen formation in Li-O2 cells","date_published":"2020-12-01T00:00:00Z","volume":362,"publisher":"Elsevier","month":"12","date_updated":"2024-10-09T20:59:27Z","has_accepted_license":"1","language":[{"iso":"eng"}],"author":[{"first_name":"Aleksej","full_name":"Samojlov, Aleksej","last_name":"Samojlov"},{"first_name":"David","full_name":"Schuster, David","last_name":"Schuster"},{"last_name":"Kahr","full_name":"Kahr, Jürgen","first_name":"Jürgen"},{"orcid":"0000-0003-2902-5319","last_name":"Freunberger","first_name":"Stefan Alexander","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425"}],"type":"journal_article","status":"public","external_id":{"isi":["000582869700060"]},"abstract":[{"text":"Large overpotentials upon discharge and charge of Li-O2 cells have motivated extensive research into heterogeneous solid electrocatalysts or non-carbon electrodes with the aim to improve rate capability, round-trip efficiency and cycle life. These features are equally governed by parasitic reactions, which are now recognized to be caused by the highly reactive singlet oxygen (1O2). However, the link between the presence of electrocatalysts and 1O2 formation in metal-O2 cells is unknown. Here, we show that, compared to pristine carbon black electrodes, a representative selection of electrocatalysts or non-carbon electrodes (noble metal, transition metal compounds) may both slightly reduce or severely increase the 1O2 formation. The individual reaction steps, where the surfaces impact the 1O2 yield are deciphered, showing that 1O2 yield from superoxide disproportionation as well as the decomposition of trace H2O2 are sensitive to catalysts. Transition metal compounds in general are prone to increase 1O2.","lang":"eng"}],"acknowledgement":"S.A.F. thanks the International Society of Electrochemistry for awarding the Tajima Prize 2019 “in recognition of outstanding re- searches on Li-Air batteries by the use of a range of in-situ elec- trochemical methods to achieve comprehensive understanding of the reactions taking place at the oxygen electrode”. This article is dedicated to the special issue of Electrochmica Acta associated with the awarding conference. S.A.F. is indebted to and the Austrian Federal Ministry of Science, Research and Economy and the Austrian Research Promotion Agency (grant No. 845364 ) and the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 636069). The authors thank J. Schlegl for manufacturing instrumentation, M. Winkler of Acib GmbH and G. Strohmeier for help with HPLC measurements, S. Eder for cyclic voltammetry measurements, and C. Slugovc for discussions and continuous support. We thank S. Borisov for access and advice with fluorescence measurements. We thank EL-Cell GmbH, Hamburg, Germany for providing the PAT-Cell-Press electrochemical cell.","intvolume":"       362","day":"01","file_date_updated":"2020-10-01T13:20:45Z","user_id":"4359f0d1-fa6c-11eb-b949-802e58b17ae8"},{"title":"Competitive salt precipitation/dissolution during free‐water reduction in water‐in‐salt electrolyte","_id":"7847","volume":59,"date_published":"2020-09-07T00:00:00Z","month":"09","publisher":"Wiley","pmid":1,"date_updated":"2023-09-05T16:02:53Z","author":[{"last_name":"Bouchal","first_name":"Roza","full_name":"Bouchal, Roza"},{"first_name":"Zhujie","full_name":"Li, Zhujie","last_name":"Li"},{"first_name":"Chandra","full_name":"Bongu, Chandra","last_name":"Bongu"},{"full_name":"Le Vot, Steven","first_name":"Steven","last_name":"Le Vot"},{"full_name":"Berthelot, Romain","first_name":"Romain","last_name":"Berthelot"},{"last_name":"Rotenberg","first_name":"Benjamin","full_name":"Rotenberg, Benjamin"},{"first_name":"Fréderic","full_name":"Favier, Fréderic","last_name":"Favier"},{"id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","full_name":"Freunberger, Stefan Alexander","first_name":"Stefan Alexander","last_name":"Freunberger","orcid":"0000-0003-2902-5319"},{"full_name":"Salanne, Mathieu","first_name":"Mathieu","last_name":"Salanne"},{"last_name":"Fontaine","first_name":"Olivier","full_name":"Fontaine, Olivier"}],"type":"journal_article","external_id":{"isi":["000541488700001"],"pmid":["32390281"]},"status":"public","has_accepted_license":"1","language":[{"iso":"eng"}],"intvolume":"        59","abstract":[{"lang":"eng","text":"Water-in-salt electrolytes based on highly concentrated bis(trifluoromethyl)sulfonimide (TFSI) promise aqueous electrolytes with stabilities nearing 3 V. However, especially with an electrode approaching the cathodic (reductive) stability, cycling stability is insufficient. While stability critically relies on a solid electrolyte interphase (SEI), the mechanism behind the cathodic stability limit remains unclear. Here, we reveal two distinct reduction potentials for the chemical environments of 'free' and 'bound' water and that both contribute to SEI formation. Free-water is reduced ~1V above bound water in a hydrogen evolution reaction (HER) and responsible for SEI formation via reactive intermediates of the HER; concurrent LiTFSI precipitation/dissolution establishes a dynamic interface. The free-water population emerges, therefore, as the handle to extend the cathodic limit of aqueous electrolytes and the battery cycling stability. "}],"file_date_updated":"2020-09-17T08:57:16Z","user_id":"c635000d-4b10-11ee-a964-aac5a93f6ac1","day":"07","issue":"37","date_created":"2020-05-14T21:00:30Z","tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png"},"publication_status":"published","article_type":"original","isi":1,"citation":{"ieee":"R. Bouchal <i>et al.</i>, “Competitive salt precipitation/dissolution during free‐water reduction in water‐in‐salt electrolyte,” <i>Angewandte Chemie International Edition</i>, vol. 59, no. 37. Wiley, pp. 15913–1591, 2020.","ista":"Bouchal R, Li Z, Bongu C, Le Vot S, Berthelot R, Rotenberg B, Favier F, Freunberger SA, Salanne M, Fontaine O. 2020. Competitive salt precipitation/dissolution during free‐water reduction in water‐in‐salt electrolyte. Angewandte Chemie International Edition. 59(37), 15913–1591.","chicago":"Bouchal, Roza, Zhujie Li, Chandra Bongu, Steven Le Vot, Romain Berthelot, Benjamin Rotenberg, Fréderic Favier, Stefan Alexander Freunberger, Mathieu Salanne, and Olivier Fontaine. “Competitive Salt Precipitation/Dissolution during Free‐water Reduction in Water‐in‐salt Electrolyte.” <i>Angewandte Chemie International Edition</i>. Wiley, 2020. <a href=\"https://doi.org/10.1002/anie.202005378\">https://doi.org/10.1002/anie.202005378</a>.","mla":"Bouchal, Roza, et al. “Competitive Salt Precipitation/Dissolution during Free‐water Reduction in Water‐in‐salt Electrolyte.” <i>Angewandte Chemie International Edition</i>, vol. 59, no. 37, Wiley, 2020, pp. 15913–1591, doi:<a href=\"https://doi.org/10.1002/anie.202005378\">10.1002/anie.202005378</a>.","ama":"Bouchal R, Li Z, Bongu C, et al. Competitive salt precipitation/dissolution during free‐water reduction in water‐in‐salt electrolyte. <i>Angewandte Chemie International Edition</i>. 2020;59(37):15913-1591. doi:<a href=\"https://doi.org/10.1002/anie.202005378\">10.1002/anie.202005378</a>","short":"R. Bouchal, Z. Li, C. Bongu, S. Le Vot, R. Berthelot, B. Rotenberg, F. Favier, S.A. Freunberger, M. Salanne, O. Fontaine, Angewandte Chemie International Edition 59 (2020) 15913–1591.","apa":"Bouchal, R., Li, Z., Bongu, C., Le Vot, S., Berthelot, R., Rotenberg, B., … Fontaine, O. (2020). Competitive salt precipitation/dissolution during free‐water reduction in water‐in‐salt electrolyte. <i>Angewandte Chemie International Edition</i>. Wiley. <a href=\"https://doi.org/10.1002/anie.202005378\">https://doi.org/10.1002/anie.202005378</a>"},"quality_controlled":"1","publication":"Angewandte Chemie International Edition","article_processing_charge":"No","year":"2020","page":"15913-1591","doi":"10.1002/anie.202005378","scopus_import":"1","file":[{"file_name":"2020_AngChemieINT_Buchal.pdf","date_created":"2020-09-17T08:57:16Z","access_level":"open_access","date_updated":"2020-09-17T08:57:16Z","relation":"main_file","creator":"dernst","success":1,"file_id":"8400","file_size":1966184,"content_type":"application/pdf","checksum":"7b6c2fc20e9b0ff4353352f7a7004e2d"}],"ddc":["540","546"],"publication_identifier":{"issn":["1433-7851"],"eissn":["1521-3773"]},"oa":1,"department":[{"_id":"StFr"}],"oa_version":"Published Version"}]