--- _id: '9301' 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. acknowledged_ssus: - _id: EM-Fac 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. article_number: e2021893118 article_processing_charge: No article_type: original author: - first_name: Christian full_name: Prehal, Christian last_name: Prehal - first_name: Aleksej full_name: Samojlov, Aleksej last_name: Samojlov - first_name: Manfred full_name: Nachtnebel, Manfred last_name: Nachtnebel - first_name: Ludek full_name: Lovicar, Ludek id: 36DB3A20-F248-11E8-B48F-1D18A9856A87 last_name: Lovicar orcid: 0000-0001-6206-4200 - first_name: Manfred full_name: Kriechbaum, Manfred last_name: Kriechbaum - first_name: Heinz full_name: Amenitsch, Heinz last_name: Amenitsch - first_name: Stefan Alexander full_name: Freunberger, Stefan Alexander id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425 last_name: Freunberger orcid: 0000-0003-2902-5319 citation: 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. Proceedings of the National Academy of Sciences. 2021;118(14). doi:10.1073/pnas.2021893118 apa: Prehal, C., Samojlov, A., Nachtnebel, M., Lovicar, L., Kriechbaum, M., Amenitsch, H., & Freunberger, S. A. (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. National Academy of Sciences. https://doi.org/10.1073/pnas.2021893118 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.” Proceedings of the National Academy of Sciences. National Academy of Sciences, 2021. https://doi.org/10.1073/pnas.2021893118. ieee: C. Prehal et al., “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, 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. 118(14), e2021893118. mla: Prehal, Christian, et al. “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, vol. 118, no. 14, e2021893118, National Academy of Sciences, 2021, doi:10.1073/pnas.2021893118. short: C. Prehal, A. Samojlov, M. Nachtnebel, L. Lovicar, M. Kriechbaum, H. Amenitsch, S.A. Freunberger, Proceedings of the National Academy of Sciences 118 (2021). date_created: 2021-03-31T07:00:01Z date_published: 2021-04-06T00:00:00Z date_updated: 2023-09-05T13:27:18Z day: '06' department: - _id: StFr - _id: EM-Fac doi: 10.1073/pnas.2021893118 external_id: isi: - '000637398300050' intvolume: ' 118' isi: 1 issue: '14' keyword: - small-angle X-ray scattering - oxygen reduction - disproportionation - Li-air battery language: - iso: eng main_file_link: - open_access: '1' url: https://doi.org/10.26434/chemrxiv.11447775 month: '04' oa: 1 oa_version: Preprint publication: Proceedings of the National Academy of Sciences publication_identifier: eissn: - 1091-6490 issn: - 0027-8424 publication_status: published publisher: National Academy of Sciences quality_controlled: '1' status: public title: In situ small-angle X-ray scattering reveals solution phase discharge of Li–O2 batteries with weakly solvating electrolytes type: journal_article user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1 volume: 118 year: '2021' ... --- _id: '9980' 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. 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. " article_processing_charge: No author: - first_name: Christian full_name: Prehal, Christian last_name: Prehal - first_name: Sara Drvarič full_name: Talian, Sara Drvarič last_name: Talian - first_name: Alen full_name: Vizintin, Alen last_name: Vizintin - first_name: Heinz full_name: Amenitsch, Heinz last_name: Amenitsch - first_name: Robert full_name: Dominko, Robert last_name: Dominko - first_name: Stefan Alexander full_name: Freunberger, Stefan Alexander id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425 last_name: Freunberger orcid: 0000-0003-2902-5319 - first_name: Vanessa full_name: Wood, Vanessa last_name: Wood citation: ama: Prehal C, Talian SD, Vizintin A, et al. Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries. Research Square. doi:10.21203/rs.3.rs-818607/v1 apa: Prehal, C., Talian, S. D., Vizintin, A., Amenitsch, H., Dominko, R., Freunberger, S. A., & Wood, V. (n.d.). Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries. Research Square. https://doi.org/10.21203/rs.3.rs-818607/v1 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.” Research Square, n.d. https://doi.org/10.21203/rs.3.rs-818607/v1. ieee: C. Prehal et al., “Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries,” Research Square. . 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, 10.21203/rs.3.rs-818607/v1. mla: Prehal, Christian, et al. “Mechanism of Li2S Formation and Dissolution in Lithium-Sulphur Batteries.” Research Square, doi:10.21203/rs.3.rs-818607/v1. short: C. Prehal, S.D. Talian, A. Vizintin, H. Amenitsch, R. Dominko, S.A. Freunberger, V. Wood, Research Square (n.d.). date_created: 2021-09-02T08:45:00Z date_published: 2021-08-16T00:00:00Z date_updated: 2021-12-03T10:35:42Z day: '16' ddc: - '621' department: - _id: StFr doi: 10.21203/rs.3.rs-818607/v1 keyword: - Li2S - Lithium Sulphur Batteries - SAXS - WAXS language: - iso: eng main_file_link: - open_access: '1' url: https://www.researchsquare.com/article/rs-818607/v1 month: '08' oa: 1 oa_version: Preprint page: '21' publication: Research Square publication_status: submitted status: public title: Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries tmp: image: /images/cc_by.png legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0) short: CC BY (4.0) type: preprint user_id: 8b945eb4-e2f2-11eb-945a-df72226e66a9 year: '2021' ... --- _id: '8067' abstract: - lang: eng text: "With the lithium-ion technology approaching its intrinsic limit with graphite-based anodes, lithium metal is recently receiving renewed interest from the battery community as potential high capacity anode for next-generation rechargeable batteries. In this focus paper, we review the main advances in this field since the first attempts in the\r\nmid-1970s. Strategies for enabling reversible cycling and avoiding dendrite growth are thoroughly discussed, including specific applications in all-solid-state (polymeric and inorganic), Lithium-sulphur and Li-O2 (air) batteries. A particular attention is paid to review recent developments in regard of prototype manufacturing and current state-ofthe-art of these battery technologies with respect to the 2030 targets of the EU Integrated Strategic Energy Technology Plan (SET-Plan) Action 7." alternative_title: - IST Austria Technical Report article_processing_charge: No author: - first_name: Alberto full_name: Varzi, Alberto last_name: Varzi - first_name: Katharina full_name: Thanner, Katharina last_name: Thanner - first_name: Roberto full_name: Scipioni, Roberto last_name: Scipioni - first_name: Daniele full_name: Di Lecce, Daniele last_name: Di Lecce - first_name: Jusef full_name: Hassoun, Jusef last_name: Hassoun - first_name: Susanne full_name: Dörfler, Susanne last_name: Dörfler - first_name: Holger full_name: Altheus, Holger last_name: Altheus - first_name: Stefan full_name: Kaskel, Stefan last_name: Kaskel - first_name: Christian full_name: Prehal, Christian last_name: Prehal - first_name: Stefan Alexander full_name: Freunberger, Stefan Alexander id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425 last_name: Freunberger orcid: 0000-0003-2902-5319 citation: ama: Varzi A, Thanner K, Scipioni R, et al. Current Status and Future Perspectives of Lithium Metal Batteries. IST Austria doi:10.15479/AT:ISTA:8067 apa: Varzi, A., Thanner, K., Scipioni, R., Di Lecce, D., Hassoun, J., Dörfler, S., … Freunberger, S. A. (n.d.). Current status and future perspectives of Lithium metal batteries. IST Austria. https://doi.org/10.15479/AT:ISTA:8067 chicago: Varzi, Alberto, Katharina Thanner, Roberto Scipioni, Daniele Di Lecce, Jusef Hassoun, Susanne Dörfler, Holger Altheus, Stefan Kaskel, Christian Prehal, and Stefan Alexander Freunberger. Current Status and Future Perspectives of Lithium Metal Batteries. IST Austria, n.d. https://doi.org/10.15479/AT:ISTA:8067. ieee: A. Varzi et al., Current status and future perspectives of Lithium metal batteries. IST Austria. ista: Varzi A, Thanner K, Scipioni R, Di Lecce D, Hassoun J, Dörfler S, Altheus H, Kaskel S, Prehal C, Freunberger SA. Current status and future perspectives of Lithium metal batteries, IST Austria, 63p. mla: Varzi, Alberto, et al. Current Status and Future Perspectives of Lithium Metal Batteries. IST Austria, doi:10.15479/AT:ISTA:8067. short: A. Varzi, K. Thanner, R. Scipioni, D. Di Lecce, J. Hassoun, S. Dörfler, H. Altheus, S. Kaskel, C. Prehal, S.A. Freunberger, Current Status and Future Perspectives of Lithium Metal Batteries, IST Austria, n.d. date_created: 2020-06-30T07:37:39Z date_published: 2020-07-01T00:00:00Z date_updated: 2023-08-22T09:20:36Z day: '01' ddc: - '540' department: - _id: StFr doi: 10.15479/AT:ISTA:8067 file: - access_level: open_access checksum: d183ca1465a1cbb4f8db27875cd156f7 content_type: application/pdf creator: dernst date_created: 2020-07-02T07:36:04Z date_updated: 2020-07-14T12:48:08Z file_id: '8076' file_name: 20200612_JPS_review_Li_metal_submitted.pdf file_size: 2612498 relation: main_file file_date_updated: 2020-07-14T12:48:08Z has_accepted_license: '1' keyword: - Battery - Lithium metal - Lithium-sulphur - Lithium-air - All-solid-state language: - iso: eng month: '07' oa: 1 oa_version: Published Version page: '63' publication_identifier: issn: - 2664-1690 publication_status: submitted publisher: IST Austria related_material: record: - id: '8361' relation: later_version status: public status: public title: Current status and future perspectives of Lithium metal batteries type: technical_report user_id: 8b945eb4-e2f2-11eb-945a-df72226e66a9 year: '2020' ...