TY - JOUR A1 - Koyutürk, B. A1 - Farber, E. A1 - Wagner, F. A1 - Fellinger, Tim-Patrick A1 - Eisenberg, D. T1 - A simple decagram-scale synthesis of an atomically dispersed, hierarchically porous Fe–N–C catalyst for acidic ORR N2 - Carbons doped with iron and nitrogen (Fe–N–Cs) are highly promising electrocatalysts for energy conversion reactions in the oxygen, nitrogen and carbon cycles. Containing no platinum group metals, they nevertheless compete with platinum-based catalysts in crucial fuel cell reactions, such as oxygen reduction in acid. Yet deployment of Fe–N–Cs in fuel cells requires also a flow-enhancing pore structure, and a scalable synthesis procedure – a rarely-met combination of requirements. We now report such a simple synthesis of over 10 g of an Fe–N–C catalyst with high activity towards oxygen reduction in acid. Atomically-dispersed Fe–N4 active sites were designed orthogonally and simultaneously with hierarchical micro-, meso- and macroporosity, by exploiting a dual role of magnesium ions during pyrolysis. Combining the “active site imprinting” and “self-templating” strategies in a single novel magnesium iminodiacetate precursor yielded a catalyst with high specific surface area (SSA > 1600 m2 g−1), a flow-enhancing hierarchical porosity, and high relative abundance of the most desirable D1-type Fe–N4 sites (43%, by Mössbauer spectroscopy at 4.2 K). Despite the relatively low iron contents, the catalysts feature halfwave potentials up to 0.70 V vs. RHE at pH 1 and a mass activity of 1.22 A g−1 at 0.8 V vs. RHE in RDE experiments. Thanks to the simple and scalable synthesis, this active and stable catalyst may serve as a workhorse in academic and industrial research into atomically-dispersed ORR electrocatalysis. KW - Catalysis KW - Fe-N-C catalysts KW - Fuel Cells KW - Electrochemistry PY - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-550113 SN - 2050-7488 SP - 1 EP - 10 PB - Royal Society of Chemistry AN - OPUS4-55011 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Titirici, M. A1 - Baird, S. G. A1 - Sparks, T. D. A1 - Yang, S. M. A1 - Brandt-Talbot, A. A1 - Hosseinaei, O. A1 - Harper, D. P. A1 - Parker, R. M. A1 - Vignolini, S. A1 - Berglund, L. A. A1 - Li, Y. A1 - Gao, H.-L. A1 - Mao, L.-B. A1 - Yu, S.-H. A1 - Díez, N. A1 - Ferrero, G. A. A1 - Sevilla, M. A1 - Szilágyi, P. Á. A1 - Stubbs, C. J. A1 - Worch, J. C. A1 - Huang, Y. A1 - Luscombe, C. K. A1 - Lee, K.-Y. A1 - Luo, H. A1 - Platts, M. J. A1 - Tiwari, D. A1 - Kovalevskiy, D. A1 - Fermin, D. J. A1 - Au, H. A1 - Alptekin, H. A1 - Crespo-Ribadeneyra, M. A1 - Ting, V. P. A1 - Fellinger, Tim-Patrick A1 - Barrio, J. A1 - Westhead, O. A1 - Roy, C. A1 - Stephens, I. E. L. A1 - Nicolae, S. A. A1 - Sarma, S. C. A1 - Oates, R. P. A1 - Wang, C.-G. A1 - Li, Z. A1 - Loh, X. J. A1 - Myers, R. J. A1 - Heeren, N. A1 - Grégoire, A. A1 - Périssé, C. A1 - Zhao, X. A1 - Vodovotz, Y. A1 - Earley, B. A1 - Finnveden, G. A1 - Björklund, A. A1 - Harper, G. D. J. A1 - Walton, A. A1 - Anderson, P. A. T1 - The sustainable materials roadmap N2 - Our ability to produce and transform engineered materials over the past 150 years is responsible for our high standards of living today, especially in the developed economies. Yet, we must carefully think of the effects our addiction to creating and using materials at this fast rate will have on the future generations. The way we currently make and use materials detrimentally affects the planet Earth, creating many severe environmental problems. It affects the next generations by putting in danger the future of economy, energy, and climate. We are at the point where something must drastically change, and it must change NOW. We must create more sustainable materials alternatives using natural raw materials and inspiration from Nature while making sure not to deplete important resources, i.e. in competition with the food chain supply. We must use less materials, eliminate the use of toxic materials and create a circular materials economy where reuse and recycle are priorities. We must develop sustainable methods for materials recycling and encourage design for disassembly. We must look across the whole materials life cycle from raw resources till end of life and apply thorough life cycle assessments based on reliable and relevant data to quantify sustainability. KW - Electrochemistry KW - Fe-N-C catalysts KW - Fuel cells KW - Catalysis PY - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-550126 SN - 2515-7639 VL - 5 IS - 3 SP - 1 EP - 98 PB - IOP Publishing CY - Bristol AN - OPUS4-55012 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bloi, L. M. A1 - Hippauf, F. A1 - Boenke, T. A1 - Rauche, M. A1 - Paasch, S. A1 - Schutjajew, K. A1 - Pampel, Jonas A1 - Schwotzer, F. A1 - Dörfler, S. A1 - Althues, H. A1 - Oschatz, M. A1 - Brunner, E. A1 - Kaskel, S. T1 - Mechanistic insights into the reversible lithium storage in an open porous carbon via metal cluster formation in all solid-state batteries N2 - Porous carbons are promising anode materials for next generation lithium batteries due to their large lithium storage capacities. However, their highsloping capacity during lithiation and delithiation as well as capacity fading due to intense formation of solid electrolyte interphase (SEI) limit their gravimetric and volumetric energy densities. Herein we compare a microporous carbide-derived carbon material (MPC) as promising future anode for all solid-state batteries with a commercial high-performance hard carbon anode. The MPC obtains high and reversible lithiation capacities of 1000 mAh g−1carbon in half-cells exhibiting an extended plateau region near 0 V vs. Li/Li+ preferable for full-cell application. The well-defined microporosity of the MPC with a specific surface area of >1500 m2 g−1 combines well with the argyrodite-type electrolyte (Li6PS5Cl) suppressing extensive SEI formation to deliver high coulombic efficiencies. Preliminary full-cell measurements vs. nickel-rich NMC-cathodes (LiNi0.9Co0.05Mn0.05O2) provide a considerably improved average potential of 3.76 V leading to a projected energy density as high as 449 Wh kg−1 and reversible cycling for more than 60 cycles. 7Li Nuclear Magnetic Resonance spectroscopy was combined with ex-situ Small Angle X-ray Scattering to elucidate the storage mechanism of lithium inside the carbon matrix. The formation of extended quasi-metallic lithium clusters after electrochemical lithiation was revealed. KW - All solid-state battery KW - Microporous carbon KW - Lithium battery KW - Anode PY - 2022 U6 - https://doi.org/10.1016/j.carbon.2021.11.061 SN - 0008-6223 VL - 188 SP - 325 EP - 335 PB - Elsevier Ltd. AN - OPUS4-54079 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Menga, D. A1 - Low, J. L. A1 - Li, Y.-S. A1 - Arcon, I. A1 - Koyutürk, B. A1 - Wagner, F. A1 - Ruiz-Zepeda, F. A1 - Gaberscek, M. A1 - Paulus, B. A1 - Fellinger, Tim-Patrick T1 - Resolving the Dilemma of Fe-N-C Catalysts by the Selective Synthesis of Tetrapyrrolic Active Sites via an Imprinting Strategy N2 - Combining the abundance and inexpensiveness of their constituent elements with their atomic dispersion, atomically dispersed Fe−N−C catalysts represent the most promising alternative to precious-metal-based materials in proton Exchange membrane (PEM) fuel cells. Due to the high temperatures involved in their synthesis and the sensitivity of Fe ions toward carbothermal reduction, current synthetic methods are intrinsically limited in type and amount of the desired, catalytically active Fe−N4 sites, and high active site densities have been out of reach (dilemma of Fe−N−C catalysts). We herein identify a paradigm change in the synthesis of Fe−N−C catalysts arising from the developments of other M−N−C single-atom catalysts. Supported by DFT calculations we propose fundamental principles for the synthesis of M−N−C materials. We further exploit the proposed principles in a novel synthetic strategy to surpass the dilemma of Fe−N−C catalysts. The selective formation of tetrapyrrolic Zn−N4 sites in a tailor-made Zn−N−C material is utilized as an active-site imprint for the preparation of a corresponding Fe−N−C catalyst. By successive low- and high-temperature ion exchange reactions, we obtain a phase-pure Fe−N−C catalyst, with a high loading of atomically dispersed Fe (>3 wt %). Moreover, the catalyst is entirely composed of tetrapyrrolic Fe−N4 sites. The density of tetrapyrrolic Fe−N4 sites is more than six times as high as for previously reported tetrapyrrolic single-site Fe−N−C fuel cell catalysts. KW - Fe-N-C catalyst KW - Precious-group metal-free catalyst KW - Tetrapyrrolic active-site KW - Single-site catalyst KW - Fuel cell KW - Carbon materials PY - 2021 U6 - https://doi.org/10.1021/jacs.1c04884 SN - 1520-5126 VL - 143 IS - 43 SP - 18010 EP - 18019 PB - American Chemical Society AN - OPUS4-53657 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dayani, Shahabeddin A1 - Markötter, Henning A1 - Schmidt, Anita A1 - Widjaja, Martinus Putra A1 - Bruno, Giovanni T1 - Multi-level X-ray computed tomography (XCT) investigations of commercial lithium-ion batteries from cell to particle level N2 - Adopting X-ray computed tomography (XCT) for ex-situ characterization of battery materials has gained interest in the past decade. The main goal of this paper is to demonstrate the effectiveness of several X-ray computer tomography techniques to study commercial batteries. General guidelines are provided to select the most suitable imaging equipment and parameters for investigations of lithium-ion batteries, spanning the length scales from cell to electrode, down to particle level. Relevantly, such parameters would also be suitable for operando experiments. Safety mechanisms and manufacturing inconsistencies at cell level as well as defects and inhomogeneity in cathode and anode is illustrated and quantified. Furthermore, relation of beam energy and sample-detector-distance on contrast retrieved from attenuation and phase shift is inspected using Synchrotron XCT. KW - Non-destructive testing KW - X-ray computed tomography KW - Synchrotron X-ray computed tomography KW - Lithium-ion battery PY - 2023 U6 - https://doi.org/10.1016/j.est.2023.107453 SN - 2352-152X VL - 66 SP - 107453 PB - Elsevier Ltd. AN - OPUS4-57512 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dayani, Shahabeddin A1 - Markötter, Henning A1 - Krug von Nidda, Jonas A1 - Schmidt, Anita A1 - Bruno, Giovanni T1 - Quantification of the Deep Discharge Induced Asymmetric Copper Deposition in Lithium‐Ion Cells by Operando Synchrotron X‐Ray Tomography N2 - AbstractLithium‐ion cells connected in series are prone to an electrical safety risk called overdischarge. This paper presents a comprehensive investigation of the overdischarge phenomenon in lithium‐ion cells using operando nondestructive imaging. The study focuses on understanding the behavior of copper dissolution and deposition during overdischarge, which can lead to irreversible capacity loss and internal short‐circuits. By utilizing synchrotron X‐ray computed tomography (SXCT), the concentration of dissolved and deposited copper per surface area is quantified as a function of depth of discharge, confirming previous findings. The results also highlight for the first time a nonuniform distribution pattern for copper deposition on the cathode. This research provides insights for safer battery cell design. KW - Lithium Ion Batteries KW - Deep Discharge KW - Computer Tomography KW - Copper Deposition KW - Litium Ion Cells PY - 2023 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-592717 SP - 1 EP - 7 PB - Wiley AN - OPUS4-59271 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Böttcher, Nils A1 - Dayani, Shahabeddin A1 - Markötter, Henning A1 - Bau, Alexander A1 - Setzchen, Max A1 - Schmidt, Anita A1 - Kowal, Julia A1 - Krug von Nidda, Jonas T1 - High Precision Nail‐Penetration Setup for the Controlled Thermal Runaway Initiation of Lithium‐Ion Cells at Very Low Temperatures N2 - A high precision nail‐penetration (NP) tool for characterizing the mechanically induced thermal‐runaway (TR) of lithium‐ion battery (LIB) cells in a defined range of temperatures down to −140 °C was developed. To understand the cell specific behavior at low temperatures aiming at the determination of safe handling conditions, different scenarios are analyzed. First, accuracy tests of the NP‐tool regarding motion and penetration depth are conducted with cylindrical cells at different temperatures. Thus, postmortem computer tomographic (CT) images are compared to the data measured with the newly integrated 3‐axis force sensor which is further combined with a high‐resolution position sensor. The herein developed setup allows evaluation of the NP‐metrics at an accuracy of ±1 pierced electrode layer without CT‐scans. Further NP examinations at 20 °C of fully charged cylindrical lithium nickel manganese cobalt oxide cells reveal a reproducible minimum damage as a reliable TR‐trigger. Moreover, NP‐tests at low temperature disclose a relation of the short circuit conductivity and TR‐reactions during subsequent rethermalization to room temperature. Finally, the implementation of a novel fixture for a controlled very fast cooling of LIB‐cells during critical damage opens the way to investigate the individual steps during a TR and, thus, to gain important information of the specific TR‐mechanism of different LIB‐cells. KW - Battery Safety KW - High-precision nail penetration KW - Lithium-ion batteries KW - Abuse testing KW - Thermal runaway PY - 2024 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-598127 SN - 2194-4288 SP - 1 EP - 13 PB - Wiley VHC-Verlag AN - OPUS4-59812 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rappsilber, Tim A1 - Yusfi, Nawar A1 - Krüger, Simone A1 - Hahn, S.-K. A1 - Fellinger, Tim-Patrick A1 - Krug von Nidda, Jonas A1 - Tschirschwitz, Rico T1 - Meta-analysis of heat release and smoke gas emission during thermal runaway of lithium-ion batteries N2 - Herein a meta-analysis of 76 experimental research papers from 2000 to 2021 is given about possible effects on the thermal runaway of lithium-ion battery cells. Data on the hazards of gas emissions and released heat are related to each other and differentiated by cell properties such as, cell geometry, cathode type or state of charge. Quantitative information on the total heat release in the range of 2.0–112.0 kJ Wh−1, the peak heat release rate in the range of 0.006–2.8 kW Wh−1and the smoke gas emission were extracted, normalized in terms of cell energy (Wh), combined in a data library and compared graphically. The total amount of gas emitted (3–48 mmol Wh−1) as well as the released amount of carbon monoxide (1–161 mg Wh−1) and hydrogen fluoride (2–197 mg Wh−1) were investigated as a function of the state of charge and cell geometry. The analysis reveals that the measured values are significantly influenced by the types of calorimeters and smoke gas analyzers used as well as by the type of thermal runaway trigger. This meta-analysis can serve as an important basis for any risk assessment of lithium-ion batteries. KW - Lithium-ion battery KW - Thermal runaway KW - Cathode active material KW - Heat release KW - Smoke gas emission PY - 2023 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-568071 SN - 2352-152X VL - 60 SP - 1 EP - 15 PB - Elsevier CY - Amsterdam AN - OPUS4-56807 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -