Casper Skautvedt

• North, Erlend Tiberg; Skautvedt, Casper; Thiagarajan, Abilash Kanish; Michiel, Marco Di; Checchia, Stefano & Koposov, Alexey [Show all 7 contributors for this article] (2025). X-ray Beam Damage Effects in a Lithium-Ion Battery Probed by Spatially Resolved X-ray Diffraction. ACS Energy Letters. 10(10), p. 4930–4932. doi: 10.1021/acsenergylett.5c02442. Full text in Research Archive Show summary

  The use of synchrotron radiation has become common for probing the structural changes in rechargeable batteries, particularly for operando analysis. Herein, we report the exposure of the electrode to high photon flux during an operando study shutting down electrochemical transformations in the irradiated area of an electrode and causing a gradient of lithiation around the operando beam position. We rationalize such beam damage through radiation induced ionization and, consequently, electrolyte decomposition.

• Brennhagen, Anders; Skautvedt, Casper; Cavallo, Carmen; Wragg, David Stephen; Koposov, Alexey & Sjåstad, Anja Olafsen [Show all 7 contributors for this article] (2024). Unraveling the (De)sodiation Mechanisms of BiFeO<inf>3</inf> at a High Rate with Operando XRD. ACS Applied Materials & Interfaces. ISSN 1944-8244. 16(10), p. 12428–12436. doi: 10.1021/acsami.3c17296. Full text in Research Archive Show summary

  Development of new anode materials for Na-ion batteries strongly depends on a detailed understanding of their cycling mechanism. Due to instrumental limitations, the majority of mechanistic studies focus on operando materials’ characterization at low cycling rates. In this work, we evaluate and compare the (de)sodiation mechanisms of BiFeO3 in Na-ion batteries at different current densities using operando X-ray diffraction (XRD) and ex situ X-ray absorption spectroscopy (XAS). BiFeO3 is a conversion-alloying anode material with a high initial sodiation capacity of ∼600 mAh g–1, when cycled at 0.1 A g–1. It does not change its performance or cycling mechanism, except for minor losses in capacity, when the current density is increased to 1 A g–1. In addition, operando XRD characterization carried out over multiple cycles shows that the Bi ⇋ NaBi (de)alloying reaction and the oxidation of Bi at the interface with the Na–Fe–O matrix are detrimental for cycling stability. The isolated NaBi ⇋ Na3Bi reaction is less damaging to the cycling stability of the material.

• Wragg, David Stephen; Skautvedt, Casper; Brennhagen, Anders; Geiss, Carina; Checchia, Stefano & Koposov, Alexey (2023). Tracking Lithiation of Si-Based Anodes in Real Time by Total Scattering Computed Tomography. Journal of Physical Chemistry C. ISSN 1932-7447. 127(48), p. 23149–23155. doi: 10.1021/acs.jpcc.3c06414. Full text in Research Archive Show summary

  The existing set of characterization tools does not permit a full description of the three-dimensional (3D) structure and operating mechanisms of amorphous, low-scattering alloying active materials in metal-ion batteries. In this article, we describe and demonstrate a new methodology for analysis of this class of materials based on total scattering computed tomography. Using silicon (Si)-based anodes as a testing platform, we can not only visualize the chemical changes taking place in the electrodes during lithiation but also create a 3D mapping of the electrode components including amorphous active and inactive materials. The mapping was used to select a region of interest in the electrode from which the best possible operando pair distribution function (PDF) of the active material could be obtained. Finally, we deployed differential analysis to highlight the small but systematic changes in the PDF during lithiation, revealing subtle structural transformations at the atomic scale.

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• Wragg, David Stephen; Koposov, Alexey; Ulvestad, Asbjørn; Skare, Marte Orderud; Skautvedt, Casper & Geiss, Carina [Show all 7 contributors for this article] (2024). Where’s my silicon battery? Amorphous battery materials and how to study them. Full text in Research Archive
• Brennhagen, Anders; Skurtveit, Amalie; Skautvedt, Casper; Cavallo, Carmen; Wragg, David Stephen & Vajeeston, Ponniah [Show all 9 contributors for this article] (2024). Revealing the (de)sodiation mechanisms of Bi-metallates through operando X-ray characterisation. Full text in Research Archive Show summary

  Na-ion batteries is entering the battery market as an alternative to Li-ion batteries. To improve their overall performance it is crucial to develop new types of anode materials with high capacity and long cycle life. Materials combing conversion and alloying mechanisms (CAMs) are promising anodes with their high capacity, but obtaining good cycling stability is still challenging. A comprehensive understanding of the cycling and degradation mechanism of these materials is crucial to improve their performance. Bi-metallates, with a general formula of Bi−TM−O (TM = transition metal) is a group of ternary CAMs. Their general cycling mechanism consists of an irreversible conversion reaction forming nanoparticles of Bi-metal embedded in a Na-TM-O matrix during the first sodiation, followed by a reversible two-step alloying reaction forming Na3Bi with NaBi as an intermediate phase. In this work, we have used operando X-ray diffraction (XRD), pair distribution function (PDF) analysis and X-ray absorption spectroscopy (XAS) to investigate the desodiation mechanisms of Bi2MoO6 and BiFeO3. Through this work, we discovered that Bi2MoO6 forms the cubic version of Na3Bi (c-Na3Bi) while BiFeO3 forms hexagonal Na3Bi (h-Na3Bi) in addition to c-Na3Bi during the first sodiation. In the desodiated state, the Bi-particles are partially oxidised, while still maintaining the Bi-metal structure, indicating that it is only the Bi atoms at the interface between the Bi nanoparticles and the Na−TM−O matrix that is oxidised. During cycling the NaxBi particles grow larger thus increasing the distance between them and increasing the impedance in the material. This is considered to be the main driver for the capacity degradation that was observed during the first 20 cycles. The operando XAS data also revealed that Mo6+ in Bi2MoO6 does not change oxidation state during cycling, but changes coordination between tetrahedral and distorted octahedral coordination during cycling. The cycling and degradation mechanisms of Bi2MoO6 is summarised in Figure 1.

• North, Erlend Tiberg; Skautvedt, Casper; Thiagarajan, Abilash Kanish; Checchia, Stefano; Koposov, Alexey & Wragg, David Stephen (2024). Spatially Resolved Beam Damage on a Graphite Anode in Operando. Full text in Research Archive Show summary

  Modern synchrotron beam lines can offer higher luminance and energy, providing more opportunities for scientists performing structural analysis of materials. However, this benefit comes with a risk of questionable results as continual exposure can lead to damage to the studied materials. This effect is well established in protein crystallography but has recently gained attention in the field of material science including operando studies of battery materials. We have investigated the electrochemical cycling of a graphite-based anode for Li-ion batteries under continuous exposure to high-energy X-ray radiation, exploring the consequences of the exposure on the structure and cycling capabilities. We analyze damage by correlating the dose of radiation to the inhibition of electrochemistry.

• Brennhagen, Anders; Skautvedt, Casper; Cavallo, Carmen; Skurtveit, Amalie; Wragg, David Stephen & Koposov, Alexey [Show all 9 contributors for this article] (2023). Revealing the Cycling and Degradation Mechanism of Bi-Metallates as Anode Materials fro Na-ion Batteries. Full text in Research Archive Show summary

  Na-ion batteries (NIBs) represent an emerging alternative to modern Li-ion batteries. To improve the overall performance of NIBs it is crucial to develop new types of anode materials with high capacity and long cycle life. Among the anode candidates, materials operating under combined conversion and alloying mechanisms (CAMs) are considered as promising. They are capable of delivering high capacity, however, despite theoretical predictions the cycling stability is still below expectations. Therefore, a comprehensive understanding of the cycling and degradation mechanisms of CAMs is crucial to improve their performance. However, these materials undergo multiple chemical transformations, which often involves formation of amorphous and nanocrystalline phases during cycling. Such chemical complexity substantially impedes their full characterization and understanding. Bismuth metallates, with a general formula of Bi-TM-O (TM = transition metal), is a group of ternary CAMs. Their general cycling mechanism consists of an irreversible conversion reaction, which leads to formation of Bi nanoparticles embedded in a Na-TM-O matrix during the first sodiation. This is followed by a reversible two-step alloying reaction leading to formation of Na3Bi with NaBi as an intermediate phase. In this work, we have used operando X-ray diffraction over the course of ∼30 cycles to study the cycling and degradation mechanisms of two CAMs - Bi2MoO6 and BiFeO3. With the help of ex situ X-ray absorption spectroscopy and pair distribution function (PDF) analysis, we have revealed new insights into these materials in addition to confirming the general cycling mechanism. Both materials form the cubic phase of Na3Bi (c-Na3Bi) in the sodiated state with some noticeable differences. While, the hexagonal Na3Bi (h-Na3Bi) phase starts to form after 10 cycles in Bi2MoO6, a combination of c-Na3Bi and h-Na3Bi can be observed after the first cycle in BiFeO3. The formation of c-Na3Bi is kinetically favorable in these systems, while h-Na3Bi is the more thermodynamically stable and, therefore, forms later in the cycling process. Both materials shows three distinct regions of capacity degradation, where the first is initiated by a growth in the crystallite sizes of Bi-particles. This is followed by a disappearance of the Bi-phase as the second step. The last degradation phase is related to the disappearance of the NaBi-phase and locking the system in the sodiated state. The present talk will discuss the mechanisms of these degradation steps in view of the future development of CAMs in greater details.

• Skautvedt, Casper; Fjellvåg, Helmer; Koposov, Alexey; Brennhagen, Anders; Cavallo, Carmen & Sjåstad, Anja Olafsen (2022). Syntese og karakterisering av BiFeO3 som anodemateriale i Na-ionebatterier. Universitetet i Oslo. Full text in Research Archive Show summary

  Na-ion batteries (NIBs) are currently an immature technology but have gained interest in research in the last years. A big field within NIBs is on the anode since there is none good enough yet. In this work, we have looked at BiFeO3 as an anode material for NIBs. Bi-based anodes have been investigated in the group before this work and have shown promising results. The choice of BiFeO3 was based on the interesting mechanism that occurs during charging and discharging when used as an anode. The mechanism is a conversion-alloying reaction and combines conversion and alloying reactions when BiFeO3 is sodiated. We have investigated this mechanism in detail with combined X-ray diffraction (XRD) and galvanostatic cycling (GS) with operando-XRD in the RECX-lab at the Department of Chemistry. BiFeO3 was synthesized by ceramic solid-state synthesis and sol-gel synthesis as part of the work. It has previously been synthesised with these syntheses but has proven to be difficult to be phase pure. The product of the syntheses has been characterized with XRD and refined with the Rietveld method. The ceramic solid-state synthesis gave a low yield of BiFeO3 and several impurities, but the sol-gel synthesis gave a high yield of BiFeO3 and few impurities. Various treatments of BiFeO3 were investigated, including ball milling, leaching and doping, to provide increased performance as a battery material. These tests showed that ball milling of the material gave the best results, but it was still not possible to find an optimisation that avoided a large drop in capacity during the first 30 cycles. To characterise BiFeO3 as an anode material, we test it in half-cells against Na metal. These half-cells were electrochemically analyzed by GS and cyclic voltammetry (SV). We also tested different mixtures of electrode composition and electrolytes to optimise battery properties. These showed that NaPF6 was the best salt and propylene carbonate (PC) + 5 wt% fluoroethylene carbonate (FEC) gave the most stable battery cells. The data from the electrochemical characterization and operando-XRD were used together to interpret the reaction mechanisms of BiFeO3. We saw from these that there were similarities in the alloying reaction between Na and Bi with other Bi-based anodes, with NaBi and Na3Bi as different stages in the reaction. However, there were no indications of the phase(s) of Fe after the reaction.

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