Browsing by Author "Mikhailova, Daria"

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    Comparative Study of Onion-like Carbons Prepared from Different Synthesis Routes towards Li-Ion Capacitor Application
    (Basel : MDPI, 2022) Permana, Antonius Dimas Chandra; Ding, Ling; Gonzalez-Martinez, Ignacio Guillermo; Hantusch, Martin; Nielsch, Kornelius; Mikhailova, Daria; Omar, Ahmad
    Li-ion capacitors (LIC) have emerged as a promising hybrid energy storage system in response to increasing energy demands. However, to achieve excellent LIC performance at high rates, along with cycling stability, an alternative anode to graphite is needed. Porous high-surface-area carbons, such as onion-like carbons (OLCs), have been recently found to hold high potential as high-rate-capable LIC anodes. However, a systematic understanding of their synthesis route and morphology is lacking. In this study, OLCs prepared from self-made metal organic frameworks (MOFs) Fe-BTC and Fe-MIL100 by a simple pyrolysis method were compared to OLCs obtained via high-temperature annealing of nanodiamonds. The LICs with OLCs produced from Fe-BTC achieved a maximum energy density of 243 Wh kg−1 and a power density of 20,149 W kg−1. Furthermore, excellent capacitance retention of 78% after 10,000 cycles was demonstrated. LICs with MOF-derived OLCs surpassed the energy and power density of LICs with nanodiamond-derived OLCs. We determined the impact of the MOF precursor structure and morphology on the resulting OLC properties, as well as on the electrochemical performance. Thus, MOF-derived OLCs offer significant potential toward high-performance anode material for LICs, enabling control over structure and morphology, as well as easy scalability for industrial implementation.
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    Directly Anodized Sulfur-Doped TiO2 Nanotubes as Improved Anodes for Li-ion Batteries
    (Basel : MDPI, 2020) Sabaghi, Davood; Madian, Mahmoud; Omar, Ahmad; Oswald, Steffen; Uhlemann, Margitta; Maghrebi, Morteza; Baniadam, Majid; Mikhailova, Daria
    TiO2 represents one of the promising anode materials for lithium ion batteries due to its high thermal and chemical stability, relatively high theoretical specific capacity and low cost. However, the electrochemical performance, particularly for mesoporous TiO2, is limited and must be further developed. Elemental doping is a viable route to enhance rate capability and discharge capacity of TiO2 anodes in Li-ion batteries. Usually, elemental doping requires elevated temperatures, which represents a challenge, particularly for sulfur as a dopant. In this work, S-doped TiO2 nanotubes were successfully synthesized in situ during the electrochemical anodization of a titanium substrate at room temperature. The electrochemical anodization bath represented an ethylene glycol-based solution containing NH4F along with Na2S2O5 as the sulfur source. The S-doped TiO2 anodes demonstrated a higher areal discharge capacity of 95 µAh·cm−2 at a current rate of 100 µA·cm−2 after 100 cycles, as compared to the pure TiO2 nanotubes (60 µAh·cm−2). S-TiO2 also exhibited a significantly improved rate capability up to 2500 µA·cm−2 as compared to undoped TiO2. The improved electrochemical performance, as compared to pure TiO2 nanotubes, is attributed to a lower impedance in S-doped TiO2 nanotubes (STNTs). Thus, the direct S-doping during the anodization process is a promising and cost-effective route towards improved TiO2 anodes for Li-ion batteries.
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    A Facile Chemical Method Enabling Uniform Zn Deposition for Improved Aqueous Zn-Ion Batteries
    (Basel : MDPI, 2021) Liu, Congcong; Lu, Qiongqiong; Omar, Ahmad; Mikhailova, Daria
    Rechargeable aqueous Zn-ion batteries (ZIBs) have gained great attention due to their high safety and the natural abundance of Zn. Unfortunately, the Zn metal anode suffers from dendrite growth due to nonuniform deposition during the plating/stripping process, leading to a sudden failure of the batteries. Herein, Cu coated Zn (Cu–Zn) was prepared by a facile pretreatment method using CuSO4 aqueous solution. The Cu coating transformed into an alloy interfacial layer with a high affinity for Zn, which acted as a nucleation site to guide the uniform Zn nucleation and plating. As a result, Cu–Zn demonstrated a cycling life of up to 1600 h in the symmetric cells and endowed a stable cycling performance with a capacity of 207 mAh g−1 even after 1000 cycles in the full cells coupled with a V2O5-based cathode. This work provides a simple and effective strategy to enable uniform Zn deposition for improved ZIBs.
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    Flux Growth and Characterization of Bulk InVO4 Crystals
    (Basel : MDPI, 2023) Voloshyna, Olesia; Gorbunov, Mikhail V.; Mikhailova, Daria; Maljuk, Andrey; Seiro, Silvia; Büchner, Bernd
    The flux growth of InVO4 bulk single crystals has been explored for the first time. The reported eutectic composition at a ratio of V2O5:InVO4 = 1:1 could not be used as a self-flux since no sign of melting was observed up to 1100 °C. Crystals of InVO4 of typical size 0.5 × 1 × 7 mm3 were obtained using copper pyrovanadate (Cu2V2O7) as a flux, using Pt crucibles. X-ray powder diffraction confirmed the orthorhombic Cmcm structure. Rests of the flux material were observed on the sample surface, with occasional traces of Pt indicating some level of reaction with the crucible. X-ray absorption spectroscopy showed that oxidation states of indium and vanadium ions are +3 and +5, respectively. The size and high quality of the obtained InVO4 crystals makes them excellent candidates for further study of their physical properties.
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    Freestanding MXene‐based macroforms for electrochemical energy storage applications
    (Hoboken, NJ : Wiley, 2023) Lu, Qiongqiong; Liu, Congcong; Zhao, Yirong; Pan, Wengao; Xie, Kun; Yue, Pengfei; Zhang, Guoshang; Omar, Ahmad; Liu, Lixiang; Yu, Minghao; Mikhailova, Daria
    Freestanding MXene-based macroforms have gained significant attention as versatile components in electrochemical energy storage applications owing to their interconnected conductive network, strong mechanical strength, and customizable surface chemistries derived from MXene nanosheets. This comprehensive review article encompasses key aspects related to the synthesis of MXene nanosheets, strategies for structure design and surface medication, surface modification, and the diverse fabrication methods employed to create freestanding MXene-based macroform architectures. The review also delves into the recent advancements in utilizing freestanding MXene macroforms for electrochemical energy storage applications, offering a detailed discussion on the significant progress achieved thus far. Notably, the correlation between the macroform's structural attributes and its performance characteristics is thoroughly explored, shedding light on the critical factors influencing efficiency and durability. Despite the remarkable development, the review also highlights the existing challenges and presents future perspectives for freestanding MXene-based macroforms in the realms of high-performance energy storage devices. By addressing these challenges and leveraging emerging opportunities, the potential of freestanding MXene-based macroforms can be harnessed to enable groundbreaking advancements in the field of energy storage.
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    High-Entropy Metal-Organic Frameworks for Highly Reversible Sodium Storage
    (Weinheim : Wiley-VCH, 2021) Ma, Yanjiao; Ma, Yuan; Dreyer, Sören Lukas; Wang, Qingsong; Wang, Kai; Goonetilleke, Damian; Omar, Ahmad; Mikhailova, Daria; Hahn, Horst; Breitung, Ben; Brezesinski, Torsten
    Prussian blue analogues (PBAs) are reported to be efficient sodium storage materials because of the unique advantages of their metal-organic framework structure. However, the issues of low specific capacity and poor reversibility, caused by phase transitions during charge/discharge cycling, have thus far limited the applicability of these materials. Herein, a new approach is presented to substantially improve the electrochemical properties of PBAs by introducing high entropy into the crystal structure. To achieve this, five different metal species are introduced, sharing the same nitrogen-coordinated site, thereby increasing the configurational entropy of the system beyond 1.5R. By careful selection of the elements, high-entropy PBA (HE-PBA) presents a quasi-zero-strain reaction mechanism, resulting in increased cycling stability and rate capability. The key to such improvement lies in the high entropy and associated effects as well as the presence of several active redox centers. The gassing behavior of PBAs is also reported. Evolution of dimeric cyanogen due to oxidation of the cyanide ligands is detected, which can be attributed to the structural degradation of HE-PBA during battery operation. By optimizing the electrochemical window, a Coulombic efficiency of nearly 100% is retained after cycling for more than 3000 cycles.
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    Lifetime vs. rate capability: Understanding the role of FEC and VC in high-energy Li-ion batteries with nano-silicon anodes
    (Amsterdam : Elsevier, 2016) Jaumann, Tony; Balach, Juan; Langklotz, Ulrike; Sauchuk, Viktar; Fritsch, Marco; Michaelis, Alexander; Teltevskij, Valerij; Mikhailova, Daria; Oswald, Steffen; Klose, Markus; Stephani, Guenter; Hauser, Ralf; Eckert, Jürgen; Giebeler, Lars
    Fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are the most frequently used electrolyte components to enhance the lifetime of anode materials in Li-ion batteries, but for silicon it is still ambiguous when FEC or VC is more beneficial. Herein, a nanostructured silicon/carbon anode derived from low-cost HSiCl3 is tailored by the rational choice of the electrolyte component, to obtain an anode material outperforming current complex silicon structures. We demonstrate highly reversible areal capacities of up to 5 mA h/cm2 at 4.4 mg/cm2 mass loading, a specific capacity of 1280 mA h/gElectrode, a capacity retention of 81% after 500 deep-discharge cycles versus lithium metal and successful full-cell tests with high-voltage cathodes meeting the requirements for real application. Electrochemical impedance spectroscopy and post-mortem investigation provide new insights in tailoring the interfacial properties of silicon-based anodes for high performance anode materials based on an alloying mechanism with large volume changes. The role of fluorine in the FEC-derived interfacial layer is discussed in comparison with the VC-derived layer and possible degradation mechanisms are proposed. We believe that this study gives a valuable understanding and provides new strategies on the facile use of additives for highly reversible silicon anodes in Li-ion batteries.
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    NaOH protective layer for a stable sodium metal anode in liquid electrolytes
    (Amsterdam [u.a.] : Elsevier, 2024) Thomas, Alexander; Pohle, Björn; Schultz, Johannes; Hantusch, Martin; Mikhailova, Daria
    Sodium is known as a soft metal that can easily change its particle morphology. It can form outstretched and rolled fibers with plastic or brittle behavior, and cubes. In Na-batteries, metallic Na anodes demonstrate a high reactivity towards the majority of electrolyte solutions, volume change and a random deposition process from the electrolyte, accompanied by dendrite formation. In order to smooth the electrochemical Na deposition, we propose NaOH as a simple artificial protective layer for sodium, formed by its exposure to ambient conditions for a certain period of time. The formed NaOH layer on top of the metallic sodium suppresses the volume change and dendrite growth on the sodium surface. Additionally, the protected sodium does not change its morphology after a prolonged contact with carbonate-based electrolytes. In symmetric Na-batteries, the NaOH layer increases the lifetime of the electrochemical cell by eight times in comparison to non-protected Na. In the full-cell with a layered sodium oxide cathode, the NaOH-protected sodium anode also leads to a high cycling stability, providing 81 % of the initial cell capacity after 500 cycles with a 1C current rate. In contrast, batteries with a non-protected Na-anode reach only 20 % of their initial capacity under the same conditions. Therefore, the main benefits of the NaOH artificial layer are the chemical compatibility with the carbonate-based electrolytes, the protection of Na metal against reaction with the electrolyte solution, the rapid Na-ion diffusion through the layer and the formation of a mechanical barrier, mitigating Na-dendrite growth. This work presents an easily scalable method to protect sodium without any additional chemicals or a special environment for this reaction.
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    P2-type layered high-entropy oxides as sodium-ion cathode materials
    (Bristol : IOP Science, 2022) Wang, Junbo; Dreyer, Sören L; Wang, Kai; Ding, Ziming; Diemant, Thomas; Karkera, Guruprakash; Ma, Yanjiao; Sarkar, Abhishek; Zhou, Bei; Gorbunov, Mikhail V; Omar, Ahmad; Mikhailova, Daria; Presser, Volker; Fichtner, Maximilian; Hahn, Horst; Brezesinski, Torsten; Breitung, Ben; Wang, Qingsong
    P2-type layered oxides with the general Na-deficient composition NaxTMO2 (x < 1, TM: transition metal) are a promising class of cathode materials for sodium-ion batteries. The open Na+ transport pathways present in the structure lead to low diffusion barriers and enable high charge/discharge rates. However, a phase transition from P2 to O2 structure occurring above 4.2 V and metal dissolution at low potentials upon discharge results in rapid capacity degradation. In this work, we demonstrate the positive effect of configurational entropy on the stability of the crystal structure during battery operation. Three different compositions of layered P2-type oxides were synthesized by solid-state chemistry, Na0.67(Mn0.55Ni0.21Co0.24)O2, Na0.67(Mn0.45Ni0.18Co0.24Ti0.1Mg0.03)O2 and Na0.67(Mn0.45Ni0.18Co0.18Ti0.1Mg0.03Al0.04Fe0.02)O2 with low, medium and high configurational entropy, respectively. The high-entropy cathode material shows lower structural transformation and Mn dissolution upon cycling in a wide voltage range from 1.5 to 4.6 V. Advanced operando techniques and post-mortem analysis were used to probe the underlying reaction mechanism thoroughly. Overall, the high-entropy strategy is a promising route for improving the electrochemical performance of P2 layered oxide cathodes for advanced sodium-ion battery applications.
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    Polypyrrole Wrapped V2O5 Nanowires Composite for Advanced Aqueous Zinc-Ion Batteries
    (Lausanne : Frontiers Media, 2020) Qin, Xinghua; Wang, Xinyu; Sun, Juncai; Lu, Qiongqiong; Omar, Ahmad; Mikhailova, Daria
    Aqueous zinc-ion batteries (ZIBs) have obtained increasing attention owing to the high safety, material abundance, and environmental benignity. However, the development of cathode materials with high capacity and stable cyclability is still a challenge. Herein, the polypyrrole (PPy)-wrapped V2O5 nanowire (V2O5/PPy) composite was synthesized by a surface-initiated polymerization strategy, ascribing to the redox reaction between V2O5 and pyrrole. The introduction of PPy on the surface of V2O5 nanowires not only enhanced the electronic conductivity of the active materials but also reduced the V2O5 dissolution. As a result, the V2O5/PPy composite cathode exhibits a high specific capacity of 466 mAh g–1 at 0.1 A g–1 and a superior cycling stability with 95% capacity retention after 1000 cycles at a high current density of 5 A g–1. The superior electrochemical performance is ascribed to the large ratio of capacitive contribution (92% at 1 mV s–1) and a fast Zn2+ diffusion rate. This work presents a simple method for fabricating V2O5/PPy composite toward advanced ZIBs.
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    Preparation and Application of ZIF-8 Thin Layers
    (Basel : MDPI, 2021) Schernikau, Martin; Sablowski, Jakob; Gonzalez Martinez, Ignacio Guillermo; Unz, Simon; Kaskel, Stefan; Mikhailova, Daria
    Herein we compare various preparation methods for thin ZIF-8 layers on a Cu substrate for application as a host material for omniphobic lubricant-infused surfaces. Such omniphobic surfaces can be used in thermal engineering applications, for example to achieve dropwise condensation or anti-fouling and anti-icing surface properties. For these applications, a thin, conformal, homogeneous, mechanically and chemically stable coating is essential. In this study, thin ZIF-8 layers were deposited on a Cu substrate by different routes, such as (i) electrochemical anodic deposition on a Zn-covered Cu substrate, (ii) doctor blade technique for preparation of a composite layer containing PVDF binder and ZIF-8, as well as (iii) doctor blade technique for preparation of a two-layer composite on the Cu substrate containing a PVDF-film and a ZIF-8 layer. The morphology and topography of the coatings were compared by using profilometry, XRD, SEM and TEM techniques. After infusion with a perfluorinated oil, the wettability of the surfaces was assessed by contact angle measurements, and advantages of each preparation method were discussed.
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    Progress and challenges in using sustainable carbon anodes in rechargeable metal-ion batteries
    (Amsterdam [u.a.] : Elsevier, 2021) Soltani, Niloofar; Bahrami, Amin; Giebeler, Lars; Gemming, Thomas; Mikhailova, Daria
    Rechargeable lithium-ion batteries (LIBs) are one of the most promising alternatives to effectively bypass fossil fuels. However, long-term energy application of LIBs could be restricted in the future due to the increased production cost of LIB arising from the shortage and inaccessibility of Li in the Earth's crust. Na or K have been considered as substitutes for Li but in spite of their natural abundance, they suffer from low gravimetric/volumetric energy density. An alternative to increase the efficiency of sodium-ion battery (SIBs) and potassium-ion battery (KIBs) is to focus on finding the high‐performing negative electrode, the anode. The large volume changes of alloying and conversion type anodes for KIBs and SIBs make hard carbons to a better option on this regard than usual graphitic carbons, but a key obstacle is the reliance on unsustainable sources. Thus, biomass-derived carbon could offer a promising alternative, and it has indeed been in the focus of much recent work. This review highlights the recent advances in using carbon extracted from various biomass sources in rechargeable Li-, Na-, and K-ion batteries. Maximizing the energy and power densities as well as the lifetime of carbon anodes require an exploration of the right balance between carbon structures, pore morphology, chemical composition and alkali metal-ion storage. Thus, in this review, first, we take stock of key challenges and opportunities to extract carbon from various plants structural components and identify the extracted carbon structure compared to graphite-like structure. Then, we provide an overview on morphological and structural modification of the extracted carbons. Finally, we show how the physicochemical properties, structural alignment and morphological variation of the biomass-derived carbon can affect the storage mechanism and electrochemical performance. The extensive overview of this topic provided here is expected to stimulate further work on environmentally friendly battery design and towards the optimization of the battery performance. Electrode materials in alkali-metal-ion batteries that are based on biomass-derived carbon may allow not only a technical breakthrough, but also an ethically and socially acceptable product.
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    The Role of Al2O3 ALD Coating on Sn-Based Intermetallic Anodes for Rate Capability and Long-Term Cycling in Lithium-Ion Batteries
    (Weinheim : Wiley-VCH, 2022) Soltani, Niloofar; Abbas, Syed Muhammad; Hantusch, Martin; Lehmann, Sebastian; Nielsch, Kornelius; Bahrami, Amin; Mikhailova, Daria
    The electrochemical performances of CoSn2 and Ni3Sn4 as potential anode materials in lithium-ion batteries (LIBs) are investigated using varying thicknesses of an alumina layer deposited by the atomic layer deposition (ALD) technique. Rate capability results showed that at high current densities, Al2O3-coated CoSn2 and Ni3Sn4 electrodes after 10-ALD cycles outperformed uncoated materials. The charge capacities of coated CoSn2 and Ni3Sn4 electrodes are 571 and 134 mAh g−1, respectively, at a high current density of 5 A g−1, while the capacities of uncoated electrodes are 363 and 11 mAh g−1. When the current density is reduced to 1 A g−1, however, the cycling performances of Al2O3-coated CoSn2 and Ni3Sn4 electrodes fade faster after almost 40 cycles than uncoated electrodes. The explanation is found in the composition of the solid-electrolyte interface (SEI), which strongly depends on the current rate. Thus, X-ray photoelectron spectroscopy analysis of SEI layers on coated samples cycles at a low current density of 0.1 Ag−1, revealed organic carbonates as major products, which probably have a low ionic conductivity. In contrast, the SEI of coated materials cycled at 5 Ag−1 consists mostly of mixed inorganic/organic fluorine-rich Al-F and C-F species facilitating a higher ionic transport, which improves electrochemical performance.
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    Sodium-Vanadium Bronze Na9V14O35: An Electrode Material for Na-Ion Batteries
    (Basel : MDPI, 2021) Kirsanova, Maria A.; Akmaev, Alexey S.; Gorbunov, Mikhail V.; Mikhailova, Daria; Abakumov, Artem M.
    Na9V14O35 (η-NaxV2O5) has been synthesized via solid-state reaction in an evacuated sealed silica ampoule and tested as electroactive material for Na-ion batteries. According to powder X-ray diffraction, electron diffraction and atomic resolution scanning transmission electron microscopy, Na9V14O35 adopts a monoclinic structure consisting of layers of corner- and edge-sharing VO5 tetragonal pyramids and VO4 tetrahedra with Na cations positioned between the layers, and can be considered as sodium vanadium(IV,V) oxovanadate Na9V104.1+O19(V5+O4)4. Behavior of Na9V14O35 as a positive and negative electrode in Na half-cells was investigated by galvanostatic cycling against metallic Na, synchrotron powder X-ray diffraction and electron energy loss spectroscopy. Being charged to 4.6 V vs. Na+/Na, almost 3 Na can be extracted per Na9V14O35 formula, resulting in electrochemical capacity of ~60 mAh g−1. Upon discharge below 1 V, Na9V14O35 uptakes sodium up to Na:V = 1:1 ratio that is accompanied by drastic elongation of the separation between the layers of the VO4 tetrahedra and VO5 tetragonal pyramids and volume increase of about 31%. Below 0.25 V, the ordered layered Na9V14O35 structure transforms into a rock-salt type disordered structure and ultimately into amorphous products of a conversion reaction at 0.1 V. The discharge capacity of 490 mAh g−1 delivered at first cycle due to the conversion reaction fades with the number of charge-discharge cycles.
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    Structural and Electrochemical Properties of Layered P2-Na0.8Co0.8Ti0.2O2 Cathode in Sodium-Ion Batteries
    (Basel : MDPI, 2022) Pohle, Björn; Gorbunov, Mikhail V.; Lu, Qiongqiong; Bahrami, Amin; Nielsch, Kornelius; Mikhailova, Daria
    Layered Na0.8Co0.8Ti0.2O2 oxide crystallizes in the β-RbScO2 structure type (P2 modification) with Co(III) and Ti(IV) cations sharing the same crystallographic site in the metal-oxygen layers. It was synthesized as a single-phase material and characterized as a cathode in Na- and Na-ion batteries. A reversible capacity of about 110 mA h g−1 was obtained during cycling between 4.2 and 1.8 V vs. Na+/Na with a 0.1 C current density. This potential window corresponds to minor structural changes during (de)sodiation, evaluated from operando XRD analysis. This finding is in contrast to Ti-free NaxCoO2 materials showing a multi-step reaction mechanism, thus identifying Ti as a structure stabilizer, similar to other layered O3- and P2-NaxCo1−yTiyO2 oxides. However, charging the battery with the Na0.8Co0.8Ti0.2O2 cathode above 4.2 V results in the reversible formation of a O2-phase, while discharging below 1.5 V leads to the appearance of a second P2-layered phase with a larger unit cell, which disappears completely during subsequent battery charge. Extension of the potential window to higher or lower potentials beyond the 4.2–1.8 V range leads to a faster deterioration of the electrochemical performance. After 100 charging-discharging cycles between 4.2 and 1.8 V, the battery showed a capacity loss of about 20% in a conventional carbonate-based electrolyte. In order to improve the cycling stability, different approaches including protective coatings or layers of the cathodic and anodic surface were applied and compared with each other.
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    Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries
    (Weinheim : Wiley-VCH, 2021) Yang, Liangtao; Kuo, Liang-Yin; López del Amo, Juan Miguel; Nayak, Prasant Kumar; Mazzio, Katherine A.; Maletti, Sebastian; Mikhailova, Daria; Giebeler, Lars; Kaghazchi, Payam; Rojo, Teófilo; Adelhelm, Philipp
    A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na0.67Mn0.6Ni0.2Li0.2O2 is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g-1 after 100 cycles. In contrast, the Li-free compositions Na0.67Mn0.6Ni0.4O2 and Na0.67Mn0.8Ni0.2O2 show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni3+/Ni4+ and O2-/O2-δ redox processes by DFT, although a small contribution from Mn4+/Mn5+ to the capacity cannot be excluded. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
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    Structural Behaviour and Charge-Compensation Mechanism in Li2Fe1−xCoxSeO Solid Solutions during Reversible Delithiation
    (Basel : MDPI, 2024) Gorbunov, Mikhail V.; Mikhailova, Daria
    The constantly growing demand for renewable electrical energy keeps the continuation of battery-related research imperative. In spite of significant progress made in the development of Na- and K-ion systems, Li-ion batteries (LIBs) still prevail in the fields of portative devices and electric or hybrid vehicles. Since the amount of lithium on our planet is significantly limited, studies dedicated to the search for and development of novel materials, which would make LIBs more efficient in terms of their specific characteristics and life lengths, are necessary. Investigations of less industry-related systems are also important, as they provide general knowledge which helps in understanding directions and strategies for the improvement of applied materials. The current paper represents a comprehensive study of cubic Li2Fe1−xCoxSeO compounds with an anti-perovskite structure. These solid solutions demonstrate both cationic and anionic electrochemical activity in lithium cells while being applied as cathodes. Cobalt cations remain inactive; however, their amount in the structure defines if the Se0/Se2− or Fe3+/Fe2+ redox couple dominates the charge compensation mechanism upon (de)lithiation. Apart from that, cobalt affects the structural stability of the materials during cycling. These effects were evaluated by means of operando XRD and XAS techniques. The outcomes can be useful for both fundamental and practice-relevant research.
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    Studies of Li2Fe0.9M0.1SO Antiperovskite Materials for Lithium–Ion Batteries: The Role of Partial Fe2+ to M2+ Substitution
    (Lausanne : Frontiers Media, 2021) Gorbunov, Mikhail V.; Carocci, Salvatore; Gonzalez Martinez, Ignacio G.; Baran, Volodymyr; Mikhailova, Daria
    Cubic Li2Fe0.9M0.1SO antiperovskites with M–Co2+, or Mn2+ were successfully synthesized by a solid-state technique, and studied as cathode materials in Li-batteries. The influence of the Co, and Mn cation substitution of Fe in Li2FeSO on the resulting electrochemical performance was evaluated by galvanostatic cycling, while the reaction mechanism was explored by applying operando X-ray absorption and X-ray diffraction techniques using synchrotron radiation facilities. Even 10% Fe-substitution by these metals completely changes the structural behavior of the material upon Li-removal and insertion, in comparison to Li2FeSO. The Co-substitution significantly improves cyclability of the material at high current densities in comparison to the non-substituted material, reaching a specific capacity of 250 mAh/g at 1C current density. In contrast, the Mn-substitution leads to deterioration of the electrochemical performance because of the impeded kinetics, which may be caused by the appearance of a second isostructural phase due to formation of Jahn-Teller Mn3+ cations upon delithiation.
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    Synthesis of Cellulose Acetate Butyrate Microspheres as Precursor for Hard Carbon-Based Electrodes in Symmetric Supercapacitors
    (Basel : MDPI, 2024) Fischer, Johanna; Thümmler, Katrin; Zlotnikov, Igor; Mikhailova, Daria; Fischer, Steffen
    Cellulose microspheres have a wide range of applications due to their unique properties and versatility. Various preparation methods have been explored to tailor these microspheres for specific applications. Among these methods, the acetate method using cellulose acetate is well known. However, replacement of the acetate group through the butyrate group significantly extends the variety of morphological properties. In the present work, microspheres based on cellulose acetate butyrate are being developed with modified characteristics in terms of particle size, porosity, surface morphology and the inner structure of the microspheres. While the inner structure of cellulose acetate microspheres is predominantly porous, microspheres prepared from cellulose acetate butyrate are mainly filled or contain several smaller microspheres. Carbon materials from cellulose acetate butyrate microspheres exhibit a high specific surface area of 567 m2 g−1, even without further activation. Activation processes can further increase the specific surface area, accompanied by an adaptation of the pore structure. The prepared carbons show promising results in symmetrical supercapacitors with aqueous 6 M KOH electrolytes. Activated carbons derived from cellulose acetate butyrate microspheres demonstrate an energy density of 12 Wh kg−1 at a power density of 0.9 kW kg−1.
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    TiNb2O7 and VNB9O25 of ReO3 type in hybrid Mg−Li batteries: Electrochemical and interfacial insights
    (Washington, DC : American Chemical Society, 2020) Maletti, Sebastian; Herzog-Arbeitman, Abraham; Oswald, Steffen; Senyshyn, Anatoliy; Giebeler, Lars; Mikhailova, Daria
    As one of the beyond-lithium battery concepts, hybrid metal-ion batteries have aroused growing interest. Here, TiNb2O7 (TNO) and VNb9O25 (VNO) materials were prepared using a high-temperature solid-state synthesis and, for the first time, comprehensively examined in hybrid Mg−Li batteries. Both materials adopt ReO3-related structures differing in the interconnection of oxygen polyhedra and the resulting guest ion diffusion paths. We show applicability of the compounds in hybrid cells providing capacities comparable to those reached in Li-ion batteries (LIBs) at room temperature (220 mAh g−1 for TNO and 150 mAh g−1 for VNO, both at 0.1 C), their operability in the temperature range between −10 and 60 °C, and even better capacity retention than in pure LIBs, rendering this hybrid technology superior for long-term application. Post mortem X-ray photoelectron spectroscopy reveals a cathode−electrolyte interface as a key ingredient for providing excellent electrochemical stability of the hybrid battery. A significant contribution of the intercalation pseudocapacitance to charge storage was observed for both materials in Li- and Mg−Li batteries. However, the pseudocapacitive part is higher for TNO than for VNO, which correlates with structural distinctions, providing better accessibility of diffusion pathways for guest cations in TNO and, as a consequence, a higher ionic transport within the crystal structure. © 2020 American Chemical Society