Search

In this study tin-functionalized silicon oxycarbide, Sn/SiOC, composite anode materials are synthesized using a carbon-rich polysiloxane as the preceramic polymer and nano-sized SnO2, which converts to metallic tin via carbothermal reduction at approximately 700 °C. The in-situ Sn formation leads to a uniform distribution of tin particles within a carbon-rich SiOC matrix. Raman spectra show no significant changes despite the carbothermal reduction of SnO2. The composite material provides a stable reversible capacity of 234 mAh g-1. By adjusting the composition and pyrolysis temperature a reversible capacity of 131 mAh g-1 at a high current rate of 2380 mA g-1 is achieved.

In the last decade, Sodium-Ion-Batteries (SIB) started to gain interest as a possible complementary candidate to support the overburdened lithium technology, but the manufacturing of a proper anode material is one of the challenging factors for the development of performing SIB. Among others, porous polymer-derived ceramics have been widely explored as suitable anodes despite the production of such materials being time and energy-consuming. In this work, we investigate the feasibility of adopting a low-cost ultra-fast high-temperature pyrolysis for the ceramic conversion of a polymer-derived SiOC aerogel to be employed as anode material. A comprehensive study including N2 physisorption, 29Si MAS NMR and Raman spectroscopy provides the insights of the effect of ultra-fast and conventional heating rates (i.e., 200 °C·s−1 vs. 5 °C·min−1) on the microstructural features and ceramic yield of the SiOC aerogels. As a consequence of the ultra-fast heating rate, a compositional drift towards oxygen-rich SiOC is observed and discussed. The electrochemical performance of both ceramics has been tested and related to the observed compositional differences, revealing a stable capacity of 103 mAh·g−1 for the ultra-fast pyrolyzed SiOC anode, and 152 mAh·g−1 for SiOC ceramized at 5 °C·min−1.

Abstract Since the 1960s, a new class of Si-based advanced ceramics called polymer-derived ceramics (PDCs) has been widely reported because of their unique capabilities to produce various ceramic materials (e.g., ceramic fibers, ceramic matrix composites, foams, films, and coatings) and their versatile applications. Particularly, due to their promising structural and functional properties for energy conversion and storage, the applications of PDCs in these fields have attracted much attention in recent years. This review highlights the recent progress in the PDC field with the focus on energy conversion and storage applications. Firstly, a brief introduction of the Si-based polymer-derived ceramics in terms of synthesis, processing, and microstructure characterization is provided, followed by a summary of PDCs used in energy conversion systems (mainly in gas turbine engines), including fundamentals and material issues, ceramic matrix composites, ceramic fibers, thermal and environmental barrier coatings, as well as high-temperature sensors. Subsequently, applications of PDCs in the field of energy storage are reviewed with a strong focus on anode materials for lithium and sodium ion batteries. The possible applications of the PDCs in Li-S batteries, supercapacitors, and fuel cells are discussed as well. Finally, a summary of the reported applications and perspectives for future research with PDCs are presented.

Abstract Besides the original acknowledgements, the authors Ralf Riedel and Magdalena Graczyk-Zajac would like to also acknowledge EU support in the frame of H2020 project SIMBA under grant agreement number 963542.

As a promising matrix material for anchoring sulfur in the cathode for lithium-sulfur (Li-S) batteries, porous conducting supports have gained much attention. In this work, sulfur-containing C-rich SiCN composites are processed from silicon carbonitride (SiCN) ceramics, synthesized at temperatures from 800 to 1100 °C. To embed sulfur in the porous SiCN matrix, an easy and scalable procedure, denoted as melting-diffusion method, is applied. Accordingly, sulfur is infiltrated under solvothermal conditions at 155 °C into pores of carbon-rich silicon carbonitride (C-rich SiCN). The impact of the initial porosity and microstructure of the SiCN ceramics on the electrochemical performance of the synthesized SiCN-sulfur (SiCN-S) composites is analysed and discussed. A combination of the mesoporous character of SiCN and presence of a disordered free carbon phase makes the electrochemical performance of the SiCN matrix obtained at 900 °C superior to that of SiCN synthesized at lower and higher temperatures. A capacity value of more than 195 mAh/g over 50 cycles at a high sulfur content of 66 wt.% is achieved.

Within this work we define structural properties of the silicon carbonitride (SiCN) and silicon oxycarbide (SiOC) ceramics which determine the reversible and irreversible lithium storage capacities, long cycling stability and define the major differences in the lithium storage in SiCN and SiOC. For both ceramics, we correlate the first cycle lithiation or delithiation capacity and cycling stability with the amount of SiCN/SiOC matrix or free carbon phase, respectively. The first cycle lithiation and delithiation capacities of SiOC materials do not depend on the amount of free carbon, while for SiCN the capacity increases with the amount of carbon to reach a threshold value at ~50% of carbon phase. Replacing oxygen with nitrogen renders the mixed bond Si-tetrahedra unable to sequester lithium. Lithium is more attracted by oxygen in the SiOC network due to the more ionic character of Si-O bonds. This brings about very high initial lithiation capacities, even at low carbon content. If oxygen is replaced by nitrogen, the ceramic network becomes less attractive for lithium ions due to the more covalent character of Si-N bonds and lower electron density on the nitrogen atom. This explains the significant difference in electrochemical behavior which is observed for carbon-poor SiCN and SiOC materials.