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.

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.

Herein we present a study on polymer-derived silicon oxycarbide (SiOC)/graphite composites for a potential application as an electrode in high power energy storage devices, such as Lithium-Ion Capacitor (LIC). The composites were processed using high power ultrasound-assisted sol-gel synthesis followed by pyrolysis. The intensive sonication enhances gelation and drying process, improving the homogenous distribution of the graphitic flakes in the preceramic blends. The physicochemical investigation of SiOC/graphite composites using X-ray diffraction, ²⁹Si solid state NMR and Raman spectroscopy indicated no reaction occurring between the components. The electrochemical measurements revealed enhanced capacity (by up to 63%) at high current rates (1.86 A g⁻¹) recorded for SiOC/graphite composite compared to the pure components. Moreover, the addition of graphite to the SiOC matrix decreased the value of delithiation potential, which is a desirable feature for anodes in LIC.