Silicon is one of the most promising materials when it comes to lithium-ion battery anodes because of its high theoretical capacity and the low working potential versus Li/Li + . However, the drastic volume change during lithiation and delithiation leads to a rapid failure of the electrode. In order to accommodate the large volume change, Si@C core−shell nanocomposites have been investigated, as they efficiently protect the Si surface from being exposed to the electrolyte and thus limit side reactions and improve the cycling stability through a stable solid electrolyte interface layer. In recent years, phenolic resins have been investigated as the carbon source due to their facile synthesis and the possibility of scale-up. Here, the influence of the chemical structure of the Si−C interface on electrochemical performance has been analyzed by comparing pristine, silanol-rich and epoxide-functionalized Si/ phenolic resin-derived nanocomposites. Whereas pristine Si@C exhibits the highest initial specific capacity of around 2000 mA h/g Si , introduction of silanol groups to the native surface leads to a more homogeneous carbon shell around the Si and thus to an overall higher Coulombic efficiency and a more stable cycling behavior. Additional epoxide functionalization, however, leads to a drastic decrease in initial capacity due to an overall increased resistance and prolongs the activation process. Nevertheless, in the long term, the additional layer leads to more stable cycling, especially at high current rates. For all nanocomposites, the electrochemical performance, characterized by cyclic voltammetry, cycling experiments, and electrochemical impedance spectroscopy, is correlated with the structure of the Si−C interface, determined by transition electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Raman, scanning electron microscopy, and IR-spectroscopy. To the best of our knowledge, the influence of the Si−C interface of a core−shell nanocomposite on structure and electrochemistry by chemically modifying the silicon surface is analyzed and reported for the first time.

Lithium–sulfur (Li–S) batteries are among the most promising candidates for next-generation high-energy-density batteries; however, the polysulfide shuttle represents a major drawback in their application. Here, we report on sulfurized poly­(norbornadiene) (S/pNBD) and its analogue, sulfurized poly­(dicyclopentadiene) (S/pDCPD), two polysulfide shuttle-free and cheap cathode materials with good performance in Li–S battery technology. Both S/pNBD and S/pDCPD can be prepared in a straightforward two-step procedure. Time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy measurements, and cyclic voltammetry indicate that all sulfur in S/pNBD and S/pDCPD is covalently bound to the polymer matrix in the form of C–S x –C units. Li–S cells based on an S/pNBD cathode exhibit a high discharge capacity up to 1050 mA h/g sulfur at 1 C with a good capacity retention of 62 % after 1900 cycles. The structurally similar analogue S/pDCPD shows comparable electrochemical performance, again with excellent capacity retention. The high reversibility and ultra-long cycle life of both, S/pNBD and S/pDCPD, are attributed to the covalent binding of sulfur to the polymer backbone.