Hierarchical porous carbon (HPC, DUT‐106) with tailored pore structure is synthesized using a versatile approach based on ZnO nanoparticles avoiding limitations present in conventional silica hard templating approaches. The benefit of the process presented here is the removal of all pore building components by pyrolysis of the ZnO/carbon composite without any need for either toxic/reactive gases or purification of the as‐prepared hierarchical porous carbon. The carbothermal reduction process is accompanied by an advantageous growing of distinctive micropores within the thin carbon walls. The resulting materials show not only high internal porosity (total pore volume up to 3.9 cm3 g−1) but also a large number of electrochemical reaction sites due to their remarkably high specific surface area (up to 3060 m2 g−1), which renders them particularly suitable for the application as sulfur host material. Applied in the lithium‐sulfur battery, the HPC/sulfur composite exhibits a capacity of >1200 mAh g−1‐sulfur (>750 mAh g−1 electrode) at a high sulfur loading of ≥ 3 mg cm−2 as well as outstanding rate capability. In fact, this impressive performance is achieved even using a low amount of electrolyte (6.8 μl mg−1 sulfur) allowing for further weight reduction and maintenance of high energy density on cell level.

The lithium sulfur battery system has been studied since the late 1970s and has seen renewed interest in recent years. However, even after three decades of intensive research, prolonged cycling can only be achieved when a large excess of electrolyte and lithium is used. Here, for the first time, a balanced and stable lithium sulfur full cell is demonstrated with silicon–carbon as well as all‐carbon anodes. More than 1000 cycles, a specific capacity up to 1470 mAh g−1 sulfur (720 mAh g−1 cathode), and a high coulombic efficiency of over 99% even with a low amount of electrolyte are achieved. The alternative anodes do not suffer from electrolyte depletion, which is found to be the main cause of cell failure when using metallic lithium anodes.

The lithium-sulfur (Li-S) battery is a promising alternative to overcome capacity and specific energy limitation of common lithium-ion batteries. Highly porous carbons with nitrogendoping as conductive host structure for sulfur/lithiumsulfide deposition are shown herein to play a critical role in reversible cycling at low electrolyte/sulfur ratio. The pore geometry is precisely controlled by an efficient, scalable ZnO hard templating process. By using an electrolyte volume as low as 4 μl mg-1 S , the beneficial nitrogen functionality leads to a twofold increased cell lifetime turning our findings highly favorable for real applications. Stable cycling of up to 156 cycles (59 cycles with undoped carbon) with high sulfur loadings of 3 mg cm-2 is achieved. Operando X-ray diffraction patterns during cycling show the transformation pathway of the sulfurpolysulfide-Li 2 S species. The observed intermediates critically depend on the nitrogen doping in the cathode carbon matrix. Nitrogen doped carbons facilitate polysulfide adsorption promoting the nucleation of crystalline Li 2 S. These results provide new insights into the significant role of heteroatom doping for carbons in Li-S batteries with high specific energy.

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