The use of lithium–sulfur batteries under high sulfur loading and low electrolyte concentrations is severely restricted by the detrimental shuttling behavior of polysulfides and the sluggish kinetics in redox processes. Two‐dimensional (2D) few layered black phosphorus with fully exposed atoms and high sulfur affinity can be potential lithium–sulfur battery electrocatalysts, which, however, have limitations of restricted catalytic activity and poor electrochemical/chemical stability. To resolve these issues, we developed a multifunctional metal‐free catalyst by covalently bonding few layered black phosphorus nanosheets with nitrogen‐doped carbon‐coated multiwalled carbon nanotubes (denoted c‐FBP‐NC). The experimental characterizations and theoretical calculations show that the formed polarized P–N covalent bonds in c‐FBP‐NC can efficiently regulate electron transfer from NC to FBP and significantly promote the capture and catalysis of lithium polysulfides, thus alleviating the shuttle effect. Meanwhile, the robust 1D‐2D interwoven structure with large surface area and high porosity allows strong physical confinement and fast mass transfer. Impressively, with c‐FBP‐NC as the sulfur host, the battery shows a high areal capacity of 7.69 mAh cm⁻² under high sulfur loading of 8.74 mg cm⁻² and a low electrolyte/sulfur ratio of 5.7 μL mg⁻¹. Moreover, the assembled pouch cell with sulfur loading of 4 mg cm⁻² and an electrolyte/sulfur ratio of 3.5 μL mg⁻¹ shows good rate capability and outstanding cyclability. This work proposes an interfacial and electronic structure engineering strategy for fast and durable sulfur electrochemistry, demonstrating great potential in lithium–sulfur batteries.

Preparing carbon nanosheets with precise control of open porous morphology via universal process and understanding the relationship between structure and capacitive performance are very urgent for achieving advanced supercapacitors. Herein, we propose a simple yet effective additive‐free method to transform a bulk layered potassium phthalimide salt to novel nitrogen‐doped two‐dimensional carbon sheets by self‐activation during calcination. The obtained samples showed large‐sized and flat structure with lateral size around 10 µm, uniform sub‐nanometer micropore size distribution of about 0.65 nm dimension, large specific surface area up to 2276.7 m² g⁻¹, and suitable nitrogen doping. Benefited from these merits, the optimized sample delivers a high specific capacitance of 345 F g⁻¹ at 1 A g⁻¹ and retains 270 F g⁻¹ even at 50 A g⁻¹ in 6.0 M KOH electrolyte. Remarkably, the symmetric supercapacitor shows maximum energy densities of 16.43Wh kg⁻¹ and 23.6 Wh kg⁻¹ in 6.0 M KOH and 1.0 M Na₂SO₄ electrolytes, respectively. Importantly, on account the universality and simplicity of this method, the undoped as‐prepared carbon sheet with uniform sub‐nanometer micropore distribution can be synthesized from different potassium‐containing salts with layered structure, which can be employed as a model for a deep understanding the effect of sub‐nanometer micropores on capacitive performances. We find the number of micropores centered at 0.65 nm can be applied as one indicator to clarify the correlation between capacitance and critical pore size below 1 nm.