Coal‐tar‐pitches‐based hard carbons (HCs) are regarded as promising anode materials for sodium‐ion batteries (SIBs). However, designing optimal microstructures and surface chemical states of carbon anodes to enhance Na ⁺ diffusion kinetics remains a key challenge for superior sodium storage. Herein, a novel strategy of molecular crosslinking‐coupled chemical vapor deposition (CVD) with further post‐heat treatment is proposed. This approach utilizes molecular cross‐linking to restrict the strong π – π interactions among the aromatic rings of polycyclic aromatic hydrocarbons (PAHs) in the coal tar pitches (CTPs) when simultaneously introducing the developed pore structures with large interlayer spacing into the carbon matrix. The surface carbon coatings by the CVD method can facilitate the transition from the open pores to closed pores. The subsequent post‐treatment can effectively regulate the surface chemistry of carbon anodes. Benefiting from the dual regulations on structure‐interface, the optimized HPCV5‐1200 exhibited a high initial cycle efficiency (ICE) of 91.6% and 320.2 mAh g ⁻¹ after 300 cycles at 0.2 A g ⁻¹ . Moreover, the HPCV5‐1200 demonstrated the superior rate capacity (112.6 mAh g ⁻¹ at 10 A g ⁻¹ ) with 53.1% of reversible capacity below 0.1 V. Furthermore, the Na ₃ V ₂ (PO ₄ ) ₃ (NVP)//HPCV5‐1200 full cell exposes the high energy density of 233.5 Wh kg ⁻¹ , with desirable cycling stability and rate performance.

Silicon anode is considered as one of the candidates for graphite replacement due to its highest known theoretical capacity and abundant reserve on earth. However, poor cycling stability resulted from the “volume effect” in the continuous charge-discharge processes become the biggest barrier limiting silicon anodes development. To avoid the resultant damage to the silicon structure, some achievements have been made through constructing the structured space and pore design, and the cycling stability of the silicon anode has been improved. Here, progresses on designing nanostructured materials, constructing buffered spaces, and modifying surfaces/interfaces are mainly discussed and commented from spatial structure and pore generation for volumetric stress alleviation, ions transport, and electrons transfer improvement to screen out the most effective optimization strategies for development of silicon based anode materials with good property.

Linking to the S element hybrid strategies, S-doped carbon materials having different macrostructures and defect concentrations are prepared by using sulfur and coal-tar-pitch as raw materials in a carbonization temperature range of 700–1000 °C. The evaluations of macrostructure and surface characteristics are performed through XRD, TEM, Raman and XPS measurements. Through the linear fitting among the Na⁺ storage capacity with I_D/I_G and d₀₀₂ values, the correlations of Na⁺ storage capacity with macrostructures and defects are respectively investigated in detail. It is observed that S-doped carbon materials exhibit storage capacity at 120 mAh/g after the charge-discharge is being carried out 2000 cycles at 2.0 A/g. Studies have shown that adsorptions of introduced defects on graphene-like carbon sheets mainly play the role to enhance the storage capacity, and the expanded carbonaceous lamellar spaces of highly disordered and pseudo-graphitic macrostructures provide the channels for fast transfer of Na⁺. Our studies are able to provide references for designs and fabrications of coal tar pitch based soft carbon materials as sodium-ion batteries (SIBs) anodes when using heteroatoms doping methods.

Self-assembled nanofibers with different morphologies were successfully fabricated using amphiphilic low-molecular-weight (LMW) azopyridinium compounds having hydrophobic substituents on benzene groups. The possible driving force and self-assembly principles in nanofiber formation processes were proposed based on measurements of X-ray diffraction (XRD), UV-vis absorption spectra and polarizing optical microscopy (POM). The complicated stackings between azopyridinium salts which were constructed by three aromatic units in azopyridinium molecules, i.e. the stackings between benzene groups (Bz–Bz), pyridine groups (Py–Py) and those of benzene with pyridine groups (Bz–Py), mainly acted as the driving force for formation of LMW-AzPy nanofibers. The changed steric hindrance and hydrophobic properties of substituents on benzene groups resulted in the two aggregation types, head–tail and head–head–tail–tail, of LMW-AzPy molecules. In these cases, the head and tail are hydrophilic and hydrophobic parts of LMW-AzPys molecules, respectively. The analyses and understanding of the driving force and aggregation types of LMW-AzPy nanofibers provides references for fabrication of supramolecularly self-assembled nanofibers with controllable behaviours.