Sulfide-based solid-state electrolytes (SSEs) with high Li⁺ conductivity ( ${\sigma }_{{\mathrm{L}\mathrm{i}}^{+}}$) and trifling grain boundaries have great potential for all-solid-state lithium-metal batteries (ASSLMBs). Nonetheless, the in-situ development of mixed ionic-electronic conducting solid-electrolyte interphase (SEI) at sulfide electrolyte/Li-metal anode interface induces uneven Li electrodeposition, which causes Li-dendrites and void formation, significantly severely deteriorating ASSLMBs. Herein, we propose a dual anionic, e.g., F and N, doping strategy to Li₇P₃S₁₁, tuning its composition in conjunction with the chemistry of SEI. Therefore, novel Li_6.58P_2.76N_0.03S_10.12F_0.05 glass-ceramic electrolyte (Li₇P₃S₁₁-5LiF-3Li₃N-gce) achieved superior ionic (4.33 mS·cm⁻¹) and lowest electronic conductivity of 4.33 × 10⁻¹⁰ S·cm⁻¹ and thus, offered superior critical current density of 0.90 mA·cm⁻² (2.5 times > Li₇P₃S₁₁) at room temperature (RT). Notably, Li//Li cell with Li_6.58P_2.76N_0.03S_10.12F_0.05-gce cycled stably over 1000 and 600 h at 0.2 and 0.3 mA·cm⁻² credited to robust and highly conductive SEI (in-situ) enriched with LiF and Li₃N species. Li₃N’s wettability renders SEI to be highly Li⁺ conductive, ensures an intimate interfacial contact, blocks reductive reactions, prevents Li-dendrites and facilitates fast Li⁺ kinetics. Consequently, LiNi_0.8Co_0.15Al_0.05O₂ (NCA)/Li_6.58P_2.76N_0.03S_10.12F_0.05-gce/Li cell exhibited an outstanding first reversible capacity of 200.8/240.1 mAh·g⁻¹ with 83.67% Coulombic efficiency, retained 85.11% of its original reversible capacity at 0.3 mA·cm⁻² over 165 cycles at RT.

The low intrinsic activity of Fe/N/C oxygen catalysts restricts their commercial application in the fuel cells technique; herein, we demonstrated the interface engineering of plasmonic induced Fe/N/C-F catalyst with primarily enhanced oxygen reduction performance for fuel cells applications. The strong interaction between F and Fe-N₄ active sites modifies the catalyst interfacial properties as revealed by X-ray absorption structure spectrum and density functional theory calculations, which changes the electronic structure of Fe-N active site resulting from more atoms around the active site participating in the reaction as well as super-hydrophobicity from C–F covalent bond. The hybrid contribution from active sites and carbon support is proposed to optimize the three-phase microenvironment efficiently in the catalysis electrode, thereby facilitating efficient oxygen reduction performance. High catalytic performance for oxygen reduction and fuel cells practical application catalyzed by Fe/N/C-F catalyst is thus verified, which offers a novel catalyst system for fuel cells technique.

Artificial defect engineering in transition metal oxides is of important terms for numerous applications. In the present work, we proposed an in-situ gas reduction strategy to introduce ordered defects into titanium niobium oxide embedding on vapor grew carbon fibers (Ti₂Nb₁₀O_29–x@VGCFs). High-resolution transmission electron microscopy (HRTEM) and fast Fourier transform (FFT) simulation indicate that the ordered oxygen defects locate at interval layers, which leads to a new superstructure in Ti₂Nb₁₀O₂₉. The ordered defects could provide extra active sites for lithium-ion storage and modulate ionic migration, resulting an enhanced pseudocapacitive performance. In addition, the excellent structural stability of the superstructure was proved by in-situ HRTEM under a harsh electrochemical process. Our work provides a directly observation of orderly defective superstructure in transition metal oxide, and its functionality on electrochemistry was revealed.