Protein‐Guided Biomimetic Calcification Constructing 3D Nitrogen‐Rich Core‐Shell Structures Realizing High‐Performance Lithium‐Sulfur Batteries

Biomimetic calcification is a micro-crystallization process that mimics the natural biomineralization process, where biomacromolecules regulate the formation of inorganic minerals. In this study, it is presented that a protein-assisted biomimetic calcification method for the in situ synthesis of nitrogen-doped metal-organic framework (MOF) materials. A series of unique core-shell structures are created by utilizing proteins as templates and guiding agents in the nucleation step, creating ideal conditions for shell growth. To further understand the influence of the protein and organic ligand on the morphology of the MOF shell, the competing mechanism toward metal ions is supposed. Through systematic experiments and analyses, a strategy to construct unique precursor structures by controlling calcification nucleation is proposed. After carbonization, protein-containing precursors exhibit exceptional porous characteristics, stability, and high nitrogen content. These attributes make them promising materials as sulfur hosts in lithium-sulfur batteries (LSB). Electrochemical tests confirm that biomimetic calcification-assisted 3D carbonaceous structure can effectively immobilize dissolved polysulfides, demonstrating strong adsorption and catalytic capabilities. This discovery not only opens up new avenues for employing biomimetic calcification as a sustainable method for batteries but also enlightens the fields of materials science, catalytic chemistry, and energy storage.