▎ 摘　　要

Phosphorus (P) has been regarded as one of promising anodic materials for Li- and Na-ion batteries owing to the merits of high theoretical specific capacity and natural abundance. Nevertheless, its practical applications suffer from huge volumetric change during cycling and low electronic conductivity with the result of fast capacity decay and low Coulombic efficiency (CE). To be noted that, amorphous red P (RP) is universally used as the SIB anodic material in most of the reported works. Herein, we successfully construct crystalline red P (CRP) nanorods confined within 3D rGA (CRP-rGA) architecture composite via prepositioned nanoseeds following with secondary growth method. The unique composite was investigated as anode for sodium-ion batteries (SIBs) for the first time and presents competitive sodium storage performance. For instance, with an ultra-high P loading (75.9%) in the electrode, it delivers an initial specific capacity of 2427 mA h g(-1) (93.5% of the theoretical capacity) with Columbic efficiency of similar to 82% at 0.1 A g(-1), and the relatively higher capacity can be retained at 1 and 2 A g(-1) with progressive cycling. The evolutions of CRP-rGA during charging and discharging have also been investigated systematically through ex-situ characterizations such as XPS, TEM, Raman and SEM. It is believed that the good electrochemical Na-ion storage performance of the CRP-rGA composite can be attributed to high dispersion of CRP in rGA, strong interaction between CRP and rGA together with unique porous structure of the electrode. This work may provide some new insights into alloy reaction of crystalline phosphorus and demonstrate a promising new anode design strategy for next-generation batteries.