N‐Containing Carbon‐Coated β‐Si₃N₄ Enhances Si Anodes for High‐Performance Li‐Ion Batteries

Abstract

The lithiation/delithiation properties of 𝜶-Si 3 N 4 and 𝜷-Si 3 N 4 are compared and the carbon coating effects are examined. Then, 𝜷-Si 3 N 4 at various fractions is used as the secondary phase in a Si anode to modify the electrode properties. The incorporated 𝜷-Si 3 N 4 decreases the crystal size of Si and introduces a new N-Si-O species at the 𝜷-Si 3 N 4 /Si interface. The nitrogen from the milled 𝜷-Si 3 N 4 diffuses into the surface carbon coating during the carbonization heat treatment, forming pyrrolic nitrogen and C-N-O species. The synergistic effects of combining 𝜷-Si 3 N 4 and Si phases on the specific capacity are confirmed. The operando X-ray diffraction and X-ray photoelectron spectroscopy data indicate that 𝜷-Si 3 N 4 is partially consumed during lithiation to form a favorable Li 3 N species at the electrode. However, the crystalline structure of the hexagonal 𝜷-Si 3 N 4 is preserved after prolonged cycling, which prevents electrode agglomeration and performance deterioration. The carbon-coated 𝜷-Si 3 N 4 /Si composite anode shows specific capacities of 1068 and 480 mAh g −1 at 0.2 and 5 A g −1 , respectively. A full cell consisting of the carbon-coated 𝜷-Si 3 N 4 /Si anode and a LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode is constructed and its properties are evaluated. The potential of the proposed composite anodes for Li-ion battery applications is demonstrated.