Lithium‐7 Nuclear Magnetic Resonance Investigation of Lithium Insertion in Hard Carbon

Abstract

Lithium battery anodes based on disordered, hard carbon were prepared by low‐temperature (1000°C) pyrolysis of cotton cloth. Samples were lithiated in an electrochemical cell. The Li insertion (potential vs. capacity) curve exhibits two different regions: a sloping one, from 1.1 to 0.1 V (vs. ) denoted as the high‐voltage region (HVR), and a plateau between 0.1 and zero V, denoted as the low‐voltage plateau (LVP). Lithium‐7 high‐resolution (magic angle spinning) nuclear magnetic resonance measurements in fully lithiated samples reveal three main features: a broad line at ca. 50 ppm, a relatively sharp line at 17 ppm, with a shoulder at about zero ppm (all shifts relative to aqueous LiCl). The 50 ppm component is attributed to Li intercalated between turbostratically disordered graphene planes and is associated with the LVP part of the potential curve. The 17 ppm signal arises from a Li site which resides in amorphous hydrogen‐containing regions of the carbon and is correlated with the HVR part of the curve. The zero ppm component is attributed to the irreversible portion of the Li (up to ∼20% of the total) which constitutes the solid electrolyte interphase on the surface of the carbon grains formed by electrochemical reduction of the electrolyte. These spectral assignments were verified by running other samples which were electrochemically delithiated to varying degrees.