Practical Prelithiation of 4.5 V LiCoO2||Graphite Batteries by a Passivated Lithium‐Carbon Composite

Abstract Prelithiation can replenish active Li into the battery to compensate the Li consumption due to the formation of solid electrolyte interphase (SEI) on the electrode surface, therefore improving the energy density of Li‐ion batteries (LIBs), especially for batteries using electrode materials with low initial Coulombic efficiency (ICE). However, practical prelithiation in LIBs is a challenge since most lithiated compounds with high specific capacity are unstable and industrially incompatible. Herein, an effective prelithiation strategy is demonstrated by using a lithium‐carbon (Li‐C) microsphere composite. These Li‐C microspheres are passivated by a self‐assembled monolayer of octadecylphosphonic acid, which suppresses the reaction between Li and commonly used slurry solvent 1‐methyl‐2‐pyrrolidinone (NMP). After the addition of passivated Li‐C into the NMP‐based graphite slurry, the ICE of the graphite||Li half‐cell boosts from 88.5% to 100.5%. In a 4.5 V LiCoO 2 (LCO)||graphite full‐cell, the supplementary Li source avoids excessive delithiation of LCO, thus suppressing the destructive phase transformation at high delithiation potential. As a result, the prelithiated LCO||graphite full‐cell presents an initial discharge capacity of 201 mAh g −1 and the capacity retention after 100 cycles increases by 7.1 %. This work provides a practical approach for developing high energy density and long cycle life LIBs.