Feasibility of Prelithiation in LiFePO₄

Abstract

Lithium iron phosphate (LiFePO4) is widely applied as the cathode material for the energy storage Li‐ion batteries due to its low cost and high cycling stability. However, the low theoretical specific capacity of LiFePO4 makes its initial capacity loss more concerning. Therefore, lithium compensation by way of prelithiation and applications of sacrificial Li‐rich additives in LiFePO4 is imminent in elevating the energy density and/or prolonging the lifetime of the LiFePO4‐based Li‐ion batteries (LIBs). Prelithiation in LiFePO4 is herein carried out by electrochemical and chemical methods and its feasibility is proved on the basis of the electrochemical evaluations such as the initial charge capacity and the cycling stability. In addition, the site of the pre‐intercalated Li‐ions is found via comprehensive physical characterizations and the density functional theory (DFT) calculations. These findings open a new avenue for elevating the energy density and/or prolonging the lifetime of the high‐energy‐density batteries.

Recognition and Application of Catalysis in Secondary Rechargeable Batteries

“…The introduction of M (M = Mn, Co, Fe, and so on) in antifluorite materials could effectively reduce its decomposition potential via regulating the energy level/band structure. These materials have been proven to be effective prelithiation additives which has gradually been adopted by various companies such as Huawei Technologies Co., Ltd. and Contemporary Amperex Technology Co., Limited. ,, Although these antifluorite materials can meet the criteria to be cathode prelithiation additives (donable capacity, appropriate decomposition potential, industrial compatibility and scalability), some other problems or challenges are still thought-provoking and need to be addressed such as safety hazards of prelithiation, residues and side reactions, chemical and ambient stability, and so on. ,− …”

Prelithiation: A Critical Strategy Towards Practical Application of High‐Energy‐Density Batteries

“…Additionally, the over-lithiated Fe-LNMO//prelithiated graphite cell with a high mass loading (3.2 mAh cm −2 ) provides 80% of its original capacity after 300 cycles at C/2-1C rate. Amazingly, Cao et al [215] over-lithiated LiFePO 4 by the chemical and electrochemical over-lithiation. The over-lithiated LiFePO 4 can release an extra charge capacity of 25-30 mAh g −1 without degrading the electrochemical and mechanical performance.…”

“…Amazingly, Cao et al. [ 215 ] over‐lithiated LiFePO 4 by the chemical and electrochemical over‐lithiation. The over‐lithiated LiFePO 4 can release an extra charge capacity of 25–30 mAh g −1 without degrading the electrochemical and mechanical performance.…”

Co-recovery of spent LiCoO2 and LiFePO4 by paired electrolysis

“…8,9 For typical LIBs, there are three types of cathode materials: layered oxides (e.g., LiCoO 2 (LCO) and LiNi x Co y Mn 1−x−y O 2 (NCM)), 10 spinel-type (e.g., LiMn 2 O 4 (LMO)) 3 and olivine-type (e.g., LiFePO 4 (LFP)). 11 However, the recycling efficiency of spent LIBs lags far behind their generation. 12 Therefore, it is critical to develop efficient recycling processes for meeting the pro-duction demands of LIBs and greatly reducing the pollution of the environment.…”