Enhancing Cycle Life of Graphite‖LiFePO₄ Batteries via Copper Substituted Li₂Ni_1-xCu_xO₂ Cathode Prelithiation Additive

Abstract

Lithium nickel oxide (Li₂NiO₂), as a sacrificial cathode prelithiation additive, has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries (LIBs). However, high-cost Li₂NiO₂ suffers from inferior delithiation kinetics during the first cycle. Herein, we investigated the effects of the cost-effective copper substituted Li₂Ni_1-xCu_xO₂ (x = 0, 0.2, 0.3, 0.5, 0.7) synthesized by a high-temperature solid-phase method on the structure, morphology, electrochemical performance of graphite‖LiFePO₄ battery. The X-ray diffraction (XRD) refinement result demonstrated that Cu substitution strategy could be favorable for eliminating the NiO_x impurity phase and weakening Li-O bond. Analysis on density of states (DOS) indicates that Cu substitution is good for enhancing the electronic conductivity, as well as reducing the delithiation voltage polarization confirmed by electrochemical characterizations. Therefore, the optimal Li₂Ni_0.7Cu_0.3O₂ delivered a high delithiation capacity of 437 mAh·g^-1, around 8% above that of the pristine Li₂NiO₂. Furthermore, a graphite‖LiFePO₄ pouch cell with a nominal capacity of 3000 mAh demonstrated a notably improved reversible capacity, energy density and cycle life through introducing 2 wt% Li₂Ni_0.7Cu_0.3O₂ additive, delivering a 6.2 mAh·g^-1 higher initial discharge capacity and achieving around 5% improvement in capacity retentnion at 0.5P over 1000 cycles. Additionally, the post-mortem analyses testified that the Li₂Ni_0.7Cu_0.3O₂ additive could suppress solid electrolyte interphase (SEI) decomposition and homogenize the Li distribution, which benefits to stabilizing interface between graphite and electrolyte, and alleviating dendritic Li plating. In conclusion, the Li₂Ni_0.7Cu_0.3O₂ additive may offer advantages such as lower cost, lower delithiation voltage and higher prelithiation capacity compared with Li₂NiO₂, making it a promising candidate of cathode prelithiation additive for next-generation LIBs.

Keywords

Li₂Ni_1-xCu_xO₂ / cathode prelithiation additive / LiFePO₄ battery / cycle life / grid energy storage

References

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