Lithiophilic Wetting Agent Inducing Interfacial Fluorination for Long‐Lifespan Anode‐Free Lithium Metal Batteries

Abstract

Anode‐free Li metal batteries (AFLMBs) are highly advantageous due to their high energy density, low cost, and simple fabrication. However, severe challenges, such as uncontrolled dendrite formation and low coulombic efficiency, restrict their practical application. Herein, this work introduces a silver nanoparticles incorporated p‐doped conjugated polymer (Ag‐PCP) wetting agent on the copper current collector, which promotes both uniform Li nucleation and rapid formation of a LiF‐rich solid electrolyte interphase (SEI) at the early stage, resulting in interfacial stabilization and high Li utilization efficiency. Moreover, this work verifies the interfacial fluorinated mechanism of the Ag‐PCP to efficiently achieve a favorable SEI chemistry, which serves as an intermediate process for promoting LiF formation. Benefiting from the synergistic effect of Ag–Li alloying and F‐doping chemistry of the Ag‐PCP chains, the deposited Li exhibits a compact column‐like structure with dendrite‐free morphology, and the anode‐free cells display superior cycling stability with long lifespan even under harsh conditions, with the LFP//Ag‐PCP│Cu full cell having a high capacity retention of 72% (Li inventory retention rate, 99.8%) at 1 C‐rate after 200 cycles.

Nucleophilic deposition behavior of metal anodes

“…can be smaller or even offset which means a smaller overpotential. 70–72 The experimental proof is further shown in Fig. S2 (ESI†).…”

Gradient Host for Bottom-Up Deposition of Lithium Metal Anode

“…Lithiophilicity is an important factor in the design of the hosts of LMBs, which is mainly achieved by strong affinity with Li. , Numerous studies have demonstrated that functional groups such as −CN, −O, −F, −OH, −COOH, , active compounds such as Ag, Au, Zn, Si, SiO 2 , and ZnO − are all lithiophilic. Generally, Li metal hosts with high lithiophilicity can minimize the Li nucleation overpotential and efficiently boost the Li + flux, resulting in good Li + conductivity of the hosts.…”

Ionovoltaics in energy harvesting and applications: A journey from early development to current state‐of‐the‐art

“…54 Based on the fundamental theory of the ionovoltaics, the potential for developing novel biological/chemical sensing platforms and improving the performance of lithium-ion batteries and neuromorphic devices was confirmed. 51,52,[55][56][57][58][59][60] The fundamental principle of the continuous energy generation phenomenon by the ionic interfacial interactions in porous structures is still an unresolved question, leading some researchers to speculate that it is a phenomenon similar to streaming potential. 12,[22][23][24] On the contrary, the established theory of ionovoltaics and the exploration of the voltage drop effect due to the 42 resistance of semiconductor electrodes were utilized as a fundamental theory for interpreting the core driving principle of the device.…”