Electrochemical Activation of Ordered Mesoporous Solid Electrolyte Interphases to Enable Ultra‐Stable Lithium Metal Batteries

Abstract

In Li metal batteries, the rational construction of artificial solid electrolyte interphase (ASEI) can homogenize the Li‐ion flowing and Li‐mass plating/stripping, and reinforce the mechanical and electrochemical stabilities of electrode–electrolyte interface. Here, an ordered‐mesoporous powder zirconium oxophosphate (ZrOP) is proposed to construct a Li‐ion conductive ASEI by brushing ZrOP on metallic Li. The P‐induced amorphization in ZrOP is expected to accelerate the spontaneous lithiation reaction and promote the generation of P‐contained Li‐ion conductors and LiF domains in ASEI during Li anode cycling. The electrochemical activation of ASEI with promoted ionic conductivity and interconnected porous network is favorable for the homogeneous nucleation and growth of Li metal grains (with ≈10 µm in size), and the suppression of Li dendrites and volume expansion during long‐term Li plating and stripping. The ZrOP‐modified Li symmetric cell enables a long lifespan of over 1600 h at 1 mA cm−2, and the corresponding LiNi0.8Co0.1Mn0.1O2 (NCM811) based full cell displays a stable cycling for at least 300 cycles with a capacity retention of 80% at 1 C. The modified thin Li foil (40 µm in thickness) anode also enables a multilayered pouch cell based on a high‐loading NCM811 cathode with stable cycling and reversible capacity over 1 Ah.

Enhanced Ionic Conduction in Metal–Organic-Framework-Based Quasi-Solid-State Electrolytes: Mechanistic Insights

“…Nonetheless, a notable challenge emerges during battery cycling, as these electrolytes react with lithium metal to form an ion–electron mixed conductive interface (MCI) layer, causing electrolyte erosion and potential short-circuiting. , Organic solid electrolytes, known for their softness, affordability, and compatibility with lithium metal, face limitations as a result of their narrow potential window, hindering their use with high-voltage cathode materials . Moreover, their room-temperature conductivity may be insufficient for optimal battery cycling performance . In contrast, quasi-solid-state electrolytes offer a safer operational environment compared to liquid electrolytes and exhibit superior interfacial properties relative to solid-state electrolytes. , Metal–organic frameworks (MOFs) are emerging as promising candidates for quasi-solid-state electrolytes, leveraging their fast ionic transfer kinetics to advance this field. − …”

“…26 Moreover, their roomtemperature conductivity may be insufficient for optimal battery cycling performance. 27 In contrast, quasi-solid-state electrolytes offer a safer operational environment compared to liquid electrolytes and exhibit superior interfacial properties relative to solid-state electrolytes. 28,29 Metal−organic frameworks (MOFs) are emerging as promising candidates for quasisolid-state electrolytes, leveraging their fast ionic transfer kinetics to advance this field.…”

Superwettable Electrolyte Engineering for Fast Charging Li-Ion Batteries

“…Lithium-ion batteries (LIBs) have emerged as the prevailing energy storage technology that ubiquitously exists in portable electronics and electric vehicles (EVs). , Despite their extensive adoption and associated benefits, LIBs encounter notable hurdles in regard to cycle stability, safety, and fast charging capabilities. These challenges predominantly stem from the formation of the solid electrolyte interphase (SEI) layer on the graphite anode, which is the primary anode material in commercial LIBs due to their cost-effectiveness and low potential (∼0.1 V vs Li/Li + ) for lithium lithiation/delithiation reactions. − The SEI layer, formed by the irreversible decomposition of electrolyte components at the anode/electrolyte interface, is a critical component in maintaining the electrochemical stability of the anode and preventing excessive electrolyte consumption. − Additionally, the SEI layer facilitates the transport of lithium ions across the interface. − However, the presence of undesired SEI layers can have negative implications for graphite anodes . There are two main reasons for this.…”