Lithium (Li) metal is among the most promising anode materials for nextgeneration high-energy-density batteries. However, both dendrite growth and unstable solid electrolyte interphases have hindered its practical applications. Herein, we propose a coralloid carbon fiber-based composite lithium anode, which is an initially Li-containing structured anode. Such electrode design renders dendrite-free morphology during repeated stripping/plating cycles and extraordinary electrochemical performance in Li-LiFePO 4 and Li-sulfur cells.

Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN O on a working lithium metal anode with dendrite-free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first-principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries.

No abstract

Lithium‐metal electrodes have undergone a comprehensive renaissance to meet the requirements of high‐energy‐density batteries due to their lowest electrode potential and the very high theoretical capacity. Unfortunately, the unstable interface between lithium and nonaqueous electrolyte induces dendritic Li and low Coulombic efficiency during repeated Li plating/stripping, which is one of the huge obstacles toward practical lithium‐metal batteries. Here, a composite mixed ionic/electronic conductor interphase (MCI) is formed on the surface of Li by in situ chemical reactions of a copper‐fluoride‐based solution and Li metal at room temperature. The as‐obtained MCI film acts like the armor of a soldier to protect the Li‐metal anode by its prioritized lithium storage, high ionic conductivity, and high Young's modulus. The armored MCI can effectively suppress Li‐dendrite growth and work effectively in LiNi0.5Co0.2Mn0.3O2/Li cells. The armored MCI presents fresh insights into the formation and regulation of the stable electrode–electrolyte interface and an effective strategy to protect Li‐metal anodes in working Li‐metal batteries.

Lithium and sodium metal batteries are considered as promising next-generation energy storage devices due to their ultrahigh energy densities. The high reactivity of alkali metal toward organic solvents and salts results in side reactions, which further lead to undesirable electrolyte depletion, cell failure, and evolution of flammable gas. Herein, first-principles calculations and in situ optical microscopy are used to study the mechanism of organic electrolyte decomposition and gas evolution on a sodium metal anode. Once complexed with sodium ions, solvent molecules show a reduced LUMO, which facilitates the electrolyte decomposition and gas evolution. Such a general mechanism is also applicable to lithium and other metal anodes. We uncover the critical role of ion-solvent complexation for the stability of alkali metal anodes, reveal the mechanism of electrolyte gassing, and provide a mechanistic guidance to electrolyte and lithium/sodium anode design for safe rechargeable batteries.

Lithium (Li) metal‐based battery is among the most promising candidates for next‐generation rechargeable high‐energy‐density batteries. Carbon materials are strongly considered as the host of Li metal to relieve the powdery/dendritic Li formation and large volume change during repeated cycles. Herein, we describe the formation of a thin lithiophilic LiC6 layer between carbon fibers (CFs) and metallic Li in Li/CF composite anode obtained through a one‐step rolling method. An electron deviation from Li to carbon elevates the negativity of carbon atoms after Li intercalation as LiC6, which renders stronger binding between carbon framework and Li ions. The Li/CF | Li/CF batteries can operate for more than 90 h with a small polarization voltage of 120 mV at 50% discharge depth. The Li/CF | sulfur pouch cell exhibits a high discharge capacity of 3.25 mAh cm−2 and a large capacity retention rate of 98% after 100 cycles at 0.1 C. It is demonstrated that the as‐obtained Li/CF composite anode with lithiophilic LiC6 layers can effectively alleviate volume expansion and hinder dendritic and powdery morphology of Li deposits. This work sheds fresh light on the role of interfacial layers between host structure and Li metal in composite anode for long‐lifespan working batteries.

The intrinsic instability of organic electrolytes seriously impedes practical applications of high-capacity metal (Li, Na) anodes.I on-solvent complexes can even promote the decomposition of electrolytes on metal anodes. Herein, first-principles calculations were performed to investigate the origin of the reduced reductive stability of ionsolvent complexes.Both ester and ether electrolyte solvents are selected to interact with Li + ,N a + ,K + ,M g 2+ ,a nd Ca 2+ .T he LUMO energy levels of ion-ester complexes exhibit al inear relationship with the binding energy,r egulated by the ratio of carbon atomic orbital in the LUMO,w hile LUMOs of ionether complexes are composed by the metal atomic orbitals. This work shows why ion-solvent complexes can reduce the reductive stability of electrolytes,reveals different mechanisms for ester and ether electrolytes,a nd provides at heoretical understanding of the electrolyte-anode interfacial reactions and guidance to electrolyte and metal anode design.

Practical application of lithium (Li) metal anodes has been hindered by Li dendrite growth, which renders a low Coulombic efficiency and short lifespan of working Li metal batteries. A stable solid electrolyte interphase (SEI) is crucial in suppressing the formation of Li dendrites. Herein the local stress and deformation evolvement status of a SEI layer during Li electrodeposition are investigated through a quantitative electrochemical–mechanical model based on a finite element method. Furthermore, the impacts of structural uniformity and mechanical strength on the stability of the SEI under different working conditions are investigated. Improving the structural uniformity of SEI is the most effective way to enhance the stability of SEI, which regulates ion transportation. In addition, pursuing extremely high mechanical strength is shown to be pointless, and a moderate elastic modulus of 3.0 GPa is suggested. This work affords an insight into the rational design of stable SEI layers and sheds light on a possible pathway toward practical applications of Li metal anodes.