In-situ construction of high-mechanical-strength and fast-ion-conductivity interphase for anode-free Li battery

The solid electrolyte interphase(SEI)with strong mechanical strength and high ion conductivity is highly desired for Li metal batteries,especially for harsh anode-free batteries.Herein,we report a pragmatic approach to the in-situ construction of high-quality SEI by applying synergistic additives of Li NO_(3)and ethylene sulfite(ES)in the electrolyte.The obtained SEI exhibits a high average Young’s modulus(9.02GPa)and exchanging current density(4.59 mA cm^(-2)),which are 3.0 and 1.2 times as large as those using the sole additive of LiNO_(3),respectively.With this improved SEI,Li-dendrite growth and side reactions are effectively suppressed,leading to an ultra-high Coulombic efficiency(CE)of 99.7%for Li plating and stripping.When applying this improved electrolyte in full cells,it achieves a high capacity retention of 89.7%for over 150 cycles in a LiFePO_(4)||Li battery(~12 mg cm^(-2)cathode,50μm Li)and of 44.5%over 100 cycles in a LiFePO_(4)||Cu anode-free battery.

Progress in electrolytes for rechargeable Li-based batteries and beyond

Owing to almost unmatched volumetric energy density, Li-based batteries have dominated the portable electronic industry for the past 20 years. Not only will that continue, but they are also now powering plug-in hybrid electric vehicles and zero-emission vehicles. There is impressive progress in the exploration of electrode materials for lithium-based batteries because the electrodes(mainly the cathode) are the limiting factors in terms of overall capacity inside a battery. However, more and more interests have been focused on the electrolytes, which determines the current(power) density, the time stability, the reliability of a battery and the formation of solid electrolyte interface. This review will introduce five types of electrolytes for room temperature Li-based batteries including 1) non-aqueous electrolytes, 2) aqueous solutions, 3)ionic liquids, 4) polymer electrolytes, and 5) hybrid electrolytes. Besides, electrolytes beyond lithium-based systems such as sodium-, magnesium-, calcium-, zinc-and aluminum-based batteries will also be briefly discussed.

Tuning the solution structure of electrolyte for optimal solid-electrolyte-interphase formation in high-voltage lithium metal batteries

The continuous reduction of electrolytes by Li metal leads to a poor lifespan of lithium metal batteries(LMBs). Low Coulombic efficiency(CE) and safety concern due to dendrite growth are the challenging issues for LMB electrolyte design. Novel electrolytes such as highly concentrated electrolytes(HCEs) have been proposed for improving interphase stability. However, this strategy is currently limited for high cost due to the use of a large amount of lithium salts as well as their high viscosity, reduced ion mobility, and poor wettability. In this work, we propose a new type of electrolyte having a moderate concentration. The electrolyte has the advantage of HCEs as the anion is preferentially reduced to form inorganic solidelectrolyte-interphase(SEI). Such optimization has been confirmed through combined spectroscopic and electrochemical characterizations and supported with the first-principle molecular dynamics simulation. We have shown the intrinsic connections between solution structure and their electrochemical stability. The 2.0 M LiDFOB/PC electrolyte, as predicted by our characterizations and simulations, allows stable charge–discharge of LNMO|Li cells at 5C for more than 1500 cycles. The 2.0 M electrolyte generates a dense layer of SEI containing fluoro-oxoborates, Li_(3)BO_(3), LiF, Li_(2)CO_(3), and some organic species effectively passivating the lithium metal, as confirmed by electron microscopy, X-ray photoelectron spectroscopy,and solid-state nuclear magnetic resonance.