Charge transport in highly acidic glass-forming protic ionic liquids tailored by zwitterionic precursors.

Highly acidic protic ionic liquids (PILs) are promising materials for potential electrochemical applications due to their high proton conductivity and excellent thermal stability. Still, little is known about the correlation between charge transport and structural dynamics as well as the proton transport mechanism despite the large body of literature on this topic. Here, we have examined the charge transport and structural dynamics by employing broadband dielectric spectroscopy in two highly acidic PILs in their supercooled liquid and glassy states, which included the same anion [TfO]- and different cations, [Tau]+ vs [Ahs]+. Unlike many other ionic liquids, the conductivity relaxation time τe of two studied PILs is substantially faster than the structural relaxation time τα. The decoupling behavior between charge transport and structural dynamics of two materials, which is manifested by a decoupling index Rτ, varies between 0.3 and 2.3 over the temperature range above Tg. Moreover, "Walden" plots of the molar conductivity vs the viscosity qualify both compounds as "Super ILs." All findings support the physical picture of large, polar, and orientationally correlated ion clusters, where the slow α-relaxation can be identified as structural relaxation associated with cooperative reorientations of the cluster macrodipole. In contrast, the shortest timescale for diffusive charge transport, τe, is 1-2 decades shorter than τα, implying that proton hopping is triggered by "single particle" (ions or ion pair) rotations and jumps on a sub-length scale of the cluster size, a dynamics being present even in the glassy state as indicated by a strong ß-relaxation. These results demonstrate the practicality of employing highly acidic PILs in electrochemical fields.

A Natural Biopolymer Film as a Robust Protective Layer to Effectively Stabilize Lithium-Metal Anodes.

Li metal is considered as an ideal anode for Li-based batteries. Unfortunately, the growth of Li dendrites during cycling leads to an unstable interface, a low coulombic efficiency, and a limited cycling life. Here, a novel approach is proposed to protect the Li-metal anode by using a uniform agarose film. This natural biopolymer film exhibits a high ionic conductivity, high elasticity, and chemical stability. These properties enable a fast Li-ion transfer and feasiblity to accomodate the volume change of Li metal, resulting in a dendrite-free anode and a stable interface. Morphology characterization shows that Li ions migrate through the agarose film and then deposit underneath it. A full cell with the cathode of LiFPO4 and an anode contaning the agarose film exhibits a capacity retention of 87.1% after 500 cycles, much better than that with Li foil anode (70.9%) and Li-deposited Cu anode (5%). This study provides a promising strategy to eliminate dendrites and enhance the cycling ability of lithium-metal batteries through coating a robust artificial film of natural biopolymer on lithium-metal anode.

Stabilized and Almost Dendrite-Free Li Metal Anodes by In Situ Construction of a Composite Protective Layer for Li Metal Batteries.

Li metal anodes (LMAs) are promising candidates for the anodes of high-energy-density batteries due to their lower reduction potential and high specific capacity. Unfortunately, LMAs usually suffer from uncontrollable Li plating and insecure solid electrolyte interphase layers, especially when used in conjunction with carbonate-based electrolytes. Herein, we proposed using metal alkoxides of titanium butyrate to react with hydroxyl groups on Li metal. A composite protective layer containing TiO2 and ROLi was generated to modify Li (designated as treated Li), leading to dendrite-free LMAs and achieving significantly enhanced cycling stability. Notably, symmetric cells using treated Li electrodes can deliver over 1500 h of stable cycling under a current density of 2 mA cm-2 in an ether-based electrolyte. Moreover, under extreme conditions of 5 mA cm-2 using a carbonate-based electrolyte, symmetric cells employing a treated Li electrode demonstrated stable cycling for over 80 h, as compared to the fluctuating voltage seen after only 10 h of cycling when using a bare Li electrode. Furthermore, full cells using a treated Li anode coupled with a high loading of LiCoO2 cathode (≈15 mg cm-2) displayed excellent cycling stability at 0.2 C over 150 cycles with a high capacity retention of 98.1% and an enhanced average Coulombic efficiency above 99.6%. By comparison, full cells using the bare Li anode drop to 125.4 mA h g-1 with a capacity retention of just 83.3%. The treated Li exhibited superior rate performance and delivered 132.7 mA h g-1 even at 5 C. This strategy provided a facile and effective option for the construction of advanced LMAs.

Ultra-Low Concentration Electrolyte Enabling LiF-Rich SEI and Dense Plating/Stripping Processes for Lithium Metal Batteries.

The interface structure of the electrode is closely related to the electrochemical performance of lithium-metal batteries (LMBs). In particular, a high-quality solid electrode interface (SEI) and uniform, dense lithium plating/stripping processes play a key role in achieving stable LMBs. Herein, a LiF-rich SEI and a uniform and dense plating/stripping process of the electrolyte by reducing the electrolyte concentration without changing the solvation structure, thereby avoiding the high cost and poor wetting properties of high-concentration electrolytes are achieved. The ultra-low concentration electrolyte with an unchanged Li+ solvation structure can restrain the inhomogeneous diffusion flux of Li+ , thereby achieving more uniform lithium deposition and stripping processes while maintaining a LiF-rich SEI. The LiIICu battery with this electrolyte exhibits enhanced cycling stability for 1000 cycles with a coulombic efficiency of 99% at 1 mA cm-2 and 1 mAh cm-2 . For the LiIILiFePO4 pouch cell, the capacity retention values at 0.5 and 1 C are 98.6% and 91.4%, respectively. This study offers a new perspective for the commercial application of low-cost electrolytes with ultra-low concentrations and high concentration effects.

Aluminum-Based Metal-Organic Frameworks Derived Al2O3-Loading Mesoporous Carbon as a Host Matrix for Lithium-Metal Anodes.

Li-metal anode attracts great focus owing to its ultra-high specific capacity and the lowest redox potential. However, the uncontrolled growth of Li dendrite leads to severe security issues and limited cycle life. Herein, Al2O3 loading mesoporous carbon (Al2O3@MOF-C) derived from Al-based metal-organic frameworks (Al-MOFs) was investigated as the stable host matrix for Li metal, in which, Al2O3 was served as nano seeds for the Li deposition and decrease the Li nucleation overpotential. Except that, the high specific surface area and wide pore distribution can also buffer the volume changes of Li and fasten electron transfer, hence a dendrite-free morphology was observed even after 50 cycles at 2 mA cm-2. High Li coulombic efficiency of 97.9% after 100 cycles at 1 mA cm-2, 1 mAh cm-2, and 97.6% after 50 cycles at 1 mA cm-2 and 6 mAh cm-2 were performed by Al2O3@MOF-C electrodes. Good performances were also obtained for Li-sulfur and LiFePO4 batteries. The performances of Al2O3@MOF-C@Li were compared with Li foil and Cu@Li in full cell configurations. The electrochemical tests of full cells based on Al2O3@MOF-C@Li indicated that this Al-based functional host matrix can enhance the Li-utilization and lead to significant enhancement of the cycling performance of Li anodes.