Mirror-Like Electrodeposition of Lithium Metal under a Low-Resistance Artificial Solid Electrolyte Interphase Layer
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Engineering topics
Publications and source records attributed to Wang, Shaofei.
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The insulating nature of sulfur, polysulfide shuttle effect, and lithium metal deterioration cause a decrease in practical energy density and fast capacity fade in lithium-sulfur batteries. Here, we present an integrated strategy for the development of hybrid Li-S batteries based on a gel sulfur cathode, a solid electrolyte, and a protective anolyte composed of highly-concentrated salt electrolyte containing mixed additives. The dense solid electrolyte completely blocks polysulfide diffusion, and also makes it possible to investigate the cathode and anode independently. This gel cathode effectively traps the polysulfide active material while maintaining a low electrolyte to sulfur ratio (E/S) of 5.2 mL/g. The anolyte effectively protects the Li metal and suppresses the consumption of liquid electrolyte, enabling stable long-term cycling for over 700 hours in Li symmetric cells. This advanced design can simultaneously suppress the polysulfide shuttle, protect Li metal, and reduce the liquid electrolyte usage. The assembled hybrid batteries exhibit remarkably stable cycling performance over 300 cycles with high capacity. Finally, surface-sensitive techniques were carried out to directly visualize and to probe the interphase formed on the surface of the LAGP pellet, which may help stabilize the solid-liquid interface.
Benefitting from extremely high shear modulus and high ionic transference number, solid electrolytes are promising candidates to address both the dendrite growth and electrolyte consumption problems inherent to the widely adopted liquid-phase electrolyte batteries. However, solid electrolyte/electrode interfaces present high resistance and complicated morphology, hampering the development of solid-state battery systems, while requiring advanced analysis for rational improvement. Here, we employ an ultra-sensitive three-dimensional (3D) chemical analysis to uncover the dynamic formation of interphases at the solid electrolyte/electrode interface. While the formation of interphases widens the electrochemical window, their electronic and ionic conductivities determine the electrochemical performance and has a large influence on dendrite growth. Our results suggest that, contrary to the general understanding, highly stable solid electrolytes with metal anodes in fact promote fast dendritic formation, as a result of less Li consumption and much larger curvature of dendrite tips that leads to an enhanced electric driving force. Detailed thermodynamic analysis shows an interphase with low electronic conductivity, high ionic conductivity, chemically stable yet having a dynamic thickness and uniform coverage is needed to prevent dendrite growth. Finally, this work provides a paradigm for interphase design to address the dendrite challenge, paving the way for the development of robust, fully operational solid-state batteries.
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Rechargeable batteries based on an abundant metal such as aluminum with a three-electron transfer per atom are promising for large-scale electrochemical energy storage. Aluminum can be handled in air, thus offering superior safety, easy fabrication, and low cost. But, the development of Al-ion batteries has been challenging due to the difficulties in identifying suitable cathode materials. This study presents the use of a highly open framework Mo 2.5 + y VO 9 + z as a cathode for Al-ion batteries. The open-tunnel oxide allows a facile diffusion of the guest species and provides sufficient redox centers to help redistribute the charge within the local host lattice during the multivalent-ion insertion, thus leading to good rate capability with a specific capacity among the highest reported in the literature for Al-based batteries. Our study also presents the use of Mo 2.5 + y VO 9 + z as a model host to develop a novel ultrafast technique for chemical insertion of Al ions into host structures. The microwave-assisted method employing diethylene glycol and aluminum diacetate (Al(OH)(C 2 H 3 O 2 ) 2 ) can be performed in air in as little as 30 min, which is far superior to the traditional chemical insertion techniques involving moisture-sensitive organometallic reagents. The Al-inserted Al x Mo 2.5 + y VO 9 + z obtained by the microwave-assisted chemical insertion can be used in Al-based rechargeable batteries.
This study presents a battery concept with a “mediator-ion” solid electrolyte for the development of next-generation electrochemical energy storage technologies. The active anode and cathode materials in a single cell can be in the solid, liquid, or gaseous form, which are separated by a sodium-ion solid-electrolyte separator. The uniqueness of this mediator-ion strategy is that the redox reactions at the anode and the cathode are sustained by a shuttling of a mediator sodium ion between the anolyte and the catholyte through the solid-state electrolyte. Use of the solid-electrolyte separator circumvents the chemical-crossover problem between the anode and the cathode, overcomes the dendrite-problem when employing metal-anodes, and offers the possibility of using different liquid electrolytes at the anode and the cathode in a single cell. The battery concept is demonstrated with two low-cost metal anodes (zinc and iron), two liquid cathodes (bromine and potassium ferricyanide), and one gaseous cathode (air/O2) with a sodium-ion solid electrolyte. This novel battery strategy with a mediator-ion solid electrolyte is applicable to a wide range of electrochemical energy storage systems with a variety of cathodes, anodes, and mediator-ion solid electrolytes.