Electrochemical Activation of Fe-LiF Conversion Cathodes in Thin-Film Solid-State Batteries.

Transition metal fluoride (TMF) conversion-type cathodes promise up to 4 times higher gravimetric energy densities compared to those of common intercalation-type cathodes. However, TMF cathodes demonstrate sluggish kinetics, poor efficiencies, and incompatibility with many liquid electrolytes. In this work, coevaporated heterostructured iron and lithium fluoride (Fe-LiF) cathodes are investigated in thin-film solid-state batteries with a LiPON electrolyte and a lithium metal anode. The cells were cycled 2000 times at a cycling rate of 6C. They show a gradual improvement in voltaic efficiency (37-53%) and specific capacity (146-216 mAh/g) during cycling. After 2000 cycles, the cathode capacity reaches 480 mAh/g at a cycling rate of C/3.6, close to its theoretical capacity of 498 mAh/g, at room temperature conditions. This capacity gain is correlated with an observed electrochemically activated nanorestructuring of the cathode, characterized by cycling-induced coarsening (from 2.8 to 4.2 nm) of the metallic iron phase and its accumulation near the current collector interface, as well as lithium fluoride phase accumulation near the LiPON interface.

Influence of Au, Pt, and C Seed Layers on Lithium Nucleation Dynamics for Anode-Free Solid-State Batteries.

In the concept of anode-free lithium-ion batteries, cells are manufactured with a bare anode current collector where the lithium metal anode is electrochemically formed from the lithium-containing cathode during the first charge cycle. While this concept has many attractive aspects from a manufacturing and energy density standpoint, stable plating and stripping remain challenging. We have investigated gold, platinum, and amorphous carbon as seed layers placed between the copper current collector and the lithium phosphorus oxynitride thin-film solid electrolyte. These layers guide lithium nucleation and improve the plating and stripping dynamics. All seed layers facilitate reversible lithium plating and stripping even at high current densities up to 8 mA cm-2. Of particular note is the amorphous carbon seed layer, which allowed a significant reduction in plating potential from 300 mV to as low as 50 mV. These results underscore the critical role of seed layers in improving the efficiency of anode-free solid-state batteries and open the door to simplified manufacturing of anode-free battery designs.

Monolithically-stacked thin-film solid-state batteries.

The power capability of Li-ion batteries has become increasingly limiting for the electrification of transport on land and in the air. The specific power of Li-ion batteries is restricted to a few thousand W kg-1 due to the required cathode thickness of a few tens of micrometers. We present a design of monolithically-stacked thin-film cells that has the potential to increase the power ten-fold. We demonstrate an experimental proof-of-concept consisting of two monolithically stacked thin-film cells. Each cell consists of a silicon anode, a solid-oxide electrolyte, and a lithium cobalt oxide cathode. The battery can be cycled for more than 300 cycles between 6 and 8 V. Using a thermo-electric model, we predict that stacked thin-film batteries can achieve specific energies >250 Wh kg-1 at C-rates above 60, resulting in a specific power of tens of kW kg-1 needed for high-end applications such as drones, robots, and electric vertical take-off and landing aircrafts.