No abstract

Lithium/air batteries, based on their high theoretical specific energy, are an extremely attractive technology for electrical energy storage that could make long-range electric vehicles widely affordable. However, the impact of this technology has so far fallen short of its potential due to several daunting challenges. In nonaqueous Li/air cells, reversible chemistry with a high current efficiency over several cycles has not yet been established, and the deposition of an electrically resistive discharge product appears to limit the capacity. Aqueous cells require water-stable lithium-protection membranes that tend to be thick, heavy, and highly resistive. Both types of cell suffer from poor oxygen redox kinetics at the positive electrode and deleterious volume and morphology changes at the negative electrode. Closed Li/air systems that include oxygen storage are much larger and heavier than open systems, but so far oxygen-and OH − -selective membranes are not effective in preventing contamination of cells. In this review we discuss the most critical challenges to developing robust, high-energy Li/air batteries and suggest future research directions to understand and overcome these challenges. We predict that Li/air batteries will primarily remain a research topic for the next several years. However, if the fundamental challenges can be met, the Li/air battery has the potential to significantly surpass the energy storage capability of today's Li-ion batteries.

The Li/oxygen battery may achieve a high practical specific energy as its theoretical specific energy is 11,400 Wh/kg Li assuming Li 2 O 2 is the product. To help understand the physics of the Li/oxygen battery we present the first physics-based model that incorporates the major thermodynamic, transport, and kinetic processes. We obtain a good match between porous-electrode experiments and simulations by using an empirical fit to the resistance of the discharge products ͑which include carbonates and oxides when using carbonate solvents͒ as a function of thickness that is obtained from flat-electrode experiments. The experiments and model indicate that the discharge products are electronically resistive, limiting their thickness to tens of nanometers and their volume fraction in one of our discharged porous electrodes to a few percent. Flat-electrode experiments, where pore clogging is impossible, show passivation similar to porous-electrode experiments and allow us to conclude that electrical passivation is the dominant capacity-limiting mechanism in our cells. Although in carbonate solvents Li 2 O 2 is not the dominant discharge product, we argue that the implications of this model, ͑i.e., electrical passivation by the discharge products limits the capacity͒ also apply if Li 2 O 2 is the discharge product, as it is an intrinsic electronic insulator.

While solid-state batteries are tantalizing for achieving improved safety and higher energy density, solid ion conductors currently available fail to satisfy the rigorous requirements for battery electrolytes and electrodes. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact and impedes device integration and stability.Conversely, flexible polymeric ion conductors provide better interfacial compatibility and mechanical tolerance, but suffer from inferior ionic conductivity (< 10 −5 S cm −1 at room temperature) due to the coupling of ion transport with the polymer chain motion 1-3 . In this work, we report a general design strategy for achieving one-dimensional (1D), high-performance polymer solid-state ion conductors through molecular channel engineering, which we demonstrate via Cu 2+ -coordination of cellulose nanofibrils. The cellulose nanofibrils by themselves are not ionic conductive; however, by opening the molecular channels between the cellulose chains through Cu 2+ coordination we are able to achieve a Li-ion conductivity as high as 1.5×10 −3 S cm −1 at room temperature-a record among all known polymer ion conductors. This improved conductivity is enabled by a unique Li + hopping mechanism that is decoupled from the polymer segmental motion. Also benefitted from such decoupling, the cellulose-based ion conductor demonstrates multiple advantages, including a high transference number (0.78 vs. 0.2-0.5 in other polymers 2 ), low activation energy (0.19 eV), and a wide electrochemical stability window (4.5 V) that accommodate both Li metal anode and high-voltage cathodes. Furthermore, we demonstrate this 1D ion conductor not only as a thin, high-conductivity solid-state electrolyte but also as an effective ion-conducting additive for the solid cathode, providing continuous ion transport pathways with a low percolation threshold, which allowed us to utilize the thickest LiFePO4 solidstate cathode ever reported for high energy density. This approach has been validated with other 3 polymers and cations (e.g., Na + and Zn 2+ ) with record-high conductivities, offering a universal strategy for fast single-ion transport in polymer matrices, with significance that could go far beyond safe, high-performance solid-state batteries.

Solid-state batteries utilizing Li metal anodes have the potential to enable improved performance (specific energy >500 Wh/kg, energy density >1,500 Wh/L), safety, recyclability, and potentially lower cost (< $100/kWh) compared to advanced Li-ion systems. 1,2 These improvements are critical for the widespread adoption of electric vehicles and trucks and could create a short haul electric aviation industry. [1][2][3] Expectations for solid-state batteries are high, but there are significant materials and processing challenges to overcome.On May 15 th , 2020, Oak Ridge National Laboratory (ORNL) hosted a 6-hour, national online workshop to discuss recent advances and prominent obstacles to realizing solid-state Li metal batteries. The workshop included more than 30 experts from national laboratories, universities, and companies, all of whom have worked on solid-state batteries for multiple years. The participants' consensus is that, although recent progress on solid-state batteries is exciting, much has yet to be researched, discovered, scaled, and developed. Our goal was to examine the issues and identify the most pressing needs and most significant opportunities. The organizers asked workshop participants to present their views by articulating fundamental knowledge gaps for materials and processing science, mechanical behavior and battery architectures critical to advancing solid-state battery technology. The organizers used this input to set the workshop agenda. The group also considered what would incentivize the adoption of US manufacturing and how to accelerate and focus research attention for the benefit of the US energy, climate, and economic interests. The participants identified pros and cons for sulfide, oxide, and polymerbased solid-state batteries and identified common science gaps among the different chemistries. Addressing these common science gaps may reveal the most promising systems to pursue in the future.