(Best Student Presentation) Extending the NaCl-AlCl3 Phase Diagram to Enable Low-Cost, Long-Duration Na-Al Batteries for the Grid

Achieving deep grid decarbonization via intermittent renewable power sources requires extensive grid-scale energy storage technologies to deliver stable power during periods of low generation. Doing so at scale and at low cost further adds to this challenge, as current solutions generally rely on geographically limited solutions such as pumped hydro storage, or costly battery chemistries focusing primarily on Li-ion technologies. As an alternative, battery systems based on lower cost materials such as sodium offer an attractive alternative for low-cost, scalable, and non-geographically limited electrochemical energy storage. This work combines an abundant and inexpensive molten sodium metal anode with a cost-effective aluminum cathode to provide a proof-of-concept alternative for grid-scale energy storage. Building on prior work utilizing the high reversibility of the neutral sodium chloroaluminate (NaAlCl 4 ) molten salt electrolyte commonly used for classic molten sodium batteries, this work demonstrates greater capacity utilization of the NaCl-AlCl 3 binary system by ‘overcharging’ this Na-Al battery to form an acidic chloroaluminate catholyte, NaAl 2 Cl 7 . Leveraging the reaction between NaAlCl 4 and NaAl 2 Cl 7 in conjunction with that between Al/NaCl and NaAlCl 4 advantageously utilizes the majority of Na available in the cathode for capacity, in addition to providing a higher discharge voltage (~ 2 V compared to ~ 1.6 V for the NaAlCl 4 reaction), thereby adding ~ 119 Wh kg -1 additional specific energy, on top of the 493 Wh kg -1 theoretical specific energy of the neutral Na-Al battery reaction between Al/NaCl and NaAlCl 4 . Fundamental aspects of the acidic chloroaluminate reaction are investigated, showing that cells using only the acidic reaction are able to cycle for hundreds of cycles. The acidic reaction between NaAlCl 4 and NaAl 2 Cl 7 occurs via a solution-phase reaction, unlike the two-phase neutral reaction between NaCl/Al and NaAlCl 4 , and we confirm via Raman and NMR spectroscopies that complete conversion to NaAl 2 Cl 7 occurs at end of charge. Na-Al batteries utilizing both reactions demonstrate high areal capacity (~ 46 mAh cm -2 ) and excellent reversibility. Enabled by the rapid mass transfer and solid-liquid reaction mechanism of the chloroaluminate catholyte, a higher areal capacity cell with ~ 132 mAh cm -2 is demonstrated, allowing a discharge duration of 28.2 h, implying that this Na-Al battery chemistry may be suitable for long-duration energy storage for grid applications. Finally, the raw active materials cost of this battery is estimated to be only ~ $7 kWh -1 , which is promising for enabling low-cost renewable power utilization for the grid. Figure 1