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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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165 records · Page 10

Quantification of Anionic Redox Chemistry in a Prototype Na-Rich Layered Oxide

Harnessing anionic redox reactions is of prime importance for boosting the capacity of sodium-ion batteries (NIBs). However, quantifying the cyclability of anionic redox reactions is still challenging. Herein, we conduct a qualitative and quantitative investigation of the cationic and anionic redox reactions of a prototype Na-rich layered oxide, namely, Na 3 RuO 4 , by a combination of bulk-sensitive X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering. We unequivocally reveal that both Ru cations and oxygen anions are involved in the charge compensation process of Na 3 RuO 4 . Ru redox is highly reversible over extended electrochemical cycles, while the cyclability of lattice oxygen redox gradually decreases with the retention of only 36% after 30 cycles, which is mainly responsible for the capacity fading of Na 3 RuO 4 . Finally, our findings provide deeper insights into the complex oxygen redox mechanism, which plays a decisive role for designing high-energy Na-rich electrode materials for NIBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating the Link Between Alkali Metal Ions and Reaction-Transport Mechanisms in Cathode Electrodes for Alkali-ion Batteries

Our long-term goal is to improve the reliability of electrode materials and their ability to transport and store various metal ions for electrochemical energy storage applications. The main objective of this work was to investigate the intrinsic relationship between the role of alkali metal ions and electrochemically driven mechanical stability and kinetic properties of battery materials. The overall question was “What is the role of alkali metal ions on the electrochemical and mechanical behavior of cathode electrodes? Our guiding hypothesis was that intercalation of larger alkali metal ions (Na and K) inevitably alters the coupled transport-reaction processes during battery operation in organic electrolytes, leading to more intensive chemo-mechanical instabilities in cathode electrodes, resulting in rapid capacity fade. To validate the hypothesis, we experimentally characterized the reaction-transport processes and governing forces driving the instability of electrode materials in different alkali metal-ion environments. The project had three main tasks. The first one was to investigate intercalation-induced strains and associated stress generation, and their impact on structural deformations in composite cathode electrodes. The second task focused on identifying potential-dependent dynamic changes in the electrode-electrolyte interface in alkali metal ion batteries. The last task was focused on determining how larger alkali metal ions with slower diffusivity affect the transport-mechanics coupling at faster scan rates, compared to smaller ions with faster diffusivity in electrodes. We shortly provided the outcome of each task in the accomplishment section. This project produced 10 peer-reviewed publications (9 research papers and one review manuscript) and supported two Ph.D. students, who graduated from Oklahoma State University.

25 ENERGY STORAGE↗

Anion Coordination Improves High-Temperature Performance and Stability of NaPF 6 -Based Electrolytes for Supercapacitors

Electrolyte stability can be improved by incorporating complexing agents that bind key decomposition intermediates and slow down decomposition. We show that hexamethyl-phosphoramide (HMPA) extends both the thermal stability threshold of sodium hexafluorophosphate (NaPF 6 ) in dimethoxyethane (DME) electrolyte and the cycle life of double-layer capacitors. HMPA forms a stable complex with PF 5 , an intermediate in PF 6 anion thermal degradation. Unbound, this intermediate leads to autocatalytic degradation of the electrolyte solution. The results of electrochemical impedance spectroscopy (EIS) and galvanostatic cycling measurements show large changes in the cell without the presence of HMPA at higher temperatures (≥60 °C). Fourier transform infrared spectroscopy (FTIR) on the liquid and gas phase of the electrolyte shows without HMPA the formation of measurable amounts of PF 5 and HF. The complimentary results of these measurements proved the usefulness of using Lewis bases such as HMPA to inhibit the degradation of the electrolyte solution at elevated temperatures and potentially lead to improve cycle life of a nonaqueous capacitor. The results showed a large increase in capacitance retention during cycling (72% retention after 750,000 cycles). The results also provide evidence of major decomposition processes (0% capacitance retention after 100,000 cycles) that take place at higher temperatures without the additive of a thermal stability additive such as HMPA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗