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Stable all-solid-state sodium-sulfur batteries for low-temperature operation enabled by sodium alloy anode and confined sulfur cathode

All-solid-state sodium-sulfur (Na-S) batteries are promising for stationary energy storage devices because of their low operating temperatures (less than 100 °C), improved safety, and low-cost fabrication. Using Na alloy instead of Na metal as an anode in Na-S batteries can prevent dendrite growth and improve interfacial stability between the anode and solid electrolytes to achieve long-cycling stability. A high-sulfur content cathode possessing high sulfur utilization is also important to enable an energy-dense Na-S battery. In this work, we studied Na-Sb and Na- Sn alloy anodes and demonstrated the superiority of Na 3 Sb alloy undergoing a stable Na alloying/dealloying process at 0.04 mA cm -2 for over 500 hours. Combining the optimized Na3Sb alloy anode with sulfur-carbon composites prepared by the vapor deposition approach, the full cell shows a high sulfur specific capacity and improved rate performance. Moreover, the all-solid-state Na alloy-S battery can deliver a high initial discharge specific capacity of 1377 mAh g -1 and maintain good capacity retention of 70 % after 180 cycles at 60 °C. Further, post-cycle characterizations show that both the anode and cathode perform a reversible discharge/charge process after the 1st cycle, and the cathode undergoes significantly rearranged distributions of carbon and solid-state electrolytes after 180 cycles due to severe volume change induced by repeated sodiation/desodiation process.

25 ENERGY STORAGE↗

Materials Data on NaSb by Materials Project

NaSb crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six Sb1- atoms to form a mixture of distorted edge and corner-sharing NaSb6 octahedra. The corner-sharing octahedra tilt angles range from 25–60°. There are a spread of Na–Sb bond distances ranging from 3.27–3.39 Å. In the second Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six Sb1- atoms. There are a spread of Na–Sb bond distances ranging from 3.26–3.42 Å. There are two inequivalent Sb1- sites. In the first Sb1- site, Sb1- is bonded in a 8-coordinate geometry to six Na1+ and two equivalent Sb1- atoms. There are one shorter (2.89 Å) and one longer (2.90 Å) Sb–Sb bond lengths. In the second Sb1- site, Sb1- is bonded in a 8-coordinate geometry to six Na1+ and two equivalent Sb1- atoms.

36 MATERIALS SCIENCE↗

Materials Data on Na3Sb by Materials Project

Na3Sb is Sodium arsenide structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to four equivalent Sb3- atoms to form a mixture of distorted face, edge, and corner-sharing NaSb4 tetrahedra. There are one shorter (3.18 Å) and three longer (3.49 Å) Na–Sb bond lengths. In the second Na1+ site, Na1+ is bonded in a trigonal planar geometry to three equivalent Sb3- atoms. All Na–Sb bond lengths are 3.10 Å. Sb3- is bonded in a 5-coordinate geometry to eleven Na1+ atoms.

36 MATERIALS SCIENCE↗