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At least 73 records · Page 4

A family of dual-anion-based sodium superionic conductors for all-solid-state sodium-ion batteries

The sodium (Na) superionic conductor is a key component that could revolutionize the energy density and safety of conventional Na-ion batteries. However, existing Na superionic conductors are primarily based on a single-anion framework, each presenting inherent advantages and disadvantages. Here we introduce a family of amorphous Na-ion conductors (Na 2 O 2 –MCl y , M = Hf, Zr and Ta) based on the dual-anion framework of oxychloride. Benefiting from a dual-anion chemistry and with the resulting distinctive structures, Na 2 O 2 –MCl y electrolytes exhibit room-temperature ionic conductivities up to 2.0 mS cm -1 , wide electrochemical stability windows and desirable mechanical properties. All-solid-state Na-ion batteries incorporating amorphous Na 2 O 2 –HfCl 4 electrolyte and a Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 cathode exhibit a superior rate capability and long-term cycle stability, with 78% capacity retention after 700 cycles under 0.2 C (1C = 120 mA g -1 ) at room temperature. The discoveries in this work could trigger a new wave of enthusiasm for exploring new superionic conductors beyond those based on a single-anion framework.

25 ENERGY STORAGE↗

Progress Report on Performance of A709 and G91 Steels in Sodium

Specimens in six different processing and heat treatment conditions of A709 H58776 were exposed to sodium at 550, 600, and 650°C, respectively for various exposure times. G91 base metal was tested in sodium at 550, 600, and 650°C, and G91 weldment at 550 and 600°C, respectively. Parallel thermal aging experiments were conducted on G91 and A709 to obtain thermal aging data for comparison with sodium exposure results to separate the thermal and sodium effects. The corrosion data obtained on A709 steel continue to show low corrosion rates, which indicate good compatibility of A709 with sodium when oxygen content is controlled. G91 has also shown acceptable corrosion rates over the temperature range of 550-650°C in sodium. Thermal aging or sodium exposures reduced the tensile strength, uniform elongation, and total elongation for A709 ESR, AOD specimens. These specimens consistently showed higher yield stress and tensile strength and lower uniform and total elongations after sodium exposure than after thermal aging under comparable testing conditions. It implies that there was an additional effect of sodium exposure that gave rise to an increase in tensile strength of A709. Dynamic strain aginginduced flow serrations were completely removed by either thermal aging or sodium exposure at 650°C, which imply that carbon or nitrogen in solution was removed from the solution and formed precipitates during aging or sodium exposures. The tensile data ruled out the possibility of decarburization under the sodium exposure conditions. The HOMO specimens behaved somewhat differently from the ESR and AOD specimens in sodium. While thermal aging and sodium exposures at 550 and 600°C decreased the yield stress and the ultimate tensile strength of G91, there was virtually no additional effect resulting from sodium exposures at these two temperatures. In contrast, sodium exposures at 650°C had a drastic effect on the yield stress and the ultimate tensile strength of G91. It is suggested that G91 experienced decarburization in the 650°C sodium environments. Carbon concentrations in sodium in the SMT-1 and SMT-2 loops were determined by a foil equilibration method. The estimated carbon concentration was in the range of 0.8-1.2 ppm in the SMT-1 loop and 0.3-0.7 ppm in the SMT-2 loop. The carbon activity in sodium in the SMT-2 loop was estimated to be 0.03-0.08 at 600°C, and 0.08-0.2 at 550°C. The carbon activity in sodium at 650°C in the SMT-1 loop was 0.04-0.07. Equilibrium simulation of the carburization – decarburization processes was conducted for A709 and G91 steels exposed in sodium environments at temperatures of 550-700°C. The carbon activity-concentration relationship for G91 was re-evaluated by considering four phases in G91, i.e. bcc ferrite, M 23 C 6 , NbC and VC carbides. It was found that the carburization-decarburization process in G91 steel was dictated by M 23 C 6 carbides at high carbon activities, while NbC carbides dominated the process at low carbon activities. Formation of NbC increases the decarburization resistance of G91 steel. It remains to be understood whether the decarburization resistance provided by MC carbides in G91 can be maintained during long-term operations of SFRs. The carbon concentration-activity relationship for A709 was calculated based on the equilibrium of fcc-austenite and M 23 C 6 carbide phase. The calculations showed that A709 decarburizes at 650°C in the SMT-1 loop environments, which is different from the experimental findings. The carbon concentration-activity relationship in A709 was further evaluated by considering four phases, including fcc-austenite, M 23 C 6 , NbC, and TiC carbide phases. TiC is the most stable carbides among the three carbide phases. The carburization-decarburization process in A709 is dictated by M 23 C 6 carbides at high carbon activities and by TiC at low carbon activities. Formation of TiC increases the decarburization resistance of A709 steel. Because of the complexity of the precipitation process in A709 during sodium exposures, detailed characterization of precipitates in sodium-exposed specimens and improved thermodynamic models are needed to understand the carburization-decarburization behavior of A709. Kinetic analysis of carbon transfer will be investigated for G91 and A709 in future work.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Sodium Exposure Tests of A709 Steel (FY2020 Progress Report)

Sodium exposure tests were conducted on the first commercial heat, H58776 of A709 steel. Six different processing and heat treatment conditions were investigated, including three processing conditions, namely, Argon-Oxygen-Decarburization (AOD), Electro-slag Remelting (ESR), and Electro-slag Remelting with subsequent homogenization (HOMO), and two heat treatment conditions, i.e. solution annealing at 1100°C (SA1100°C) or 1150°C (SA1150°C). Specimens of AOD-SA1100°C, AOD-SA1150°C, ESR-SA1100°C, ESR-SA1150°C, HOMO-SA1100°C, and HOMO-SA1150°C were tested in sodium at 650°C and for times up to 10,152 h. Specimens in the AOD-SA1100°C and AOD-SA1150°C conditions were also tested in sodium at 550 and 600°C. Parallel thermal aging experiments were carried out for comparison with sodium exposure tests to separate the thermal and sodium effects. It was found that A709 H58776 generally showed a weight loss after sodium exposures at 650°C except a few data points of the ESR-SA1100°C specimens. The corrosion rate showed large variations in the initial stage and decreased with increasing exposure time. Long-term exposure tests are needed to determine its steady-state corrosion rate. The AOD-SA1100°C and HOMO-SA1100°C specimens showed similar tensile responses after thermal or sodium exposures at 650°C. The yield stress increased, the ultimate tensile strength decreased, and the uniform and total elongations were reduced after thermal or sodium exposures. A longer exposure time had a minimal effect on the tensile strength but further reduced the tensile ductility. The sodium-exposed specimens had higher tensile strength than the thermally-aged specimens. In contrast, the ESR-SA1100°C specimens showed an increase in the yield stress and the ultimate tensile strength after thermal or sodium exposures at 650°C and ~10,000 h. The AOD-SA1150°C and ESR-SA1150°C specimens showed similar tensile behavior after thermal or sodium exposures at 650°C.Thermal or sodium exposures at 650°C increased the yield stress, decreased the ultimate tensile strength, and reduced uniform and total elongations. There were minimal differences in tensile properties between the sodium-exposed and thermally-aged specimens after an ~3000 h exposure. After an exposure for ~10,000 h the sodium-exposed specimens showed higher yield stress and ultimate tensile strength and lower uniform and total elongations than the thermally-aged specimens. For the HOMO-SA1150°C specimens, thermal or sodium exposures at 650°C significantly increased the yield stress but had a minimal effect on the ultimate tensile strength. Both uniform and total elongations were significantly reduced at an exposure time of ~3,000 h, and they were further reduced after an exposure of ~10,000 h. The sodium-exposed specimens had lower tensile ductility than the thermally-aged specimens. Before exposure, the stress-strain curves of the specimens in all six processing-heat treatment conditions showed serrations indicating the dynamic aging effect at 650°C. Thermal aging or sodium exposures at 650°C after ~10,000 h completely removed the serrations of the flow curves in A709 H58776, indicating strong precipitation during thermal or sodium exposures. Longer-term sodium exposure tests are needed to determine the steady-state corrosion rates in sodium for A709 H58776 and fully understand the influence of sodium exposures on its mechanical performance.

36 MATERIALS SCIENCE↗