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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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At least 325 records · Page 18

Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode.

25 ENERGY STORAGE↗

Effect of material composition of diamond field emission array cathodes on quality of transversely shaped beams

Diamond field emitter array field emission cathodes (DFEA FECs) are attractive for the next generation of injectors due to their ability to produce transversely shaped beams without the need for complex masking or laser schemes. However, reliability of this cathode technology remains a challenging issue as principal mechanisms guiding and allowing for output beam shaping remained poorly understood. Here, this paper reports the results of testing two DFEA FECs with the same pattern and emitter tip geometry. Although both cathodes were able to sustain gradients of 44 MV/m and produce maximum output integral charge of 0.5 nC per radio frequency pulse, their emission patterns were different. One cathode did not produce a shaped beam, while the other one did. This difference was explained by the extent of the local variations of the diamond material across the arrays as discovered by spatially resolved Raman spectroscopy. The main practical takeaways were (i) tip sharpness was not a prerequisite for producing a shaped beam and instead (ii) material characteristics resulting in different cathode ballast resistance affected emission spatial uniformity across the array and hence the beam shaping.

36 MATERIALS SCIENCE↗

Theory of the thermionic current beyond the traditional space charge limit enabled by trapped ions in the virtual cathode

We show that trapped ions in virtual cathode potential wells can raise the transmitted current of emitted electrons into a plasma much closer to the full emission than is predicted by cathode sheath theories without trapped ions. The transmitted current is controlled by the well barrier voltage, which must adjust to balance the creation of low-energy ions within the well, and their loss. Our model considers the case of a plasma-facing cathode where trapped ions are created passively via charge-exchange collisions and lost passively via thermal leakage over the well. We quantify these rates and estimate the current in terms of system parameters for thermionic emission into a plasma with several cathode geometries. A general prediction is that the current as a function of emitted flux does not saturate at the traditional space charge limit (the onset of a well) but can reach far higher values until the trapped ion balance breaks down, causing instability. The maximum stable current depends on parameters but in principle can be arbitrarily high if active techniques are used to manipulate the trapped ion balance. We conclude that major improvements in plasma technologies with hot cathodes might be achieved by optimizing the current enhancement enabled by trapped ions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Voltage and cathode emission mechanisms of a magnetized, constricted, orbiting plasma in helium 6.7–850 Pa

Abstract We present a semiquantitative description of several important properties of a magnetized cold-cathode plasma in helium over a wide pressure range 6.7–850 Pa. We focus on the ‘constricted orbiting’ mode where the plasma attaches to the cathode as a moving ‘dot’ and the voltage and rate of cathode erosion are both unusually low. We propose that the low plasma voltage and observed motion of the plasma adjacent to the cathode can be attributed to field emission as the source of electrons from the cathode, a process that is aided by the charging of an oxide film by ions. We find that the observed dependence of plasma voltage on pressure is consistent with the assumption that the axial electric field must increase in regions of strong crossed magnetic field to maintain current continuity.

Physics↗

Effects of cathode loadings and anode protection on the performance of lithium metal batteries

Abstract While lithium-ion batteries (LIBs) are approaching their energy limits, lithium metal batteries (LMBs) are undergoing intensive investigation for higher energy density. Coupling LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode with lithium (Li) metal anode, the resultant Li||NMC811 LMBs are among the most promising technologies for future transportation electrification, which have the potential to realize an energy density two times higher than that of state-of-the-art LIBs. To maximize their energy density, the Li||NMC811 LMBs are preferred to have their cathode loading as high as possible while their Li anode as thin as possible. To this end, we investigated the effects of different cathode active material loadings (2–14 mg cm −2 ) on the performance of the Li||NMC811 LMBs. Our study revealed that the cathode loadings have remarkably affected the cell performance, in terms of capacity retention and sustainable capacity. Cells with high cathode loadings are more liable to fade in capacity, due to more severe formation of the CEI and more sluggish ion transport. In this study, we also verified that the protection of the Li anode is significant for achieving better cell performance. In this regard, our newly developed Li-containing glycerol (LiGL) via molecular layer deposition (MLD) is promising to help boost the cell performance, which was controllably deposited on the Li anode.

Materials Science↗

Origin of Capacity Degradation of High-Voltage KVPO 4 F Cathode

Potassium vanadium fluorophosphate (KVPO 4 F) is one of the most promising cathode candidates for K-ion batteries because of its high specific capacity, voltage, and energy density. However, reducing its capacity fade remains an important challenge. This work leverages structure and electrochemical analysis to understand the capacity degradation mechanism of the KVPO 4 F cathode. Interestingly, no structural degradation of the KVPO4F cathode is detected after 200 cycles in the wide voltage window of 5.0-2.5 V (vs K/K + ). Instead, the capacity degradation is attributed to electrolyte decomposition at high voltage ( > 4.5 V vs K/K + ), which causes drying of the electrolyte and the formation of insulating layers on the cathode surface, significantly increasing the polarization. The properties of four KPF 6 - A nd carbonate-based K electrolytes are compared, and 0.7 M KPF 6 in ethylene carbonate/propylene carbonate exhibits the highest oxidation stability and results in the best cycling stability for the KVPO 4 cathode. These findings suggest that the key to improving the cycling stability of KVPO 4 F is to develop novel K electrolytes with even higher oxidation stability.

25 ENERGY STORAGE↗

Lithium Ion Cathode Materials Prepared Using Glycerol as Solvent and Reactant

Two different types of cathode materials were prepared using glycerol as a solvent and reactant. The LiMn1/3Ni1/3Co1/3O2 layered oxide cathode material was successfully synthesized with a shorter time of heat treatment of 8hr at 900°C. An appreciated capacity retention of 83.7% after 100 cycles with an initial discharge capacity of 177.1 mAh/g at 0.1C (discharge rate) has been achieved. Another cathode material with the formula of Li1.2 Mn0.51Ni0.145+xCo0.145-xO2 (x=0 (LR2), 0.0725 (LR1)), as a Li-rich cathode material, has been also successfully synthesized using glycerol. It was shown that LR1 discharge capacity was increased from 185 to 213 mAh/g after 20 cycles and ended up with 194.9 mAh/g after 60 cycles at 0.1C (discharge rate). This material shows an exceptional discharge capacity retention, lower toxic cobalt component, and lower production cost comparing with other Li-rich cathode materials. Detailed results of powder material synthesis, characterization, and battery testing will be presented to demonstrate that glycerol as a green solvent in the synthesis of battery materials.

25 ENERGY STORAGE↗

Cobalt-Free Cathodes for Next Generation Li-Ion Batteries

In this U.S. Department of Energy sponsored project Nexceris, in collaboration with project partners; The Ohio State University and Navitas Advanced Systems have advanced the technical maturity of a non-cobalt containing cathode for next-generation Li-ion batteries. The cathode is based on the lithium manganese nickel-titanium oxide, LiNi 0.5 Mn 1.5 TiO 4 (LNMTO) high voltage spinel. To address limitations with poor cycle and calendar life an microstucturally hierarchical LNMO/LNMTO core-shell cathode powder has been developed that enables the formation of a solid-electrolyte interface that effectively passivates the cathode surface. The microstructural enhancements of the cathode material focus on preferentially enriching the surface with titanium. In parallel, new, optimized binder and electrolyte chemistries have been incorporated to address degradation mechanisms associated with high-voltage systems. Single-layer pouch cell and large-format 2-Ah cell testing have shown that an optimized LNMO/LNMTO core-shell powder significantly improves initial cell capacity and cycle life compared to homogeneous LNMO powder. To support development and the fabrication of 2-Ah cells a novel Hybrid Alternative Wet-Chemical Synthesis (HAWCS) process have been developed. This low-cost, synthesis approach enables the excellent compositional and particle morphology control achieved with co-precipitation without the strict process controls and associated expensive process equipment.

25 ENERGY STORAGE↗

The Effect of a Carbon Fiber Layer Between the Cathode and the Current Collector on Battery Cell Performance

Contact resistance between the cathode active material (CAM) and the Al current collector can be reduced by applying carbon coatings to the Al current collector surface. However, this process requires an additional step of carbon layer coating on the current collector, which increases both manufacturing costs and processing time. In the present work, an interlayer of continuous unsized carbon fibers aligned in one direction (CF interlayer), is introduced between the Al current collector and the NMC811 cathode during cathode deposition on the Al current collector. This single-step approach eliminates the need for the additional carbon layer coating on the current collector. Additionally, this approach removes the use of toxic solvents and insulative polymers used for making the carbon coating. The CF interlayer improves the rate capability at higher C-rates. The CF interlayer lowers the contact resistance between the cathode particles and the current collector while improving the activation energy of charge transfer. The peel test showed that the CF interlayer does not affect the adhesion strength of the cathode layer with the current collector.

25 ENERGY STORAGE↗

Effect of Cathode Cooling in Three-Dimensional Simulations of an Atmospheric Pressure Glow Discharge

The Atmospheric Pressure Glow Discharge (APGD) is a relatively simple and versatile plasma source used in a wide range of applications. Active cooling of the cathode can effectively mitigate instabilities, leading to glow-to-arc transitions. This study investigates the effect of varying the degree of cathode cooling in APGD with a planar cathode in helium. The plasma flow model incorporates mass conservation, chemical species transport, momentum conservation, conservation of thermal energy of heavy species and of electrons, and electrostatics. The model is applied to time-dependent simulations through a three-dimensional computational domain describing the whole discharge, without geometric symmetry or steady-state assumptions. Simulations of an experimentally characterized APGD explore the effects of electric current and cathode cooling—ranging from thermally insulated to extreme convective cooling. Results show the formation of an annular region with high electric field over the cathode surface under conditions of high current and low cooling.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Cold cathode switching device and converter

A cold-cathode switching device is presented. The cold-cathode switching device includes a housing defining a chamber; an ionizable gas disposed in the chamber; and a plurality of electrodes disposed in the chamber. The plurality of electrodes includes a cathode and an anode defining a discharge gap, and wherein at least one of the cathode and anode comprises a material that is liquid at an operating temperature of the cathode or the anode.

42 ENGINEERING↗

Thermionic cathode with a graphene sealing layer and method of making the same

According to an embodiment of the present disclosure, a thermionic cathode includes: a cathode body having an outer surface, and a sealing layer including one or more graphene sheets on the outer surface of the cathode body. According to another embodiment of the present disclosure, a method for manufacturing a thermionic cathode includes: depositing a sealing layer including one or more graphene sheets on an outer surface of a cathode body.

42 ENGINEERING↗

High capacity and stable cathode materials

High energy density cathode materials, such as LiNixMnyCozO2 (NMC) cathode materials, with improved discharge capacity (hence energy density) and enhanced cycle life are described. A solid electrolyte, such as lithium phosphate infused inside of secondary particles of the cathode material demonstrates significantly enhanced structural integrity without significant or without any observable particle cracking occurring during charge/discharge processes, showing high capacity retention of more than 90% after 200 cycles at room temperature. In certain embodiments the disclosed cathode materials (and cathodes made therefrom) are formed using nickel-rich NMC and/or are used in a battery system with a non-aqueous dual-Li salt electrolytes.

25 ENERGY STORAGE↗

Oxide mixture and complex oxide coatings for cathode materials

Cathode active materials are provided. The cathode active material can include a plurality of cathode active compound particles. A coating is disposed over each of the cathode active compound particles. The coating can include at least one of ZrO 2 , La 2 O 3 , a mixture of Al 2 O 3 and ZrO 2 or a mixture of Al 2 O 3 and La 2 O 3 . The battery cells that include the cathode active material are also provided.

Wang, Dapeng↗

Fuel cell cathode and fuel cell system including a polymeric additive

A cathode configured for use within a fuel cell system is provided. The cathode includes a cathode substrate. The cathode further includes a coating disposed upon the cathode substrate and including a fluorocarbon polymer additive configured for sintering at a temperature of less than 200° C. The fluorocarbon polymer additive may be mixed with a catalyst ink coating or may be applied separately as a topcoat layer.

Ramaswamy, Nagappan↗

Garnet solid electrolyte blended LiNi 0.6 Mn 0.2 Co 0.2 O 2 as high-voltage stable cathodes for advanced lithium-ion batteries

Ni-rich LiNi 1-x Co x/2 Mn x/2 O 2 layered materials have been widely adopted as cathodes for current electric vehicles (EVs) due to their high gravimetric and volumetric energy densities. However, their high-voltage instability (e.g., > 4.3 V vsLi ) limited their usable capacities corresponding to about 60 – 70 % of theoretical capacities. The major problems of high-voltage operation stem from instability of Ni 3+/4+ at cathode-electrolyte interphase (CEI) in contact with electrolytes. Here we propose garnet-type Li 6.7 La 3 Zr 1.7 Ta 0.3 O 12 (LLZT) solid-electrolyte-blended LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC) as high-voltage stable cathodes. The LLZT not only passivates the CEI but scavenges protons and moisture in electrolytes. From well-balanced ionic and electronic transport properties, 5 wt% LLZT blended NMC cathodes delivered enhanced electrochemical performances in full-cells. Unlike other complicated coating processes, our proposed solid-electrolyte blending approach can be readily implementable in commercial Li-ion batteries due to its manufacturing friendliness, energy saving, and cost effectiveness.

33 ADVANCED PROPULSION SYSTEMS↗

Correlative electron and ion beam analysis of the electrochemical performances of LiV 3 O 8 cathode films as a function of microstructures

Degradation mechanisms in LiV 3 O 8 cathode films (~500 nm) with different initial microstructures i.e., globular nanocrystals in amorphous matrix and needle-like nanocrystals, synthesized by annealing the cathodes at 150 °C and 300 °C for 6 h are studied by Transmission Electron Microscopy (TEM) and Auger Electron Spectroscopy (AES). In addition, a unique in-situ combination of TEM and Secondary Ion Mass Spectrometry (SIMS) imaging techniques, namely Parallel Ion and Electron beam Spectrometry (PIES) is carried out to measure the 3D distribution of V and Li with nanoscale resolution. These characterization studies focus on correlating the pre- and post-cycling microstructure to observed electrochemical performance. The LiV 3 O 8 cathode film with needle-like nanocrystals (300 °C) shows a higher initial capacity but it degrades rapidly compared to the film with globular nanocrystals embedded in amorphous matrix (150 °C). We observed that LiV 3 O 8 films with needle-like nanocrystals are more susceptible to cathode decohesion and vanadium dissolution than the films with globular nanocrystals embedded in amorphous matrix, explaining the differences in their electrochemical performance. The findings from this study have relevance to the development of thin film electrode microstructures for high capacity and cyclic stability.

25 ENERGY STORAGE↗

Influence of Electrolyte Additives on Interfacial Stability of Manganese-Rich Lithium-Ion Battery Cathodes

Affordable, long-lasting energy storage has become critical to support increased electricity demand in recent years. Cobalt-free, lithium- and manganese-rich lithium nickel manganese oxide (LMR-NM) cathodes stand to reduce cost and supply-chain concerns associated with traditional cobalt-containing cathodes for lithium-ion batteries by leveraging more earth-abundant materials; however, they have shown issues with long-term cycling stability. Here, we investigate lithium difluoro(oxalate)borate (LiDFOB), tris(trimethylsilyl) phosphite (TMSPi), and vinylene carbonate (VC) electrolyte additives for their ability to improve cycling performance of LMR-NM (0.3 Li 2 MnO 3 + 0.7 LiMn 0.5 Ni 0.5 0 2 ) cells. Cryogenic scanning transmission electron microscopy (cryo-STEM) with electron energy loss spectroscopy enables the construction of a structure–function relationship between cathode electrolyte interphase (CEI) characteristics and the electrochemical performance of cells aged with these additives. We find the combination of 2 wt % TMSPi + 1 wt % LiDFOB performs better than any single additive, achieving a 28% improvement in specific capacity over the baseline electrolyte after long-term cycling. We attribute this to LiDFOB mitigating Mn ion dissolution, with cryo-STEM showing Mn stabilized up to the CEI surface, coupled with improved CEI structure and chemistry enabled by TMSPi, evidenced by a moderately thick (∼7–15 nm) CEI that appears to protect against further electrolyte reactions with the particle. These results, achieved through site-specific nanoscale characterization, directly reveal mechanisms through which electrolyte engineering can improve the performance of earth-abundant cathodes, enabling informed development of more affordable and reliable batteries to meet future energy storage needs.

25 ENERGY STORAGE↗