Search NASA⌕ Search

SEARCH · Search NASA

Results for “Cathode limitations”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2

Toward Realizing the Potential of Practical Li-O2 Batteries for Electric Aircraft

Electrochemical power sources based on the Li-O2 couple have potential to achieve more than two-times the specific energy that is achievable with state-of-the-art Li-ion technologies. Despite considerable research, significant practical limitations continue to impede the successful realization of the Li-O2 electrochemistry as a power source in electric and hybrid-electric aviation. In practice, power capability and cycle life present formidable challenges. In this work, projections are presented for Li-O2prismatic cells with lightweight construction and the effect of cathode-limited capacity and discharge rate on specific energy and power are presented.

William R Bennett↗

High Energy Aqueous Lithium-Ion Batteries (Final Report)

Lithium-ion batteries (LIBs) are a widely used energy storage device. For decades, researchers have been studying aqueous electrolytes due to their non-flammability and environmental friendless. However, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) of water greatly limit the voltage window of the aqueous electrolyte. The recent concept of ‘solvent-in-salt’ electrolytes, namely ‘water-in-salt’ electrolytes (WISE) for aqueous batteries and ‘super-concentrated’ electrolytes for non-aqueous batteries, greatly expands the electrochemical window of these battery systems and consequently their energy density. This expansion occurs because the large number of salt aggregates in ‘solvent-in-salt’ electrolytes enables preferential salt decomposition over solvent decomposition to form robust interphase layers on electrodes, thus enhancing their stability in a wide range of operating voltages. However, even when the salt concentration reached 63m, regardless of cost, the cathodic potential of the WISE expanded only to 1.75V with an overall electrochemical stability window of <3.25V. To design the next generation of high energy aqueous LIBs, electrolytes that possess a wider electrochemical stability window and lower cost but still maintain the merit of non-flammability are much needed. In this project, we designed the aqueous LIBs with widened voltage window. We reported a cheap and non-flammable ternary eutectic electrolyte that can form a robust solid electrolyte interface (SEI)so that the cathodic limiting potential can be decreased to <1.5 V for Li 4 Ti 5 O 12 anodes, while maintaining both a high ionic conductivity of >10 -3 S cm –1 and a low viscosity. We demonstrated the super-stable2.5V LiMn 2 O 4 ||Li 4 Ti 5 O 12 pouch cell with mass loading of 2.5 mAh/cm. Further, LiCl-LiBr-Graphite/Li full cells were designed with high energy density. Finally, we use a bi-layer design to enlarge the voltage window of aqueous electrolyte, which can endow the stable cycling of aqueous Lithium metal batteries.

25 ENERGY STORAGE↗

Yolk–Shelled C@Fe 3 O 4 Nanoboxes as Efficient Sulfur Hosts for High‐Performance Lithium–Sulfur Batteries

Owing to the high theoretical specific capacity (1675 mA h g −1 ) and low cost, lithium–sulfur (Li–S) batteries offer advantages for next‐generation energy storage. However, the polysulfide dissolution and low electronic conductivity of sulfur cathodes limit the practical application of Li–S batteries. To address such issues, well‐designed yolk–shelled carbon@Fe 3 O 4 (YSC@Fe 3 O 4 ) nanoboxes as highly efficient sulfur hosts for Li–S batteries are reported here. With both physical entrapment by carbon shells and strong chemical interaction with Fe 3 O 4 cores, this unique architecture immobilizes the active material and inhibits diffusion of the polysulfide intermediates. Moreover, due to their high conductivity, the carbon shells and the polar Fe 3 O 4 cores facilitate fast electron/ion transport and promote continuous reactivation of the active material during the charge/discharge process, resulting in improved electrochemical utilization and reversibility. With these merits, the S/YSC@Fe 3 O 4 cathodes support high sulfur content (80 wt%) and loading (5.5 mg cm −2 ) and deliver high specific capacity, excellent rate capacity, and long cycling stability. This work provides a new perspective to design a carbon/metal‐oxide‐based yolk–shelled framework as a high sulfur‐loading host for advanced Li–S batteries with superior electrochemical properties.

He, Jiarui↗

F and N Rich Solid Electrolyte for Stable All-Solid-State Battery

We report the instability of sulfide solid electrolytes to Li anode and high-voltage LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes limits the cyclic performance of all-solid-state lithium battery (ASSLB). Herein, the stability of Li 6 PS 5 Cl against Li anode is enhanced by mixing a small amount (0.32 wt%) of CuF 2 -LiNO 3 (CL) into Li 6 PS 5 Cl electrolyte layer to in-situ form a mixed-conductive-lithiophobic and self-healing LiF-Li 3 N-Cu solid electrolyte interphase (SEI) at Li 6 PS 5 Cl-CL/Li interface. The critical current density (CCD) of Li 6 PS 5 Cl-CuF 2 -LiNO 3 increases to 1.4 mA cm –2 /1.4 mAh cm –2 at room temperature, which is much higher than that of pristine Li 6 PS 5 Cl (0.4 mA cm –2 /0.4 mAh cm –2 ) even though mixing 0.32 wt% CL into Li 6 PS 5 Cl slightly reduces the ionic conductivity from 2.9 × 10 –3 to 1.5 × 10 –3 S cm –1 . The compatibility of Li 6 PS 5 Cl-CL electrolyte to single-crystalline NMC811 (S-NMC811) is further enhanced by adding a small amount (0.02 wt%) of AlF 3 into Li 6 PS 5 Cl-CL forming Li 6 PS 5 Cl-CuF 2- LiNO 3 -AlF 3 (Li 6 >PS 5 Cl-CLA) as a cathode electrolyte and by doing Cl – on S-NMC811 (Cl@S-NMC811) surface. The Cl@S-NMC811-Li 6 PS 5 Cl-CLA|Li 6 PS 5 Cl-CL|Li cells with areal capacity of 2.55 mAh cm -2 achieve a capacity retention of 69.4% after 100 cycles at 1C (1C = 200 mAh g -1 ). Adding a small amount of SEI and cathode/electrolyte interphase (CEI) former into the sulfide electrolytes with minimal reduction (48.3%) of ionic conductivity is an effective method to enhance the performance of ASSLB.

36 MATERIALS SCIENCE↗

Tailoring a Three-Phase Microenvironment for High-Performance Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

Despite tremendous progress in catalyst development for rate-limiting cathodic oxygen reduction reaction (ORR), reducing Pt usage while meeting performance requirements in practical proton exchange membrane fuel cells (PEMFCs) remains a challenge. The ORR in PEMFCs occurs at a catalyst–electrolyte–gas three-phase interface. A desirable interface should exhibit highly active and available catalytic sites, as well as allow efficient oxygen and proton feeding to the catalytic sites and timely removal of water to avoid interface flooding. In this work, we report the design of a three-phase microenvironment in PEFMCs, showing that carbon surface chemistry can be tuned to modulate its interaction with the ionomers and create favorable transport paths for rapid delivery of both reactants and products. With such an elaborate interfacial design, for the first time we have demonstrated PEMFCs with all key ORR catalyst performance metrics, including mass activity, rated power, and durability, surpassing the US Department of Energy targets.

25 ENERGY STORAGE↗

Activity and Stability of Nanoscale Oxygen Reduction Catalysts

Design of highly active and stable nanoscale catalysts for electro-oxidation of small organic molecules is of great importance to the development of efficient fuel cells. The amount and instability of Pt-based catalysts in the cathode limits the cost, efficiency and lifetime of proton exchange membrane fuel cells. We developed a microscopic understanding of the factors governing activity and stability in Pt and PtM alloys. Experimental efforts were focused on probing the size and shape dependence of ORR activity of Pt-based nanoparticles supported on carbon nanotubes. A microscopic understanding of the activity was achieved by correlating voltammetry and rotating ring disk electrodes to surface atomic and electronic structures, which were elucidated predominantly by high-resolution transmission electron microscopy (HRTEM), Scanning transmission electron microscopy energy dispersive X-ray Spectroscopy (STEM-EDS) and synchrotron X-ray absorption spectroscopy (XAS).

30 DIRECT ENERGY CONVERSION↗

Heat generation rates in lithium thionyl chloride cells

An empirical equation that is useful for good first approximation in thermal modeling is presented. Indications and measurements of electrochemical heat effects were investigated. The particular cells of interest are of the D size, with spiral wound configuration and were instrumented with a thermocouple. It is found that cathode limited cells can explode on reversal at moderate temperatures.

Frank, H.↗

forced overdischarge related safety aspects of Li/SO2 and Li/SOCl2 cells

Results of an experiment investigating overdischarge behavior of two types of Li/SO2 cells are presented. Forced overdischarges of the Li/LiBr, CH3CN/SO2 cell can result in unsafe behavior such as venting with fire and release of toxic gases. The hazards may be minimized or eliminated by careful cell design considerations and practice of high standards of quality contol in cell manufacture. Seemingly safe cells at 25 C when forced overdischarged at -25 C, even at low currents, exhibited incipient signs of hazards. Their cathodes indicated signs of shock sensitivity. Cathode limited Li/SOCl2 cells were safe during forced overdischarge for long periods of time. Lithium limited Li/SOCl2 cells in which practically all Li had been used up before cell reversal did not exhibit hazardous behavior. Anode limited Li/SOCl2 cells, but not Li limited, exhibited detonations, all during overdischarges at relatively low current densities of or = 1 mA/sq cm 2. Anode potentials 4v with large oscillations preceeded the events. The events were confined to the anode and the temperature rose high enough to melt Ni grids.

Abraham, K. M.↗

Preventing Overcharge And Overdischarge Of Lithium Cells

Secondary lithium cells operating at ambient temperature protected against overcharge and overdischarge by use of cathode additives acting as sources and sinks of electroactive chemical species, which is lithium. Additive in cathode limits excursion of voltage of cell during both overcharge and overdischarge. In addition to protecting cell, also serves as part of state-of-charge indicator: attainment of greater or lesser limiting voltage indicates end of charge or end of discharge, respectively. Concept applied to Li/TiS2 system, and also applicable to such other lithium systems as Li/MoS2, Li/NbSe3, and Li/V2O5.

Huang, Chen-Kuo↗

Design and Preliminary Testing Plan of Electronegative Ion Thruster

Electronegative ion thrusters are a new iteration of existing gridded ion thruster technology differentiated by their ability to produce and accelerate both positive and negative ions. The primary motivations for electronegative ion thruster development include the elimination of lifetime-limiting cathodes from a thruster system and the ability to generate appreciable thrust through the acceleration of both positive or negative-charged ions. Proof-of-concept testing of the PEGASES (Plasma Propulsion with Electronegative GASES) thruster demonstrated the production of positively and negatively-charged ions (argon and sulfur hexafluoride, respectively) in an RF discharge and the subsequent acceleration of each charge species through the application of a time-varying electric field to a pair of metallic grids similar to those found in gridded ion thrusters. Leveraging the knowledge gained through experiments with the PEGASES I and II prototypes, the MINT (Marshall's Ion-ioN Thruster) is being developed to provide a platform for additional electronegative thruster proof-of-concept validation testing including direct thrust measurements. The design criteria used in designing the MINT are outlined and the planned tests that will be used to characterize the performance of the prototype are described.

Schloeder, Natalie R.↗

Initial Thrust Measurements of Marshall's Ion-ioN Thruster

Electronegative ion thrusters are a variation of tradition gridded ion thruster technology differentiated by the production and acceleration of both positive and negative ions. Benefits of electronegative ion thrusters include the elimination of lifetime-limiting cathodes from the thruster architecture and the ability to generate appreciable thrust from both charge species. Following the continued development of electronegative ion thruster technology as exhibited by the PEGASES (Plasma Propulsion with Electronegative GASES) thruster, direct thrust measurements are required to push interest in electronegative ion thruster technology forward. For this work, direct thrust measurements of the MINT (Marshall's Ion-ioN Thruster) will be taken on a hanging pendulum thrust stand for propellant mixtures of Sulfur Hexafluoride and Argon at volumetric flow rates of 5-25 sccm at radio frequency power levels of 100-600 watts at a radio frequency of 13.56 MHz. Acceleration grid operation is operated using a square waveform bias of +/-300 volts at a frequency of 25 kHz.

Schloeder, Natalie R.↗

Initial Thrust Measurements of Marshall's Ion-ioN Thruster

Electronegative ion thrusters are a variation of traditional gridded ion thruster technology differentiated by the production and acceleration of both positive and negative ions. Benefits of electronegative ion thrusters include the elimination of lifetime-limiting cathodes from the thruster architecture and the ability to generate appreciable thrust from both charge species. While much progress has been made in the development of electronegative ion thruster technology, direct thrust measurements are required to unambiguously demonstrate the efficacy of the concept and support continued development. In the present work, direct thrust measurements of the thrust produced by the MINT (Marshall's Ion-ioN Thruster) are performed using an inverted-pendulum thrust stand in the High-Power Electric Propulsion Laboratory's Vacuum Test Facility-1 at the Georgia Institute of Technology with operating pressures ranging from 4.8 x 10(exp -5) and 5.7 x 10(exp -5) torr. Thrust is recorded while operating with a propellant volumetric mixture ratio of 5:1 argon to nitrogen with total volumetric flow rates of 6, 12, and 24 sccm (0.17, 0.34, and 0.68 mg/s). Plasma is generated using a helical antenna at 13.56 MHz and radio frequency (RF) power levels of 150 and 350 W. The acceleration grid assembly is operated using both sinusoidal and square waveform biases of +/-350 V at frequencies of 4, 10, 25, 125, and 225 kHz. Thrust is recorded for two separate thruster configurations: with and without the magnetic filter. No thrust is discernable during thruster operation without the magnetic filter for any volumetric flow rate, RF forward Power level, or acceleration grid biasing scheme. For the full thruster configuration, with the magnetic filter installed, a brief burst of thrust of approximately 3.75 mN +/- 3 mN of error is observed at the start of grid operation for a volumetric flow rate of 24 sccm at 350 W RF power using a sinusoidal waveform grid bias at 125 kHz and +/- 350 V. Similar bursts in thrust are observed using a square waveform grid bias at 10 kHz and +/- 350 V for volumetric flow rates of 6, 10, and 12 sccm at 150, 350, and 350 W respectively. The only operating condition that exhibits repeated thrust spikes throughout thruster operation is the 24 sccm condition with a 5:1 mixture ratio at 150 W RF power using the 10 kHz square waveform acceleration grid bias. Thrust spikes for this condition measure 3 mN with an error of +/- 2.5 mN. There are no operating conditions tested that show continuous thrust production.

Caruso, Natalie R. S.↗

Space-charge-limited currents for cathodes with electric field enhanced geometry

This paper presents the approximate analytic solutions of current density for annulus and circle cathodes. The current densities of annulus and circle cathodes are derived approximately from first principles, which are in agreement with simulation results. The large scaling laws can predict current densities of high current vacuum diodes including annulus and circle cathodes in practical applications. In order to discuss the relationship between current density and electric field on cathode surface, the existing analytical solutions of currents for concentric cylinder and sphere diodes are fitted from existing solutions relating with electric field enhancement factors. It is found that the space-charge-limited current density for the cathode with electric-field enhanced geometry can be written in a general form of J = g(β{sub E}){sup 2}J{sub 0}, where J{sub 0} is the classical (1D) Child-Langmuir current density, β{sub E} is the electric field enhancement factor, and g is the geometrical correction factor depending on the cathode geometry.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Understanding extraction limits of plasma cathodes with experiment and simulation

The project is focused on computations for enhanced ionization near the exit orifice of a plasma cathode and how the cathode extraction electrode geometry and stray magnetic field structure influence available extractable current. The computational effort will take place at the Princeton Collaborative Research Laboratory (PCRF). The specific modeling platform to be utilized from PCRF is the electrostatic direct implicit particle in cell (EDIPIC) code. EDIPIC will be used to study ionization processes in the electron extraction region of the cathode. The control of electron energy is a key aspect to minimizing power losses in the plasma. Exiting electrons ionize gas leaving the orifice and in the process produce the dense plasma from which large amounts of current can be extracted. Project activities include studying processes that determine the energy distribution of the exiting electrons thus providing insight into how to optimize the source. The model will be validated and developed using experimental measurements as warranted. The familiarity and expertise of the team at PPPL with this type of plasma and the challenges posed greatly enhances the likelihood of gaining insight into the extraction sheath under the duration of the proposed activity. The effort is expected to shed a great deal of insight into electron extraction processes and pathways for optimization.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Topological cathodes: Controlling the space charge limit of electron emission using metamaterials

The space charge limit (SCL) of emission from photocathodes sets an upper limit on the performance of both high- and low-field electron guns. Generally, one is forced to strike a compromise between the space charge limit and the cathode’s intrinsic emittance [I. Bazarov et al., Phys. Rev. Lett. 102, 104801 (2009)]. However, it is possible to nearly eliminate the SCL due to the image charge by engineering the topography of the cathode’s surface. A cathode with a surface plasma frequency below the frequency spectrum of the accelerating electrons will greatly reduce the polarization of the cathode and its image-charge field, thereby mitigating the cathode’s space charge limit for photoelectric, thermionic, and field emission. In the work presented here, a theory for the image-charge field of a disk of charge being accelerated from the cathode surface is developed which includes the frequency-dependent effects of the cathode’s dielectric function. This theory verifies the concept of SCL mitigation with a wire array metamaterial to design a metacathode with greatly reduced image-charge fields. The details of the holistic metacathode design spanning 6 orders of magnitude in scale are described.

47 OTHER INSTRUMENTATION↗

Elucidating the impact of the ionomer equivalent weight on a platinum group metal-free PEMFC cathode via oxygen limiting current

Leveraging the interactions between ionomer and catalyst can increase the performance of proton exchange membrane fuel cells. The impacts of the equivalent weight (EW) of perfluorosulfonic acid–based ionomers on the platinum group metal-free electrode structure and fuel cell performance have not been fully explored. Four membrane electrode assemblies (MEAs) were prepared by using a commercial Fe–N–C catalyst, two perfluorosulfonic acid ionomers with different EWs, that is, Aquivion 720 (A720) and Nafion 1100 (N1100), and two ionomer-to-catalyst (I/C) ratios. The four MEAs were characterized to understand the impact of the ionomer EW and content on the capacitance, proton conductivity, and mass transport on the cathode. The mass transport resistance was measured for the first time using a new oxygen reduction reaction limiting current method enabling to couple the effects of oxygen diffusion with liquid water generation. Low EW ionomer combined with a moderate I/C results in improved performance due to its enhanced proton conductivity. However, when used at high I/C, it can cause severe water flooding at high current density due to the enhanced liquid water uptake, especially at high relative humidity, resulting in lower catalyst utilization and higher mass transport resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On Rate-Limiting Mechanisms in NMC Cathodes: The Interplay of Low and High Current Constraints

In this study, we investigate the rate performance limits in LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathodes for lithium-ion batteries, focusing on how cathode thickness, porosity, and threshold voltage impact discharge capacity. By conducting galvanostatic discharge experiments across a wide range of current densities using cathodes of varying thicknesses and porosities, we identify two distinct rate-limiting mechanisms: ionic liquid-diffusion and Ohmic/charge-transfer limitations. Our findings show that thick, dense cathodes are primarily limited by lithium diffusion in the electrolyte, while thinner and more porous cathodes are dominated by Ohmic/charge-transfer limitations, particularly at higher lower cutoff voltages. Crucially, these results allow us to identify the rate-limiting mechanisms in different cathode configurations, offering clear insights into how cathode design can be optimized for improved performance. Understanding these mechanisms is essential for designing next-generation batteries with enhanced rate performance, which is critical for applications such as electric vehicles and renewable energy storage systems.

Brischetto, Martin (ORCID:0000000339865813)↗

Formation and Transportation of an Intense Sub-Millisecond Electron Beam in a Longitudinal Magnetic Field in the Source with a Mesh Plasma Cathode

The limiting parameters of an intense sub-millisecond electron beam generated in the source with a plasma cathode on the basis of a low-pressure multi-arc discharge with mesh stabilization of the cathode (emission) plasma boundary and mobile anode (beam) plasma boundary are investigated. It is demonstrated that the limiting parameters of the electron beam in the examined electrode system are limited by its energy content on a level of about 4 kJ the excess of which leads to an electric breakdown of the accelerating gap. The optimal pressures are determined at which the beam during its transportation in the longitudinal magnetic field with a preset configuration has maximal parameters for the given electrode system. Different mechanisms of electric breakdown initiation and methods for increasing the electric strength of the high-voltage accelerating gap in this electrode system are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗