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All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

A reduced temperature solid oxide fuel cell with three-dimensionally ordered macroporous cathode

Three-dimensionally ordered macroporous cathode was fabricated for a zirconia based micro-tubular solid oxide fuel cells (SOFCs). Three different cathodes (cathode A, no pore former; cathode B, with pore former (1.5 {micro}m in diameter); cathode C, with pore former (0.8 {micro}m in diameter)) were compared to investigate how the microstructure of it affected the cell performance at various operating temperatures. Micro-sized pores were well distributed within cathode B and C. The total porosity of cathode A is 35%, while it respectively reached 42 and 50% for cathodes B and C. At the same time, the specific surface area of them was 28.8 and 52.0% larger than that of the cathode A. As a result, the peak power density of the zirconia based cell, with cathode C, was 0.25 and 0.56 W cm{sup -2} at 550 and 600 C, while the respective value was just 0.11 and 0.30 W cm{sup -2} for the cell with cathode A. Thus, optimizing microstructure of cathode should be one of the best approaches for lowering the operating temperature for SOFCs.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2013

Effect of scandia doping method on the emission uniformity of scandate cathode with Sc{sub 2}O{sub 3}–W matrix

Graphical abstract: Emission uniformity of the cathodes prepared by mechanical mixing (a) and spray drying method (b). - Highlights: • The emission uniformity of scandate cathodes has been quantitively obtained. • The nanoparticles on the cathode surface lead to the electric field enhancement. • The cathode prepared by spray drying method exhibits good emission uniformity. - Abstract: Scandia doped tungsten matrix dispenser cathodes were manufactured using scandia doped tungsten powder prepared by mechanical mixing, liquid–solid doping and a spray drying method. It is found the macrostructure of the cathode depended on the powder preparation method. The cathode prepared using the powder prepared by spray drying method had a homogenous and porous matrix characterized with grains with a diameter of less than 1 μm and with many nanoparticles distributing uniformly around these grains. The cathode with submicron structure and uniform distribution of scandia exhibited good emission uniformity. The emission uniformity ΔJ/J of the cathode prepared by spray drying method was 0.17, about 6 times lower than that of the cathode prepared by mechanical mixing method. The calculation results showed that the nanoparticles led to electric field enhancement. A Ba–Sc–O multilayer on the cathode surface and nanoparticles distributing mainly on W grains contributed to the emission property of the cathode.

36 MATERIALS SCIENCE↗
DOE OSTI2025

In-Situ FTIR Detection of Transition Metal (TM)-Ion Dissolution From Cathodes in Li-Ion Batteries

Transition metal (TM) ions, commonly Ni and Mn, play a crucial role in Li-ion battery cathodes as the reaction centers for rapid redox reactions. A major challenge with TM-based cathodes is capacity degradation, particularly at higher operating voltages. This degradation is closely linked to the dissolution of TMs from the cathode materials and their subsequent deposition on the anode. This process not only modifies the surface structure of the cathode but, more significantly, alters the SEI composition on the anode [1-2]. The dissolution of TMs cations into a liquid electrolyte from cathode materials, such as Mn-ion dissolution from Mn-rich cathode (LMR), is detrimental to the cycling performance of Li-ion batteries [3-4]. Much attention has been paid to this issue but there remains a lack of characterization techniques which can detect the TM-ion dissolution from the cathode during electrochemical measurements. In our study, we use in-situ ATR-FTIR as an effective technique to probe the TM-ion dissolution from the cathode. We have first demonstrated the detrimental effects of TM ions on the electrochemical performance of Li-ion batteries by adding a small amount of TM salt (50 mM Mn(PF6)) to the electrolyte of a Li-ion coin cell with LFP and graphite electrode. We observed a rapid capacity fade after the first delithiation cycle. To investigate TM ion dissolution, we established a baseline IR spectrum for various TM solvation states (such as Mn and Ni) by measuring concentration-dependent IR spectra. This baseline spectrum helps us detect TM ion dissolution during battery cycling. In this work, we discuss in detail the effect of TM ions on the electrochemical performance of Li-ion batteries and the detection of TM ions during battery cycling using in-situ FTIR spectroscopy. We will compare TM dissolution between coated and uncoated cathodes to examine the effect of cathode coatings to mitigate degradation due to TM dissolution and cross-over from cathode to anode. References: (1) Zhan, C.; Wu, T.; Lu, J.; Amine, K. Dissolution, migration, anddeposition of transition metal ions in Li-ion batteries exemplified byMn-based cathodes - a critical review. Energy Environ. Sci. 2018, 11,243-257. (2) Jung, R.; Linsenmann, F.; Thomas, R.; Wandt, J.; Solchenbach,S.; Maglia, F.; Stinner, C.; Tromp, M.; Gasteiger, H. A. Nickel,Manganese, and Cobalt Dissolution from Ni-Rich NMC and TheirEffects on NMC622-Graphite Cells. J. Electrochem. Soc. 2019, 166,A378-A389. (3) Zhao, L.; Chenard, E.; Capraz, O. O.; Sottos, N. R.; White, S.R. Direct Detection of Manganese Ions in Organic Electrolyte by UV-Vis Spectroscopy. J. Electrochem. Soc. 2018, 165, A345-A348 (4) Zhang, Y.; Hu, A.; Xia, D.; Hwang, S.; Sainio, S.; Nordlund, D.;Michel, F. M.; Moore, R. B.; Li, L.; Lin, F. Operando characterization and regulation of metal dissolution and redeposition dynamics nearbattery electrode surface. Nat. Nanotechnol. 2023, 18, 790.

25 ENERGY STORAGE↗
DOE OSTI2023

Chromium Tolerant, Highly Active and Stable Electrocatalytic Internal Surface Coating for Cathode of Commercial SOFCs (Final Report)

This project is aimed to develop a chromium (Cr) tolerant, highly active, and stable coating layer on the internal surfaces of the porous composite cathode from commercially available SOFCs. Such coating layer was developed using the additive manufacturing process of Atomic Layer Deposition (ALD) and has been applied on the cathode consisting of either an electronic conductor of LaxSr 1-x MnyO 3-δ (LSM) or mixed ionic and electronic conducting La x Sr 1-x Co y Fe 1-y O 3-δ (LSCF). PI's work has demonstrated that the internal surface of cathode from the commercial cells, can be further tailored using ALD coating to dramatically enhance the cell performance. For instance, ALD layer consisting heterostructured nano composite of nano-Pt and nano-(Mn 0.8 Co 0.2 ) 3 O 4 oxide on the internal surface of porous LSM/YSZ cathode from SOFCs, has resulted in the large reduction of the cell polarizations resistance by up to 53%, and enormous increase of power density over 370%. For the cells with LSCF/Sm 2 O 3 doped CeO 2 (SDC) cathode, the conformal layer of nano-composite consisting of superjacent CoOx and subjacent minimum amount of Pt nano-grains has resulted in the power density enhancement by 126% for the large scale industry tubular cells at 750°C, and both the performance enhancement and nanostructure of the ALD layer are stable over ~ 2000 h continuous operation performed at industry test station. In the meanwhile, those ALD coating layer developed by PI's work is also inherently Cr-tolerant, and could act as physical barrier for preventing Cr diffusion into the cathode backbone, so as to mitigate the Cr poisoning effect on the cathode. In this project, the impact of Cr on the performance of those ALD coated commercial cells has been evaluated. Based on evolution of the cell performance, the ALD coating layer chemistry and ALD coating layer thickness has been optimized to maximize the overall Cr tolerance, cell power density and cell longevity. Different ALD coating has been applied onto the internal surface of LSM/YSZ and LSCF/SDC backbone respectively. The architecture/scaffold structures on the internal surface of different cathode, designed by this project, was catalogued and analyzed using High Resolution Transmission Electron Microscopy (HRTEM), and cell power/durability performance are assured via comprehensive electrochemical performance testing in the industry operation relevant conditions. The impact of the electrochemical operation current density, the water humidity, the cell operation temperature, and cell operation duration on the Cr tolerance of ALD coated cells has been systematically investigated. There is completely different nanostructure degradation mechanisms between LSM and LSCF cells induced by Cr contamination. For the LSCF/SDC baseline cell, With the Cr source, there is no apparent Sr surface segregation phase even for the baseline cell operated for 3000 h at 750 °C. With the Cr source, there is significant amorphous (SrCr)Ox phase accumulated in the original pore region. For the commercial baseline cells, Cr contaminants on the LSM electrode severely impacted the entire cell's electrochemical performance and nanostructure degradation. Those degradations include (1). Peak power density loss of 64 % after 109 h of operation. The dramatic increase in Rp (2). They are cracking at LSM/SSZ interface, LSM grains. SSZ remains intact but with (CrMn)Ox. By contrast, ALD coating (MnCo)Ox/Pt dramatically improves the Cr resistance, as follows (1). ALD-coated cell with a power density is 280-380 % of the baseline cell, depending on the ALD layer thickness. (2). For a cell with a 20 nm thick ALD layer, there is a large performance enhancement (> 200 % power density) induced by ALD coating of Cr-tolerant Mn 0.8 Co 0.2 Ox. (3). For a cell with a 20 nm thick ALD layer, after 168 h at 750 °C power density of the ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination for 109 h. The ALD coating on the internal surface of cathode developed by this project integrated multi-functions. Those multi-functions include (1). Dramatically improving the cell power density for the commercial cells; (2). Dramatically improving contamination resistance of the cathode, for being an excellent protection coating layer sealing off Cr contamination. (3). Dramatically increasing the cell longevity by potentially preventing the microstructure evolution and grain coarsening of the cathode. Overall, this project will provide a simple solution to simultaneously enhance power density and increase the reliability, robustness, and endurance of commercial SOFCs, over the entire operating temperature range of 650-800 °C. For the inherently functional SOFC, the ALD coating of LSM based cathode mitigate the Cr-contamination. Power density of ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination. In addition to SOFCs, the novel on-demand design approach and creation of multifunctional heterogeneous architecture on the electrode surface presented in this work opens further research for their application in other types of fuel cells, batteries, and sensors for which electrochemical reactions on the surface are similarly critical.

36 MATERIALS SCIENCE↗
DOE OSTI2023

High-Performance Low-Cobalt Cathode Materials for Li-ion Batteries

The layer-structured Li[Ni x Co y Mn 1-x-y ]O 2 (NCM) cathode materials have been the best choice for increasing electric vehicle driving distance per charge. The high Ni layered oxide represents successfully commercialized NCM cathodes (such as NCM622 and NCA) in lithium-ion batteries (LIBs) for EV applications due to their high energy density and acceptable cycling stability. However, the price of cobalt, the key element within LIBs for stability, has nearly tripled over the past few years due to increased demand from the cell phone industry. As mentioned in the DOE Funding Opportunity Announcement, the current materials shortage will also cause speculation for a future global shortage. Therefore, to meet the requirement and sustainability of the next-generation long-range and low-cost EVs, developing cathode materials with low-Co content to achieve higher energy density and lower cost is both essential and urgent. The overarching objective of this work is to develop stabilized NCM cathode materials with low Co content (namely LiNi x Co y Mn 1-x-y O 2 , y ≤ 0.04) to meet DOE’s goal of reducing Co loading below 50 mg Wh -1 while maintaining energy density greater than 600 Wh kg -1 based on cathode material. Via various dopings and coatings scalable methods, we explored and enhanced the cycling performance of low-cobalt cathodes. The final obtained NCM cathodes paired with graphite anode aim to deliver batteries with a high initial specific energy density of over 240 Wh kg -1 and a low capacity fading rate of less than 20% in 1000 cycles under a C/3 discharge rate. To accomplish this goal, a multidisciplinary team with several co-investigators has been formed from three organizations: The Pennsylvania State University (PSU), Oak Ridge National Laboratory (ORNL), and Pacific Northwest National Laboratory (PNNL). The PI and co-investigators are Dr. Donghai Wang (PI) from PSU with expertise in the synthesis of nanostructured materials and manipulation of interfacial properties of electrochemically active materials, Dr. Jagjit Nanda, with substantial knowledge of and expertise in state-of-the-art cathodes from ORNL, Dr. Chao-Yang Wang with significant experience in advanced cell design and fabrication and cell diagnostics from PSU, and Dr. Chongmin Wang with world-wide known expertise of advance atomic scale characterization of electrode materials from PNNL. Furthermore, this project will leverage and synergistically work with the current DOE-funded programs on battery materials at PSU and ORNL and electrode materials characterization at PNNL. During this funded period, we have accomplished milestones stated as follows: • Scale up production of LiFePO 4 (LFP) coated NCM811 with a production of 300g/batch. Fifteen (≥2 Ah) pouch cells with LFP-coated NCM811 cathode are delivered. Self-evaluated pouch cells in PSU show superior over 80% capacity retention performance even after 1500 cycles at C/3 rate. • Various cations (Al, Ti, Zr, and Mo) substitute cobalt in low-cobalt partially and Co-free cathodes. Their effects on crystal structure and electrochemical behavior are explored. • Phosphate compounds as coating materials represent promising surface protection precursors for low-cobalt cathode materials. Therefore, several metal phosphates were selected for improving the NMC cycling performance and are regarded as effective approaches for a scalable and practical surface protection method. • Production of NCM92, where Nickel content is 92% among transition metals, is scaled up from synthesis to coating and heat treatment procedures. Fifteen 2.7Ah pouch cells with Ti-doped NCM92 cathodes and industrial graphite anode are delivered to Idaho National Lab for testing.

25 ENERGY STORAGE↗
DOE OSTI2022

Enabling Extreme Fast-Charging: Challenges at the Cathode and Mitigation Strategies

We report charging lithium-ion batteries (LiBs) in 10 to 15 min via extreme fast-charging (XFC) is important for the widespread adoption of electric vehicles (EVs). Lately, the battery research community has focused on identifying XFC bottlenecks and determining novel design solutions. Like other LiB components, cathodes can present XFC bottlenecks, especially when considering long-term battery life. Therefore, it is necessary to develop a comprehensive understanding of how XFC conditions degrade LiB cathodes. The present article reviews relevant cathode-focused studies and summarizes the current understanding regarding cathode performance and aging issues under XFC conditions. Dominant aging modes and mechanisms are identified at different length-scales with electrochemical correlations for LiNi x Mn y Co z O 2 (NMC)-based cathodes. A range of electrochemical techniques and models provide key insights into cathode performance and life issues. A suite of multimodal and multiscale microscopy and X-ray techniques is surveyed to quantify chemical, structural, and crystallographic NMC-cathode degradation. Cathode cycle-life is scaled to equivalent EV miles to illustrate how cathode degradation translates to real-world scenarios and quantifies cathode-related bottlenecks that hinder XFC adoption. Finally, the article discusses several cathode cycle-life aging mitigation strategies with example case studies and identifies remaining challenges.

25 ENERGY STORAGE↗
DOE OSTI2016

Modeling and validation of single-chamber microbial fuel cell cathode biofilm growth and response to oxidant gas composition

This work describes experiments and computational simulations to analyze single-chamber, air-cathode microbial fuel cell (MFC) performance and cathodic limitations in terms of current generation, power output, mass transport, biomass competition, and biofilm growth. Steady-state and transient cathode models were developed and experimentally validated. Two cathode gas mixtures were used to explore oxygen transport in the cathode: the MFCs exposed to a helium-oxygen mixture (heliox) produced higher current and power output than the group of MFCs exposed to air or a nitrogen-oxygen mixture (nitrox), indicating a dependence on gas-phase transport in the cathode. Multi-substance transport, biological reactions, and electrochemical reactions in a multi-layer and multi-biomass cathode biofilm were also simulated in a transient model. The transient model described biofilm growth over 15 days while providing insight into mass transport and cathodic dissolved species concentration profiles during biofilm growth. Lastly, simulation results predict that the dissolved oxygen content and diffusion in the cathode are key parameters affecting the power output of the air-cathode MFC system, with greater oxygen content in the cathode resulting in increased power output and fully-matured biomass.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2013

Joule heat generation in thermionic cathodes of high-pressure arc discharges

The nonlinear surface heating model of plasma-cathode interaction in high-pressure arcs is extended to take into account the Joule effect inside the cathode body. Calculation results are given for different modes of current transfer to tungsten cathodes of different configurations in argon plasmas of atmospheric or higher pressures. Special attention is paid to analysis of energy balances of the cathode and the near-cathode plasma layer. In all the cases, the variation of potential inside the cathode is much smaller than the near-cathode voltage drop. However, this variation can be comparable to the volt equivalent of the energy flux from the plasma to the cathode and then the Joule effect is essential. Such is the case of the diffuse and mixed modes on rod cathodes at high currents, where the Joule heating causes a dramatic change of thermal and electrical regimes of the cathode. The Joule heating has virtually no effect over characteristics of spots on rod and infinite planar cathodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Charge state, angular distribution, and kinetic energy of ions from multicomponent-cathodes in vacuum arc devices

We present research results on vacuum arc plasma produced with multicomponent cathode made of several different elements. The ion mass-to-charge-state spectra of the plasmas were studied by time-of-flight spectrometry. The angular distributions of different ion species were measured, and the kinetic energy of their directed (streaming) motion was determined. It is shown that the fractional composition of ions of different cathode components in the plasma flow from the cathode spot closely matches the fractional content of these components in the composite cathode. The charge states of ions of the various cathode components are determined by the average electron temperature in the cathode spot plasma. The angular distribution of lower mass ions in the plasma from a multicomponent cathode is less isotropic and broader than for the plasma from a single-component cathode of the same light element. The directed kinetic energies of the ions of the different components for plasma from a multicomponent cathode are lower for lighter elements and greater for heavier elements compared to the ion directed energy for plasmas from single-component cathodes made of the same materials. The physical processes responsible for these changes in the ion charge states in multicomponent-cathode vacuum arc plasma are discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Effect of N{sub 2} and Ar gas on DC arc plasma generation and film composition from Ti-Al compound cathodes

DC arc plasma from Ti, Al, and Ti{sub 1−x}Al{sub x} (x = 0.16, 0.25, 0.50, and 0.70) compound cathodes has been characterized with respect to plasma chemistry (charged particles) and charge-state-resolved ion energy for Ar and N{sub 2} pressures in the range 10{sup −6} to 3 × 10{sup −2} Torr. Scanning electron microscopy was used for exploring the correlation between the cathode and film composition, which in turn was correlated with the plasma properties. In an Ar atmosphere, the plasma ion composition showed a reduction of Al of approximately 5 at. % compared to the cathode composition, while deposited films were in accordance with the cathode stoichiometry. Introducing N{sub 2} above ∼5 × 10{sup −3} Torr, lead to a reduced Al content in the plasma as well as in the film, and hence a 1:1 correlation between the cathode and film composition cannot be expected in a reactive environment. This may be explained by an influence of the reactive gas on the arc mode and type of erosion of Ti and Al rich contaminations, as well as on the plasma transport. Throughout the investigated pressure range, a higher deposition rate was obtained from cathodes with higher Al content. The origin of generated gas ions was investigated through the velocity rule, stating that the most likely ion velocities of all cathode elements from a compound cathode are equal. The results suggest that the major part of the gas ions in Ar is generated from electron impact ionization, while gas ions in a N{sub 2} atmosphere primarily originate from a nitrogen contaminated layer on the cathode surface. The presented results provide a contribution to the understanding processes of plasma generation from compound cathodes. It also allows for a more reasonable approach to the selection of composite cathode and experimental conditions for thin film depositions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Investigation of the flickering of La{sub 2}O{sub 3} and ThO{sub 2} doped tungsten cathodes

Short-arc lamps are equipped with tungsten electrodes due to their ability to withstand a high thermal load during operation. Nominal currents of more than one hundred amperes lead to a cathode tip temperature near the melting point of tungsten. To reduce the electrode temperature and, thereby, to increase the maintenance of such lamps, ThO{sub 2} or tentatively La{sub 2}O{sub 3} are added to the electrode material. They generate a reduced work function by establishing a monolayer of emitter atoms on the tungsten surface. Emitter enrichments on the lateral surface of doped cathodes are formed. They are traced back to transport mechanisms of emitter oxides in the interior of the electrode and on the electrode surface in dependence of the electrode temperature and to the redeposition of vaporized and ionized emitter atoms onto the cathode tip by the electric field in front. The investigation is undertaken by means of glow discharge mass spectrometry, scanning electron microscope images, energy dispersive x-ray spectroscopy, and through measurements of the optical surface emissivity. The effect of emitter enrichments on the stability of the arc attachment is presented by means of temporally resolved electrode temperature measurements and by measurements of the luminous flux from the cathode-near plasma. They show that the emitter enrichments on the lateral surface of the cathode are attractive for the arc attachment if the emitter at the cathode tip is depleted. In this case, it moves along the lateral surface from the cathode tip to sections of the cathode with a reduced work function. It induces a temporary variation of the cathode tip temperature and of the light intensity from the cathode-near plasma, a so-called flickering. In particular, in case of lanthanated cathodes, strong flickering is observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effect of thermionic cathode heating current self-magnetic field on gaseous plasma generator characteristics

The performance capabilities of the PINK, a plasma generator with a thermionic cathode mounted in the cavity of a hollow cathode, depending for its operation on a non-self-sustained low-pressure gas discharge have been investigated. It has been shown that when a single-filament tungsten cathode 2 mm in diameter is used and the peak filament current is equal to or higher than 100 A, the self-magnetic field of the filament current significantly affects the discharge current and voltage waveforms. This effect is due to changes in the time and space distributions of the emission current density from the hot cathode. When the electron mean free path is close to the characteristic dimensions of the thermionic cathode, the synthesized plasma density distribution is nonuniform and the cathode is etched nonuniformly. The cathode lifetime in this case is 8–12 h. Using a cathode consisting of several parallel-connected tungsten filaments ∼0.8 mm in diameter moderates the effect of the self-magnetic field of the filament current and nearly doubles the cathode lifetime. The use of this type of cathode together with a discharge igniting electrode reduces the minimum operating pressure in the plasma generator to about one third of that required for the generator operation with a single-filament cathode (to 0.04 Pa)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Dynamic thermal behavior of polycrystalline LaB 6 hollow cathodes

Lanthanum hexaboride (LaB6) hollow cathodes have demonstrated a capability for long life operation, which is critical to many space exploration missions. Thermal characterization of LaB6 hollow cathodes has revealed lower than expected electron emitter temperatures when the cathode reaches a steady state. This phenomenon is observed at discharge currents ranging from 5 to 35 A and xenon mass flow rates of 5–25 SCCM in cathodes with three different orifice diameters. Thus, the currently accepted value of the work function for polycrystalline LaB 6 , 2.67 eV, does not describe well the emission characteristics of LaB6 hollow cathodes operating with internal gas discharges at a steady state. We use empirically measured temperatures combined with a model of the hollow cathode emitter and xenon discharge to estimate the value of the work function, yielding a value ranging from 2.1 to 2.44 eV. This lower work function value implies that LaB6 hollow cathodes are expected to have even longer lifetimes than previously anticipated, further establishing them as a more suited alternative to other conventional cathode technologies for the task of long duration travel. Direct measurements of the work function as a function of depth on a hollow cathode emitter using x-ray photoelectron spectroscopy and ion beam milling indicate that the work function decreases with depth. We postulate several mechanisms that could explain the observed work function enhancement. Altogether, our results have important implications to the design, study approach, and operation of LaB 6 cathodes and potentially other cathodes with hollow configuration. Finally, our work opens the question of why the work function is reduced upon interaction with Xe plasma.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Observation of radio frequency ring-shaped hollow cathode discharge plasma with MgO and Al electrodes for plasma processing

Various high-density plasma sources have been proposed for plasma processing. Especially, the hollow cathode discharge is one of the powerful ones. In this work, radio-frequency (RF) driven ring-shaped hollow cathode discharges with high secondary-electron emission have been investigated, using an aluminum (Al) cathode, coated or not with magnesium oxide (MgO). The thickness of MgO thin film is approximately 200 nm. The RF discharge voltage for the coated cathode is almost the same as that for the uncoated one, in a wide range of Ar gas pressure, from 5.3 to 53.2 Pa. The results reveal that the plasma density has a peak at an Ar gas pressure of 10.6 Pa for both cathodes. The plasma density for the coated cathode is about 1.5–3 times higher than that for the uncoated one, at various gas pressures. To the contrary, the electron temperature for the coated cathode is lower than temperature obtained with the uncoated cathode, at various gas pressures. Radial profiles of electron saturation current, which is proportional to plasma flux, are also examined for a wide range of gas pressure. Radial profiles of electron temperature at various axial positions are almost uniform for both cathodes so that the diffusion process due to density gradient is dominant for plasma transport. The secondary electrons emitted from the coated cathode contribute to the improvement of the plasma flux radial profile obtained using the uncoated cathode.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Tailored Core Shell Cathode Powders for Solid Oxide Fuel Cells

In this Phase I SBIR project, a “core-shell” composite cathode approach was evaluated for improving SOFC performance and reducing degradation of lanthanum strontium cobalt ferrite (LSCF) cathode materials, following previous successful demonstrations of infiltration approaches for achieving the same goals. The intent was to establish core-shell cathode powders that enabled high performance to be obtained with “drop-in” process capability for SOFC manufacturing (i.e., rather than adding an infiltration step to the SOFC manufacturing process). Milling, precipitation and hetero-coagulation methods were evaluated for making core-shell composite cathode powders comprised of coarse LSCF “core” particles and nanoscale “shell” particles of lanthanum strontium manganite (LSM) or praseodymium strontium manganite (PSM). Precipitation and hetero-coagulation methods were successful for obtaining the targeted core-shell morphology, although perfect coverage of the LSCF core particles by the LSM and PSM particles was not obtained. Electrochemical characterization of core-shell cathode powders and conventional (baseline) cathode powders was performed via electrochemical impedance spectroscopy (EIS) half-cell measurements and single-cell SOFC testing. Reliable EIS testing methods were established, which enabled comparative area-specific resistance measurements to be obtained. A single-cell SOFC testing approach also was established that enabled cathode resistance to be separated from overall cell resistance, and for cathode degradation to be separated from overall cell degradation. The results of these EIS and SOFC tests conclusively determined that the core-shell cathode powders resulted in significant lowering of performance, compared to the baseline cathodes. Based on the results of this project, it was concluded that the core-shell cathode approach did not warrant further investigation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Highly Loaded Sulfur Cathode, Coated Separator and Gel Electrolyte for High Rate Li-Sulfur Batteries

As one of DOE Battery 500 Seedling projects, Cornell University and EIC Labs investigated and developed i) highly loaded sulfur cathodes (> 3 mg/cm 2 ), ii) hybrid separators, and iii) gel ceramic electrolytes (GCE) to mitigate the low rate capability, shuttling effect and limited cycle life in high performance Li-Sulfur batteries. Scalable nanomanufacturing processes such as air-controlled electrospray (ACES) and gas-assisted electrospinning (GAES) have been utilized to develop directly deposited electrodes and polymer/ceramic hybrid separators. First, in the development of highly loaded cathodes, alternating layers of sulfur impregnated mesoporous carbon and graphene were fabricated via ACES and the resulting layered cathodes and coated separators exhibit higher capacity and capacity retention (about 1,000 mAh/g capacity with less than 0.02% fade/cycles) than single layer cathode or cathode prepared by conventional slurry cast. Alternating layer approach via ACES has been applied to high loading systems (3 - 5 mg S/cm 2 ), demonstrating the potential to increase sulfur utilization and capacity retention. We have also incorporated iron oxides (Fe 3 O 4 ) into S/mesoporous carbon/graphene cathodes to enhance sulfur utilization and mitigation of polysulfide shuttling. and the effect of Fe 3 O 4 in mesoporous carbon and Gr is highly pronounced at high C rates of 1C and 2C cycling performance. To further improve the cathodes at high rates, graphene nanoribbons (GNR) which can promote ion transport were incorporated in the cathode, resulting in 550 mAh/g at 5C/5C rates. Hybrid Li-ion/Li-S cathodes has also been explored to better engage unreacted polysulfides during charge/discharge. S/LFP hybrid cathodes offer higher sulfur utilization and enhanced rate capability, as well as higher areal loading. This study suggests inclusion of iron phosphide (Fe2P) which can chemically interact with polysulfides can further enhance sulfur utilization and mitigation of soluble polysulfides at high rates. Secondly, in the development of hybrid separators, we first employed graphene coating on the commercial polyolefin separators, which exhibits higher capability, better capacity retention and enhanced rate capability. To improve the rate capability with enhanced safety features such as thermal stability and nonflammability, we developed polymer/ceramic hybrids based on thermally stable polyimide (PI) and room temperature curable ceramic precursors such as organopolysilazane (OPSZ) or polysilsesquioxanes (PSSQ), which exhibit no shrinkages up to 300 ºC and non-flammability. To improve mechanical properties and electrochemical stability, polybenzimidazole (PBI) and alumina have been incorporated in polymer/ceramic hybrid separator, replacing PI and OPSZ/PSSQ, respectively. Finally, the gel ceramic electrolyte (GCE) based on ceramic cross linkers have been applied to make Li-S cells even safer and also to mitigate the polysulfide shuttling further. The resulting gel ceramic electrolyte offers improved capacity retention and rate capability, and also effectively mitigates polysulfide shuttling which was also confirmed by modeling. Inclusion of high ion conducting additives into GCE together with polymer/ceramic hybrid separators exhibit the higher ionic conductivity than liquid electrolyte with commercial polyolefin separator. We demonstrated that the developed highly loaded sulfur cathodes, polymer/ceramic hybrid separators and gel ceramic electrolyte can effectively mitigate the low rate capability, shuttling effect and limited cycle life in high performance Li-Sulfur batteries with improved safety.

25 ENERGY STORAGE↗
DOE OSTI2023

Computationally Guided Design of Multiple Impurities Tolerant Cathode for Solid Oxide Fuel Cell Applications

Solid oxide fuel cells (SOFCs) have been recognized as promising candidates in the demand of reducing the dependence on fossil fuels, which is one of the solutions to the threat of global warming. It was reported that the direct chemical-to-electrical energy conversion in SOFCs comes with negligible emission of greenhouse gases and up to 60% working efficiency. SOFC has unique advantages over traditional power generation technologies and other types of fuel cells due to the use of relatively inexpensive materials, low sensitivity to poisoning impurities in fuels, relatively high conversion efficiency, and fuel flexibility (like carbon-based fuels). However, during the SOFC operation, the cathode is exposed to intrinsic and extrinsic airborne contaminants at high temperatures (600–900°C), leading to their reaction with electrode materials, irreversible chemical and structural changes, and electrochemical performance degradation. of which CO2, SO2, Cr6+ and H2O are known to be concerns. Thus, developing a comprehensive understanding of the multiple impurities poisoning of SOFC cathodes in the presence of single or multiple impurities is necessary to address the long-term degradation of the SOFC cathode systems at operating conditions. An integrated computational and experimental approach has been utilized in the current work aiming at the comprehensive investigation of the cathode materials under single or multiple impurities poisoning effects, understanding the multiple impurities poisoning mechanism(s), and improving the long-term durability of the SOFC cathodes to develop better performing impurity-tolerant cathode materials. We first examined the agreement between the simulation approach and the experimental observations at various atmospheric and temperature conditions to confirm the reliability of CALPHAD for poisoning simulations in these cathodes. Then, using this approach, we investigated the accelerated testing protocol, which has become the standard method for conducting impurity poisoning experiments involving these cathode materials. We found our simulation approach is able to predict in which systems, i.e., cathode material and treatment environment, the accelerated testing protocols reflect actual operating conditions. Finally, in-depth simulations were done for these three candidate cathodes under different experimental conditions and suggested directions toward alternative cathode materials that have superior impurity tolerance.

36 MATERIALS SCIENCE↗
DOE OSTI2023

SYNTHESIS AND MODIFICATION OF HIGH-NICKEL CATHODE MATERIALS FOR NEXT GENERATION LITHIUM-ION BATTERIES

The limited worldwide Cobalt resource has spurred demand for new cathode materials with reduced Cobalt reliance. Substituting Cobalt with Nickel giving high-Nickel cathode material is a promising solution due to its high energy density and cheaper price. However, the poor cycling stability of high-nickel cathode materials is the major challenge that hinders their widespread adoption in electric vehicles and other energy storage applications. This work reports a significant advance in the development of high-nickel cathode materials with improved cycling stability. Firstly, a scalable synthesis route is developed to produce high-nickel cathodes with favorable morphology and high nickel content of 92%. Various low-cost doping elements including Mg, Al and Ti are screened to improve the structure of high-nickel cathodes during cycling. A Dual Protective strategy with AlPO4 nanoparticles as a representative is introduced as a low cost and effective approach to prolong the cycle stability of high-nickel cathodes. Finally, single-crystalline high-nickel cathodes are synthesized, and their electrochemical performance is compared with polycrystalline cathodes. The synthesized high-nickel cathode materials exhibit excellent electrochemical performance and significantly improved cycling stability. This work demonstrates promising pathways towards the commercialization of high-nickel cathode materials for Lithium Ion Batteries.

25 ENERGY STORAGE↗