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At least 217 records · Page 12

Unravelling electro-chemo-mechanical interplay in layered oxide cathode degradation in solid-state batteries

Solid-state batteries (SSBs) hold notable promise for advancing energy storage technologies. However, their commercial viability is limited by the poor cycle stability and complex degradation mechanism. This study underscores the pivotal role of electro-chemo-mechanical interactions in driving the failure of SSBs. Leveraging advanced x-ray imaging and spectroscopy techniques, we analyzed LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes from cycled Li x In||Li 6 PS 5 Cl (LPSC)||NMC811 SSBs, uncovering the interplay between microstructure, chemical heterogeneity, mechanical characteristics, and electrochemical performance. Our results show that revealing electro-chemo-mechanical interactions is essential to develop strategies to suppress the degradation of SSBs. Particularly, we revisit a LiNbO 3 (LNO) coating layer to mitigate electrochemical degradation. The LNO@NMC811 cathode retains 116 milliampere-hours per gram after 200 cycles, showing excellent stability, while the uncoated NMC811 cathode keeps degrading over time, with suppressed chemical heterogeneity and mechanical failure. This work highlights the importance of synergizing advanced material design with coating techniques, ensuring uniform lithium flux and improving mechanical properties to achieve stable, high-performance SSBs.

Zheng, Xueli [SLAC National Accelerator Laboratory↗

Precision surface modification of solid oxide fuel cells via layer-by-layer surface sol–gel deposition

While solid oxide fuel cells (SOFCs) are a promising technology for a clean and sustainable future, their commercialization is hindered by limited durability and performance. Here, we report our findings on the application of a layer-by-layer surface sol–gel (SSG) coating of catalysts to dramatically enhance the electro-catalytic activity and durability of SOFC cathodes. The SSG process is capable of penetrating and preserving complex backbone microstructures of porous electrodes, creating highly conformal coatings of controlled morphology, while tailoring the composition of the surface to improve catalytic properties and durability. For example, the application of an SSG coating of PrO x to a La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ (LSCF) cathode has reduced the polarization resistance from 1.136 to 0.117 Ω cm 2 at 600 °C and the degradation rate from 1.13 × 10 –3 to 2.67 × 10 –4 Ω cm 2 h –1 at 650 °C. In addition, a continuous improvement in electrode performance is demonstrated as the thickness of the coating is increased, corresponding to the linear addition of catalyst. Furthermore, this first application of the SSG technique to SOFC systems opens the door for the controlled surface modification of porous components in electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduction of Methane Leaks through Corrosion Mitigation Pre-treatments for Pipelines with Field Applied Coatings

Corrosion of buried, coated steel pipelines transporting natural gas is a significant source of methane emissions, from pipeline venting required for maintenance and repairs and from pipeline leaks and incidents. Corrosion of steel under field applied coatings is an important safety concern for the pipeline industry. This project investigates the application of a field applied alloy over girth welds to mitigate external corrosion of buried coated steel pipelines. Various metallic coating options were considered, which were required to meet several criteria: (1) it must resist corrosion under open-circuit or mild cathodic protection conditions, (2) it must protect the substrate steel, and (3) it must not negatively affect the adhesion of the field coating. Finite element models and lab testing were performed of alloy coating compositions to identify promising alloy types underneath disbonded coatings. Polarization curves of coating alloys were generated to provide the boundary conditions for the COMSOL model to compute potential and current distributions around coated areas. Sacrificial and corrosion-resistant metal alloy coatings were evaluated and optimized using corrosion modeling and laboratory electrochemical testing, where aluminum alloy 5356 (5% Mg) and steel alloy B9 (9% Cr) were selected. Corrosion test coupons were designed and fabricated using thermal spray aluminum 5356 and welded B9 steel overlays on API 5L grade X42 line pipe steel. The corrosion test coupons, with simulated pipe coating damage, were tested in a laboratory soil box and a field pipeline site in Texas for 3-months. Corrosion test coupons were then tested for 6-months at field pipeline sites in Texas and Tennessee to quantify corrosion rates and performance of the aluminum and steel alloys under polyethylene tape and 2-part epoxy coatings, various coating holidays, and with and without cathodic protection.

03 NATURAL GAS↗

On the Electrochemical Properties of Carbon-Coated NaCrO 2 for Na-Ion Batteries

NaCrO 2 is a promising cathode for Na-ion batteries. However, further studies of the mechanisms controlling its specific capacities and cycle stability are needed for real-world applications in the future. This study reveals, for the first time, that the typical specific capacity of ~110 mAh/g reported by many researchers when the charge/discharge voltage window is set between 2.0 and 3.6 V vs. Na/Na + is actually controlled by the low electronic conductivity at the electrode/electrolyte interface. Through wet solution mixing of NaCrO 2 particles with carbon precursors, uniform carbon coating can be formed on the surface of NaCrO 2 particles, leading to unprecedented specific capacities at 140 mAh/g, which is the highest specific capacity ever reported in the literature with the lower and upper cutoff voltages at the aforementioned values. However, such carbon-coated NaCrO 2 with ultrahigh specific capacity does not improve cycle stability because with the specific capacity at 140 mAh/g the Na deintercalation during charge is more than 50% Na ions per formula unit of NaCrO 2 which leads to irreversible redox reactions. The insights from this study provide a future direction to enhance the long-term cycle stability of NaCrO 2 through integrating carbon coating and doping.

25 ENERGY STORAGE↗

Surface Stabilization with Fluorine of Layered Ultrahigh-Nickel Oxide Cathodes for Lithium-Ion Batteries

High-nickel layered oxide cathodes are key to meet the demands of the electric vehicle industry because of their high specific capacity. However, commercialization of these materials is hindered by critical challenges, such as phase transitions, particle cracking, aggressive surface reactivity, and thermal instability. Cation doping along with surface coating has proven to be an effective way to circumvent some of these issues to a large extent. Herein, fluorine coating is employed on a high-nickel Li[Ni 0.95 Mn 0.015 Co 0.02 Al 0.01 Mg 0.005 ]O 2 (NMCAM) cathode via a solution route. Detailed structural and electrochemical analyses indicate fluorine largely decorates the surface at low enough calcination temperatures. The cathode with 1 mol % fluorine coating exhibits a capacity retention of 71% after 500 cycles as compared to 59% for the control sample when cycled to a high cutoff voltage of 4.3 V in a full cell configuration with graphite anode. Post-mortem analysis of cycled electrodes reveals that surface reactivity is a major contributor to capacity fade as compared to particle cracking. Fluorine coating reduces surface reactivity and the depth to which rock-salt phase is formed on the surface during cycling. The thermal stability is also enhanced after fluorine coating as the material shows less heat release at high states of charge. Furthermore, this work demonstrates an effective, economical, and scalable way to stabilize the surface with fluorine and enhance the electrochemical performance of high-nickel cathodes.

25 ENERGY STORAGE↗

An ultrathin solid-state electrolyte film coated on LiNi 0.8 Co 0.1 Mn 0.1 O 2 electrode surface for enhanced performance of lithium-ion batteries

We report layered Ni-rich oxide is a promising cathode material for lithium-ion batteries (LIBs) of high energy density, yet its poor electrochemical stability induced by electrode-electrolyte interfacial degradation has still needed to be addressed. Surface coating is one of the powerful techniques to tackle this issue, nevertheless, it has been extensively used on particle but not electrode regarding a larger area of protection. Herein, we have covered a nano-scaled layer of lithium phosphorus oxynitride (LiPON) on the electrode level of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM) surface and found lower impedance, longer cycle life, and better safety for treated battery. Most notably, such an NCM-LiPON based 1.3 Ah pouch cell delivers an energy density of 364.4 Wh kg -1 (based on positive and negative materials), along with the retention of 80.0% over 745 cycles at 0.5 C-rate, which is 1.3 times longer than the bare one. This results from modification of both superficial cathode-electrolyte interphase (CEI) and structure stabilization of general particle surface, therefore, role of conformal coating upon electrode surface should be highlighted.

36 MATERIALS SCIENCE↗

Solvent‐Phobic and Ionophilic Carboxylated Polythiophene Layer for Fluoride‐Rich Cathode Electrolyte Interphase

Abstract One focal area of contemporary organic mixed ionic‐electronic conductor (OMIEC) research relates to utilization of dual‐conductive properties to enhance the ion/electron transfer kinetics for energy storage applications. Insight regarding OMIEC response toward the electrolyte anion and solvent used in lithium‐ion batteries (LIBs), however, is limited. Here, for the first time, the solvent‐phobic and ionophilic (SP‐IP) properties of the OMIEC, poly[3‐(potassium‐4‐butanoate)thiophene‐2,5‐diyl] (P3KBT), are revealed through comprehensive evaluation and characterization. The solvent‐phobic characteristics arise from the cooperation of dispersive interaction, polar interaction, and hydrogen‐bonding between P3KBT and electrolyte solvent. The ionophilic nature is driven by electrostatic interactions between P3KBT side chain carboxylate groups and LiPF 6 , and the reversible electrochemical doping/de‐doping of the polythiophene backbone with PF 6 ⁻ . The SP‐IP properties induce formation of a LiF‐ rich , Li 2 CO 3 ‐ limited cathode electrolyte interphase (CEI) layer when a P3KBT coating layer is applied to the active material surface, significantly improving half‐cell life to over 1500 cycles at 2C.

Ren, Haoze [Department of Chemical and Bimolecular↗

Arc Plasma Gun With Coaxial Powder Feed

Redesigned plasma gun provides improved metallic and ceramic coatings. Particles injected directly through coaxial bore in cathode into central region of plasma jet. Introduced into hotter and faster region of plasma jet.

Zaplatynsky, Isidor↗

Enabling aqueous processing for LiNi 0.80 Co 0.15 Al 0.05 O 2 (NCA)-based lithium-ion battery cathodes using polyacrylic acid

Replacing N-methyl-2-pyrrolidone (NMP) with water in the production of lithium-ion battery cathodes is critical to realizing process cost savings and improved worker safety. LiNi 0.80 Co 0.15 Al 0.05 O 2 (NCA) is a poor fit for aqueous processing due to destructive Al current collector corrosion resulting from highly basic slurries and detrimental surface reconstruction reactions that occur in water. In this study, polyacrylic acid (PAA, MW = 450,000 g·mol -1 ) is examined as a corrosion-mitigating and surface-stabilizing agent. Adding PAA to an aqueous NCA slurry can provide a stable pH (4.0–8.5) for at least 4 h, since the carboxyl groups from PAA dissociate and increase the proton concentration in the slurry. Further, these groups can also adsorb to the surface of NCA particles and provide electrostatic stability from active material particle agglomeration, as revealed by zeta potential measurements. Minor cracking does occur at the electrode surface; this cracking likely caused poorer adhesion to the Al current collector in the aqueous-processed film when compared to the NMP-processed baseline. Electrochemically, the leached Li does cause a lower initial capacity for the aqueous-processed cathode, though the capacity retention of the aqueous-processed cathode is better than the baseline. The cracks in the coating led to a rise in charge transfer resistance that hindered rate capability above 1C.

25 ENERGY STORAGE↗

Electrochemically Stable High Energy Density Lithium-Sulfur Batteries

Lithium-Sulfur batteries (LSB) have emerged as one of the strong contenders for high energy density rechargeable batteries in the Li-ion battery domain. The LSB system is considered as the most promising to achieve the next milestone in energy density of 500 Wh/kg. However, the LSB system is plagued with problems of polysulfide formation which are soluble in the organic electrolyte leading to loss in capacity and eventual cell failure. The problem is further compounded by dendrite formation on the Li anode during electrochemical cycling leading to puncturing of the separator causing eventual short-circuiting of the cell and consequent heat generation resulting in major safety hazards of flammability of the organic liquid electrolyte and impending explosion. This chapter describes various approaches developed to combat both cathode and anode issues. These involve synthesis and characterization of complex framework materials (CFMs) for confining the polysulfides and sulfur in the LSB cathodes. The CFMs include a CFM host and a coating applied to the CFM host, which includes one or more form of an electronic conductor, a lithium-ion conductor and a functional electrocatalyst for electrocatalytically converting the soluble polysulfides to Li 2 S. Further, sulfur is infiltrated into the CFM host creating a sulfur-carbon linkage serving as effective anchors for trapping the ensuing polysulfides. The systems have been tested in coin cells and pouch cells with metallic Li anodes under lean electrolyte conditions of 3-4 μl/mg of electrolyte (E) to sulfur (S) ratios showing promise and feasibility. New emergent dendrite-free alloys have also been identified to test against pure Li and CFM cathodes in coin cell and pouch cell configurations under lean electrolyte conditions. Results of these studies are described and discussed with thoughts on future directions.

25 ENERGY STORAGE↗

Investigations of the stability of GaAs for photoelectrochemical H 2 evolution in acidic or alkaline aqueous electrolytes

The long-term stability of p-GaAs photocathodes has been investigated for the hydrogen-evolution reaction (HER) in contact with either 1.0 M H 2 SO 4 (aq) or 1.0 M KOH(aq). Stability for the HER was evaluated using p-GaAs electrodes that were either etched or coated with active HER catalysts (Pt and CoP). Changes in surface characteristics of GaAs after exposure to electrochemical conditions were monitored by X-ray photoelectron spectroscopy (XPS), and electrode dissolution processes were evaluated by inductively coupled plasma mass spectrometry (ICP-MS). Consistent with thermodynamic predictions, after operation of the HER at pH 0 or pH 14, illuminated etched p-GaAs electrodes exhibited minimal dissolution while preserving a nearly stoichiometric surface. Electrodeposition or sputtering of Pt on the p-GaAs surface promoted the formation of excess As 0 via an interfacial reaction during the HER. The resulting non-stoichiometric As 0 -rich surface of p-GaAs/Pt electrodes caused a loss in photoactivity as well as substantial cathodic dark current. In contrast, p-GaAs electrodes coated with thin-film CoP catalysts did not display an increase in surficial As 0 after operation of the HER in acidic electrolytes. Minimization of deleterious interfacial reactions is thus critical to obtain extended stability in conjunction with high performance from p-GaAs photocathodes.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Mechanistic origins of corrosion protection of aluminum alloys by graphene/polyetherimide nanocomposite coatings

Light-weighting vehicular components through adoption of light-metal structural alloys holds promise for reducing the fuel consumption of internal combustion engine vehicles and increasing the range of battery electric vehicles. However, the alloyed microstructure and surface precipitates of aluminum alloys render these materials susceptible to corrosion under modest excursions from neutral pH. Traditional chromium-based anodic passivation layers are subject to increasingly stringent environmental regulations, whereas options for sacrificial cathodic films are sparse for electropositive metals. While hybrid nanocomposite coatings have shown initial promise, mechanistic underpinnings remain poorly understood. Here, a fully imidized polyetherimide (PEI) resin is utilized as the continuous phase with inclusion of unfunctionalized exfoliated graphite (UFG). A comprehensive investigation of the mechanisms of corrosion protection reveals key fundamental design principles underpinning corrosion inhibition. First, strong interfacial adhesion, which for PEI is facilitated by binding of imide carbonyl moieties to Lewis acidic sites on Al surfaces. Second, the miscibility of ion-impervious nanoscopic UFG fillers and stabilization of a substantial interphase region at UFG/PEI boundaries that result in minimizing the free volume at the filler/polymer interface. Finally, extended tortuosity of ion diffusion pathways imbued by the below-percolation-threshold 2D fillers. These three design principles help govern and modulate ion transport from electrolyte/coating interfaces to the coating/metal interface and are crucial for the extended preservation of barrier properties. The results suggest an approach to systematically activate multiple modes of corrosion inhibition through rational design of hybrid nanocomposite coatings across hard-to-abate sectors where light metal alloys are likely to play an increasingly prominent role.

36 MATERIALS SCIENCE↗

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↗

Surface Regulating of a Double–Perovskite Electrode for Protonic Ceramic Fuel Cells to Enhance Oxygen Reduction Activity and Contaminants Poisoning Tolerance

Protonic ceramic fuel cells (PCFCs) are one of the most efficient energy conversion devices. However, the performance of current PCFCs is greatly limited by the sluggish oxygen reduction reaction (ORR) kinetics and the fast degradation of cathode due to contaminants poisoning (such as Cr species and steam). In this work, we report a surface regulating of a double perovskite PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ (PBSCF) cathode by a Pr 0.9 Fe 0.7 Co 0.3 O 3 (PFC) catalyst coating to enhance the ORR activity and stability. When tested in direct contact with Cr in the air with 3% H 2 O at 650 °C, the polarization resistance (Rp) of the PFC-PBSCF electrode increases from $\approx$0.39 to 0.45 Ω cm 2 after 100 h operation; in contrast, the R p of a PBSCF electrode increases from 0.63 to 0.82 Ω cm 2 . Further, a PCFC with the PFC-PBSCF cathode demonstrates an excellent peak power density ($\approx$1.08 W cm -2 at 650 °C) and significantly enhanced durability (degradation rate of 0.03 % h -1 ), much better than those of the cells with a PBSCF cathode ($\approx$0.75 W cm -2 and degradation rate of 0.12 % h -1 ). Raman spectroscopy and density functional theory calculations indicate that the PFC catalyst coating diminishes the formation of Cr species, such as (Ba 1-x Sr x )CrO 4 , on the cathode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Abstract Gas evolution from high‐nickel layered oxide cathodes (>90% Ni) remains a major issue for their practical application. Gaseous species, such as CO 2 , O 2 , and CO, that are evolved at high states of charge (SOC) worsen the overall safety of batteries, as pressure build‐up within the cell may lead to cell rupture. Since these gasses are produced during cathode degradation, tracking the formation of gasses is also important in diagnosing cathode failure. Online electrochemical mass spectrometry (OEMS) is a powerful in situ technique to study gas evolution from the cathode during high‐voltage charge. However, the differences in the OEMS experimental setups between different groups make it challenging to compare results between groups. In this perspective, the various factors that influence gas evolution based on the OEMS results collected in this group are presented. The focus is on the conditions that lead to gas release, with a particular emphasis on reactive oxygen formation and subsequent chemical reactions with the electrolyte. Promising strategies, such as electrolytes, compositional tuning, and surface coatings that are effective at suppressing gas evolution from the cathode are highlighted. Critical insights into mitigating cathode degradation and gas evolution are provided to guide the development of safer, high‐energy batteries.

Chemistry↗

Thermal Control using Electrochromism

The applicability of a charge balanced electrochromic device to modulate the frequencies in the thermal infrared region is examined in this study. The device consisted of a transparent conductor, WO3 anode, PMMA/LiClO4 electrolyte, V2O5 cathode and transparent conductor. The supporting structure in the device is SnO2 coated glass and the edges are sealed with epoxy to reduce moisture absorption. The performance evaluation comprised of cyclic voltammetric measurements and determination of transmittance at various wavelengths. The device was subjected to anodic and cathodic polarization by sweeping the potential at a rate of 10 mV/sec from -0.8V to 1.8V. The current versus voltage profile indicated no reaction between -0.5 and +0.5 V. The device is colored green at 1.8V with a transmittance of 5% at a wavelength, lambda=900 nm and colorless at -0.8V with a transmittance of 74% at lambda=500 nm. The optical modulation is limited to 400-1500 nm and there is no activity in the thermal infrared. The switching time is 75 seconds for transmittance to decrease from 74% to 50%. The device yielded reproducible values for transmittance when cycled between colored and bleached states by application of 1.8V and -0.8V, respectively.

Vaidyanathan, Hari↗