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At least 991 records · Page 55

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DOE OSTI2017

Thermal Decomposition of the Solid Electrolyte Interphase (SEI) on Silicon Electrodes for Lithium Ion Batteries

Here, thermal behavior of the solid electrolyte interphase (SEI) on a silicon electrode for lithium ion batteries has been investigated by TGA. In order to provide a better understanding of the thermal decomposition of the SEI on silicon, the thermal decomposition behavior of independently synthesized lithium ethylene dicarbonate (LEDC) was investigated as a model SEI. The model SEI (LEDC) has three stages of thermal decomposition. Over the temperature range of 50–300 °C, LEDC decomposes to evolve CO 2 and C 2 H 4 gases leaving lithium propionate (CH 3 CH 2 CO 2 Li) and Li 2 CO 3 as solid residues. The lithium propionate decomposes over the temperature range of 300–600 °C to evolve pentanone leaving Li 2 CO 3 as a residual solid. Finally, the Li 2 CO 3 decomposes over 600 °C to evolve CO 2 leaving Li 2 O as a residual solid. A very similar thermal decomposition process is observed for the SEI generated on cycled silicon electrodes. However, two additional thermal decomposition reactions were observed characteristic of Li x PO y F z at 300 °C and the polyimide binder at 550 °C. TGA measurements of Si electrodes after various numbers of cycles suggest that the LEDC on Si electrodes thermally decomposes during cycling to form lithium propionate and Li 2 CO 3 , resulting in increased complexity of the SEI.

36 MATERIALS SCIENCE↗

DOE OSTI2018

The Phase Evolution and Degradation Modes of $ R\overline{3}$ m Li x Ni 1-y-z Co y Al z O 2 Electrodes Cycled Near Complete Delithiation

We report that the practical utilization of energy densities near the theoretical limit for $ R\overline{3}m$ layered oxide positive electrode materials is dependent on the stability of the electrochemical performance of these materials at or near full delithiation. In order to develop new chemistries and novel approaches towards the improvement of the electrochemical performance of these materials at such high states of charge, a robust understanding of the failure mechanisms limiting current materials is necessary. Thorough analysis of Li x Co 1-y Al y O 2 and Li x Ni 1-y Al y O 2 as well as Li x Ni 0.8 Co 0.2 O 2 and Li x Ni 0.8 Co 0.15 Al 0.05 O 2 (1 ≥ x ≥ 0 and 0.2 ≥ y ≥ 0) enabled the identification of key relationships between the transition metal chemistry of the electrode, its structural stability, and cycling characteristics at or near complete delithiation (4.75 V). Extensive characterization of these materials was achieved by a multitude of physical and electrochemical techniques to investigate the relative importance of surface vs. bulk phenomena. Here, the resulting insights derived from these analyses highlight the importance of the intrinsic structural and mechanical stability of the electrode when highly delithiated and establish guidelines for identifying positive electrode materials with improved high state of charge performance. Lastly, particularly important is the contrasting electrochemical impact of Al substitution into LiCoO 2 - and LiNiO 2 -based materials, which is shown to likely arise from the enhanced propensity for Al ions to migrate to the tetrahedral site in Co-rich compounds at high states of delithiation.

25 ENERGY STORAGE↗

DOE OSTI2025

Electrolyte Vapor Induced Passivation and Transition Metal Redox on Electrode Active Materials

The gaseous environment that battery electrodes are exposed to is critical to their electrochemical performance, and yet, the impact of vapor-phase components in the glovebox is relatively unexplored. In this study, we examine how the surface of Li 4 Ti 5 O 12 and LiFePO 4 composite electrodes evolve upon exposure to 1 M LiPF 6 in ethylene carbonate:dimethyl carbonate electrolyte vapors in an argon-filled glovebox. Spatially resolved X-ray photoemission electron microscopy and X-ray photoelectron spectroscopy reveal that even brief (15 minutes) contact with electrolyte vapor initiates the formation of a LiF film and changes the oxidation state of transition metals at the particle surface. Notably, these modifications occur selectively on active material particles and not on binder or conductive carbon, underscoring the specificity of vapor-induced reactions. Prolonged exposure to electrolyte vapor over the course of 1 week yields thicker, more chemically complex interphases containing both LiF and lithium oxyfluorophosphate species (Li x PO y F z ). Subsequent electrochemical testing shows that vapor-induced passivation layers influence first cycle capacities, lithium (de)insertion overpotentials, and charge-transfer resistance values. In conclusion, these results indicate that vapor–electrode interactions may be a source of variability in electrochemical behavior over time and suggest that other, more reactive electrode materials may also be susceptible to interactions with electrolyte vapor.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Elucidating the Role of the Electric Field at the Ni/YSZ Electrode: A DFT Study

To decrease the deactivation of the Ni/YSZ electrode during hydrocarbon oxidation in solid oxide fuel cells (SOFCs) and coelectrolysis of H 2 O and CO 2 in a solid oxide electrolysis cell (SOEC), it is very important to first understand oxygen vacancy formation at the triple-phase boundary (TPB) of Ni/YSZ because such vacancies are the active sites for coke formation and sulfur poisoning. Furthermore, the effect of the electric fields on oxygen vacancy formation must be investigated because such fields could potentially be used to alter the Ni/YSZ system and directly modify its electrocatalytic performance. Here in this study, three scenarios were considered: (i) oxygen vacancy formation in YSZ with and without a Ni cluster, (ii) oxygen vacancy formation and oxygen diffusion in YSZ and Ni/YSZ at different oxygen vacancy concentrations, and (iii) the effect of the electric fields on scenarios (i) and (ii). Our computational results show that the oxygen-enriched Ni/YSZ (Ni/YSZ+O) electrode is most likely to occur in an oxygen-enriched environment, even in the presence of different electric fields. Both large negative and positive electric fields could lead to more active TPB vacancies by reducing the vacancy formation energies of the Ni/YSZ+O electrode to a certain degree. Both charge distribution and effective dipole moments verify the qualitative findings concerning field influences on oxygen vacancy formation in Ni/YSZ. Overall, this investigation provides guidance for designing a Ni/YSZ electrode with an improved electrocatalytic performance via the simulated electric fields.

25 ENERGY STORAGE↗

DOE OSTI2026

Investigating the Adsorption–Desorption Kinetics of a Molecular Water Oxidation Catalyst at an Electrode Interface

Probing the dynamics of molecular catalysts at electrode–electrolyte interfaces is essential for understanding catalytic mechanisms. Structure-specific spectroscopic methods are particularly powerful for examining electrocatalytic interfaces but are mostly used under steady-state conditions. Herein, we combined surface-enhanced infrared absorption spectroscopy (SEIRAS) with phase-sensitive detection (PSD) to investigate the dynamics of a molecular Ir-based water oxidation catalyst at the Au–electrolyte interface. We found that the amplitude of the absorbance of the catalyst is anticorrelated to that of interfacial water. This anticorrelation can be understood by the adsorption of the electrooxidized catalyst on the electrode and concurrent displacement of interfacial water. The infrared signals from the interface exhibit an increasing phase lag with respect to the electrode potential with an increasing scan rate of the potential. Kinetic modeling suggests that the potential-dependent adsorption–desorption kinetics of the molecular catalyst on the electrode gives rise to this phase lag. Furthermore, this study shows that PSD-SEIRAS is a powerful tool for investigating the interfacial dynamics of electrocatalytic systems.

Catalysts↗

DOE OSTI2021

Calibration-Free Quantitative Analysis of Lithium-Ion Battery (LiB) Electrode Materials Using Laser-Induced Breakdown Spectroscopy (LIBS)

Recent years have seen a surge in the demand for high-performance battery electrode materials for automotive and various electronic device applications. Improving battery performance requires precise knowledge of the structure–composition properties of active electrode materials. To this effect, quantitative and precise estimation of the composition of advanced electrode materials, containing trace amounts of dopants, provide immense value toward developing next-generation high-capacity battery materials. Herein, we demonstrate the application of calibration-free laser-induced breakdown spectroscopy (LIBS) as a powerful analytical tool for rapid and reliable quantitative spectrochemical characterizations of layered Li metal oxide cathodes containing Mo and Cr dopants (<5 atom %). Specifically, we employ the LIBS using an internal calibration methodology to establish the quantitative elemental ratios of major (Ni, Mn, Co) and trace dopant (Cr, Mo) transition metals to bulk Li contents in diverse cathode material samples such as LiNi 0.5 Mn 0.5 O 2 (NM-50/50), LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC), LiNi 0.317 Mn 0.317 Co 0.317 Cr 0.05 O 2 (Cr-doped NMC), and LiNi 0.5– x /2 Mn 0.5– x /2 Mo x O 2 ( x = 0.03, 0.04, 0.05) (Mo-doped NM-50/50) that were synthesized via sol–gel routes. The LIBS-estimated elemental compositions are in good agreement with the nominal stoichiometric values. Furthermore, ex situ LIBS characterizations presented here pave the path for future high-efficacy application of calibration-free quantitative LIBS for rapid in situ analyses of elemental composition changes in battery electrode materials under operation that need not resort to off-site analytical techniques requiring cumbersome sample preparations and/or external standards.

25 ENERGY STORAGE↗

DOE OSTI2022

Mechanistic Study of Controlled Zinc Electrodeposition Behaviors Facilitated by Nanoscale Electrolyte Additives at the Electrode Interface

Nanoparticle organic hybrid materials (NOHMs) are liquid-like materials composed of an inorganic core to which a polymeric canopy is ionically tethered. NOHMs have unique properties including negligible vapor pressure, high oxidative thermal stability, and the ability to bind to reactive species of interest due to the tunability of their polymeric canopy. This makes them promising multifunctional materials for a wide range of energy and environmental technologies, including electrolyte additives for electrochemical energy storage (e.g., flow batteries) and the electrochemical conversion of CO 2 to chemicals and fuels. Due to their unique transport behaviors in fluid systems, an understanding of the near-electrode surface behavior of NOHMs in electrolyte solutions and their effect on electrochemical reactions is still lacking. In this work, the complexation of zinc (Zn) by NOHMs with an ionically tethered polyetheramine canopy (HPE) (NOHM-I-HPE) was studied using attenuated total reflectance Fourier transform infrared and Carbon-13 nuclear magnetic resonance spectroscopy. Additionally, various electrochemical techniques were employed to discern the role of NOHM-I-HPE during zinc electrodeposition, and the results were compared to those of the electrochemical system containing untethered HPE polymers. Our findings confirmed that NOHM-I-HPE and HPE reversibly complex zinc in the aqueous electrolyte. NOHM-I-HPE and HPE were found to block some of the electrode active sites, reducing the overall current density during electrodeposition, while facilitating the formation of smooth zinc deposits, as revealed by surface imaging and diffraction techniques. Observed variations in the current density responses and the degree of passivation created by the NOHM-I-HPE and HPE adsorbed on the electrode surface revealed that their different packing behaviors at the electrode–electrolyte interface influence the zinc deposition mechanism. The presence of the nanoparticle and ordering offered by the NOHMs as well as the structured conformation of the polymeric canopy allowed the formation of void spaces and free volumes for enhanced transport behaviors. Furthermore, these findings provided insights into how structured electrolyte additives such as NOHMs can allow for advancements in electrolyte design for controlled deposition of metal species from energy-dense electrolytes or for other electrochemical reactions.

25 ENERGY STORAGE↗

DOE OSTI2023

Laser Scribing for Electrode Patterning of Perovskite Spectrometer-Grade CsPbBr 3 Gamma-ray Detectors

Making semiconductor radiation detectors that work at room temperature relies heavily on the deposition and pixelation of electrodes. Electrode patterning of perovskite solar cells widely implements laser scribing techniques, which is a convenient, scalable, and inexpensive technique. However, this method has not found its application in radiation detector patterning yet, and the question whether laser scribing can achieve high-quality patterns with minimum damage to a detector crystal and low interpixel cross-talk remains largely unanswered. To prove that laser scribing is a practical method for electrode patterning on perovskite CsPbBr 3 detectors, we use the material to create a variety of patterns. A very low lateral leakage current (60 nA at 10 V) and high mobility-lifetime product (9.7(3) x 10 -4 cm 2 /V) were observed between the pixel and the guard ring in tests of single-pixel devices with a separation of 200 or 100 μm between the central electrode and the guard ring. The 122 and 136 keV photopeaks in 57 Co gamma-ray spectra were very well resolved with an energy resolution of up to 6.1% at 122 keV. Finally, a further reduction in gap size to 50 mu m is conceivable, but more process optimization is needed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2025

Understanding the Dissolution and Passivation of an Aluminum Electrode during Electrocoagulation of Groundwater Using Neutron and X-ray Reflectometry

An aluminum (Al)-based electrocoagulation (EC) system can effectively remove dissolved silica and hardness in groundwater. The effectiveness of Al-EC in terms of pollutant removal, Faradaic efficiency, and energy consumption depends on the interfacial electrolysis or passivation of the electrode in water. Thus, understanding the electrolysis reaction at the liquid/electrode interface during operation is important for sustainable EC deployment. Here, a continuous flow-through Al-EC system was tested with various groundwater simulants, i.e., chloride (Cl – )-based, sulfate (SO 4 2– )-based, and mixed solutions. High pollutant removal with low energy consumption was observed in Cl – -based groundwater treatment, while low pollutant removal with high energy consumption was observed in SO 4 2– -based groundwater. For example, the required energy per unit mass of Al dosing in SO 4 2– -based groundwater is three times higher than that in Cl – -based groundwater at 10 mA/cm 2 . However, increasing the Cl – concentration significantly reduces this energy demand. In SO 4 2– -based groundwater, the silicate removal efficiency drops from 85.1% to 24.0% compared to that for Cl – -based groundwater, while Mg 2+ and Ca 2+ removal efficiencies decrease to 0.6% from 15.8% and 5.7% from 44.8%, respectively. To better understand this EC performance, we used in situ neutron reflectometry (NR) to examine the interfacial dynamics of Al dissolution and passivation at a 100 nm scale occurring on the surface of the sacrificial Al electrodes during EC. Ex situ X-ray reflectometry (XRR) was also used to support the in situ NR results. Both NR and XRR results revealed that Al dissolution is influenced by the presence of Cl – in the simulants, while a passivating layer forms on the electrode in a SO 4 2– -based solution. In the Cl – -based solution, anodic Al dissolution occurred locally and inhomogeneously across the surface of the Al anode film, resulting in a localized thickness reduction over time. In the SO 4 2– -based solution, no apparent dissolution of the Al anode was identified. Instead, Al underwent oxidation, forming an amorphous Al 2 O 3 surface layer within the Al electrode film that increased in thickness over time. In the mixed solution, both anodic Al dissolution and surface Al 2 O 3 layer formation occurred, indicating that Al dissolution and surface Al 2 O 3 layer formation are attributable to the Cl – and SO 4 2– ions, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

An Ideal Electrode Material, 3D Surface-Microporous Graphene for Supercapacitors with Ultrahigh Areal Capacitance

The efficient charge accumulation of an ideal supercapacitor electrode requires abundant micropores and its fast electrolyte-ions transport prefers meso/macropores. But, current electrode materials cannot meet both requirements, resulting in poor performance. We creatively constructed three-dimensional cabbage-coral-like graphene as an ideal electrode material, in which meso/macro channels are formed by graphene walls and rich micropores are incorporated in the surface layer of the graphene walls. The unique 3D graphene material can achieve a high gravimetric capacitance of 200 F/g with aqueous electrolyte, 3 times larger than that of commercially used activated carbon (70.8 F/g). Furthermore, it can reach an ultrahigh areal capacitance of 1.28 F/cm 2 and excellent rate capability (83.5% from 0.5 to 10 A/g) as well as high cycling stability (86.2% retention after 5000 cycles). The excellent electric double-layer performance of the 3D graphene electrode can be attributed to the fast electrolyte ion transport in the meso/macro channels and the rapid and reversible charge adsorption with negligible transport distance in the surface micropores.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2018

High-Quality AZO/Au/AZO Sandwich Film with Ultralow Optical Loss and Resistivity for Transparent Flexible Electrodes

Transparent flexible electrodes are in ever-growing demand for modern stretchable optoelectronic devices, such as, display technologies, solar cells, and smart window. Such sandwich-film-electrodes deposited on polymer substrates are unattainable because of the low quality of the films, inducing a relatively large optical loss and resistivity as well as a difficulty in elucidating the interference behavior of light. In this article, we report a high-quality AZO/Au/AZO sandwich film with excellent optoelectronic performance, e.g., an average transmittance of about 81.7% (including the substrate contribution) over the visible range, a sheet resistance of 5 Ω/sq and a figure-of-merit factor of ~55.1. These values are well ahead of those previously reported for sandwich-film-electrodes. Additionally, the interference behaviors of light modulated by the coat and metal layers have been explored with the employment of transmittance spectra and numerical simulations. In particular, a heater device based on an AZO/Au/AZO sandwich film exhibits high performance such as short response time (~5 s) and uniform temperature field. In conclusion, this work provides a deep insight into the improvement of the film quality of the sandwich electrodes and the design of high-performance transparent flexible devices by the application of a flexible substrate with an atomically smooth surface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2015

Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

Electrochemical reduction of the dizaonium complex, [Ru II (bda)(NO)(N–N 2 ) 2 ] 3+ , 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid material has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2 , is a very fast and rugged heterogeneous water oxidation catalyst with TOF i s of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

On-Surface Reactions of Electronically Active Self-Assembled Monolayers for Electrode Work Function Tuning

Self-assembled monolayers (SAMs) help improve the performance of organic electronic devices through interface passivation and enhanced carrier transport. Yet, there is limited information regarding the chemical structure of the SAMs upon functionalization and subsequent thermal treatment. Here, we studied the on-surface reaction of carbazole-derived SAMs on model gold electrodes, focusing on the chemical structure changes induced by thermal treatments. Furthermore, we correlate the microscopic changes with their impact on the electrode’s work function. The carbazole-based SAMs first transform into organometallic complexes. At higher annealing temperatures, SAMs convert to oligomeric complexes. The observed chemical reactions significantly reduce the electrode work function and facilitate electron injection in n-type organic thin-film transistors. Our results highlight the on-surface synthesis of electronically active SAMs as an alternative approach for modifying the work function of electrodes for organic electronics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2019

Mapping Charge Percolation in Flowable Electrodes Used in Capacitive Deionization

Electrical percolation in flow electrode capacitive deionization is critical to mitigate electronic resistance and maximize ion electrosorption. It is experimentally challenging to characterize mass and charge transfer phenomena in flow electrodes with space and time dimensions. In this work, we demonstrate a way to resolve charge percolation pathways at sub-micron resolutions using synchrotron X-ray tomography and computational techniques. Three-dimensional reconstructed images provide a means to measure important micro- and mesoscale electrode properties, such as pore-size distribution, aggregation size, and percolation properties. Developing this microstructural understanding of flow-electrodes is necessary to understand how transport limitations impact separations performance and to inform operating conditions at the technology level (flow regimes).

36 MATERIALS SCIENCE↗

DOE OSTI2013

Numerical solutions of sheath structures in front of an electron-emitting electrode immersed in a low-density plasma

The exact theoretical expressions involved in the formation of sheath in front of an electron emitting electrode immersed in a low-density plasma have been derived. The potential profile in the sheath region has been calculated for subcritical, critical, and supercritical emissions. The potential profiles of critical and supercritical emissions reveals that we must take into account a small, instead of zero, electric field at the sheath edge to satisfy the boundary conditions used to integrate the Poisson's equation. The I-V curves for critical emission shows that only high values of plasma-electron to emitted-electron temperature ratio can meet the floating potential of the emissive electrode. A one-dimensional fluid like model is assumed for ions, while the electron species are treated as kinetic. The distribution of emitted-electron from the electrode is assumed to be half Maxwellian. The plasma-electron enters the sheath region at sheath edge with half Maxwellian velocity distribution, while the reflected ones have cut-off velocity distribution due to the absorption of super thermal electrons by the electrode. The effect of varying emitted-electron current on the sheath structure has been studied with the help of a parameter G (the ratio of emitted-electron to plasma-electron densities)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2014

Experiments with biased side electrodes in electron cyclotron resonance ion sources

The output of highly charged ions from an electron cyclotron resonance ion source (ECRIS) consists of ionic losses from a highly confined plasma. Therefore, an increase of the output of the ions of interest always is a compromise between an increase in the confinement and an increase of the losses. One route towards a solution consists of attacking the losses in directions – i.e., radial directions – that do not contribute to the required output. This was demonstrated in an experiment (using the Kei ECRIS at NIRS, Japan) where radial losses were electrostatically reduced by positively biasing one set of six “side” electrodes surrounding the plasma in side-ward directions attached (insulated) to the cylindrical wall of the plasma chamber. Recently new studies were performed in two laboratories using two essentially different ion sources. At the BioNano ECRIS (Toyo University, Japan) various sets of electrodes were used; each of the electrodes could be biased individually. At the Atomki ECRIS (Hungary), one movable, off-axis side electrode was applied in technically two versions. The measurements show indeed a decrease of ionic losses but different effectivities as compared to the biased disk.

43 PARTICLE ACCELERATORS↗

DOE OSTI2013

Electron transfer at the contact between Al electrode and gold nanoparticles of polymer: Nanoparticle resistive switching devices studied by alternating current impedance spectroscopy

Electron transfer at the contact between an Al electrode and Au nanoparticles of polymer:nanoparticle devices is studied by ac impedance spectroscopy. The devices have a polystyrene layer embedded with Au nanoparticles capped with conjugated 2-naphthalenethiol sandwiched between Al and MoO{sub 3}/Al electrodes, and they exhibit electrode-sensitive resistive switches. The devices in the pristine or high resistance state have high capacitance. The capacitance decreases after the devices switch to a low resistance state by a voltage scan. The change in the capacitance is attributed to the voltage-induced change on the electronic structure of the contact between the Al electrode and Au nanoparticles.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2014

A study on prevention of an electric discharge at an extraction electrode of an electron cyclotron resonance ion source for cancer therapy

A compact ECR ion source has utilized for carbon radiotherapy. In order to increase beam intensity with higher electric field at the extraction electrode and be better ion supply stability for long periods, electric geometry and surface conditions of an extraction electrode have been studied. Focusing attention on black deposited substances on the extraction electrode, which were observed around the extraction electrode after long-term use, the relation between black deposited substances and the electrical insulation property is investigated. The black deposited substances were inspected for the thickness of deposit, surface roughness, structural arrangement examined using Raman spectroscopy, and characteristics of electric discharge in a test bench, which was set up to simulate the ECR ion source.

36 MATERIALS SCIENCE↗