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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Understanding why poly(acrylic acid) works: decarbonylation and cross-linking provide an ionically conductive passivation layer in silicon anodes

Poly(acrylic acid) (PAA) is commonly used as a binder for fabricating silicon (Si) anode active materials in lithium-ion batteries due to its useful properties including high polar solvent solubility, good rheology, and strong adhesive properties. However, the role and evolution of PAA during electrode fabrication, cycling, and calendar aging are not well understood. In this work, we reveal the evolution of PAA during electrode curing and relate its chemical change to the final electrode properties and performance. These studies are made possible using two types of in situ attenuated total reflectance-infrared Fourier transform (ATR-FTIR) spectroscopy: thermal ATR-FTIR to probe the cross-linking reaction, and ATR-FTIR spectroelectrochemistry of three-dimensional composite electrodes, a unique technique developed herein that probes the solvation dynamics of lithium ions at the silicon anode interface under electrochemical polarization. Specifically, we show that PAA undergoes a thermally-mediated, cross-linking decarbonylation reaction to form an ether-based network polymer. To show the importance of the polyether moieties, we synthesize partially esterified PAA analogues that do not undergo this cross-linking decarbonylation reaction and correlate the degree of cross-linking to half-cell performance metrics. Finally, we unveil the mechanism of the polyether binder performance through in situ ATR-FTIR spectroelectrochemistry and show that PAA acts as an interfacial material that conducts lithium-ions, limits solvent molecule access to the Si surface, and stabilizes the electrode against parasitic lithium inventory loss at high state of charge for an extended period of time.

25 ENERGY STORAGE↗
DOE OSTI2021

Evaluation of silicon carbide as a divertor armor material in DIII-D H-mode discharges

Silicon carbide (SiC) represents a promising but largely untested plasma-facing material (PFM) for next-step fusion devices. In this work, an analytic mixed-material erosion model is developed by calculating the physical (via SDTrimSP) and chemical (via empirical scalings) sputtering yield from SiC, Si, and C. The Si content in the near-surface SiC layer is predicted to increase during D plasma bombardment due to more efficient physical and chemical sputtering of C relative to Si. Silicon erosion from SiC thereby occurs primarily from sputtering of the enriched Si layer, rather than directly from the SiC itself. SiC coatings on ATJ graphite, manufactured via chemical vapor deposition, were exposed to repeated H-mode plasma discharges in the DIII-D tokamak to test this model. The qualitative trends from analytic modeling are reproduced by the experimental measurements, obtained via spectroscopic inference using the S/XB method. Quantitatively the model slightly under-predicts measured erosion rates, which is attributed to uncertainties in the ion impact angle distribution, as well as the effect of edge-localized modes. After exposure, minimal changes to the macroscopic or microscopic surface morphology of the SiC coatings were observed. Compositional analysis reveals Si enrichment of about 10%, in line with expectations from the erosion model. Extrapolating to a DEMO-type device, an order-of-magnitude decrease in impurity sourcing, and up to a factor of 2 decrease in impurity radiation, is expected with SiC walls, relative to graphite, if low C plasma impurity content can be achieved. Furthermore, these favorable erosion properties motivate further investigations of SiC as a low-Z, non-metallic PFM.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Two-level systems and growth-induced metastability in hydrogenated amorphous silicon

Specific heat measurements from 2 to 300 K of hydrogenated amorphous silicon prepared by hot-wire chemical vapor deposition show a large excess specific heat at low temperature, significantly larger than the Debye specific heat calculated from the measured sound velocity. The as-prepared films have a Schottky anomaly that is associated with metastable hydrogen in the amorphous network, as well as large linear and excess cubic term commonly associated with tunneling two-level systems in amorphous solids. Annealing at 200 °C, a temperature that enables hydrogen mobility but not evaporation, irreversibly reduces the heat capacity, eliminating the Schottky anomaly and leaving a reduced linear heat capacity. A non-monotonic dependence on growth temperature and H content is observed in all effects, except for sound velocity, which suggests that the tunneling two-level systems and the Schottky anomaly are associated with atomic hydrogen and require low density regions to form, while sound velocity is associated with the silicon network and increases with increasing growth temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Fiber-Optic Silicon Fabry-Perot Interferometric Bolometer: The Influence of Mechanical Vibration and Magnetic Field

Plasma radiation plays an important role in the operation and control of magnetic confinement fusion and is typically measured by bolometers. Here, we study the influence of mechanical vibration and magnetic field, which are typically present in magnetic confinement fusion devices, on the performance of a fiber-optic bolometer (FOB) based on silicon Fabry-Perot interferometer (FPI) demodulated by a scanning diode laser. It is found that both the vibration and magnetic field could cause large noise due to the birefringence of the silicon FPI. To mitigate the birefringence effects, we demonstrated two effective methods: polarization maintaining FOB and polarization scrambling. We show that two methods can be effective in mitigating the effect caused by the sensor birefringence: (1) replacing the regular single-mode fiber in the FOB system with polarization-maintaining fiber and (2) using a polarization scrambler after the laser source. For both methods, no significant increase in the noise was observed in the vibration and magnetic field tests. Finally, our research highlights the importance of the polarization management for the FOB systems toward their practical applications in magnetic-confinement fusion systems.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Insights into Na + Diffusion in Silicon Modules under Operating Conditions: Measuring Low Concentrations by D-SIMS

Sodium induced shunting under an electric field is a challenging reliability issue in crystalline Si solar modules. The source of this Potential-Induced Degradation of the Shunting type (PID-s) is well understood and its influence on power loss has been intensively studied based on phenomenological models on cell or module level relating the experimental power-loss to stressing parameters (time, temperature, voltage). However, little is known about the Na ion migration kinetics, responsible for PID on a microscopic level, and its quantitative relation to the efficiency degradation. In this paper we present our investigations of sodium ion migration in Ethylene-Vinyl Acetate (EVA) and silicon through Dynamic Secondary Ion Mass Spectroscopy (D-SIMS). Each sample was annealed at field relevant temperatures from 60-90 °C to address typical migration mechanisms of common PV installations. Analysis of the SIMS migration profiles revealed a diffusivity constant D 0,EVA = 0.09 ± 0.14 cm 2 /s and an activation energy E A,EVA = 0.85 ± .04 eV for Na in EVA and diffusivities higher than extrapolated literature values in silicon (D 0,Si = (3.03 ± 2.42)x10 -5 cm 2 /s, and E A,Si = 0.98 ± 0.02 eV). The new insight will be included in a drift-diffusion based degradation model accounting for the partition coefficient across all relevant interfaces. This model can assist in predicting PID-failure in the field based on the given model stack and the diffusion of Na + through each material. Furthermore, this tool can be used for process optimization as well as material selection significantly reducing the cost and time to validate a technology.

14 SOLAR ENERGY↗
DOE OSTI2023

Capacitance Transients, Photoconductive Decay, and Impedance Spectroscopy on 19% to 22% Efficient Silicon Solar Cells

High efficiency silicon solar cells are characterized using current-voltage curves, electroluminescence imaging, impedance spectroscopy, capacitance transients, microwave photoconductive decay, and time-resolved photoluminescence imaging. The sample set is composed of cells from different manufacturers and includes an n-type silicon heterojunction (SHJ), an n-type passivated emitter rear totally diffused (PERT), and five different p-type passivated emitter rear contact (PERC) cells. Carrier lifetimes, both photoconductivity and photoluminescence, are measured co-located with the light excitation pulse and within the cell but away from the light spot. Luminescence intensity and excess carrier lifetimes correlate to cell voltage. The capacitance transient time constants correlate to the capacitance values extracted from impedance spectroscopy.

capacitance↗
DOE OSTI2020

Busbar Design and Optimization for Voltage Overshoot Mitigation of a Silicon Carbide High-Power Three-Phase T-Type Inverter

The silicon carbide (SiC) devices have faster switching speed than that of the conventional silicon (Si) devices, which however may cause excessive device voltage overshoot. Larger gate resistance can help to restrain the overshoot, it however slows down the switching speed and increases switching losses. There are other methods that can mitigate the voltage overshoot, e.g., using low-inductance busbars, adding snubber circuits, etc. In this article, the busbar design for a 250-kW SiC three-level T-type inverter is investigated. The current commutation loops (CCLs) are first analyzed using a single-phase equivalent circuit. Then the detailed busbar design methods, especially a 3-D busbar design concept, are proposed to select the optimal stacking order for the multilayer laminated busbar and to address constraints posed by the physical terminal arrangements of SiC modules and dc-link capacitors. The stray inductance in each CCL is extracted via a finite element analysis and validated on the actual inverter busbar prototypes using an impedance analyzer. To further minimize the busbar stray inductance, a hybrid busbar structure with printed circuit board based buffer circuit using high-frequency decoupling capacitors is designed and evaluated in this article. Lastly, the effectiveness of the designed busbars as well as the buffer circuit are validated using experimental studies.

42 ENGINEERING↗
DOE OSTI2020

Observed volatilization behavior of silicon carbide in flowing hydrogen above 2000 K

In this work, the intrinsic compatibility of silicon carbide (SiC) and hydrogen (H 2 ) at high temperatures (2000-2473 K) and pressure near one atmosphere was evaluated through a combination of thermodynamic calculations and hot hydrogen exposure testing. Thermodynamic calculations predict the decomposition of SiC in a hydrogen environment to form free silicon (Si) and free carbon (C). Free Si is predicted to vaporize from the surface as a volatile species, while free C may interact with H 2 to form the hydrocarbons CH 4 (T < 2100 K) or C 2 H 2 (T > 2100 K). Coupons of high purity chemical vapor deposition (CVD) β-SiC were exposed to slowly flowing hydrogen at temperatures ranging between 2000 and 2473 K. SiC experienced active attack as the result of H 2 exposure, exhibiting linear weight loss kinetics and an Arrhenius dependence of weight loss on exposure temperature. The linear volatilization constant was experimentally evaluated to correspond with an activation energy of 370 ± 18 kJ/mol. Due to the dependence of observed corrosion rates on gas velocity, corrosion of SiC in flowing H 2 was determined to be governed by external mass transfer of volatile Si species through the boundary layer. Experimentally derived mass losses were in good agreement with mass losses predicted by a boundary layer limited gas diffusion model.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enabling Non-Carbonate Electrolytes for Silicon Anode Batteries Using Fluoroethylene Carbonate

Silicon is considered as one of the most promising anodes for next generation lithium-ion batteries, due to its high theoretical capacity and energy density. However, many technical barriers remain to its implementation, due to its high chemical/electrochemical reactivities with standard electrolytes and incomplete passivation. In this work, we take the most effective passivating additive of fluoroethylene carbonate (FEC) and study its impact on non-carbonate electrolytes. Our results indicate that esters and ureas-based electrolytes are similarly stabilized by FEC, and have very similar capacity retentions and Coulombic efficiencies to the state-of-the-art carbonate electrolyte. This study indicates the discovery of more efficient additives other than FEC is vital in developing an electrolyte that can successfully enable a silicon-anode battery.

25 ENERGY STORAGE↗
DOE OSTI2022

Capacity and Coulombic Efficiency Measurements Underestimate the Rate of SEI Growth in Silicon Anodes

Capacity measurements and related quantities are the first layer of information acquired during testing of Li-ion cells. It is generally considered that elevated values of coulombic efficiency and capacity retention are absolute indicators of the existence of a stable solid electrolyte interphase (SEI). Here, we challenge this notion by analyzing how the effect of side reactions on cell capacity depends on the choice of electrodes. More specifically, we demonstrate that the extent of measurable capacity fade due to SEI growth is modulated by the shape of the voltage profile of the cathode and anode at the end of charge and discharge half-cycles. This shape-dependency creates a mismatch between SEI growth and cell capacity loss, which is relatively small for graphite anodes but sizable for silicon-containing electrodes. We illustrate this point by showing that, at the same coulombic efficiency and capacity retention, cells containing silicon-based materials could actually exhibit rates of SEI growth that are as much as ≥ 40% higher than graphite cells. The main implication of this behavior is that, for certain systems, capacity measurements may be an unreliable source of information about the extent of reactions at the SEI, allowing other consequences of these side reactions (such as electrolyte depletion) to proceed unchecked while the cell appears to be stable.

25 ENERGY STORAGE↗
DOE OSTI2023

Assessing Electrolyte Fluorination Impact on Calendar Aging of Blended Silicon-Graphite Lithium-Ion Cells Using Potentiostatic Holds

Silicon-based lithium-ion batteries have started to meet cycle life metrics, but they exhibit poor calendar life. Here, electrolyte fluorination impact on calendar fade of blended silicon-graphite anodes is explored using a LiPF 6 in EC:EMC:FEC electrolyte vs LiBOB in EC:EMC electrolyte. We utilize a combined experimental-modeling approach applying potentiostatic voltage holds (V-hold) to evaluate electrolyte suitability for calendar life in a shortened testing timeframe (~2 months). Our theoretical framework deconvolutes the irreversible parasitic capacity losses (lithium lost to the solid electrolyte interphase) from the V-hold electrochemical data. Unfluorinated electrolyte (dominant LiBOB reduction) exhibits higher cell resistance as compared to fluorinated electrolyte (dominant FEC reduction). Both systems have similar irreversible capacities during the voltage hold duration with slower rate of parasitic capacity loss for the LiBOB system. Extrapolation of the parasitic losses to end of life capacity fade of 20% shows LiBOB electrolyte outperforming LiPF 6 electrolyte in calendar life. The results demonstrate the applicability of the V-hold protocol as a rapid material screening tool providing semi-quantitative calendar lifetime estimates.

25 ENERGY STORAGE↗
DOE OSTI2024

Unraveling Morphology and Chemistry Dynamics in Fluoroethylene Carbonate Generated Silicon Anode Solid Electrolyte Interphase Across Delithiated and Lithiated States: Relative Cycling Stability Enabled by an Elastomeric Polymer Matrix

The silicon solid electrolyte interphase (SEI) faces cyclical cracking and reconstruction due to the ∼350% volume expansion. Understanding the SEI dynamic morphology and chemistry evolution from delithiated to lithiated states is thereby paramount to engineering a stable Si anode. Fluoroethylene carbonate (FEC) is a preferred additive with widely demonstrated enhancement of the Si cycling. Thus, insights into the dynamics of the FEC-SEI may provide hints toward engineering the Si interface. Herein, complementary ATR-FTIR, AFM, tip IR, and XPS probing reveal the presence of an elastomeric polycarbonate-like matrix in the FEC-generated SEI which is absent from the FEC-free SEI. Adding FEC to the baseline 1 M LiPF 6 in EC:EMC (1:1) electrolyte promotes formation of a thinner and more conformal SEI, and subdues morphology and chemistry changes between consecutive half-cycles. From AFM, morphological stabilization of the FEC-SEI occurs earlier. Furthermore, conventional SEI biproducts such as Li 2 CO 3 and LiEDC appear in reduced quantities in the FEC-SEI implying a reduced quantity of Li-consuming species. The thin polymeric FEC-SEI enables deeper (de)lithiation of silicon. In conclusion, the enhanced mechanical compliance, chemical invariance, and reduced Li inventory consumption of the FEC-SEI are logically the key features underlying the Si cycling enhancement by FEC.

25 ENERGY STORAGE↗
DOE OSTI2025

Building High-Energy Silicon-Containing Batteries Using Off-The-Shelf Materials

The technology of silicon anodes appears to be reaching maturity, with high-energy Si cells already in pilot-scale production. However, the performance of these systems can be difficult to replicate in academic settings, making it challenging to translate research findings into solutions that can be implemented by the battery industry. Part of this difficulty arises from the lack of access to engineered Si particles and anodes, as electrode formulations and the materials themselves have become valuable intellectual property for emerging companies. Here, we summarize the efforts by Argonne’s Cell Analysis, Modeling, and Prototyping (CAMP) Facility in developing Si-based prototypes made entirely from commercially available materials. We describe the many challenges we encountered when testing high-loading electrodes (>5 mAh cm −2 ) and discuss strategies to mitigate them. With the right electrode and electrolyte design, we show that our pouch cells containing ≥ 70 wt% SiO x can achieve 600–1,000 cycles at C/3 and meet projected energy targets of 700 Wh L −1 and 350 Wh kg −1 . These results provide a practical reference for research teams seeking to advance silicon-anode development using accessible materials.

25 ENERGY STORAGE↗
DOE OSTI2023

Microporous structure in silicone polymers with polylactic acid and polyethylene glycol microspheres: Synthesis and characterization

Porosity in polymer parts could improve mechanical properties while reducing weight and density. Individual pores must be small enough that bulk mechanical properties are retained but significant enough to reduce the density of the material. Filler materials can be incorporated into polymer matrices and removed to create voids. Here, this paper focuses on creating spherical pores in silicone matrices by inserting and removing core materials or fillers during post-cure. A method was developed to incorporate pore formers into an uncured polymer resin and remove the pore former materials from the matrix. Polyethylene glycol (PEG) and polylactic acid (PLA) microspheres were created and incorporated into silicone matrices as pore formers. Microspheres with controllable size distributions were formed via an emulsion formation. Microspheres are removed from the matrix by solvent extraction and calcination. Thermogravimetric Analysis (TGA), Dynamic Mechanical Analysis (DMA), and optical imaging characterize and determine the successful creation of micropores in the polymer matrices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Screen-Printed Contacts for Crystalline Silicon Solar Cells: An Overview

Over the years, the photovoltaic market, worldwide, has been witnessing a double-digit growth rate. The silicon solar cell manufacturing technology has evolved to utilize raw materials optimally to address this growth. One of the ways in which manufacturers are addressing the challenge is by increasing the cell size and making thinner wafers. With this change in parameters, understanding the metal contact formation in solar cells becomes paramount to improve their efficiency. Screen printing is a widely used method to form metal contacts on solar cells and is ideally suited for large-volume manufacturing. This paper presents a review of the (a) role of screen printing in various solar cell architectures and (b) existing models for current conduction and contact formation mechanisms. An alternate approach to current conduction and contact formation mechanism in silicon solar cells is proposed.

contacts↗
DOE OSTI2021

Use of the Magnetic Isotope Effect for Silicon Isotopomer Chemical Separation

The goal of the Phase I work was to develop a novel approach to silicon isotope separation that will use the difference in chemical reactivity of the three naturally-occurring silicon isotopes. The 'magnetic isotope effect' (MIE) will be employed to differentially react 29Si from 28Si and 30Si. The difference in reactivity to either directly deplete 29Si to the required sub-ppm levels or deplete 29Si sufficiently to allow final purification with distillation or centrifugation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enabling New Approaches to Low-Cost Dopant Patterning for Interdigitated Back Contact Crystalline Silicon Solar Cells: Cooperative Research and Development, CRADA Number CRD-17-00665 (Final Report)

NREL is sub to the Department of Energy (DOE) Photovoltaic Research & Development (PVRD) project, titled "New Approaches to Low-Cost Scalable Doping for Interdigitated Back Contact Crystalline Silicon Solar Cells", awarded to Colorado School of Mines. The goal of this project was to develop an industrially relevant dopant patterning technique that enable high performing, cost efficient Interdigitated Back Contact (IBC) solar cells based on n-Cz silicon wafer. Several possibilities were explored at the beginning of the project and the masked plasma deposition was deselected as the most promising and industrially relevant. This method was thoroughly explored ion the course of the project, its limitations revealed and mitigated. NREL successfully the masked deposition integrated into the cell's process flow and produced the cells, alongside with numerous process development steps and application of in-house advanced characterization techniques. The report describes these developments by the task and in detail.

14 SOLAR ENERGY↗
DOE OSTI2023

Exploiting Fixed Charge at Selective Contacts for Silicon Photovoltaics

The goal of this work was to examine and exploit fixed interface charges in ultra-thin (0-3 nm thickness) tunnel dielectric layers sandwiched between silicon and selective contact metal oxides (molybdenum oxide, MoO x , titanium oxide, TiO 2 ). Specifically, the interface fixed charge was varied by changing processing conditions and materials over a wide range and the effect on the current-voltage behavior and the Schottky barrier height was quantified. In budget period 1 (year 1), the objective was to grow aluminum oxide tunnel layers with quantified fixed charge over a range of ~1E12 to ~-2E12 cm -2 and combine these with MoO x and TiO 2 layers on Czochralsi (CZ) mono p- and n-Si, respectively. We sought conditions that maximize fixed charge and minimize Schottky barrier height to MoO x contacts to p-Si. This objective, along with investigating the effects of silicon surface terminations, occupied the majority of the project timeline (Q1-Q8) due to complications with high specific contact resistivity values. In the last two quarters of the project period, the objective was to insert HfO2 layers between Si and aluminum oxide layers to quench the fixed charge for layers with otherwise identical thermal history. Another objective was to lower the barrier height at TiO 2 -based contacts on n-type Si, but that was never investigated completely.

14 SOLAR ENERGY↗