High-rate cathode CrSSe based on anion reactions for lithium-ion batteries
Explore the source record for details and available documents.
99 GENERAL AND MISCELLANEOUS↗
SEARCH · Search NASA
Results for “Si Anode”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Achieving Highly Reproducible Results in Graphite-based Li-ion Full Coin Cells
Electrode materials, cathodes or anodes, are mostly evaluated in half coin cells where lithium (Li) metal is used. However, due to the instability nature of Li metal, the cycling performances of the half cells is more likely reflecting Li anode stability instead of the coupled electrodes, questioning the conclusions. Full coin cells utilizing graphite as the anode effectively assesses materials. But the key factors of preparing full coin cells with reproducible performances have rarely been discussed and overlooked leading to many inconsistent results. This work discusses the scientific gap between cell preparation and observed electrochemical performances to unveil the key parameters for achieving consistent and reliable results in full coin cells, critical for effective evaluation of any new materials tested under relevant conditions. The knowledge from this work is broadly applicable in other full cells systems such as Si-based full cells or Na-ion batteries.
Hu, Jiangtao↗
Electrochemical Formation of Li-M-(M')-Si Phases Using Multivalent Electrolyte Salt Additives
Lithium-rich silicides (Li 15 Si 4 ), formed during the electrochemical lithiation of silicon, show high reactivity with electrolyte components that contribute to capacity decay, formal lithium loss, and low coulombic efficiency. Recently, the reactivity of lithium silicides was found to be suppressed by substituting a multivalent cation (i.e. Mg, Ca) for lithium that results in the room temperature formation of a ternary Li-M-Si phase. In this study, we explored a range of multivalent electrolyte salt additives (M = Ni, Cu, La, Ce, Sr, Ba, and Ca-Mg mixed salt) in a lithium-ion cell configuration and identified a room temperature electrochemical route to the formation of new ternary and quaternary lithium silicides. Using this method, both nickel and copper salts were found to plate onto the silicon electrode surface upon lithiation. Further, based on refined synchrotron XRD data, multivalent cations with an ionic radius similar to Na (~1.03 Å) or smaller can be inserted electrochemically into a formally cation-deficient Li 15 Si 4 host lattice to form new ternary (or quartenary) phases. The electrochemical synthesis of a new quaternary Li-M-M’-Si phase represents a facile route to preparing and scaling materials isostructural to the Heusler phase and electron-precise Li 14 MgSi 4 phase that results in enhanced cycling and calendar life performance.
25 ENERGY STORAGE↗
Understanding the Solution Dynamics and Binding of a PVDF Binder with Silicon, Graphite, and NMC Materials and the Influence on Cycling Performance
The impact of the binding, solution structure, and solution dynamics of poly(vinylidene fluoride) (PVDF) with silicon on its performance as compared to traditional graphite and Li 1.05 Ni 0.33 Mn 0.33 Co 0.33 O 2 (NMC) electrode materials was explored. Through refractive index (RI) measurements, the concentration of the binder adsorbed on the surface of electrode materials during electrode processing was determined to be less than half of the potentially available material resulting in excessive free binder in solution. Using ultrasmall-angle neutron scattering (USANS) and small-angle neutron scattering (SANS), it was found that PVDF forms a conformal coating over the entirety of the silicon particle. This is in direct contrast to graphite–PVDF and NMC–PVDF slurries, where PVDF only covers part of the graphite surface, and the PVDF chains make a network-like graphite–PVDF structure. Conversely, a thick layer of PVDF covers NMC particles, but the coating is porous, allowing for ion and electronic transport. The homogeneous coating of silicon breaks up percolation pathways, resulting in poor cycling performance of silicon materials as widely reported. These results indicate that the Si–PVDF interactions could be modified from a binder to a dispersant.
25 ENERGY STORAGE↗
2‐Aminobenzenethiol‐Functionalized Silver‐Decorated Nanoporous Silicon Photoelectrodes for Selective CO 2 Reduction
Abstract A molecularly thin layer of 2‐aminobenzenethiol (2‐ABT) was adsorbed onto nanoporous p‐type silicon (b‐Si) photocathodes decorated with Ag nanoparticles (Ag NPs). The addition of 2‐ABT alters the balance of the CO 2 reduction and hydrogen evolution reactions, resulting in more selective and efficient reduction of CO 2 to CO. The 2‐ABT adsorbate layer was characterized by Fourier transform infrared (FTIR) spectroscopy and modeled by density functional theory calculations. Ex situ X‐ray photoelectron spectroscopy (XPS) of the 2‐ABT modified electrodes suggests that surface Ag atoms are in the +1 oxidation state and coordinated to 2‐ABT via Ag−S bonds. Under visible light illumination, the onset potential for CO 2 reduction was −50 mV vs. RHE, an anodic shift of about 150 mV relative to a sample without 2‐ABT. The adsorption of 2‐ABT lowers the overpotentials for both CO 2 reduction and hydrogen evolution. A comparison of electrodes functionalized with different aromatic thiols and amines suggests that the primary role of the thiol group in 2‐ABT is to anchor the NH 2 group near the Ag surface, where it serves to bind CO 2 and also to assist in proton transfer.
Kan, Miao↗
High-efficiency thin-film GaAs solar cells, phase2
Thin GaAs epi-layers with good crystallographic quality were grown using a (100) Si-substrate on which a thin Ge epi-interlayer was grown by CVD from germane. Both antireflection-coated metal oxide semiconductor (AMOS) and n(+)/p homojunction structures were studied. The AMOS cells were fabricated on undoped-GaAs epi-layers deposited on bulk poly-Ge substrates using organo-metallic CVD film-growth, with the best achieved AM1 conversion efficiency being 9.1%. Both p-type and n(+)-type GaAs growth were optimized using 50 ppm dimethyl zinc and 1% hydrogen sulfide, respectively. A direct GaAs deposition method in fabricating ultra-thin top layer, epitaxial n(+)/p shallow homojunction solar cells on (100) GaAs substrates (without anodic thinning) was developed to produce large area (1 sq/cm) cells, with 19.4% AM1 conversion efficiency achieved. Additionally, an AM1 conversion efficiency of 18.4% (17.5% with 5% grid coverage) was achieved for a single crystal GaAs n(+)/p cell grown by OM-CVD on a Ge wafer.
Yeh, Y. C. M.↗
Si-based materials for lithium-ion batteries V. n-SiO powder
X-ray photoelectron spectroscopy was used to analyze Si powders that have a native oxide surface, obtained from Paraclete Energy, Inc. The spectra were obtained using incident monochromatic Al K α radiation at 1486.6 eV (0.834 01 nm). An initial survey spectrum together with O 1s, C 1s, and Si 2p are presented. A final survey spectrum was collected to ascertain the amount of beam-induced damage, which appears to be minimal. Finally, the spectra indicate the principal core level photoelectron and Auger electron signals with only minor nitrogen signal and show the expected oxidized carbon and silicon species related to atmospheric exposure.
25 ENERGY STORAGE↗
Mass spectral molecular mapping shows benefits of thermal evaporation in prelithiated silicon-based electrodes
Silicon based composites have become increasingly popular as potential anodes for lithium-ion batteries due to their large storage capacity and potential ability to generate batteries with energy densities greater than 350 Wh kg −1 . These anodes often see reduced initial columbic efficiency (ICE) due to disruptive volume expansionup to 300% and continuous solid electrolyte interphase (SEI) layer formation. Prelithiation, where an excess reservoir of Li is added to the electrode to compensate for irreversible SEI formation losses during their sample preparation, has proven to solve the issue of immediate capacity loss. Thermal evaporation is a prelithiation technique with limited studies on its effectiveness. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to highlight the benefits of prelithiation via thermal evaporation. ToF-SIMS provides chemical mapping and spatial information in 2D and 3D visualizing the deposition of lithium, identifying Li x Si y alloy and Li x Si y O z silicate formation, and the distribution of lithium passivation into the electrodes. Passivation under different atmospheric conditions, such as inert Argon (Ar) and Ar/ carbon dioxide (CO 2 ), highlights the impact of the environment on the passivation effectiveness and formation of Li x Si y alloy and Li x Si y O z silicate. The ToF-SIMS molecular imaging and depth profiling results indicate that prelithiation via thermal evaporation effectively distributes lithium throughout the depth profile thickness of several hundred nanometers. It induces a greater degree of Li x Si y O z silicate formation over Li x Si y alloy. Our ToF-SIMS characterization results show the effectiveness of thermal evaporation in producing a more stable electrode and an electrode with an effective lithium reserve that can preserve its capacity.
Parker, Gabriel D. [Oak Ridge National Laboratory ↗
Si-based materials for lithium-ion batteries XI. 70% surface-modified Si/C/perfluorooctene-carbon black/lithiated polyacrylic acid electrode
X-ray photoelectron spectroscopy was used to analyze a 70% Si/C/perfluorooctene-carbon black/lithiated polyacrylic acid electrode fabricated at the Cell Analysis, Modeling, and Prototyping (CAMP) Facility, Argonne National Laboratory. The spectra were obtained using incident monochromatic Al K α radiation at 1486.6 eV (0.83 401 nm). A survey spectrum together with O 1s, C 1s, and Si 2p are presented. The spectra indicate the principal core level photoelectron and Auger electron signals with only minor sodium, copper, calcium, and lithium signals and show the expected silicon-carbon, carbon-fluorine, and silicon-fluorine species related to the surface modification process in addition to oxidized carbon and silicon due to atmospheric exposure.
25 ENERGY STORAGE↗
Towards extreme fast charging of 4.6V LiCoO 2 via mitigating high-voltage kinetic hindrance
High-voltage LiCoO 2 (LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries (LIBs) in the 3C markets. However, the sluggish lithium-ion diffusion at high voltage significantly hampers its rate capability. Herein, combining experiments with density functional theory (DFT) calculations, we demonstrate that the kinetic limitations can be mitigated by a facial Mg 2+ +Gd 3+ co-doping method. The as-prepared LCO shows significantly enhanced Li-ion diffusion mobility at high voltage, making more homogenous Li-ion de/intercalation at a high-rate charge/discharge process. The homogeneity enables the structural stability of LCO at a high-rate current density, inhibiting stress accumulation and irreversible phase transition. When used in combination with a Li metal anode, the doped LCO shows an extreme fast charging (XFC) capability, with a superior high capacity of 193.1 mAhg -1 even at the current density of 20C and high-rate capacity retention of 91.3% after 100 cycles at 5C. In conclusion, this work provides a new insight to prepare XFC high-voltage LCO cathode materials.
25 ENERGY STORAGE↗
Si-based materials for lithium-ion batteries I: Surface-modified Si/C powder
X-ray photoelectron spectroscopy was used to analyze Si/C powder obtained from Paraclete Energy, Inc. The spectra were obtained using incident monochromatic Al K α radiation at 1486.6 eV (0.834 01 nm). An initial survey spectrum together with O 1s, C 1s, and Si 2p are presented. A final survey spectrum was collected to ascertain the amount of beam-induced damage, which appears to be minimal. Finally, the spectra indicate the principal core level photoelectron and Auger electron signals and show the expected silicon-carbon species related to the surface modification process in addition to oxidized carbon and silicon due to atmospheric exposure.
25 ENERGY STORAGE↗
Effect of electrochemical cycling on microstructures of nanocomposite silicon electrodes using hyperpolarized 129 Xe and 7 Li NMR spectroscopy
The microstructural stability of composite electrodes during electrochemical cycling is critically important as it dictates the performance of Li-ion batteries. The issue becomes even more important for the high capacity alloying anode such as silicon that typically exhibits dramatic lithiation–delithiation-induced volume changes. The solid electrolyte interphase (SEI) layer formed on the active electrode surface has a profound effect on the overall microstructural stability of composite electrodes. An ideal SEI layer allows Li+ ions in and out of the electrode, but is an insulator to electrons, preventing the electrolyte from being further reduced. However, the SEI layers formed during initial lithiation may experience changes or degradation with subsequent cycling, adversely affecting the electrode performance. A combination of hyperpolarized 129 Xe and 7 Li nuclear magnetic resonance spectroscopies was applied to probe the microstructures of nanocomposite silicon electrodes at various stages of the lithiation–delithiation cycle. The results obtained from this study shed light on the degradation mechanism of nanocomposite Si electrodes upon electrochemical cycling and should prove useful in the effort to design more robust electrodes in the future.
36 MATERIALS SCIENCE↗
Pilot microbial electrolysis cell closes the hydrogen loop for hydrothermal wet waste conversion to jet fuel
The global shift toward net-zero emissions necessitates resource recovery from wet waste. In this study, we demonstrate the first feasibility of combining pilot-scale microbial electrolytic cells (MECs) with hydrothermal liquefaction (HTL) for simultaneous post-hydrothermal liquefaction wastewater (PHW) treatment and efficient hydrogen (H₂) production to meet biocrude upgrading requirements. Long-term single reactor operation revealed that fixed anode potential enabled rapid startup, and low catholyte pH and high salinity were effective in suppression of cathodic methanogenesis and acetogenesis – resulting in high current density of 16.6 A m –2 and 9.3 A m –2 when feeding synthetic wastewater and PHW respectively. Additionally, the anode biofilm exhibited spatial variations in response to local environmental conditions. In conclusion, onsite parallel or serial operations of multiple MECs showed good performance using actual PHW with a record-high H 2 production rate of 0.5 L L R day –1 for MEC over 10 liters scale, and the optimal chemical oxygen demand (COD)-to-H 2 yield reached 0.127 kg-H 2 per kg-COD, supporting a self-sufficient, closed-loop upgrade to jet fuel.
08 HYDROGEN↗
Si-based materials for lithium-ion batteries IV: Surface-modified Si/C/perfluorooctene powder
X-ray photoelectron spectroscopy was used to analyze nano-Si/C/perfluorooctene powder obtained from Paraclete Energy Inc. The spectra were obtained using incident monochromatic Al K α radiation at 1486.6 eV (0.834 01 nm). An initial survey spectrum together with F 1s, O 1s, C 1s, and Si 2p are presented. A final survey spectrum was collected to ascertain the amount of beam-induced damage, which appears to be minimal. Finally, the spectra indicate the principal core level photoelectron and Auger electron signals with only minor nitrogen signal and show the expected silicon-carbon, carbon-fluorine, and silicon-fluorine species related to the surface modification process in addition to oxidized carbon and silicon due to atmospheric exposure.
25 ENERGY STORAGE↗
Texture Evolution of Plated Lithium in Anode-Free Solid-State Batteries
Here, this study investigates lithium plating texture in anode-free solid-state batteries using synchrotron-based X-ray diffraction. Conventional methods are limited by lithium’s low electron density and softness, which hinders direct interrogation in anode-free solid-state batteries. Results reveal that lithium plating texture is influenced by temperature and current density. Under mild conditions, lithium exhibited a ⟨110⟩ fiber texture. However, higher current densities and elevated temperatures led to a more randomized orientation, suggesting a dependence on plating conditions. The results highlight how the operating and processing conditions for lithium metal can influence the texture of lithium metal and reversible operation.
36 MATERIALS SCIENCE↗
Si-based materials for lithium-ion batteries VI. 15% surface-modified Si/C-graphite/carbon black/lithiated polyacrylic acid electrode
X-ray photoelectron spectroscopy was used to analyze a 15%Si/C-graphite/carbon black/lithiated polyacrylic acid electrode fabricated at the Cell Analysis, Modeling, and Prototyping Facility (CAMP), Argonne National Laboratory. The spectra were obtained using incident monochromatic Al K α radiation at 1486.6 eV (0.83 401 nm). An initial survey spectrum together with O 1s, C 1s, and Si 2p are presented. A final survey spectrum was collected to ascertain the amount of beam-induced damage, which appears to be minimal. The spectra indicate the principal core level photoelectron and Auger electron signals with only minor nitrogen and lithium signals and show the expected silicon-carbon species related to the surface modification process in addition to oxidized carbon and silicon due to atmospheric exposure as well contributions related to the binder material.
17 WIND ENERGY↗
Functionalized Silicon Particles for Enhanced Half- and Full-Cell Cycling of Si-Based Li-Ion Batteries
Vinylene carbonate (VC) and polyethylene oxide (PEO) have been investigated as functional agents that mimic the solid electrolyte interphase (SEI) chemistry of silicon (Si). VC and PEO are known to contribute to the stability of Si-based lithium-ion batteries as an electrolyte additive and as a SEI component, respectively. In this work, covalent surface functionalization was achieved via a facile route, which involves ball-milling the Si particles with sacrificial VC and PEO. Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy indicate that the additives are strongly bound to Si. In particular, MAS NMR shows Si–R or Si–O–R groups, which confirm functionalization of the Si after milling in VC or PEO. Particle size analysis by dynamic light scattering reveals that the additives facilitate particle size reduction and that the functionalized particles result in more stable dispersions based on zeta potential measurements. Raman mapping of the electrodes fabricated from the VC and PEO-coated active material with a polyacrylic acid (PAA) binder reveals a more homogenous distribution of Si and the carbon conductive additive compared to the electrodes prepared from the neat Si. Furthermore, the VC-milled Si strikingly exhibited the highest capacity in both half- and full-cell configurations, with more than 200 mAh g –1 measured capacity compared to the neat Si in the half-cell format. This is linked to an improved electrode processing based on the Raman and zeta potential measurements as well as a thinner SEI (with more organic components for the functionalized Si relative to the neat Si) based on XPS analysis of the cycled electrodes. In conclusion, the effect of binder was also investigated by comparing PAA with P84 (polyimide type), where an increased capacity is observed in the latter case.
25 ENERGY STORAGE↗