Solid-Solid Interfaces in Solid-State Batteries
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solid interface↗
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Response of Solid He-4 to External Stress: Interdigital Capacitor Solid Level Detector and Optical Interferometer
Two experiments are being conducted to observe the liquid/solid interface of He-4 near 1 K. Interesting instabilities are expected to occur when the solid is non-hydrostatically stressed. (1)A compact interdigital capacitor is used as a level detector to observe solid He-4 to which stresses are applied externally. The capacitor consists of 38 interlaced 50 m wide and 3.8 mm long gold films separated by 50 m and deposited onto a 5 mm by 5 mm sapphire substrate. The capacitor is placed on one flat end wall of a cylindrical chamber (xx mm diameter and xx mm long). The solid is grown to a known height and a stress is applied by a tubular PZT along the cylindrical axis. The observed small change in height of the solid at the wall is linearly proportional to the applied stress. The solid height decreases under compressive stress but does not change under tensile stress. The response of the solid on compressive stress is consistent with the expected quadratic dependence on strain. (2)Interferometric techniques are being developed for observing the solid He-4 surface profile. A laser light source is brought into the low temperature region via single mode optical fiber. The interference pattern is transmitted back out of the low temperature apparatus via optical fiber bundle. The solid He-4 growth chamber will be equipped with two PZT's such that stress can be applied from orthogonal directions. Orthogonally applied stress is expected to induce surface instability with island-like deformation on a grid pattern. Apparatus design and progress of its construction are described.
Fay, J.↗
Optical Measurements on Solid Specimens of Solid Rocket Motor Exhaust and Solid Rocket Motor Slag
Samples of aluminum slag were investigated to aid the Earth Science and Applications Division at the Marshall Space Flight Center (MSFC). Alumina from space motor propellant exhaust and space motor propellant slag was examined as a component of space refuse. Thermal emittance and solar absorptivity measurements were taken to support their comparison with reflectance measurements derived from actual debris. To determine the similarity between the samples and space motor exhaust or space motor slag, emittance and absorbance results were correlated with an examination of specimen morphology.
Roberts, F. E., III↗
Solid‐State Prealkylation of Electrode Architectures (SPEAR): Direct Control of Prelithiation Levels in Silicon Anodes and Electrochemical Cycling
The Solid-state Prealkylation of Electrode ARchitectures (SPEAR) is different than traditional electrochemical prealkylation processes. Through SPEAR, alkylation is driven by solid-state diffusion without the simultaneous SEI formation concomitant with polarization. Here, we investigate the prelithiation of 80 wt. % Si-based anodes to varying amounts (up to Li 1.38 Si) to understand the trade-off between improved Li capacity and expansion-induced stress. Through dilatometry, we found that solid-state lithiation led to filling of the electrode pores through silicon expansion. This swelling changed the SEI formation process and accessibility of the silicon compared to an electrochemically lithiated electrode. Indeed, optimal prelithiation to Li 0.82 Si increases the initial C/3 cycling capacity post-SEI formation up to 43%, consistent with deeper Si activation through the electrode bulk. Prelithiation and cycling cells prelithiated beyond Li 0.82 Si results in a state of charge (SOC) close to 100% which facilitates parasitic degradation mechanisms and volume expansion of the Si electrode. The results demonstrate a pathway to modify silicon activation/SEI formation to enable high-energy electrodes.
Musgrove, Amanda L. [Oak Ridge National Laboratory↗
Multinuclear Solid-State NMR and NMR Crystallography of Solid Forms of Creatine and Creatinine
Creatine is a performance-enhancing supplement with two widely available commercial solid forms, namely, creatine monohydrate (creatine·H 2 O) and creatine HCl, the latter of which does not have a reported crystal structure. Moreover, commercial formulations of creatine may contain creatinine, an undesired impurity phase resulting from the self-cyclization of creatine during manufacturing. Therefore, reliable methods for characterizing the different solid forms of creatine and detecting the presence of creatinine are essential. Herein, we address these challenges using 13 C, 15 N, and 35 Cl solid-state NMR (SSNMR) spectroscopy to obtain distinct spectral fingerprints for creatine·H 2 O and creatine HCl, along with creatinine and creatinine HCl. The acquisition of these SSNMR spectra offers a robust approach for both the rapid characterization of each solid form and the detection of the impurity phases. Additionally, quadrupolar NMR crystallography-guided crystal structure prediction (QNMRX-CSP) was applied for the de novo crystal structure determination of creatine HCl, which was validated by the subsequently determined single-crystal X-ray diffraction (SCXRD) structure. Finally, to investigate the relationship between NMR parameters and structural features, 13 C and 15 N chemical shifts and 35 Cl electric field gradient (EFG) tensors were computed from geometry-optimized structures of the four solid forms by using dispersion-corrected DFT-D2* methods. Finally, this integrative approach offers a powerful framework for advancing the structural understanding and quality control of creatine-based supplements and next-generation formulations, as well as a wide range of other solid pharmaceuticals and nutraceuticals.
NMR↗
A commentary on solid lubricants and wear resistant solids for use in extreme environments
The need for high temperature tribological coatings and self-lubricating materials in advanced technology is discussed. A qualitative model for the mechanism of solid lubrication is proposed. The model is based upon microscopic observations of the dynamics of third-body solids in lubricated contacts. In this model, the rheology of plastic flow is suggested as a more general criterion for predicting the lubricating potential of a solid material than, for example, a specific crystal structure. Some examples of layer-lattice and nonlayer-lattice solids that lubricate by virtue of their extreme plasticity, film coherence, and adhesion to the lubricated metal are described. Circumstantial evidence for the model is presented for low shear-strength solids at room temperature and for solids such as calcium fluoride that become lubricative only when their brittle-to-ductile transition temperature is exceeded. Some materials considerations in the selection of hard-coat materials for wear control are also presented.
Sliney, H. E.↗
Global Evolution of Solid Matter in Turbulent Protoplanetry Disks: Aerodynamics of Solid Particles - Part 1
The problem of planetary system formation and its subsequent character can only be addressed by studying the global evolution of solid material entrained in gaseous protoplanetary disks. We start to investigate this problem by considering the space-time development of aerodynamic forces that cause solid particles to decouple from the gas. The aim of this work is to demonstrate that only the smallest particles are attached to the gas, or that the radial distribution of the solid matter has no momentary relation to the radial distribution of the gas. We present the illustrative example wherein a gaseous disk of 0.245 solar mass and angular momentum of 5.6 x 10(exp 52) g/sq cm/s is allowed to evolve due to turbulent viscosity characterized by either alpha = 10(exp -2) or alpha = 10(exp -3). The motion of solid particles suspended in a viscously evolving gaseous disk is calculated numerically for particles of different sizes. In addition we calculate the global evolution of single-sized, noncoagulating particles. We find that particles smaller than 0.1 cm move with the gas; larger particles have significant radial velocities relative to the gas. Particles larger than 0.1 cm but smaller than 10(exp 3) cm have inward radial velocities much larger than the gas, whereas particles larger than 10(exp 4) cm have inward velocities much smaller than the gas. A significant difference in the form of the radial distribution of solids and the gas develops with time. It is the radial distribution of solids, rather than the gas, that determines the character of an emerging planetary system.
Stepinski, T. F.↗
Unveiling the Role of Lithium Iodide in Stabilizing Solid Interfaces in All-Solid-State Li Metal Batteries
A critical challenge in all-solid-state lithium metal batteries (ASSLMBs) is achieving a stable interface between the lithium metal anode and the solid electrolyte. Leveraging its success in Li/I 2 batteries, lithium iodide has garnered significant attentions for its potential to enhance interfacial stability and overall cell performance in ASSLMBs. Here, we elucidate the role of lithium iodide in stabilizing the solid interface in all-solid-state Li metal batteries with a Li argyrodite electrolyte, particularly focusing on its influence on lithium deposition behavior and interfacial evolution. Through in situ optical imaging, we demonstrate more uniform lithium deposition on an iodide-contained argyrodite electrolyte compared to a chloride-based counterpart. Complementary density functional theory calculations attribute improved lithium plating behavior to the enhanced lithiophilicity and better ionic conductivity of lithium iodide at the solid interface, effectively reducing localized current density. In conclusion, these findings provide useful insights into the mechanisms through which lithium iodide enhances the interfacial stability in ASSLMBs.
Anions↗
Performance of a single-stage transonic compressor with a blade-tip solidity of 1.5 and comparison with 1.3 and 1.7 solidity stages
The overall and blade-element performance of a transonic compressor stage with a tip solidity of 1.5 is presented over the stable operating range at rotative speeds from 50 to 100 percent of design speed. State peak efficiency of 0.82 was obtained at a weight flow of 29.4 kg.sec (200.4 (kg/sec)/m2 of annulus area) and a pressure ratio of 1.71. Stall margin at design speed was 14 percent. A comparison of three stages in a solidity study showed that the performance of the 1.5 solidity stage and the 1.3 solidity stage were nearly identical but that the performance of the 1.7 solidity stage was significantly lower.
Osborn, W. M.↗
The effects of solid rocket motor effluents on selected surfaces and solid particle size, distribution, and composition for simulated shuttle booster separation motors
A series of three tests was conducted using solid rocket propellants to determine the effects a solid rocket plume would have on thermal protective surfaces (TPS). The surfaces tested were those which are baselined for the shuttle vehicle. The propellants used were to simulate the separation solid rocket motors (SSRM) that separate the solid rocket boosters (SRB) from the shuttle launch vehicle. Data cover: (1) the optical effects of the plume environment on spacecraft related surfaces, and (2) the solid particle size, distribution, and composition at TPS sample locations.
Jex, D. W.↗
Control of Two Solid Electrolyte Interphases at the Negative Electrode of an Anode‐Free All Solid‐State Battery based on Argyrodite Electrolyte
Abstract Anode‐free all solid‐state batteries (AF‐ASSBs) employ “empty” current collector with three active interfaces that determine electrochemical stability; lithium metal – Solid electrolyte (SE) interphase (SEI‐1), lithium – current collector interface, and collector – SE interphase (SEI‐2). Argyrodite Li 6 PS 5 Cl (LPSCl) solid electrolyte (SE) displays SEI‐2 containing copper sulfides, formed even at open circuit. Bilayer of 140 nm magnesium/30 nm tungsten (Mg/W‐Cu) controls the three interfaces and allows for state‐of‐the‐art electrochemical performance in half‐cells and fullcells. AF‐ASSB with NMC811 cathode achieves 150 cycles with Coulombic efficiency (CE) above 99.8%. With high mass‐loading cathode (8.6 mAh cm −2 ), AF‐ASSB retains 86.5% capacity after 45 cycles at 0.2C. During electrodeposition of Li, gradient Li‐Mg solid solution is formed, which reverses upon electrodissolution. This promotes conformal wetting/dewetting by Li and stabilizes SEI‐1 by lowering thermodynamic driving force for SE reduction. Inert refractory W underlayer is required to prevent ongoing formation of SEI‐2 that also drives electrochemical degradation. Inert Mo and Nb layers likewise protect Cu from corroding, while Li‐alloying layers (Mg, Sn) are less effective due to ongoing volume changes and associated pulverization. Mechanistic explanation for observed Li segregation within alloying Li x Mg layer is provided through mesoscale modelling, considering opposing roles of diffusivity differences and interfacial stresses.
Wang, Yixian [Materials Science and Engineering Pr↗
Self‐Templated 3D Sulfide‐Based Solid Composite Electrolyte for Solid‐State Sodium Metal Batteries
Abstract Rechargeable solid‐state sodium metal batteries (SSMBs) experience growing attention owing to the increased energy density (vs Na‐ion batteries) and cost‐effective materials. Inorganic sulfide‐based Na‐ion conductors also possess significant potential as promising solid electrolytes (SEs) in SSMBs. Nevertheless, due to the highly reactive Na metal, poor interface compatibility is the biggest obstacle for inorganic sulfide solid electrolytes such as Na 3 SbS 4 to achieve high performance in SSMBs. To address such electrochemical instability at the interface, new design of sulfide SE nanostructures and interface engineering are highly essential. In this work, a facile and straightforward approach is reported to prepare 3D sulfide‐based solid composite electrolytes (SCEs), which utilize porous Na 3 SbS 4 (NSS) as a self‐templated framework and fill with a phase transition polymer. The 3D structured SCEs display obviously improved interface stability toward Na metal than pristine sulfide. The assembled SSMBs (with TiS 2 or FeS 2 as cathodes) deliver outstanding electrochemical cycling performance. Moreover, the cycling of high‐voltage oxide cathode Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) is also demonstrated in SSMBs using 3D sulfide‐based SCEs. This study presents a novel design on the self‐templated nanostructure of SCEs, paving the way for the advancement of high‐energy sodium metal batteries.
Guo, Xiaolin↗
Design of Sodium Chalcohalide Solid Electrolytes with Mixed Anions for All‐Solid‐State Sodium‐Ion Batteries
Solid-state sodium-ion batteries (SSNIBs) have emerged as a promising alternative to lithium-ion systems for grid-scale energy storage, owing to sodium's abundance and the improved safety of solid-state designs. Among various solid-state electrolytes (SSEs), halide-based Na + SSEs offer high electrochemical stability but are limited by low ionic conductivity and poor thermal stability. Herein, a novel class of sodium hafnium chalcohalide SSEs is reported with a dual-anion (S 2− /Cl − ) framework, with a high ionic conductivity of 4.5 × 10 −4 S cm −1 . The incorporation of sulfur enhances Na⁺ mobility by reducing the migration barrier through increased anion polarizability and expanded diffusion pathways. Additionally, S 2− contributes to stronger interatomic bonding, leading to higher cohesive energy density, improved thermal stability, and mechanical robustness. These SSEs exhibit minimal sulfur oxidation and excellent chemical/electrochemical interface stability with different cathode materials, such as O3-layered NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 , and Na 3 V 2 (PO 4 ) 3 cathodes. As a result, SSNIBs with P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 employing the sodium hafnium chalcohalide SSEs demonstrate outstanding cycling performance, achieving a capacity retention of 88.5% after 200 cycles at 0.1 C. This study establishes a new design strategy for high-performance SSEs, demonstrating that mixed-anion frameworks offer a viable route to overcome the intrinsic limitations of single-anion electrolytes in next-generation SSNIBs.
DFT calculation↗
Polycarbonate‐Based Solid‐Polymer Electrolytes for Solid‐State Sodium Batteries
Solid-polymer electrolytes comprised of polypropylene carbonate (PPC) and varied sodium bis(fluorosulfonyl)imide (NaFSI) salt concentrations are investigated for implementation as a conductive solid polymer electrolyte into solid-state cathode composites utilizing a sodium-layered oxide active material. The ionic conductivity generally increases with NaFSI salt content, reaching ≈1 mS cm −1 at 80 °C at the highest salt concentration (PPC:NaFSI = 0.5:1). Through an all-in-one slurry casting method, Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode composites are fabricated in which the dispersed PPC electrolyte acts as the primary binder. Enabled by a bilayer polymer electrolyte system, cycling performance with the PPC cathode electrolyte is optimized with respect to salt concentration and anode material. The best cyclability is achieved with a moderate salt concentration electrolyte (PPC:NaFSI = 5:1), showcasing an initial capacity of 83 mA h g −1 with a remarkable 80% capacity retention after 150 cycles at C/5 rate and 60 °C. The superior performance of the lower salt concentration electrolyte is attributed to better electrochemical stability, as confirmed by linear sweep voltammetry and online electrochemical mass spectrometry measurements. In conclusion, these results underscore the potential of carbonate-based polymer electrolytes and the importance of balancing electrolyte conductivity and stability in cell design.
25 ENERGY STORAGE↗
PARTICIPATION OF THE SOLID PHASE IN THE OSCILLATORY BURNING OF SOLID ROCKET PROPELLANTS
An experimental study of the interaction between the solid and gas phases during oscillatory burning of solid propellants has been undertaken with the objective of exploring the validity of the complex theory describing the phenomenon. The apparatus employed was a side-vented, cylindrical vessel with an end-burning propellant grain closely fitted in one end and provision for maintaining the burning zone at a fixed position. Pressure oscillations both at the gas-zone end plate and beneath the grain were recorded. Energy dissipation in the solid propellant, isolated from other losses in the system, was determined from the growth rate constants of the amplitudes of pressure oscillation for grains of varying lengths. The efficiency of acoustical energy or absorption by the grain was found to be maximum when the oscillations are at frequencies close to the natural frequency of the grain. These results confirm the description of oscillatory burning by the acoustical theory in its broad generalizations.
GAS PHASE↗
A New Class of Oxyhalide Solid Electrolytes NaNbCl 6‐2x O x for Solid‐state Sodium Batteries
Abstract Sodium‐based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid‐state sodium batteries can also provide further safety advantages. However, sodium‐based solid‐state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium‐based oxyhalide electrolytes NaNbCl 6‐2x O x with a facile mechanochemical synthesis. The oxyhalide NaNbCl 4 O exhibits close to two orders of magnitude higher ambient‐temperature sodium‐ion conductivity (1.03×10 −4 S cm −1 ) compared to the halide counterpart NaNbCl 6 (3×10 −6 S cm −1 ). Structural motifs unique to the oxygen content in NaNbCl 6‐2x O x are identified with 23 Na and 93 Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x‐ray diffraction (XRD). Solid‐state sodium batteries assembled with NaNbCl 4 O electrolyte and the cobalt‐ and nickel‐free layered Na 0.70 Fe 0.3 Mn 0.65 Al 0.05 O 2 cathode exhibit a maximum discharge capacity of 155 mAh g −1 with good cycle life at ambient temperature.
Kmiec, Steven↗
A New Class of Oxyhalide Solid Electrolytes NaNbCl 6‐2x O x for Solid‐state Sodium Batteries
Abstract Sodium‐based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid‐state sodium batteries can also provide further safety advantages. However, sodium‐based solid‐state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium‐based oxyhalide electrolytes NaNbCl 6‐2x O x with a facile mechanochemical synthesis. The oxyhalide NaNbCl 4 O exhibits close to two orders of magnitude higher ambient‐temperature sodium‐ion conductivity (1.03×10 −4 S cm −1 ) compared to the halide counterpart NaNbCl 6 (3×10 −6 S cm −1 ). Structural motifs unique to the oxygen content in NaNbCl 6‐2x O x are identified with 23 Na and 93 Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x‐ray diffraction (XRD). Solid‐state sodium batteries assembled with NaNbCl 4 O electrolyte and the cobalt‐ and nickel‐free layered Na 0.70 Fe 0.3 Mn 0.65 Al 0.05 O 2 cathode exhibit a maximum discharge capacity of 155 mAh g −1 with good cycle life at ambient temperature.
Kmiec, Steven↗
Local order, disorder, and everything in between: using 91 Zr solid-state NMR spectroscopy to probe zirconium-based metal–organic frameworks
Characterization of metal centers in metal–organic frameworks (MOFs) is critical for rational design and further understanding of structure–property relationships. The short-range structure about Zr atoms is challenging to properly elucidate in many Zr MOFs, particularly when local disorder is present. Static 91 Zr solid-state NMR spectra of the seven zirconium MOFs UiO-66, UiO-66-NH 2 , UiO-67, MOF-801, MOF-808, DUT-68 and DUT-69 have been acquired at high magnetic fields of 35.2 T and 19.6 T, yielding valuable information on the local structure, site symmetry and order about Zr. 91 Zr NMR is very sensitive to differences in MOF short-range structure caused by guest molecules, linker substitution and post-synthetic treatment. Complementary density functional theory (DFT) calculations assist in the interpretation and assignment of 91 Zr solid-state NMR spectra, lend insight into structural origins of 91 Zr NMR parameters and enable determination of local Zr coordination environments. This approach can be extended to many other materials containing zirconium.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗