Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies.

Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of the lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron X-ray, which has the unique capability of analyzing crystalline/amorphous phases quantitatively with statistical significance, we study the composition and dynamics of the LMB interphase for a newly developed important LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential roles of the anion and solvent in interphase formation during cycling. The relative ratio between Li2O and LiF first increases and then decreases during cycling, suggesting suppressed Li2O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barriers in many-electron transfer. In long extended cycles, the anion decomposition product Li2O encourages solvent decomposition by facilitating solvent adsorption on Li2O which is followed by concurrent depletion of both. This work highlights the important role of Li2O in transitioning from an anion-derived interphase to a solvent-derived one.

Spinal cord motion and CSF flow in the cervical spine of 70 healthy participants.

Pulsatile spinal cord and CSF velocities related to the cardiac cycle can be depicted by phase-contrast MRI. Among patients with spontaneous intracranial hypotension, we have recently described relevant differences compared with healthy controls in segment C2/C3. The method might be a promising tool to solve clinical and diagnostic ambiguities. Therefore, it is important to understand the physiological range and the effects of clinical and anatomical parameters in healthy volunteers. Within a prospective study, 3D T2 -weighted MRI for spinal canal anatomy and cardiac-gated phase-contrast MRI adapted to CSF flow and spinal cord motion for time-resolved velocity data and derivatives were performed in 70 participants (age 20-79 years) in segments C2/C3 and C5/C6. Correlations were analyzed by multiple linear regression models; p < 0.01 was required to assume a significant impact of clinical or anatomical data quantified by the regression coefficient B. Data showed that in C2/C3, the CSF and spinal cord craniocaudal velocity ranges were 4.5 ± 0.9 and 0.55 ± 0.15 cm/s; the total displacements were 1.1 ± 0.3 and 0.07 ± 0.02 cm, respectively. The craniocaudal range of the CSF flow rate was 8.6 ± 2.4 mL/s; the CSF stroke volume was 2.1 ± 0.7 mL. In C5/C5, physiological narrowing of the spinal canal caused higher CSF velocity ranges and lower stroke volume (C5/C6 B = +1.64 cm/s, p < 0.001; B = -0.4 mL, p = 0.002, respectively). Aging correlated to lower spinal cord motion (e.g., B = -0.01 cm per 10 years of aging, p < 0.001). Increased diastolic blood pressure was associated with lower spinal cord motion and CSF flow parameters (e.g., C2/C3 CSF stroke volume B = -0.3 mL per 10 mmHg, p < 0.001). Males showed higher CSF flow and spinal cord motion (e.g., CSF stroke volume B = +0.5 mL, p < 0.001; total displacement spinal cord B = +0.016 cm, p = 0.002). We therefore propose to stratify data for age and sex and to adjust for diastolic blood pressure and segmental narrowing in future clinical studies.

Mechanisms of alumina growth via atomic layer deposition on nickel oxide and metallic nickel surfaces.

We aim at elucidating the mechanism of the trimethyl aluminum (TMA) decomposition on oxidized nickel (NiO) and metallic nickel (Ni) facets in the absence of a source of hydroxyl groups. This TMA decomposition mechanism constitutes the earliest stage of growth of Al2O3 coatings with the atomic layer decomposition (ALD) method, which stabilizes nickel catalysts in energy-intensive processes such as the dry reforming of methane. Our first-principles calculations suggest thermodynamic favorability for the TMA decomposition on metallic nickel compared to oxidized nickel. Moreover, the decomposition of TMA on metallic nickel showed almost no differences in terms of energy barriers between flat and stepped surfaces. Regarding the impact of the CH3 radicals formed after TMA decomposition, we calculated stronger adsorption on metallic nickel facets than on oxidized nickel, and these adsorption energies are comparable to the adsorption energies calculated in earlier works on Al2O3 ALD growth on palladium surfaces. These results lead us to believe in the growth of porous Al2O3 coatings triggered by CH3 contamination rather than due to preferential TMA decomposition on stepped and/or defective facets. The CH3 radicals are likely to be thermally stable at temperatures used during Al2O3 ALD processes, partially passivating the surface towards further TMA decomposition.

Interfacial Electrochemical Lithiation and Dissolution Mechanisms at a Sulfurized Polyacrylonitrile Cathode Surface.

Advances in sulfurized-polyacrylonitrile (SPAN)-based cathode materials promise safer and more efficient lithium-sulfur (Li-S) battery performance. To elucidate electrolyte-cathode interfacial electrochemistry and polysulfide (PS) dissolution, we emulate discharge SPAN reactions via ab initio molecular dynamics (AIMD) simulations. Plausible structures and their lithiation profiles are cross-validated via Raman/IR spectroscopy and density functional theory (DFT). Lithium bis(fluorosulfonyl)imide (LiFSI) plays versatile roles in the Li-SPAN cell electrochemistry, primarily as the major source in forming the cathode-electrolyte interphase (CEI), further verified via X-ray photoelectron spectroscopy and AIMD. Besides being a charge carrier and CEI composer, LiFSI mediates the PS generation processes in SPAN electrochemical lithiation. Analysis of AIMD trajectories during progressive lithiation reveals that, compared to carbonates, ether solvents enable stronger solvation and chemical stabilization for both salt and SPAN structures. Differentiated CEI formation and electrochemical lithiation decomposition pathways and products are profoundly associated with the intrinsic nature of lithium bonding with oxygen and sulfur.

CSF Flow and Spinal Cord Motion in Patients With Spontaneous Intracranial Hypotension: A Phase Contrast MRI Study.

BACKGROUND AND OBJECTIVES: Spontaneous intracranial hypotension (SIH) is characterized by loss of CSF volume. We hypothesize that in this situation of low volume, a larger CSF flow and spinal cord motion at the upper spine can be measured by noninvasive phase contrast MRI. METHODS: A prospective, age-, sex-, and body mass index (BMI)-matched controlled cohort study on patients with SIH presenting with spinal longitudinal extradural fluid collection (SLEC) was conducted from October 2021 to February 2022. Cardiac-gated 2D phase contrast MRI sequences were acquired at segment C2/C3, and C5/C6 for CSF flow, and spinal cord motion analysis. Data processing was fully automated. CSF flow and spinal cord motion were analyzed by peak-to-peak amplitude and total displacement per segment and heartbeat, respectively. Clinical data included age, height, BMI, duration of symptoms, Bern score according to Dobrocky et al., and type of the spinal CSF leak according to Schievink et al. Groups were compared via the Mann-Whitney U test; multiple linear regression analysis was performed to address possible relations. RESULTS: Twenty patients with SIH and 40 healthy controls were analyzed; each group consisted of 70% women. Eleven patients with SIH presented with type 1 leak, 8 with type 2, and 1 was indeterminate. CSF flow per heartbeat was increased at C2/C3 (peak-to-peak amplitude 65.68 ± 18.3 vs 42.50 ± 9.8 mm/s, total displacement 14.32 ± 3.5 vs 9.75 ± 2.7 mm, p < 0.001, respectively). Craniocaudal spinal cord motion per heartbeat was larger at segment C2/C3 (peak-to-peak amplitude 7.30 ± 2.4 vs 5.82 ± 2.0 mm/s, total displacement 1.01 ± 0.4 vs 0.74 ± 0.4 mm, p = 0.006, respectively) and at segment C5/C6 (total displacement 1.41 ± 0.7 vs 0.97 ± 0.4 mm, p = 0.021). DISCUSSION: SLEC-positive patients with SIH show higher CSF flow and higher spinal cord motion at the upper cervical spine. This increased craniocaudal motion of the spinal cord per heartbeat might produce increased mechanical strain on neural tissue and adherent structures, which may be a mechanism leading to cranial nerve dysfunction, neck pain, and stiffness in SIH. Noninvasive phase contrast MRI of CSF flow and spinal cord motion is a promising diagnostic tool in SIH. TRIAL REGISTRATION INFORMATION: German Clinical Trials Register, identification number: DRKS00017351. CLASSIFICATION OF EVIDENCE: This study provides Class III evidence that noninvasive phase contrast MRI of the upper spine identifies differences in CSF flow and spinal cord motion in patients with SIH compared with healthy controls.

Density functional theory and ab initio molecular dynamics reveal atomistic mechanisms for carbonate clumped isotope reordering.

Carbon (13C) and oxygen (18O) isotopes in carbonates form clumped isotope species inversely correlated with temperature, providing a valuable paleothermometer for sedimentary carbonates and fossils. However, this signal resets ("reorders") with increasing temperature after burial. Research on reordering kinetics has characterized reordering rates and hypothesized the effects of impurities and trapped water, but the atomistic mechanism remains obscure. This work studies carbonate-clumped isotope reordering in calcite via first-principles simulations. We developed an atomistic view of the isotope exchange reaction between carbonate pairs in calcite, discovering a preferred configuration and elucidating how Mg2+ substitution and Ca2+ vacancies lower the free energy of activation (ΔA‡) compared to pristine calcite. Regarding water-assisted isotopic exchange, the H+-O coordination distorts the transition state configuration and reduces ΔA‡. We proposed a water-mediated exchange mechanism showing the lowest ΔA‡ involving a reaction pathway with a hydroxylated four-coordinated carbon atom, confirming that internal water facilitates clumped isotope reordering.

Direct in situ measurements of electrical properties of solid-electrolyte interphase on lithium metal anodes.

The solid-electrolyte interphase (SEI) critically governs the performance of rechargeable batteries. An ideal SEI is expected to be electrically insulative to prevent persistently parasitic reactions between the electrode and the electrolyte and ionically conductive to facilitate Faradaic reactions of the electrode. However, the true nature of the electrical properties of the SEI remains hitherto unclear due to the lack of a direct characterization method. Here we use in situ bias transmission electron microscopy to directly measure the electrical properties of SEIs formed on copper and lithium substrates. We reveal that SEIs show a voltage-dependent differential conductance. A higher rate of differential conductance induces a thicker SEI with an intricate topographic feature, leading to an inferior Coulombic efficiency and cycling stability in Li∣∣Cu and Li∣∣LiNi0.8Mn0.1Co0.1O2 cells. Our work provides insight into the targeted design of the SEI with desired characteristics towards better battery performance.

Matrix transformation of lunar regolith and its use as a feedstock for additive manufacturing.

Building a sustainable human habitat on the Moon requires advances in excavation, paving, and additive manufacturing to construct landing pads, surface transportation arteries, resilient shelters, and scientific outposts. Construction of infrastructure elements on the lunar surface necessitates exploration of the interfacial reactivity of locally sourced regolith and the adaptation of Earth-based construction techniques. Various crosslinking frameworks and sintering methods have been proposed as a means of consolidating lunar regolith into load-bearing structures but each have challenges related to incomplete understanding of reaction chemistry, excessive thermal budgets, and lack of universal applicability to different mineral components of regolith. We describe here a versatile experimental and computational study of the consolidation of a regolith simulant through formation of siloxane networks enmeshing mineral particles by surface dissolution-precipitation and polycondensation reactions. Furthermore, by tailoring the rheological properties of the formulation an additive manufacturing feedstock can be developed for the construction of lunar infrastructure.

Toggling Stereochemical Activity through Interstitial Positioning of Cations between 2D V2O5 Double Layers.

The 5/6s2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V2O5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s2 cations situated in interlayer sites between condensed [V4O10]n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered MxV2O5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s2-O 2p-hybridized mid-gap states mediated by second-order Jahn-Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V-V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V-V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg0.5V2O5 and δ-Tl0.5V2O5, respectively, as compared to 7 K for δ-Pb0.5V2O5. In δ-Pb0.5V2O5, the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V4O10] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions.

Sulfurized Polyacrylonitrile for High-Performance Lithium-Sulfur Batteries: In-Depth Computational Approach Revealing Multiple Sulfur's Reduction Pathways and Hidden Li+ Storage Mechanisms for Extra Discharge Capacity.

Like no other sulfur host material, polyacrylonitrile-derived sulfurized carbon (SPAN) promises improved electrochemical performance for lithium-sulfur batteries, based on its compatibility with carbonate solvents and ability to prevent self-discharge and shuttle effect. However, a complete understanding of the SPAN's lithiation mechanism is still missing because its structural features vary widely with synthesis conditions, and its electrochemical performance deviates from elemental sulfur. This study continues our research on the elucidation of the SPAN's structural characteristics and lithiation mechanisms via computational approaches. Our models reproduce most experimental data regarding carbon's graphitization level and conjugated ordering, sulfur-carbon covalent bonding, sulfur loading, and elemental composition. Our simulations emulate the discharge voltage observed in experiments for the first discharge, which reveals that sulfur follows multiple reduction pathways based on its interaction with the carbon backbone. Sulfur reduction takes place above 1.0 V vs Li/Li+ mostly in the SPAN-like material, with no long-chain lithium polysulfide formation. Below 1.0 V vs Li/Li+, the backbone's electrochemical activity occurs via multiple C-Li and N-Li interactions, mostly with edge carbon atoms and pyridinic nitrogen. Moreover, we identify Li+ binding sites throughout the graphitized backbone that might lead to prohibited energy costs for Li+ deintercalation, which may explain the irreversible capacity loss between the first and second discharges. This work improves understanding of lithiation mechanisms in sulfurized carbon, which is useful for rationally designing SPAN synthesis pathways tailored to increase sulfur loading and enhanced electrochemical performance.

Spinal Cord Motion in Degenerative Cervical Myelopathy: The Level of the Stenotic Segment and Gender Cause Altered Pathodynamics.

In degenerative cervical myelopathy (DCM), focally increased spinal cord motion has been observed for C5/C6, but whether stenoses at other cervical segments lead to similar pathodynamics and how severity of stenosis, age, and gender affect them is still unclear. We report a prospective matched-pair controlled trial on 65 DCM patients. A high-resolution 3D T2 sampling perfection with application-optimized contrasts using different flip angle evolution (SPACE) and a phase-contrast magnetic resonance imaging (MRI) sequence were performed and automatically segmented. Anatomical and spinal cord motion data were assessed per segment from C2/C3 to C7/T1. Spinal cord motion was focally increased at a level of stenosis among patients with stenosis at C4/C5 (n = 14), C5/C6 (n = 33), and C6/C7 (n = 10) (p < 0.033). Patients with stenosis at C2/C3 (n = 2) and C3/C4 (n = 6) presented a similar pattern, not reaching significance. Gender was a significant predictor of higher spinal cord dynamics among men with stenosis at C5/C6 (p = 0.048) and C6/C7 (p = 0.033). Age and severity of stenosis did not relate to spinal cord motion. Thus, the data demonstrates focally increased spinal cord motion depending on the specific level of stenosis. Gender-related effects lead to dynamic alterations among men with stenosis at C5/C6 and C6/C7. The missing relation of motion to severity of stenosis underlines a possible additive diagnostic value of spinal cord motion analysis in DCM.

Focal cervical spinal stenosis causes mechanical strain on the entire cervical spinal cord tissue - A prospective controlled, matched-pair analysis based on phase-contrast MRI.

BACKGROUND: Focally increased spinal cord motion at the level of cervical spinal stenosis has been revealed by phase-contrast MRI (PC-MRI). OBJECTIVE: To investigate spinal cord motion among patients suffering of degenerative cervical myelopathy (DCM) across the entire cervical spine applying automated segmentation and standardized PC-MRI post-processing protocols. METHODS: Prospective, matched-pair controlled trial on 29 patients with stenosis at C5/C6. MRI-protocol covering all cervical segments: 3D T2-SPACE, prospectively ECG-triggered sagittal PC-MRI. Segmentation by trained 3D hierarchical deep convolutional neural network and data processing were conducted via in-house software pipeline. Parameters per segment: maximum velocity, peak-to-peak (PTP)-amplitude, total displacement, PTP-amplitudeHB (PTP-amplitude per duration of heartbeat), and, for characterization of intraindividual alterations, the PTP-amplitude index between the cervical segments C3/C4-C7/T1 and C2/C3. RESULTS: Spinal cord motion was increased at C4/C5, C5/C6 and C6/C7 among patients (all parameters, p < 0.001-0.025). The PTP-amplitude index revealed an increase from C3/C4 to C4/C5 (p = 0.002), C4/C5 to C5/C6 (p = 0.037) and a decrease from C5/C6 to C6/C7 and C6/C7 to C7/T1 (p < 0.001, each). This implied an up-building stretch on spinal cord tissue cranial and a mechanical compression caudal of the stenotic level. Furthermore, significant far range effects across the entire cervical spinal cord were observed (e.g. PTP-amplitude C2/C3 vs. C6/C7, p = 0.026) in contrast to controls (p = 1.00). CONCLUSION: This study revealed the nature and extends of mechanical stress on the entire cervical spinal cord tissue due to focal stenosis. These pathophysiological alterations of spinal cord motion can be expected to be clinically relevant.

Formation of Multilayer Graphene Domains with Strong Sulfur-Carbon Interaction and Enhanced Sulfur Reduction Zones for Lithium-Sulfur Battery Cathodes.

A newly designed sulfur/graphene computational model emulates the electrochemical behavior of a Li-S battery cathode, promoting the S-C interaction through the edges of graphene sheets. A random mixture of eight-membered sulfur rings mixed with small graphene sheets is simulated at 64 wt %sulfur loading. Structural stabilization and sulfur reduction calculations are performed with classical reactive molecular dynamics. This methodology allowed the collective behavior of the sulfur and graphene structures to be accounted for. The sulfur encapsulation induces ring opening and the sulfur phase evolves into a distribution of small chain-like structures interacting with C through the graphene edges. This new arrangement of the sulfur phase not only leads to a less pronounced volume expansion during sulfur reduction but also to a different discharge voltage profile, in qualitative agreement with earlier reports on sulfur encapsulation in microporous carbon structures. The Li2 S phase grows around ensembles of parallel graphene nanosheets during sulfur reduction. No diffusion of sulfur or lithium between graphene nanosheets is observed, and extended Li2 S domains bridging the space between carbon ensembles are suppressed. The results emphasize the importance of morphology on the electrochemical performance of the composite material. The sulfur/graphene model outlined here provides new understanding of the graphene effects on the sulfur reduction behavior and the role that van der Waals interactions may play in promoting formation of multilayer graphene ensembles and small Li2 S domains during sulfur reduction.