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At least 181 records · Page 10

Interfacial Defect of Lithium Metal in Solid-State Batteries

All-solid-state battery with Li metal anode is a promising rechargeable battery technology with high energy density and improved safety. Currently, the application of Li metal anode is plagued by the failure at the interfaces between lithium metal and solid electrolyte (SE). However, little is known about the defects at Li–SE interfaces and their effects on Li cycling, impeding further improvement of Li metal anodes. Herein, by performing large-scale atomistic modeling of Li metal interfaces with common SEs, we discover that lithium metal forms an interfacial defect layer of nanometer-thin disordered lithium at the Li–SE interfaces. Further, this interfacial defect Li layer is highly detrimental, leading to interfacial failure such as pore formation and contact loss during Li stripping. By systematically studying and comparing incoherent, coherent, and semi-coherent Li–SE interfaces, we find that the interface with good lattice coherence has reduced Li defects at the interface and has suppressed interfacial failure during Li cycling. Our finding discovered the critical roles of atomistic lithium defects at interfaces for the interfacial failure of Li metal anode, and motivates future atomistic-level interfacial engineering for Li metal anode in solid-state batteries.

25 ENERGY STORAGE↗

Unveiling the critical role of interfacial ionic conductivity in all-solid-state lithium batteries

Advancement of all-solid-state lithium-ion (Li + ) batteries (ASSLIBs) has been hindered by the large interfacial resistance mainly originating from interfacial reactions between oxide cathodes and solid-state sulfide electrolytes (SEs). To suppress the interfacial reactions, an interfacial coating layer between cathodes and SEs is indispensable. However, the kinetics of interfacial Li + transport across the coating layer has not been well understood yet. Herein, we tune the interfacial ionic conductivity of the coating layer LiNb 0.5 Ta 0.5 O 3 (LNTO) by manipulating post-annealing temperature. It is found that the interfacial ionic conductivity determines interfacial Li + transport kinetics and enhancing the interfacial ionic conductivity can significantly boost the electrochemical performance of SE-based ASSLIBs. A representative cathode LiNi 0.5 Mn 0.3 Co 0.2 O 2 coated by LNTO with the highest interfacial ionic conductivity exhibits a high initial capacity of 152 mAh.g -1 at 0.1 C and 107.5 mAh.g -1 at 1C. This work highlights the importance of increasing interfacial ionic conductivity for high-performance SE-based ASSLIBs.

25 ENERGY STORAGE↗

Interfacial Electromechanics Predicts Phase Behavior of 2D Hybrid Halide Perovskites

Quasi-two-dimensional (2D) mixed-cation hybrid halide perovskites (A' 2 A N–1 M N X 3N+1 ; A' = large organic molecule with cationic group, A = [Cs + , CH 3 NH 3 + , HC(NH 2 ) 2 + ], M = [Pb, Sn, Ge], X = [I – , Br – , Cl – ]) have rapidly emerged as candidates to improve the structural stability and device lifetime of 3D perovskite semiconductor devices under operating conditions. The addition of the large A' cation to the traditional AMX 3 structure introduces several synthetic degrees of freedom and breaks M–X bonds, giving rise to peculiar critical phase behavior in the phase space of these complex materials. In this work, we propose a thermodynamic model parametrized by first-principles calculations to generate the phase diagram of 2D and quasi-2D perovskites (q-2DPKs) based on the mechanics and electrostatics of the interface between the A' cations and the metal halide octahedral network. Focusing on the most commonly studied methylammonium lead iodide system where A' is n-butylammonium (BA; CH 3 (CH 2 ) 3 NH 3 + ), we find that the apparent difficulty in synthesizing phase-pure samples with a stoichiometric index N > 5 can be attributed to the energetic competition between repulsion of opposing interfacial dipole layers and mechanical relaxation induced by interfacial stress. Our model shows quantitative agreement with experimental observations of the maximum phase-pure stoichiometric index (N crit ) and explains the nonmonotonic evolution of the lattice parameters with increasing stoichiometric index (N). This model is generalizable to the entire family of q-2DPKs and can guide the design of photovoltaic and optical materials that combine the structural stability of the q-2DPKs while retaining the charge carrier properties of their 3D counterparts.

14 SOLAR ENERGY↗

Effect of Co-Reactants on Interfacial Oxidation in Atomic Layer Deposition of Oxides on Metal Surfaces

We have examined the ALD of Al 2 O 3 using TMA as the precursor and t-BuOH and H 2 O as the co-reactants, focusing on the effects of the latter on both the ALD process and the possible modification of the underlying substrate. We have employed a quartz-crystal microbalance (QCM) to monitor ALD in situ and in real-time, and the deposited thin films have been characterized using X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and X-ray reflectivity. Growth of thin films of Al 2 O 3 using TMA and either t-BuOH or H 2 O as the co-reactant at T = 285 °C produces thin films of similar physical properties (density, stoichiometry, minimal carbon incorporation), and the growth rate per cycle is similar for the two co-reactants at this temperature. At a lower temperature of T = 120 °C, the behavior is starkly different, where growth occurs with H 2 O but not with t-BuOH. At either process temperature, we find no evidence for significant coverages of a long-lived tert-butoxy species from the reaction of t-BuOH. Deposition of thin films of Al 2 O 3 on metal surfaces of Cu and Co has been examined for evidence of interfacial oxidation. While growth with either co-reactant does not lead to the oxidation of the underlying Cu substrate, use of H 2 O leads to the oxidation of Co, while use of t-BuOH as the co-reactant does not. Thermodynamic factors may affect early stages of growth as Al species will likely scavenge all free O species. In contrast, at later times diffusion of species through the deposited Al 2 O 3 thin film could result in oxidation at the Al 2 O 3 |metal interface, a process that is strongly hindered in the case of t-BuOH due to its size. Furthermore, this observation highlights the importance of the choice of the co-reactant concerning ALD of oxides on metal surfaces.

36 MATERIALS SCIENCE↗

Final Technical Report for DE-SC0021049: Manipulating interfacial reactivity with atomically layered heterostructures

This final technical report summarizes the work accomplished in this DOE Early Career Research Program project that has established moiré superlattice materials and two-dimensional (2D) heterostructures as a highly tunable platform for controlling heterogeneous charge transfer (ET) kinetics at solid-liquid interfaces. By precisely engineering van der Waals heterostructures of atomically thin 2D materials, particularly bilayer and trilayer graphene with controlled twist angles, this project demonstrated systematic control of interfacial charge transfer rates spanning three orders of magnitude. This research addresses fundamental questions about how electronic structure, charge localization, and atomic layer-dependent properties govern charge transfer at electrochemical interfaces, with broad implications for energy conversion, electrocatalysis, and next-generation electrochemical devices.

36 MATERIALS SCIENCE↗

Photoelectron Spectroscopic Determination of the Interfacial Energetics of Metal Oxide Protection Layers on p-InP Photocathodes

The interfacial energetics between p-type InP and a series of metal oxides, including TiO 2 , Nb 2 O 5 , Ta 2 O 5 , and HfO 2 , were evaluated using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and optical absorption spectroscopy. The energy of the conduction-band minimum ( E cb ) of TiO 2 and Nb 2 O 5 was more negative (i.e., further from the vacuum level) than the conduction-band minimum at the surface of InP ( E cb,s ), whereas E cb for Ta 2 O 5 and HfO 2 was more positive than E cb,s for InP. The data are consistent with the electrochemical behavior of p-InP coated with various metal oxide candidate protection layers, with TiO 2 and Nb 2 O 5 facilitating interfacial transfer of photogenerated minority-carrier electrons in p-InP photocathodes, and Ta 2 O 5 and HfO 2 blocking photogenerated electrons in p-InP from readily transferring across the oxide-coated photocathodes. The energy of the valence-band maximum ( E vb ) for all of the oxides was much more negative than E vb,s for InP, consistent with observations that these protection layers effectively block hole transport and consequently suppress oxidative degradation of the underlying p-InP photocathodes.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Boosting the Oxygen Evolution Reaction by Tuning the Interfacial Iron Adsorption on Layered Double Hydroxide

Understanding the interaction between ions in the electrolyte and electrode materials plays an important role in optimizing the water electrolysis performance for hydrogen production. Herein, the synergistic effect of iron (Fe) in the electrolyte and interlayer anions within the layered structure on the oxygen evolution reaction (OER) has been investigated by combining material synthesis with controlled structure, multiple characterization techniques, and first-principles calculations. Nickel aluminum layered double hydroxides (NiAl-LDHs) with different interlayer anions (CO 3 2– , Cl – , and Br – ) show similar oxygen evolution activity in the absence of Fe species in the electrolyte. The addition of Fe into the electrolyte results in improved performance for all of the NiAl-LDHs, following the rank LDH-Br > LDH-Cl > LDH-CO 3 , under all of the conditions with varied concentration of Fe. X-ray absorption spectroscopy and identical location electron microscopy analyses show that the LDH structure remains unchanged after the OER activity test, while in situ stationary probe rotating disk electrode inductively coupled plasma mass spectrometry (SPRDE-ICP-MS) measurements show partial dissolution of the intercalating halide ions during cycling, with less dissolution for Br-intercalated materials. Insights from theoretical calculations demonstrate the thermodynamic preference of Br – to remain intercalated in the presence of Fe, while the stronger adsorption of Fe(OH) 3 species on the LDH-Br sample promotes the OER activity. In conclusion, these results provide mechanistic insights into the rational design of active layered materials with an enhanced OER performance for efficient water electrolysis.

58 GEOSCIENCES↗

Cations Affect Water Activation on Pt(111) in Alkaline Media

Water activation, oxidatively to produce surface-bound hydroxide (OH*) or reductively to form surface-bound hydrogen (H*) atoms, is ubiquitous in electrocatalysis. We report the impact of cations on the kinetics of the OH* and H* formation from water on single-crystal Pt(111) in alkaline using fast-scan-rate cyclic voltammetry. Isolating the dependence of the electro-adsorption kinetics on pH and ionic strength led to the observation that ion concentrations affected the OH* formation kinetics more strongly than pH. The H* formation exhibited similar behavior, even though the OH* formation rate was observed to be faster by >10x. We attributed the observed ion concentration effect to cations, given that switching cations (from Na + to Li + ) had a bigger impact on the H* and OH* formation rates than switching pH (effectively changing OH – to F – ). We hypothesize the cations softened and allowed the interfacial water layer to more easily reorganize. This result suggests that interfacial water disruption should benefit both H* and OH* electro-adsorption kinetics in alkaline electrolytes.

Lin, Chia-Yi [Cornell Univ., Ithaca, NY (United St↗

Structure and Dynamics of CO 2 at the Air–Water Interface from Classical and Neural Network Potentials

The accurate description of the structure and dynamics of CO 2 at the instantaneous air–water interface, along with the effects of surface fluctuations on the CO 2 -transport processes, is essential for the development of negative emission technologies aimed at minimizing climate change. In this study, we performed molecular dynamics simulations of CO 2 at the air–water interface using neural network potentials (NNPs) trained on ab initio data generated through density-functional-theory-based molecular dynamics simulations. We compared these results with classical force fields to assess their performance in modeling interfacial CO 2 behavior. Our findings revealed that the asymmetric interactions, coupled with thermal surface fluctuations at the air–water interface, significantly influence CO 2 transport into the aqueous phase. The simulations demonstrate that classical force fields underestimate both the free energy of CO 2 transport and the strength of its interactions at the interface compared with the neural network potentials. In conclusion, the free energy and the interfacial dynamics of CO 2 are primarily influenced by the distribution of water within the instantaneous interfacial water layer, responsible for creating an asymmetric intermolecular interaction environment within the interfacial region.

Ab initio molecular dynamics↗

Study of the magnetic interface and its effect in Fe/NiFe bilayers of alternating order

We present a comprehensive study on the magnetization reversal in the Fe/NiFe bilayer system by alternating the order of the magnetic layers. All the samples show growth-induced uniaxial magnetic anisotropy due to the oblique angle deposition technique. Strong interfacial exchange coupling between the Fe and NiFe layers leads to single-phase hysteresis loops in the bilayer system. The strength of coupling being dependent on the interface changes upon alternating the order of magnetic layers. The magnetic parameters such as coercivity H C , and anisotropy field H K become almost doubled when a NiFe layer is grown over the Fe layers. This enhancement in the magnetic parameters is primarily dependent on the increase of the thickness and magnetic moment of the Fe–NiFe interfacial layer as revealed from the polarized neutron reflectivity (PNR) data of the bilayer samples. The difference in the thickness and magnetization of the Fe–NiFe interfacial layer indicates the modification of the microstructure by alternating the order of the magnetic layers of the bilayers. The interfacial magnetic moment increased by almost 18% when the NiFe layer was grown over the Fe layer. In spite of the different values of anisotropy fields and modified interfacial exchange coupling, the Gilbert damping constant values of the ferromagnetic bilayers remain similar to the single NiFe layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application of the Refined Zigzag Theory to the Modeling of Delaminations in Laminated Composites

The Refined Zigzag Theory is applied to the modeling of delaminations in laminated composites. The commonly used cohesive zone approach is adapted for use within a continuum mechanics model, and then used to predict the onset and propagation of delamination in five cross-ply composite beams. The resin-rich area between individual composite plies is modeled explicitly using thin, discrete layers with isotropic material properties. A damage model is applied to these resin-rich layers to enable tracking of delamination propagation. The displacement jump across the damaged interfacial resin layer is captured using the zigzag function of the Refined Zigzag Theory. The overall model predicts the initiation of delamination to within 8% compared to experimental results and the load drop after propagation is represented accurately.

Groh, Rainer M. J.↗

Probing Interfacial Reaction Pathways in Atomic Layer Deposition on Sulfide Superionic Conductors

Sulfide superionic conductors (e.g., argyrodite Li 6 PS 5 Cl, LPSCl) are extremely promising for all solid-state batteries, but poor atmospheric stability and high interfacial reactivity limit widespread adoption. Coating LPSCl powders with ultrathin coatings using atomic layer deposition (ALD) mitigates these problems, protecting against atmospheric degradation and reducing reactivity with Li metal, yielding more stable cycling. Despite significant promise, the ALD mechanism is unknown, hampering the development of new coating chemistries. In this study, we elucidate the mechanism for Al 2 O 3 ALD on LPSCl using trimethyl aluminum (TMA) and H 2 O by combining in situ Fourier transform infrared spectroscopy, ex situ solid-state magic angle spinning nuclear magnetic resonance, UV Raman spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We determine that ALD Al 2 O 3 nucleates promptly via TMA reaction with native —OH, —SH, and PS 3 -OH groups to form transient C–Al–O(S) species that are rapidly hydrolyzed during the subsequent H 2 O exposure. This reversible transformation maintains surface nucleophilicity and prevents sulfide decomposition. The resulting layer-by-layer growth leads to highly conformal Al 2 O 3 coatings on LPSCl that are readily scalable to ≥ 50 g quantities using a rotating drum fixture. This detailed understanding of ALD surface reactions provides critical insights guiding the selection of future ALD chemistries with improved performance.

atomic layer deposition↗

Ambient pressure x-ray photoelectron spectroscopy study of water formation and adsorption under two-dimensional silica and aluminosilicate layers on Pd(111)

Ambient pressure x-ray photoelectron spectroscopy (AP-XPS) supported by density functional theory (DFT) calculations was used to characterize the interaction of water with two-dimensional (2D) silica and aluminosilicate bilayers on Pd(111). Starting with oxygen adsorbed at the SiO2/Pd interface, exposure to water caused the SiO 2 -derived XPS peaks to shift to higher binding energy and the removal of an O 1s feature associated with interfacial adsorbed oxygen. These observations were attributed to the formation of a mixed water–hydroxyl interface, which eliminates the interfacial dipolar layer, and its associated electrostatic potential, created by adsorbed oxygen. Interfacial oxygen also reacted with H 2 to produce adsorbed water which also caused an upward binding energy shift of the SiO 2 peaks. Spectra recorded under 0.5 Torr water revealed additional water adsorption and a further shift of the overlayer peaks to higher binding energy. Incorporating Al into the 2D material caused the bilayer peaks to shift to lower binding energy which could be explained by electron donation from the metal to the bilayer. Although the stronger interaction between the bilayer and Pd substrate should restrict interfacial adsorption and reaction, similar trends were observed for water and hydrogen exposure to interfacial adsorbed oxygen. Less water adsorption was observed at the aluminosilicate interface which is a consequence of Al strengthening the bond to the metal substrate. The results reveal how the sensitivity of XPS to interfacial dipoles can be exploited to distinguish reactions taking place in confined spaces under 2D layers and how tuning the composition of the 2D layer can impact such reactions.

Density functional theory↗

Nanometer-Thick Sr 2 IrO 4 Freestanding Films for Flexible Electronics

In this article, we report the structural and optical properties of nanoscale Sr 2 IrO 4 freestanding thin-films fabricated using a water-soluble Sr 3 Al 2 O 6 layer. The coherent lattice structure, phonon modes, two-magnon Raman scattering, and optical absorption spectra of the Sr 2 IrO 4 nanomembrane are analogous to those of the layered iridate epitaxial thin-films and single crystals. Remarkably, the formation of 3-unit-cell-thick SrIrO 3 and interfacial composite layers alleviates the antiphase boundaries at the Sr 2 IrO 4 /Sr 3 Al 2 O 6 interface, resulting in structurally-robust nanomembranes. Our experimental results show that this freestanding thin-film approach of layered oxides can provide techniques for tuning or realizing unprecedented states beyond conventional thin-film methods, suggesting a pathway in achieving flexible layered-oxide electronics.

36 MATERIALS SCIENCE↗

Simulated Start-Stop and the Impact of Catalyst Layer Redox on Degradation and Performance Loss in Low-Temperature Electrolysis

Stress tests are developed that focus on anode catalyst layer degradation in proton exchange membrane electrolysis due to simulated start-stop operation. Ex situ testing indicates that repeated redox cycling accelerates catalyst dissolution, due to near-surface reduction and the higher dissolution kinetics of metals when cycling to high potentials. Similar results occur in situ, where a large decrease in cell kinetics (>70%) is found along with iridium migrating from the anode catalyst layer into the membrane. Additional processes are observed, however, including changes in iridium oxidation, the formation of thinner and denser catalyst layers, and platinum migration from the transport layer. Increased interfacial weakening is also found, adding to both ohmic and kinetic loss by adding contact resistances and isolating portions of the catalyst layer. Repeated shutoffs of the water flow further accelerate performance loss and increase the frequency of tearing and delamination at interfaces and within catalyst layers. These tests were applied to several commercial catalysts, where higher loss rates were observed for catalysts that contained ruthenium or high metal content. These results demonstrate the need to understand how operational stops occur, to identify how loss mechanisms are accelerated, and to develop strategies to limit performance loss.

08 HYDROGEN↗

Similarities and differences between nickelate and cuprate films grown on a SrTiO 3 substrate

The recent discovery of superconductivity in Sr-doped NdNiO 2 films grown on SrTiO 3 started a novel field within unconventional superconductivity. Therefore, to understand the similarities and differences between nickelate and cuprate layers on the same SrTiO 3 substrate, here based on the density functional theory we have systematically investigated the structural, electronic, and magnetic properties of NdNiO 2 / SrTiO 3 and CaCuO 2 / SrTiO 3 systems. Our results revealed a strong lattice reconstruction in the case of NdNiO 2 / SrTiO 3 , resulting in a polar film, with the surface and interfacial NiO 2 layers presenting opposite displacements. To avoid the “polar catastrophe,” the NiO 2 surface to the vacuum reconstructs as well. However, for CaCuO 2 / SrTiO 3 , the distortions of those same two CuO 2 layers were in the same direction. In addition, we found this distortion to be approximately independent of the studied range of film thickness for the nickelate films. Furthermore, we also observed a two-dimensional electron gas at the interface between NdNiO 2 and SrTiO 3 , caused by the polar discontinuity, in agreement with recent literature. For NdNiO 2 / SrTiO 3 the two-dimensional electron gas extends over several layers, while for CaCuO 2 / SrTiO 3 this electronic rearrangement is very localized at the interface between CaCuO 2 and SrTiO 3 . The electronic reconstruction found at the interface involves a strong occupation of the Ti 3 d x y state. In both cases, there is a significant electronic charge transfer from the surface Ni or Cu layers to the Ti interface layer. The interfacial Ni and Cu layers are hole and electron doped, respectively. By introducing magnetism and electronic correlation, we observed that the d 3 z 2 - r 2 orbital of Ni becomes itinerant while the same orbital for Cu remains doubly occupied, establishing a clear two- vs one-orbital active framework for the description of these systems. Furthermore, we also observed a strong magnetic reconstruction at the NdNiO 2 surface to vacuum layer where magnetism is basically suppressed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantitative Analysis of the Semiconductor–Electrolyte Interface Using Cyclic Voltammetry Measurements

Small changes in the chemical potential at a semiconductor interface can result in dramatic changes to the space-charge layer that underpins applications in the electronic and photovoltaic industries as well as in photoelectrochemical cells for fuel production. There has hence been great interest in techniques that directly probe the space-charge layer, yet many fail at the semiconductor–electrolyte interface due to the potential drop in the electric double-layer region of the electrolyte. This article demonstrates that photovoltages, obtained from straightforward cyclic voltammetry measurements, provide an experimental and quantitative approach for characterizing the semiconductor–electrolyte interface. Key parameters accessible through this approach include the flat-band potential ( E fb ), the fraction of the total potential that drops across the space-charge layer (γ sc ) and the electric double layer, as well as the surface recombination lifetime (τ s ). Here, we report photovoltage measurements for p -type Si(111) photoelectrodes in contact with electrolytes containing redox-active species with a range of known reduction potentials that exceed the 1.1 eV bandgap. In tetrabutylammonium [NBu 4 ] + electrolyte, the flat-band potential determined for hydrogen-terminated ( p -Si–H), methyl-terminated ( p -Si–CH 3 ), and chemically oxidized ( p -Si–cSiO x ) surfaces were −0.02, −0.31, and 0.30 V vs Fc +/0 , respectively, agreeing well with expected shifts arising from surface dipole modifications. The quantitative analysis also reveals that 67% of the applied bias drops across the space-charge layer for p -Si–H, 73% for p -Si–CH 3 , and only 44% for p -Si–cSiO x . The remaining potential drop is attributed to the interfacial surface layer, which consists of a molecular dipole or oxide overlayer, and the Helmholtz layer within the electrolyte. When the larger [NBu 4 ] + electrolyte was replaced with Li + , the flat-band position showed minimal changes, but the fraction of the potential drop across the space-charge layer increased significantly, consistent with the small cation altering the structure of the electric double layer.

electrolytes↗

Time-Evolved Hetero-Alkali Interphases Enable Long-Life Sulfide-Based Anode-Free Solid-State Batteries

Sulfide-based anode-free solid-state batteries (AFSSBs) offer compelling advantages in terms of energy density and safety, yet their practical implementation is severely hindered by undesirable interfacial reactions between sulfide solid electrolytes (SEs) and freshly plated lithium (Li), as well as non-uniform Li plating/stripping behavior. Herein, an effective interfacial stabilization strategy by incorporating sodium bis(fluorosulfonyl)imide (NaFSI) additive into the Li5.4PS4.4Cl1.6 (LPSC) is investigated. Unlike conventional Li-based additives that form static passivation layers, NaFSI introduces a transient hetero-alkali chemistry that kinetically governs interphase evolution during fresh Li plating. NaFSI induces a timesequenced interphase evolution: an initial NaF/LiF-rich layer that suppresses early sulfide reduction, followed by a LiF/Li3N-rich layer that optimizes Li⁺ transport during repeated anode-free cycling. This evolved robust and fast ion conducting layer mitigates interfacial impedance growth, enhances Li + transport kinetics, and suppresses localized Li growth and filamentary shorting. As a result, the anode-free full cell with NaFSI modified LPSC as the interlayer exhibits an excellent cycling stability over 500 cycles at 0.2 C with a capacity retention of 77.6%, whereas the cell with bare LPSC suffers from rapid capacity decay after 100 cycles, retaining only 32.1% of its initial capacity. This work establishes dynamic heteroalkali additive chemistry as a general strategy to kinetically program solid-solid interphases, guiding the interface design in anode-free solid-state batteries.

25 ENERGY STORAGE↗