Search NASA⌕ Search

SEARCH · Search NASA

Results for “Interfacial instability”

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.

At least 55 records · Page 3

An In Situ Formed Surface Coating Layer Enabling LiCoO 2 with Stable 4.6 V High‐Voltage Cycle Performances

Abstract The development of high‐voltage LiCoO 2 is essential for achieving lithium‐ion batteries with high volumetric energy density, however, it faces a great deal of challenges owing to the materials, structure and interfacial instability issues. In this work, a strategy is developed, through heat annealing a precoated surface layer to in situ form a high‐voltage‐stable surface coating layer, which is demonstrated to be highly effective to improve the high‐voltage performance of LiCoO 2 . It is discovered that LiCoO 2 reacts with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) at 700 °C to form exclusively spinel phases in addition to Li 3 PO 4 , which are structurally coherent to the layered lattice of LiCoO 2 . The heat annealing of the precoated thin layer of LATP enables the formation of a high‐quality surface layer. Spinel phases possess high‐voltage‐stable structures with much weaker oxidizing ability of lattice oxygen than layered structure. In addition, the Li 3 PO 4 is a good lithium‐ion conductor with excellent chemical stability at high voltages. All these benefits contribute to the construction of a uniform and conformal high‐voltage‐stable surface layer with favorable lithium conducting kinetics at the LiCoO 2 surface. The modified LiCoO 2 shows excellent 4.6 V high‐voltage cycle performance at both room temperature and 45 °C. The thermal stability is greatly enhanced as well.

Wang, Yi↗

Tailoring Na⁺ Chelation Dynamics for Expedient Sulfur Redox Kinetics in Low‐Temperature Sodium–Sulfur Batteries

Sodium–sulfur (Na–S) batteries have attracted considerable attention due to their high theoretical energy density and the abundant natural availability of sodium and sulfur. However, sluggish kinetics of sulfur conversion, slow Na⁺ transport, and interfacial instability at low temperatures pose significant challenges for their operation and limit their practical application. Herein, three solvents with well-designed molecular configurations are examined. We systematically investigate the impact of chelation effect on the desolvation behavior, sulfur conversion process, ion dynamics, and Na⁺ plating/stripping behavior. Compared with conventional linear ether solvents, the incorporation of methyl groups not only weaken the chelation capability and tailors the inner solvation sheath, but also reduces the energy barrier for Na⁺ transport, thus promoting enhanced sulfur conversion kinetics under low temperature conditions. This work elucidates the relationship among solvent molecules, Na⁺ desolvation behavior, and sulfur reaction kinetics, and offers a strategy for rational design of electrolytes for low-temperature metal–sulfur batteries.

25 ENERGY STORAGE↗

Binder Effects on Processing, Mechanical Properties, and Performance of Thin Sulfide Solid‐State Electrolytes

All‐solid‐state batteries (ASSBs) offer enhanced safety and energy density compared to conventional lithium‐ion batteries by replacing flammable liquid electrolytes with solid‐state electrolytes (SSEs). Among SSEs, sulfide‐based electrolytes exhibit high ionic conductivity and mechanical deformability, making them promising candidates for next‐generation energy storage. However, their practical implementation is hindered by interfacial instability, mechanical brittleness, and challenges in fabricating ultrathin electrolyte membranes (<30 μm) with robust mechanical integrity. Here, this study systematically examines the influence of polymeric binders—polyisobutylene, hydrogenated nitrile butadiene rubber, and styrene–ethylene–butylene–styrene (SEBS)—on the structural, mechanical, and electrochemical performance of thin sulfide SSE membranes. Key findings reveal that SEBS enables the fabrication of ultrathin, uniform membranes, while binder elasticity significantly affects structural stability during cycling. Operando stack pressure measurements indicate that binder properties directly influence adhesion force for LPSCl particles, influencing their stabilizing cycling period. These results underscore the critical role of polymer binders beyond mechanical reinforcement, positioning them as essential design variables in sulfide SSE engineering. By linking binder chemistry to processability and electrochemical performance, this study provides insights into optimizing sulfide SSEs, advancing their commercial viability in ASSBs.

argyrodite sulfide electrolyte↗

Delineating the Impact of Diluent on High-Concentration Electrolytes for Developing High-Voltage LiNi 0.5 Mn 1.5 O 4 Spinel Cathode

LiNi 0.5 Mn 1.5 O 4 (LNMO) is a high-voltage spinel cathode with low nickel content, making it an attractive candidate for next-generation lithium-ion batteries (LIBs). However, its application is limited by interfacial instability with conventional carbonate-based electrolytes at high voltages. In this work, a localized saturated electrolyte (LSE) capable of stably operating up to 4.85 V is investigated. Molecular dynamics simulations and Fourier transform infrared spectroscopy reveal that adding “non-solvating” 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether diluent in the saturated electrolyte, more PF 6 − anions are present in the first solvation shell of Li + , at the expense of solvent molecules. This tailored solvation environment promotes the formation of a robust, LiF-rich cathode-electrolyte interphase that mitigates transition metal dissolution and parasitic side reactions. The optimized LSE enables excellent cycling performance, with 95% capacity retention in Li|LNMO half-cells after 100 cycles and 94% retention in Li 4 Ti 5 O 12 |LNMO full cells after 250 cycles, even at a practically relevant LNMO cathode loading of ≈15 mg cm −2 . In conclusion, these results highlight the benefits of electrolyte engineering and solvation structure control in advancing high-voltage LIB technologies.

LNMO cathode↗

Atomic- and Molecular-Scale Interphase Engineering for High-Performance Solid-State Batteries

Solid-state batteries (SSBs) promise a decisive advance beyond conventional Li-ion systems, yet their development remains constrained by persistent solid–solid interfacial instabilities that degrade performance and durability. Interfaces between solid electrolytes and both cathodes and Li metal often exhibit poor wettability, limited physical contact, and high charge–transfer resistance, leading to chemical decomposition, mechanical failure, and impedance growth. Overcoming these limitations requires interphase engineering with atomic-scale precision—capabilities that conventional coating methods cannot reliably deliver. Atomic layer deposition (ALD) and molecular layer deposition (MLD) uniquely meet this need by enabling ultrathin, conformal, and composition-tunable films that stabilize reactive surfaces, suppress parasitic reactions, and regulate Li-metal morphology. Importantly, this Perspective highlights ALD/MLD systems that have already demonstrated effectiveness in liquid-electrolyte cells and discusses how these validated strategies can be deliberately translated to solid-state architectures. By grounding future directions in experimentally proven concepts rather than speculative hypotheses, we outline how atomic- and molecular-scale design principles can accelerate the development of robust, high-performance SSB technologies.

atomic and molecular layer deposition↗

Multifunctional nitrile additives for inducing pseudo-concentration gel-polymer electrolyte: Enabling stable high-voltage lithium metal batteries

High-voltage lithium metal batteries (LMBs) are promising for next-generation high-energy storage systems. Unfortunately, their implementation has been severely plagued by the interfacial instability between the high-voltage cathodes/lithium metal (LM) anodes and electrolytes. To tackle these challenges, a novel nitrile additive, 1,4-dicyanobenzene (DCB) (Synonyms: terephthalonitrile), is added to the in situ polymerized pentaerythritol tetraacrylate-based gel polymer electrolyte (GPE). The DCB additive, as demonstrated both theoretically and experimentally, plays a crucial role in altering the Li+ coordinated solvation structure within the GPE. This alteration leads to the formation of a pseudo-concentrated electrolyte with a tightly packed Li+ cluster, expanding the electrochemical stability window of the electrolyte. Moreover, the DCB-included GPE significantly improves its compatibility with both LM anode and high-voltage cathode, attributed to the modified solvation structure and the generated LiF-rich electrolyte/electrode interphases. Accordingly, the GPE enables stable cyclic performance of LMBs based on a 4.9 V LiNi 0.5 Mn 1.5 O 4 cathode at a low relative negative/positive ratio of 4, achieving a high reversible capacity of 123.8 mAh g -1 with a capacity retention of 87.7% over 500 cycles at 0.5 C. This work provides new insights into enhancing the cyclability of high-voltage LMBs via the synergistic effect of additives and GPE.

25 ENERGY STORAGE↗

Stability-based optimization of ACRT for the growth of CZT by the traveling heater method

Numerical modeling is employed to study the effects of several accelerated crucible rotation technique (ACRT) rotation schedules on the growth of cadmium zinc telluride (CZT) by the traveling heater method (THM). In conjunction with these analyses, a measure is developed to estimate the amplitude of disturbances associated with cellular interface growth morphologies that develop over time and across the melt-solid interface. Furthermore, this disturbance amplitude measure is used to assess the ability of ACRT to stabilize the growth interface and thereby minimize inclusion formation processes. Notably, our analyses reveal that interfacial instability is not well correlated with melt undercooling, explaining why classical ACRT approaches to reduce undercooling by mixing may not stabilize growth. Computations show that interface stability is best achieved via rotation schedules that accentuate outward Ekman flows during spin-up and, during spin-down, eliminate Taylor-Görtler flows and minimize inward Ekman flows.

36 MATERIALS SCIENCE↗

Manufacturing scalability implications of materials choice in inorganic solid-state batteries

The pursuit of scalable and manufacturable all-solid-state batteries continues to intensify, motivated by the rapidly increasing demand for safe, dense electrical energy storage. Here, we describe the numerous, often conflicting implications of materials choices that have been made in the search for effective mitigations to the interfacial instabilities plaguing solid-state batteries. Specifically, we show that the manufacturing scalability of solid-state batteries can be governed by at least three principal consequences of materials selection: (1) the availability, scaling capacity, and price volatility of the chosen materials’ constituents, (2) the manufacturing processes needed to integrate the chosen materials into full cells, and (3) the cell performance that may be practically achieved with the chosen materials and processes. While each of these factors is, in isolation, a pivotal determinant of manufacturing scalability, we show that consideration and optimization of their collective effects and trade-offs is necessary to more completely chart a scalable pathway to manufacturing.

25 ENERGY STORAGE↗

High voltage stable cycling of all-solid-state lithium metal batteries enabled by top-down direct fluorinated poly (ethylene oxide)-based electrolytes

Poly (ethylene oxide) (PEO)-based solid-state polymer electrolytes (SPEs) show prospects in all-solid-state lithium metal batteries. However, they suffer from low ionic conductivity at room temperature and interfacial instability with high voltage cathodes for long-term cycling. In this work, top-down fluorinated PEOs (F-PEOs) for the all-solid-state electrolytes, which are scalable and cost-effective, are developed to improve the battery performance. We demonstrate, that by enhancing the disordering of the F-PEO matrix, the SPE achieves a maximum Li + conductivity of 1.1 x 10 -4 S cm -1 at 40 °C, which is 20 times higher than the baseline. By forming robust cathode/SPE and Li/SPE interfaces, the F-PEO-based SPEs demonstrate stable cycling in the LiFePO 4 /Li and LiNi 0·8 Mn 0·1 Co 0·1 O 2 /Li (3-4.4 V, 500 cycles, capacity retention of 91.6%) based all-solid-state batteries at 40 °C. Therefore, our work highlights the significance of "disordering engineering" for energy storage materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electrolyte-driven interphase stabilization in high-voltage sodium-ion full cells

Sodium-ion batteries with a high-voltage O3-type layered oxide cathode paired with a hard carbon anode can offer high energy density; however, significant interfacial instabilities driven by electrode/electrolyte reactions limit a broader industrial adoption. Localized high concentration electrolytes (LHCEs) are a rational choice as they promote salt decomposition over solvent, forming stable, inorganic-rich electrode-electrolyte interphases (EEIs). We present here a comparison of high-voltage (4.2 V) hard carbon | NaNi 1/3 Fe 1/3 Mn 1/3 O 2 pouch cells in LHCEs and in a standard carbonate-based electrolyte by (i) examining the influence of diluent choice on the electrochemical performance of LHCEs and (ii) investigating how the electrolyte chemistry affects the composition and structure of EEIs formed. Importantly, LHCEs demonstrate superior electrochemical performance, achieving 37% higher capacity after 200 cycles (119 vs. 87 mA h g -1 ) compared to the carbonate-based electrolyte. The enhanced stabilization provided by LHCEs at the interface with high-voltage sodium layered oxide cathode is revealed by gas evolution measurements obtained through online electrochemical mass spectrometry (OEMS). Time-of-flight secondary ion mass spectrometry paired with focused ion beam and advanced statistical analyses reveal that the superior performance of LHCE stems from a robust, thin cathode electrolyte interphase formed on the sodium layered oxide cathode and a homogeneous solid electrolyte interphase formation on the hard carbon anode. Furthermore, this study highlights the critical importance of electrolyte design in interphase stabilization, which plays a key role in advancing sodium-ion batteries toward commercial viability.

25 ENERGY STORAGE↗

Formation and growth of cerium (III) oxalate nanocrystals by liquid-cell transmission electron microscopy

Using rare earth elements as analogs for actinide series elements enables studying the chemistry of these radioactive materials without the inherent risks. A fundamental understanding of the nucleation and growth of actinide oxalates is crucial for processing nuclear waste. Using in-situ liquid cell TEM (LC-TEM), we show particle attachment processes occurring during the nucleation and growth of cerium oxalate. The early stages of the observed non-classical growth mechanisms have important implications for particle evolution and predictions of final particle morphology. In this work, we observed particle formation via monomer-by-monomer addition or the particle aggregation pathway depending on the selected precursor concentration. At the highest precursor concentration at a high dose rate, we observed particle alignment in a branch structure is due to the interfacial instability. It was demonstrated that in-situ LC-TEM is an invaluable tool in studying the cerium oxalate formation and ultimately a path to understanding actinide chemistry.

36 MATERIALS SCIENCE↗

Resolving Chemical and Spatial Heterogeneities at Complex Electrochemical Interfaces in Li-Ion Batteries

The high specific capacities of Ni-rich transition metal oxides have garnered immense interest for improving the energy density of Li-ion batteries (LIBs). Despite the potential of these materials, Ni-rich cathodes suffer from interfacial instabilities that lead to crystallographic rearrangement of the active material surface as well as the formation of a cathode electrolyte interphase (CEI) layer on the composite during electrochemical cycling. While changes in crystallographic structure can be detected with diffraction-based methods, probing the chemistry of the disordered, heterogeneous CEI layer is challenging. In this work, we use a combination of ex situ solid-state nuclear magnetic resonance (SSNMR) spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information, on the nanometer length scale, on the CEI deposited on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite cathode films. XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13 C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, here we find that LiF, Li 2 CO 3 , and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1 H and 19 F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially-resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films.

36 MATERIALS SCIENCE↗

Effect of H + Exchange and Surface Impurities on Bulk and Interfacial Electrochemistry of Garnet Solid Electrolytes

Contact loss and current constriction pose significant challenges at the Li metal interface of solid-state batteries. For garnet-structured Li 7 La 3 Zr 2 O 12 (LLZO), these effects are amplified by Li + /H + exchange and surface contamination reactions, which lead to conductivity losses and poor Li wetting. In this study, we utilize a variety of surface treatment processes across 37 cells to selectively induce proton exchange and contamination reactions in LLZO. The resulting bulk and surface chemistry is systematically characterized and correlated to changes in electrochemical properties. Additionally, we combine impedance analysis and finite element method modeling to deconvolute sources of impedance contributions at the Li metal interface. Specifically, we show that constriction impedance at the Li metal interface arises not solely from voids, but also from ionically-resistive surface contaminants. Further, these findings emphasize the connection between ionic conductivity and constriction, demonstrating that micron-scale ionically-resistive components increase constriction even with identical contact geometries. Finally, we leverage our comprehensive dataset to highlight unstable overpotential growth as a failure mechanism, additionally showing that the phase of a cell’s impedance is a sensitive indicator for the onset of interfacial instability. Overall, this study clarifies the impacts of proton exchange and surface contamination on electrochemical properties at the Li|solid electrolyte interface and elucidates insights that are generalizable to other solid-state battery systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation in Ni-Rich LiNi 1– x – y Mn x Co y O 2 /Graphite Batteries: Impact of Charge Voltage and Ni Content

Ni-rich LiNi 1– x–y Mn x CoyO 2 (NMC) materials are attractive as cathodes for Li-ion batteries due to their high energy density and low Co content. However, these materials may display poor electrochemical reversibility relating to structural and interfacial instabilities. The influence of Ni content and level of delithiation during charge on degradation mechanisms and relevance to electrochemical cycling behavior are probed for LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode materials in a full cell configuration under two upper voltage limits (4.1 and 4.3 V). The combined use of dQ/dV analysis of electrochemical voltage profiles, operando XRD, and postcycling scanning electron microscopy (SEM) measurements indicates that a major contributor to capacity fade is the large anisotropic volume change from an H2 $\leftrightarrows$ H3 phase transition and associated mechanical degradation particularly for NMC811. Notably, transition metal dissolution and deposition on the negative electrode are found to correlate with the structural changes occurring in the cathode under high voltage charge. X-ray photoelectron spectroscopy (XPS) analyses of the cycled cathodes reveal a more organic-rich cathode–electrolyte interphase (CEI) when cycling to 4.3 V with lower relative amounts of LiF. Surface reconstruction is not a significant factor under these cycling conditions as determined by soft X-ray absorption spectroscopy (sXAS) analysis. The results emphasize the opportunity to match the electrochemical test parameters with the specific NMC active material to mitigate degradation and extend cycle life.

36 MATERIALS SCIENCE↗

Effects of Ball Milling on the Electrochemical Capacity and Interfacial Stability of Li 2 MnO 3 Cathode Materials

The cycling mechanism of Li 2 MnO 3 cathode materials synthesized by conventional solid-state methods at high temperatures (800-900 °C) has been intensively investigated. Previous studies showed that CO 2 and O 2 gas evolution accounts for most of the charge capacity, followed by some Mn reduction during discharge. In this work, we analyze the effects of ball milling on the structure, surface contaminant, and electrochemical capacity of Li 2 MnO 3 cathode material, with or without a graphitic fluoride (C-F) additive. At the same time, C-F is added to form a protective coating layer that reduces unwanted reactions with the electrolyte during later electrochemical cycling. We find that the C-F ball-milled material shows Li 2 MnO 3 /LiMnO 2 composite phases, while the purely ball-milled material shows a single Li 2 MnO 3 phase. Furthermore, we characterize surface species and gas evolution during the first cycle, which reveals the decomposition of Li 2 CO 3 and the carbonate electrolyte during the first charge, especially during the high potential region (>4.4 V), and the electrochemical reduction of only a small fraction of the evolved gas on the first discharge (<2.75 V). The appearance further demonstrates the repetitive nature of this process during charge and disappearance during discharge of Mn 2p 3/2 X-ray photoelectron spectroscopy (XPS) spectra signals during the first two cycles. These processes result in first discharge specific capacities of only 155 and 170 mAh/g after first charge specific capacities of 210 and 320 mAh/g for the pure ball-milled and ball-milled with C-F materials, respectively. These studies demonstrate the interfacial instability introduced by ball milling. However, the electrochemical capacity is significantly increased, necessitating further investigation to determine whether ball milling can activate Mn-containing cathode materials.

25 ENERGY STORAGE↗

Optimized Al Doping Improves Both Interphase Stability and Bulk Structural Integrity of Ni-Rich NMC Cathode Materials

Ni-rich layered transition metal oxide (NMC, LiNi1-x-yMxCoyO2, 1 – x – y = 0.6) is promising for high-energy-density lithium-ion batteries, but its large-scale application is still hindered by several technical challenges, including secondary particle cracking, interfacial instability, and cell degassing during cycling. Here, we report a facile wet-chemical method to modify both the surface and the bulk of the LiNi0.76Mn0.14Co0.10O2 (NMC76) cathode with Al doping to effectively improve the structural/interfacial stability of the cathode, and hence its long-term cycling capability. With only 1 mol% Al doping, the Al-NMC76 electrode delivers a good capacity retention of 79.2% after 500 cycles at a high voltage limit of 4.5 V, which is far better than those of undoped NMC76 under the similar condition. The enhanced performance can be attributed to the Al doping in the NMC76, which not only strengthens the bulk structural stability through doping into the lattice, but also suppresses acidic attack from the electrolyte through altered surface structure of NMC76.

Al doping, capacity retention, high voltage, elect↗

Probing the Formation of Cathode-Electrolyte Interphase on Lithium Iron Phosphate Cathodes via Operando Mechanical Measurements

Interfacial instabilities in electrodes control the performance and lifetime of Li-ion batteries. While the formation of solid-electrolyte interface (SEI) on anodes has received much attention, there is still lack of understanding about the formation of cathode-electrolyte interface (CEI) on the cathodes. To fill this gap, we report on dynamic deformations on lithium iron phosphate, LiFePO 4 cathodes during charge / discharge by utilizing in-operando digital image correlation, impedance spectroscopy and Cryo X-ray photoelectron spectroscopy. LiFePO4 cathodes were cycled in either LiPF 6 , LiClO 4 or LiTFSI- containing organic liquid electrolytes. Beyond the first cycle, Li-ion intercalation results in a nearly linear correlation between electrochemical strains and the state of (dis)-charge, regardless of the electrolyte chemistry. However, during the first charge in LiPF 6 - containing electrolyte, there is a distinct irreversible positive strain evolution at the onset of anodic current rise as well as current decay at around 4.0V. Impedance studies show the increase in surface resistance in the same potential window, suggesting the formation of CEI layers on the cathode. The chemistry of the CEI layer was characterized by X-ray photoelectron spectroscopy. LiF is detected in CEI layer starting as early as 3.4 V and Li $x$ PO $y$ F $z$ appeared at voltages higher than 4.0 V during the first charge. In conclusion, our approach offers new insights into the formation mechanism of CEI layers on the cathode electrodes, which is crucial for the development of robust cathode and electrolyte chemistries for higher performance batteries.

25 ENERGY STORAGE↗

Tracking the Oxidation of Silicon Anodes Using Cryo-EELS upon Battery Cycling

Silicon is a high-capacity material for the anode of a rechargeable lithium-ion battery. One of the fundamental challenges for using Si in anodes is capacity fading, which has been revealed to be partially associated with the interfacial instability between the Si and liquid electrolyte due to the large volume swing of Si upon charging and discharging. Smart nanoscale design concepts, either pre-synthesized or formed in-situ, have led to the mitigation of the detrimental factors associated with the volume swing of Si. However, it has never been clear as how the chemical state of Si evolves and contributes to the capacity fading upon battery cycling. Here, we use cryo-electron energy loss spectroscopy (EELS) to directly monitor, at sub-nanometer scale, the chemical evolution of Si upon battery cycling. We discover that during the cycling process, Si particles are progressively oxidized to form SiO 2 , which is initiated from the particle surface and gradually penetrates toward the interior of the particle, directly contributing to the capacity fading. Possible mechanisms of Si oxidation are postulated. We further show how the cycling stability can be improved by an electrolyte additive to form an effective passivation layer, representatively, even a small concentration of fluoroethylene carbonate (FEC) causes the formation of an LiF layer on the Si nanoparticle surface that prevents Si oxidation and improves cycling stability. Furthermore, the present work unveils Si oxidation as a previously unrecognized factor that contributes to capacity fading, therefore providing insight into the design of anodes with Si based materials.

25 ENERGY STORAGE↗