Search NASA⌕ Search

SEARCH · Search NASA

Results for “electrode interface”

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 1,333 records · Page 74
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Self-assembly of co-continuous nanostructured copolymer templates with compositional and architectural dispersity

In our previous DOE-supported project (DE-SC0016208), we demonstrated that a particular architecture dubbed ‘randomly end-linked copolymer networks’ (RECNs) led to especially robust self-assembly of disordered cocontinuous nanostructures. Such structures, wherein both microphases are fully percolating in three dimensions, are attractive for a wide-variety of energy-relevant applications including purification membranes, separators in batteries and fuel cells, catalyst supports, and high surface area electrodes. In the current project we sought to substantially extend our fundamental understanding of how different types of randomness in blocky copolymer architecture contribute to the robust formation of disordered cocontinuous nanostructures. To do so, we filled in the sizable gap between the previously studied cases of randomly linked linear multiblock copolymers and RECNs by studying two intermediate cases: (i) random miktoarm star polymers, which contain dispersity in the number of the two chemically-incompatible strands located at each junction and therefore the preferred interfacial curvature of each polymer, and (ii) randomly branched copolymers, which also possess bridging strands that stretch across domains and apply local ‘elastic’ forces to the interfaces. In addition, we studied a different network architecture, statistically crosslinked copolymer networks, that is more straightforward to prepare using chain growth polymerization methods, enabling more facile formation of cocontinuous nanostructures. Finally, we extended our approaches from model systems based on polystyrene and poly(lactic acid) to copolymer architectures containing either (i) polysulfone, an engineering polymer that provides excellent mechanical properties for membrane applications, or (ii) polyacrylonitrile, providing a convenient route to nanoporous carbon materials.

36 MATERIALS SCIENCE↗
NASA NTRS2011

Distributed Capacitive Sensor for Sample Mass Measurement

Previous robotic sample return missions lacked in situ sample verification/ quantity measurement instruments. Therefore, the outcome of the mission remained unclear until spacecraft return. In situ sample verification systems such as this Distributed Capacitive (DisC) sensor would enable an unmanned spacecraft system to re-attempt the sample acquisition procedures until the capture of desired sample quantity is positively confirmed, thereby maximizing the prospect for scientific reward. The DisC device contains a 10-cm-diameter pressure-sensitive elastic membrane placed at the bottom of a sample canister. The membrane deforms under the weight of accumulating planetary sample. The membrane is positioned in close proximity to an opposing rigid substrate with a narrow gap. The deformation of the membrane makes the gap narrower, resulting in increased capacitance between the two parallel plates (elastic membrane and rigid substrate). C-V conversion circuits on a nearby PCB (printed circuit board) provide capacitance readout via LVDS (low-voltage differential signaling) interface. The capacitance method was chosen over other potential approaches such as the piezoelectric method because of its inherent temperature stability advantage. A reference capacitor and temperature sensor are embedded in the system to compensate for temperature effects. The pressure-sensitive membranes are aluminum 6061, stainless steel (SUS) 403, and metal-coated polyimide plates. The thicknesses of these membranes range from 250 to 500 m. The rigid substrate is made with a 1- to 2-mm-thick wafer of one of the following materials depending on the application requirements glass, silicon, polyimide, PCB substrate. The glass substrate is fabricated by a microelectromechanical systems (MEMS) fabrication approach. Several concentric electrode patterns are printed on the substrate. The initial gap between the two plates, 100 m, is defined by a silicon spacer ring that is anodically bonded to the glass substrate. The fabricated proof-of-concept devices have successfully demonstrated tens to hundreds of picofarads of capacitance change when a simulated sample (100 g to 500 g) is placed on the membrane.

Toda, Risaku↗
DOE OSTI2024

When and Where Lithium Plating Occurs, Its Correlation with Microstructure Heterogeneity, and the Mechanisms That Initiate and Self-Regulate Electrochemical Heterogeneity (A02-0444)

A microstructure scale electrochemical LIB model was used to investigate lithium plating onset, material non-uniform utilization, and in-plane heterogeneities for an NMC-graphite full cell. Model predicts active material particle surface roughness and size distribution (respectively, non-uniform curvature within and between particles) initiate in-plane heterogeneity, and that particle size heterogeneity at the separator interface controls the lithium plating preferential deposition ("Where"). These in-plane heterogeneities are then exacerbated by through-plane heterogeneities induced at fast charge as electrolyte depletion occurs and concentrates intercalation reaction near the anode-separator interface. Also, magnitude and occurrence of lithium plating is controlled by effective, or macroscale, microstructure parameters ("When"). As local states of charge start to diverge between nearby active material regions, overpotential differences induced by OCP difference kick in and contribute to reduce these SOC local heterogeneities. However, for staged materials such as graphite, with OCP profile alternating between plateaus and varying regions, this balancing mechanism is, respectively, inactive and active. This leads to a dynamic, non-monotonic, in-plane heterogeneity time evolution for state of charge and Faraday current density, for which their respective in-plane heterogeneity magnitude alternates. Such behavior has been modeled both for the whole electrode at the microstructure scale and at the particle scale. In-plane heterogeneities are usually considered to be detrimental, as they result in material non-uniform utilization (i.e., under and over stressed regions) and earlier degradations. However, this work provides a more granular approach as it discriminates between a harmful in-plane heterogeneity (non-uniform curvature) that triggers SOC in-plane heterogeneity, and a beneficial in-plane heterogeneity (Faraday current density) that contributes to reduce SOC in-plane heterogeneity. This work comprehensively explains the mechanisms that initiate, exacerbate, and regulate heterogeneity at the microstructure scale, while providing some design suggestions to reduce both in-plane and through-plane heterogeneities, as summarized in the graphical abstract.

ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2026

Impact of Anode to Cathode Crossover in Lithium‐metal Batteries With High‐Nickel Cathodes

The advancement of high-energy-density lithium-metal batteries (LMBs) is hindered by the chemical instability of both lithium-metal anode and high-nickel layered oxide cathodes. While cathode-to-anode crossover is well-documented, the reverse process of anode-to-cathode crossover remains underexplored. Here, we systematically investigate such crossovers and the degradation pathway in pouch cells with a localized high-concentration electrolyte, comparing NMC622, NMC811, and NMC90 cathodes paired with lithium-metal and graphite anodes. Despite delivering higher initial capacities, LMBs exhibit faster capacity fade under long-term cycling at 45 °C. To isolate cathode-side degradation, galvanostatic electrochemical impedance spectroscopy (GEIS) measurements of cycled cathodes paired with delithiated lithium iron phosphate (LFP) counter electrodes reveal significantly higher charge-transfer resistance in cathodes cycled with lithium-metal. Surface characterization via X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) reveals greater electrolyte decomposition on cathodes cycled with lithium metal, leading to thicker, more organic-rich cathode–electrolyte interphases (CEIs), consistent with the elevated charge-transfer resistance observed in GEIS measurements. Notably, NMC90 shows the most pronounced CEI thickening, linking higher cathode surface reactivity to greater susceptibility to anode-to-cathode crossover. This work presents compelling evidence of crosstalk degradation originating from lithium-metal anodes and underscores the importance of cross-interface stability for the design of durable LMBs.

25 ENERGY STORAGE↗
DOE OSTI2018

Degradation Mechanisms of High Capacity 18650 Cells Containing Si-Graphite Anode and Nickel-Rich NMC Cathode

Application of advanced anode and cathode materials in commercial lithium-ion batteries is attracting attention due to their high capacity. Silicon (Si)/graphite anodes and nickel (Ni)-rich lithium nickel manganese cobalt oxide with layered structures have been paired in commercial 18650 high energy density cells (~270 Wh/kg). It is crucial to investigate the cell performance and the aging behavior of this commercial cell. In this study, we present commercial cell degradation mechanisms by comparing fresh and aged electrodes, including changes of crystal structure, morphology, elemental composition, and electrochemical properties. The quantitative analysis was done based on dV/dQ incremental capacity analysis of 18650 cells. To determine the amount of cyclable lithium ions (Li + ) and active material loss, the lithiation and delithiation capacity were compared for fresh and aged electrodes in half coin cells. Results showed that even with 5% (by mass) of Si added in the anode, cracks occurred across the anode leading to contact loss and thickening of the solid electrolyte interphase (SEI) layer. Additionally, the average fluorine (F) ratio of the aged anodes was higher compared to that of the fresh anodes. More severely, the F content on the Si aggregations on aged anodes increased to as high as 5 times that of the fresh anode, indicating SEI growth, especially on Si particles. Solid 7 Li nuclear magnetic resonance results showed no detectable Li metal deposition on the aged anode. On the cathode side, cracks on the primary particle interfaces contributed to cathode material loss, contact loss, and impedance rise. Furthermore, Li + loss into the thickened SEI layer, particle cracking, and impedance rise are the main reasons behind cell degradation.

25 ENERGY STORAGE↗
NASA NTRS2001

Analysis of Carbon Nanotube Metal-Semiconductor Diode Device

We study recently reported drain current I(sub d)-drain voltage V(sub d) characteristics of a carbon nanotube metal-semiconductor diode device with the gate voltage V(sub g) applied to modulate the carrier density in the nanotube. The diode was kink-shaped at the metal-semiconductor interface. It was shown that (1) larger negative V(sub g) blocked I(sub d) more effectively in the negative V(sub d) region, resulting in the rectifying I(sub d)-V(sub d) characteristics, and that (2) positive V(sub g) allowed I(sub d) in the both V(sub d) polarities, resulting in the non-rectifying characteristics. The negative V(sub d) was the Schottky reverse direction, judging from the negligible I(sub d) behavior for a wide region of -4 V (is less than) V(sub d) (is less than) 0 V, with V(sub g) = -4 V. Such negative V(sub g) would attract positive charges from the metallic electrodes (charge reservoir) to the nanotube and lower the nanotube Fermi energy (E(sub F)). With larger negative V(sub g), the experiment showed that the Schottky forward direction (V(sub d) (is greater than) 0) had a smaller turn-on voltage and the Schottky reverse direction (V(sub d) (is less than) 0) was more resistant to the tunneling breakdown. Therefore, the majority carriers in the transport would be electrons since they can see a lower tunneling barrier (shallower built-in potential) in the forward direction when E(sub F) is lowered, and a thicker tunneling barrier (Schottky barrier) in the reverse direction due to the reduction in the electron density when E(sub F) is lowered.

Yamada, Toshishige↗
DOE OSTI2019

Interrogating the Surface Intermediates and Water Oxidation Products of Boron‐Doped Diamond Electrodes with Scanning Electrochemical Microscopy

Abstract Boron‐doped diamond (BDD) electrodes are widely used in electrochemical sensing and water purification owing to their chemical and structural stability under harsh reaction conditions. Water oxidation at BDD electrodes is known to produce reactive oxygen species, but the discharged and surface chemistries involved in these processes have not been studied in depth. Here, we present scanning electrochemical microscopy (SECM) studies of electrogenerated intermediates and products formed on sp 2 carbon‐containing BDD electrodes that display stark differences in their reactivity as a function of electrolyte type and pH during water oxidation. The most reactive and abundant species discharged from the electrode were observed at pH 11 in sulfate electrolyte. With the surface interrogation mode of SECM, two kinetically distinct surface intermediates were clearly distinguished, with one forming two orders of magnitude faster than the other but displaying a slower desorption rate. The surface coverage of these species was estimated in the range of 4–7×10 −5 mol/cm 2 for the first, and 3–4.4×10 −5 mol/cm 2 for the second one. SECM imaging suggested that regions of increased product evolution have decreased electron transfer kinetics and limited surface sites for intermediate binding. This work establishes methods for studying highly reactive intermediates found in BDD and paves the way for the inspection of other interfaces where solvolysis impacts their reactivity and evolution.

Counihan, Michael J.↗
NASA NTRS1986

Diamondlike carbon films on semiconductors for insulated-gate technology

MIS structures are fabricated on p-type InP, GaAs, and Si substrated by direct ionization of 25-percent CH4 in Ar and ion-beam deposition of 70-nm-thick diamondlike films, followed by application of Al gate electrodes and ohmic contacts. The films are found to have bandgap 0.9-1.1 eV, resistivity 8.1 Mohm cm, breakdown field strength 1 MV/cm, and density 1.8 g/cu cm, to be thermally stable up to 400 C, and to undergo rapid decomposition above 450 C. The electrical properties of the MIS structures are significantly improved by sputter cleaning the substrates with a 1-keV 2-mA/sq cm Ar beam for 2 min at 300 microtorr prior to C-film deposition. The resulting structures have fixed insulator charge number densities 4 x 10 to the 12th/sq cm (InP), 7.5 x 10 to the 12th/sq cm (GaAs), and 9 x 10 to the 11th/sq cm (Si) and interface state densities (5, 200, and 0.5) x 10 to the 12th/ sq cm eV, respectively. It is suggested that the low optical bandgap and resistivity of the C films and the high insulator-charge and interface-state densities make them unstable as gate dielectrics for microelectronics.

Kapoor, V. J.↗
DOE OSTI2025

Mitigating Cyclable Li‐Ion Inventory Loss in Full Cells with Mn‐Rich Disordered Rocksalt Cathodes

Lithium (Li)- and manganese (Mn)-rich disordered rock salt (DRX) materials are promising cathode materials for next-generation Li-ion batteries. Although these cathode materials are Li-ions rich in their pristine state, their incorporation into full cells results in challenges with maintaining Li-ion inventory during cycling. Herein, the degradation mechanisms of DRX materials in different DRX||Graphite full cells are reported. It is found that DRX electrodes contain Li impurities, primarily due to the environmental sensitivity of mechanochemically synthesized DRX materials during sample transfer and storage. In addition, the structural instability of DRX triggers Mn dissolution. Dissolved Mn ions react with exposed Li x C y compounds and induce electrolyte decomposition on the anode, further depleting Li-ion inventory. Control experiments involving the pre-addition of Mn 2+ provide clear evidence of the impact of Mn dissolution on Li-ion inventory. The electrochemical activation process can stabilize DRX, alleviate Mn dissolution and thus mitigate the loss of Li-ion inventory. These mechanistic insights inform the development of chemical pre-lithiation and electrolyte additive strategies to collectively passivate interfaces, mitigate the effects of trace dissolved Mn ions, and preserve Li-ion inventory. Ultimately, the DRX||Graphite full cell achieves highly reversible electrochemical reactions with a high capacity retention. This study fills a research gap in DRX-based full cells and provides insights into degradation mechanisms and optimization strategies for their practical use.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Demystifying In Situ Pyrolysis Chemistry for High-Performance Polyanionic Cathodes in Sodium-Ion Batteries

In this article, the carbon coating strategy has emerged as an indispensable approach to improve the conductivity of polyanionic cathodes. However, owing to the complex reaction process between precursors of carbon and cathode, establishing a unified screening principle for carbonaceous precursors remains a technical challenge. Herein, we reveal that carbonaceous precursor pyrolysis chemistry undeniably influences the formation process and performance of Na 3 V 2 (PO 4 ) 3 (NVP) cathodes from in situ insights. By investigating three types of carbonaceous precursors, it is found that O/H-containing functional groups can provide more bonding sites for cathode precursors and generate a reducing atmosphere by pyrolysis, which is beneficial to the formation of polyanionic materials and a uniform carbon coating layer. Conversely, excessive pyrolysis of functional groups leads to a significant amount of gas, which is detrimental to the compactness of the carbon layer. Furthermore, the substantial presence of residual heteroatoms diminishes graphitization. In this case, it is demonstrated that carbon dots (CDs) precursors with suitable functional groups can comprehensively enhance the Na+ migration rate, reversibility, and interface stability of the cathode material. As a result, the NVP/CDs cathode displays outstanding capacity retention, maintaining 92% after 10,000 cycles at a high rate of 50 C. Altogether, these findings provide a valuable benchmark for carbon source selection for polyanionic cathodes.

25 ENERGY STORAGE↗
DOE OSTI2019

Plasmon-mediated electrochemical reactions: the influence of nanoparticle structure (Final Report)

Harnessing the energy of the sun to drive chemical reactions is an important strategy for lowering the cost and energy consumption associated with producing chemicals of interest. One challenge inherent to using solar energy is finding ways to convert the light into more useful forms of energy that can be utilized by chemical reactions. This research project focuses on using nanoscale particles of gold and silver (~10-100 nanometers in size and known as plasmonic nanoparticles) that are capable of transforming light energy into chemical energy in order to facilitate electrochemical reactions at the nanoparticle surface. These reactions involve the transfer of electrons between a molecule of interest and the plasmonic nanoparticle, which serves as an electrode. When we shine light on the nanoparticle, it helps promote the transfer of electrons, improving the reaction efficiency and yield. An open question is how the shape and size of the nanoparticle affects its ability to transform light into useful energy for electrochemical reactions that can then be utilized by molecules near the surface. This requires us to study reactions between molecules and single nanoparticles, so we can understand the role that heterogeneity in nanoparticle structure plays. To do this, we use molecules that change color and emit light when they undergo an electrochemical reaction, providing a strategy to follow these reactions at the surface of single nanoparticles. Our experiments reveal the importance of controlling the interface between the molecules and the plasmonic nanoparticles, as well as the interface between the plasmonic nanoparticles and the supporting substrate. Moreover, it is critical to find molecules that show well-behaved electrochemical behavior, in order to verify that the observed behaviors are due to the plasmonic nanoparticles and not the molecular reporters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Conformal Lithium Fluoride Protection Layer on Three-Dimensional Lithium by Nonhazardous Gaseous Reagent Freon

Research on lithium (Li) metal chemistry has been rapidly gaining momentum nowadays not only because of the appealing high theoretical capacity, but also its indispensable role in the next-generation Li–S and Li–air batteries. However, two root problems of Li metal, namely high reactivity and infinite relative volume change during cycling, bring about numerous other challenges that impede its practical applications. In the past, extensive studies have targeted these two root causes by either improving interfacial stability or constructing a stable host. However, efficient surface passivation on three-dimensional (3D) Li is still absent. Here in this paper, we develop a conformal LiF coating technique on Li surface with commercial Freon R134a as the reagent. In contrast to solid/liquid reagents, gaseous Freon exhibits not only nontoxicity and well-controlled reactivity, but also much better permeability that enables a uniform LiF coating even on 3D Li. By applying a LiF coating onto 3D layered Li-reduced graphene oxide (Li-rGO) electrodes, highly reduced side reactions and enhanced cycling stability without overpotential augment for over 200 cycles were proven in symmetric cells. Furthermore, Li–S cells with LiF protected Li-rGO exhibit significantly improved cyclability and Coulombic efficiency, while excellent rate capability (~800 mAh g -1 at 2 C) can still be retained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Combined Rotating Disk Slurry Electrodeposition–Spontaneous Galvanic Displacement for Pt-M (M = Co, Ni, and Cu) Catalyst Synthesis for the Oxygen Reduction Reaction in Alkaline Media

Here, platinum-modified first-row transition-metal catalyst (M = Ni, Co, and Cu) nanoparticles on a carbon black Vulcan XC-72R (CBV) support were synthesized using rotating disk slurry electrodeposition (RoDSE) followed by spontaneous galvanic displacement (SGD) reactions. These RoDSE–SGD catalysts were evaluated for the oxygen reduction reaction (ORR) in 0.1 M KOH using rotating disk electrode techniques. The Ni and Co RoDSEs were done by using an electrochemical applied potential of -0.75 V versus the RHE and for Cu, -0.80 V versus the RHE using a CBV slurry solution containing 0.1 M KClO 4 . These metal nanoparticles on CBV (M/CBV) catalysts were modified with a Pt precursor via a spontaneous galvanic displacement (SGD) reaction, producing a Pt-M/CBV material to catalyze the ORR in an alkaline medium. High-resolution scanning transmission electron microscopy (HR-STEM) analysis indicates that the PtM/CBV samples include M clusters and Pt single atoms. The ORR characterization measurements were done under a controlled temperature (25.0 °C) and with a mass loading of 100 μg/cm 2 on a glassy carbon (GC) rotating disk electrode at 1600 rpm. The PtCo/CBV showed the highest ORR mass activity of 0.741 A/mgPt at 0.90 V versus the reversible hydrogen electrode (RHE) compared with commercial Pt/CBV. The M/CBV RoDSE catalysts were also tested for the oxygen evolution reaction (OER), and Ni/CBV provided the lowest overpotential of 450 mV at 10 mA/cm 2 disk in 0.1 M KOH.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2017

Gate-tunable electron interaction in high-κ dielectric films

The two-dimensional (2D) logarithmic character of Coulomb interaction between charges and the resulting logarithmic confinement is a remarkable inherent property of high dielectric constant (high-k) thin films with far reaching implications. Most and foremost, this is the charge Berezinskii-Kosterlitz-Thouless transition with the notable manifestation, low-temperature superinsulating topological phase. Here we show that the range of the confinement can be tuned by the external gate electrode and unravel a variety of electrostatic interactions in high-k films. Lastly, our findings open a unique laboratory for the in-depth study of topological phase transitions and a plethora of related phenomena, ranging from criticality of quantum metal- and superconductor-insulator transitions to the effects of charge-trapping and Coulomb scalability in memory nanodevices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Uncovering phase transformation, morphological evolution, and nanoscale color heterogeneity in tungsten oxide electrochromic materials

Controlling the electrochemical interfacial processes that govern the durability of electrochromic devices represents a key challenge in developing sustainable and cost-effective smart windows. Here, we revisit the classical tungsten trioxide (WO 3 ) materials as a platform to uncover the previously unknown interrelationship between phase transformation, morphological evolution, and nanoscale color heterogeneity in these materials. Through synchrotron/electron spectroscopic and imaging analyses, we report that the WO 3 –electrolyte interface is influenced by the tungsten dissolution and redeposition during the electrochemical cycling. The tungsten redeposition provokes the in situ crystal growth, which ultimately leads to the phase transformation from the semicrystalline WO 3 to a nanoflake-shaped, proton-trapped tungsten trioxide dihydrate (H x WO 3 · 2 H 2 O). The multidimensional quantification of the electronic structure reveals that the tungsten reduction caused by the proton trapping is heterogeneous at the nanometric scale and is responsible for the nanoscale color heterogeneity. The interplay between phase transformation, morphological evolution, and nanoscale color heterogeneity results in degraded optical modulation, switching kinetics, coulombic efficiency, and bleached-state transparency. Our results highlight that the high interfacial reactivity near the electrode surface may be the underlying mechanism for undesired bulk structural changes of electrochromic materials, and calls for fundamental studies in probing and controlling the electrode–electrolyte interfacial processes in electrochromic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2023

In Situ Visualization of the Pinning Effect of Planar Defects on Li Ion Insertion

Longevity of Li ion batteries strongly depends on the interaction of transporting Li ions in electrode crystals with defects. However, detailed interactions between the Li ion flux and structural defects in the host crystal remain obscure due to the transient nature of such interactions. Here, by in situ transmission electron microscopy and density function theory calculations, we reveal how the diffusion pathways and transport kinetics of a Li ion can be affected by planar defects in a tungsten trioxide lattice. We uncover that changes in charge distribution and lattice spacing along the planar defects disrupt the continuity of ion conduction channels and dramatically increase the energy barrier of Li diffusion, thus, arresting Li ions at the defect sites and twisting the lithiation front. In conclusion, the atomic-scale understanding holds critical implications for rational interface design in solid-state batteries and solid oxide fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2026

Enhanced cycling stability of Ni-rich Li-metal cells enabled by dual vinylene carbonate and tris(trimethylsilyl)borate electrolyte additives

NMC811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) and other high-Ni chemistries are promising cathode candidates for high-performance electric vehicles, owing to their high energy density and reduced cobalt content. However, their long-term cycling stability is hindered by surface degradation, particularly when paired with conventional electrolytes and a lithium metal anode. Electrolyte additives represent a practical approach to enhance interfacial stability and improve overall battery performance by promoting the formation of a robust electrolyte–electrode interphase (EEI). In this study, we revisit the effects of vinylene carbonate (VC) and tris(trimethylsilyl)borate (TMSB) additives on single-crystal SC-NMC811||Li cells. While TMSB only increases the open-circuit voltage and initial overpotential, it delivers superior capacity retention at C/3 compared to cells containing only VC or a dual additive system (VC and TMSB). Notably, under fast-charging conditions (1C, 2C, and 5C), the dual-additive system significantly outperforms other formulations, achieving markedly enhanced long-term capacity retention. Comprehensive electrochemical and spectroscopic analyses reveal that the VC/TMSB dual-additive system suppresses surface transition in NMC811, mitigates structural degradation by forming a thin, LiF-deficient cathode-electrolyte interface (CEI) layer. Moreover, they promote smooth and dense Li deposition and generate a LiF-deficient solid-electrolyte interphase (SEI). Consequently, the synergistic stabilization of both the CEI and SEI effectively limits the overall cell impedance growth during extended cycling. These findings provide key insights into co-additive strategies for engineering stable interfaces in high-energy Ni-rich Li-metal batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Negating interfacial impedance in garnet-based solid-state Li metal batteries

Garnet-type solid-state electrolytes have attracted extensive attention due to their high ionic conductivity, approaching 1 mS cm -1 , excellent environmental stability, and wide electrochemical stability window, from lithium metal to ~6 V. However, to date, there has been little success in the development of high-performance solid-state batteries using these exceptional materials, the major challenge being the high solid–solid interfacial impedance between the garnet electrolyte and electrode materials. In this paper, we effectively address the large interfacial impedance between a lithium metal anode and the garnet electrolyte using ultrathin aluminium oxide (Al 2 O 3 ) by atomic layer deposition. Li 7 La 2.75 Ca 0.25 Zr 1.75 Nb 0.25 O 12 (LLCZN) is the garnet composition of choice in this work due to its reduced sintering temperature and increased lithium ion conductivity. A significant decrease of interfacial impedance, from 1,710 Ω cm 2 to 1 Ω cm 2 , was observed at room temperature, effectively negating the lithium metal/garnet interfacial impedance. Experimental and computational results reveal that the oxide coating enables wetting of metallic lithium in contact with the garnet electrolyte surface and the lithiated-alumina interface allows effective lithium ion transport between the lithium metal anode and garnet electrolyte. Finally, we also demonstrate a working cell with a lithium metal anode, garnet electrolyte and a high-voltage cathode by applying the newly developed interface chemistry.

25 ENERGY STORAGE↗