Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “composite electrolyte”

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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Multicomponent Phase Separation in Ternary Mixture Ionic Liquid Electrolytes

We investigate the phase behavior of ternary mixtures of ionic liquid, organic solvent, and lithium salt by molecular dynamics simulations. We find that at room temperature, the electrolyte separates into distinct phases with specific compositions; an ion-rich domain that contains a fraction of solvent molecules and a second domain of pure solvent. Here, the phase separation is shown to be entropy-driven and is independent of lithium salt concentration. Phase separation is only observed at microsecond time scales and greatly affects the transport properties of the electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ionically conductive powders and films, and methods of preparation

A solid ionically conductive composition (e.g., nanoparticles of less than 1 micron or a continuous film) comprising at least one element selected from alkali metal, alkaline earth metal, aluminum, zinc, copper, and silver in combination with at least two elements selected from oxygen, sulfur, silicon, phosphorus, nitrogen, boron, gallium, indium, tin, germanium, arsenic, antimony, bismuth, transition metals, and lanthanides. Also described is a battery comprising an anode, a cathode, and a solid electrolyte (corresponding to the above ionically conductive composition) in contact with or as part of the anode and/or cathode. Further described is a thermal (e.g., plasma-based) method of producing the ionically conductive composition. Further described is a method for using an additive manufacturing (AM) process to produce an object constructed of the ionically conductive composition by use of particles of the ionically conductive composition as a feed material in the AM process.

Kercher, Andrew K.↗
DOE OSTI2023

On Relative Importance of Vehicular and Structural Motions in Defining Electrolyte Transport

Molecular motions of ionic and neutral electrolyte species determine transport properties at the continuum scale. These molecular motions can be classified as vehicular (e.g., cations moving with a solvation shell of neighboring solvent molecules) and structural (e.g., cations hopping from one solvation shell to another) motions. While literature studies have described the presence, and relative importance, of each of these motions in various electrolytes, a clear link to macroscopic transport properties has not been made. We herein establish this link by using the fluctuation-dissipation theorem to develop theoretical expressions connecting the molecular displacements to Stefan-Maxwell diffusivities. To illustrate the usefulness of the proposed equations, we study LiPF 6 in propylene carbonate as an exemplar electrolyte. We show that its transport behavior improves at all concentrations when structural diffusion of cations is promoted. On the other hand, boosting the cation vehicular diffusion negatively affects the concentrated compositions. We extend this understanding to a generalized electrolyte of a salt dissolved in a solvent. Our theory suggests that while structural diffusion influences Stefan-Maxwell diffusivities globally, vehicular diffusion is only relevant under certain conditions. Such guidelines are critical for a bottom-up design of electrolyte transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Identification and Catalysis of the Potential-Limiting Step in Lithium-Sulfur Batteries

The Li-S chemistry is thermodynamically promising for high-density energy storage but kinetically challenging. Over the past few years, many catalyst materials have been developed to improve the performance of Li-S batteries and their catalytic role has been increasingly accepted. However, the classic catalytic behavior, i.e., reduction of reaction barrier, has not been clearly observed. Crucial mechanistic questions, including what specific step is limiting the reaction rate, whether/how it can be catalyzed, and how the catalysis is sustained after the catalyst surface is covered by solid products, remain unanswered. Herein, we report the first identification of the potential-limiting step of Li-S batteries operating under lean electrolyte conditions and its catalysis that conforms to classic catalysis principles, where the catalyst lowers the kinetic barrier of the potential-limiting step and accelerates the reaction without affecting the product composition. After carefully examining the electrochemistry under lean electrolyte conditions, we update the pathway of the Li-S battery reaction: S 8 solid is first reduced to Li 2 S 8 and Li 2 S 4 molecular species sequentially; the following reduction of Li 2 S 4 to a Li 2 S 2 -Li 2 S solid with an almost constant ratio of 1:4 is the potential-limiting step; the previously believed Li 2 S 2 -to-Li 2 S solid-solid conversion does not occur; the recharging reaction is relatively fast. We further demonstrate that supported cobalt phthalocyanine molecules can effectively catalyze the potential-limiting step. After Li 2 S 2 /Li 2 S buries the active sites, it can self-catalyze the reaction and continue driving the discharging process.

25 ENERGY STORAGE↗
DOE OSTI2025

Electrolyte Vapor Induced Passivation and Transition Metal Redox on Electrode Active Materials

The gaseous environment that battery electrodes are exposed to is critical to their electrochemical performance, and yet, the impact of vapor-phase components in the glovebox is relatively unexplored. In this study, we examine how the surface of Li 4 Ti 5 O 12 and LiFePO 4 composite electrodes evolve upon exposure to 1 M LiPF 6 in ethylene carbonate:dimethyl carbonate electrolyte vapors in an argon-filled glovebox. Spatially resolved X-ray photoemission electron microscopy and X-ray photoelectron spectroscopy reveal that even brief (15 minutes) contact with electrolyte vapor initiates the formation of a LiF film and changes the oxidation state of transition metals at the particle surface. Notably, these modifications occur selectively on active material particles and not on binder or conductive carbon, underscoring the specificity of vapor-induced reactions. Prolonged exposure to electrolyte vapor over the course of 1 week yields thicker, more chemically complex interphases containing both LiF and lithium oxyfluorophosphate species (Li x PO y F z ). Subsequent electrochemical testing shows that vapor-induced passivation layers influence first cycle capacities, lithium (de)insertion overpotentials, and charge-transfer resistance values. In conclusion, these results indicate that vapor–electrode interactions may be a source of variability in electrochemical behavior over time and suggest that other, more reactive electrode materials may also be susceptible to interactions with electrolyte vapor.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Block Copolymer-Templated Synthesis of Fe–Ni–Co-Modified Nanoporous Alumina Films

Despite intense interest in the catalytic potential of transition metal oxide heterostructures, originating from their large surface area and tunable chemistry, the fabrication of well-defined multicomponent oxide coatings with controlled architectures remains challenging. Here, we demonstrate a simple and effective swelling-assisted sequential infiltration synthesis (SIS) strategy to fabricate hierarchically porous multicomponent metal-oxide electrocatalysts with tunable bimetallic composition. A combination of solution-based infiltration (SBI) of transition metals, iron (Fe), nickel (Ni), and cobalt (Co), into a block copolymer (PS73-b-P4VP28) template, followed by vapor-phase infiltration of alumina using sequential infiltration synthesis (SIS), was employed to synthesize porous, robust, conformal and transparent multicomponent metal-oxide coatings like Fe/AlO x , Fe+Ni/AlO x , and Fe+Co/AlO x . Electrochemical assessments for the oxygen evolution reaction (OER) in a 0.1 M KOH electrolyte demonstrated that the Fe+Ni/AlO x composite exhibited markedly superior catalytic activity, achieving an impressive onset potential of 1.41 V and a peak current density of 3.29 mA/cm 2 . This superior activity reflects the well-known synergistic effect of alloying transition metals with a trace of Fe, which facilitates OER kinetics. Overall, our approach offers a versatile and scalable path towards the design of stable and efficient catalysts with tunable nanostructures, opening new possibilities for a wide range of electrochemical energy applications.

conformal films↗
DOE OSTI2021

Polyfluorinated carbonate electrolyte for high-voltage lithium batteries

A non-aqueous solvent composition for a lithium battery comprises a fluorinated solvent mixture that consists essentially of a 1,2-difluoroethylene carbonate and a fluoro-substituted dialkyl carbonate in a respective weight ratio of about 1:3 to about 1:1, and optionally up to about 30 wt % of an additional organic solvent. An electrolyte for a lithium ion battery comprises a lithium salt dissolved in a non-aqueous solvent composition comprising the fluorinated solvent mixture.

Zhang, Zhengcheng↗
DOE OSTI2025

Direct Prelithiation of Silicon-Based Composite Electrodes via Island-like Thermal Evaporation

Irreversible losses of Li during solid electrolyte interface (SEI) conditioning is a key contributor to the lower specific capacities observed in silicon-containing Li-ion batteries. Herein, thermal evaporation of between 1 and 20 µm of Li onto Si-based composite anodes has been investigated as a prelithiation method to account for such losses. To account for mechanical strain caused by Li-Si alloying during the deposition, a stainless-steel mesh is applied to the electrodes before prelithiation to form “island-like” deposition on the electrode surface. The open circuit potential was also found to decrease as a function of increased Li evaporation, consistent with the potentials of electrochemically prepared LixSi alloys. Prelithiating to account for irreversible Li losses to SEI formation resulted in full cells with a 15.8% increase in initial coulombic efficiency and a 47.8% reduction in irreversible capacity loss after SEI formation cycling. Subsequent C/3 cycling showed up to a 62.9% increase in specific capacity in prelithiated cells. X-ray photoelectron spectroscopy (XPS) revealed differences in the SEI composition that was formed by electrochemical cycling and reactively formed in prelithiated cells upon exposure to Gen2 + 3% FEC electrolyte. The reactively formed SEI from the spontaneous reaction with lithiated silicon was carbonate-rich while the electrochemical SEI formation showed significantly more LiPFx species, which could play a role in overall cycling performance.

Musgrove, Amanda↗
DOE OSTI2023

Degradation of Lithium Iron Phosphate Sulfide Solid-State Batteries by Conductive Interfaces

The superionic solid-state argyrodite electrolyte Li 6 PS 5 Br can improve lithium and lithium-ion batteries' safety and energy density. Despite many reports validating the conductivity of this electrolyte, it still suffers from passivating electrode degradation mechanisms. At first analysis, lithium iron phosphate (LFP) should be more thermodynamically stable in contact with sulfide electrolytes. However, without substantial improvements to interfacial engineering, we find that LFP is not inherently stable against Li 6 PS 5 Br. We hypothesize argyrodite oxidation favorably competes with LFPAs delithiation, insulating the electrolyte-electrode interface and causing large overpotential losses. We show that compared to LiNi x Mn y Co z O 2 , LFP has no actual electrochemical stability advantage despite operating at a lower voltage. We utilize tender energy XAS and XPS to show that chemical reactions occur between LFP and the Li 6 PS 5 Br solid electrolyte and these reactions are exacerbated by cycling. We also show that electrochemical degradation occurs at the interface between the solid electrolyte ion conductor and any electron conductor, namely the active material and carbon additives. We further demonstrate that LiNbO 3 cathode coatings on LFP can delay electrochemical degradation by electronically insulating the LFP-sulfide electrolyte interface but not prevent its occurrence at the carbon-electrolyte interface.

25 ENERGY STORAGE↗
DOE OSTI2023

A04-0491 - Reduced Electrolyte Reactivity of Pitch-Carbon Coated Si Nanoparticles for Li-Ion Battery Anodes

Silicon-based anodes for Li-ion batteries (LIB) have the potential to increase the energy density over graphite-based LIB anodes. However, silicon anodes exhibit poor cycle and calendar lifetimes due to mechanical instabilities and high chemical reactivity with the carbonate-based electrolytes that are typically used in LIBs. In this work, we synthesize a pitch-carbon coated silicon nanoparticle composite active material for LIB anodes that exhibits reduced chemical reactivity with the carbonate electrolyte compared to an uncoated silicon anode. Silicon primary particle sizes <10 nm minimize micro-scale mechanical degradation of the anode composite, while conformal coatings of pitch-carbon minimized the parasitic reactions between the silicon and the electrolyte. When matched with a high voltage NMC622 cathode, the pitch-carbon coated Si anode retains -75% of its initial capacity over 1000 cycles. Efforts to increase the areal loading of the pitch-carbon coated silicon anodes to realize real energy density improvements over graphite anodes results in severe mechanical degradation on the electrode level. Developing procedures to engineer the architecture of the composite silicon anode may be a solution to this mechanical challenge.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗
DOE OSTI2019

Scalable Freeze-Tape-Casting Fabrication and Pore Structure Analysis of 3D LLZO Solid-State Electrolytes

Nonflammable solid-state electrolytes can potentially address the reliability and energy density limitations of lithium-ion batteries. Garnet-structured oxides such as Li 7 La 3 Zr 2 O 12 (LLZO) are some of the most promising candidates for solid-state devices. Here, three-dimensional (3D) solid-state LLZO frameworks with low tortuosity pore channels are proposed as scaffolds, into which active materials and other components can be infiltrated to make composite electrodes for solid-state batteries. To make the scaffolds, we employed aqueous freeze tape casting (FTC), a scalable and environmentally friendly method to produce porous LLZO structures. Using synchrotron radiation hard X-ray microcomputed tomography, we confirmed that LLZO films with porosities of up to 75% were successfully fabricated from slurries with a relatively wide concentration range. The acicular pore size and shape at different depths of scaffolds were quantified by fitting the pore shapes with ellipses, determining the long and short axes and their ratios, and investigating the equivalent diameter distribution. The results show that relatively homogeneous pore sizes and shapes were sustained over a long range along the thickness of the scaffold. Additionally, these pores had low tortuosity and the wall thickness distributions were found to be highly homogeneous. These are desirable characteristics for 3D solid electrolytes for composite electrodes, in terms of both the ease of active material infiltration and also minimization of Li diffusion distances in electrodes. The advantages of the FTC scaffolds are demonstrated by the improved conductivity of LLZO scaffolds infiltrated with poly(ethylene oxide)/lithium bis(trifluoromethanesulfonyl)imide (PEO/LITFSI) compared to those of PEO/LiTFSI films alone or composites containing LLZO particles.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Asymmetric Composition of Ionic Aggregates and the Origin of High Correlated Transference Number in Water-in-Salt Electrolytes

"Water-in-salt" electrolytes open up exciting new avenues for expanding the electrochemical window of aqueous electrolytes. We investigated the solvation structure and dynamics of highly concentrated lithium bis(trifluoromethane)sulfonimide aqueous electrolyte using experimentally corroborated molecular dynamics simulations. The simulations revealed that the heterogeneous structure of the electrolyte comprises percolating networks of ion and water domains/aggregates. Interestingly, the ionic regions are composed of more TFSI - ions than Li + ions. The Li + -ion transport mechanism was further explored. Li + ions can hop along the coordinated TFSI- ions in the ionic aggregates. The calculated correlated transference number of the 20 m electrolyte is similar to 0.32, which is reasonably high for the high concentration due to a weak negative correlation between the motion of cations and anions within the heterogeneous microscopic domains. These molecular dynamics results connect the heterogeneous structure of the electrolyte to the correlated dynamics of the Li + ion and provide a new understanding of the Li + -ion transport mechanism in this novel electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Operating Stresses and Their Effects on Degradation of LSM-Based SOFC Cathodes

The performance of solid oxides fuel cells (SOFCs) with four different Mn excess of lanthanum strontium manganite (LSM) -based cathodes were examined under different temperatures (1,000 °C, 900 °C), current densities (0, 380, and 760 mA cm -2 ), and cathode atmospheres (p O 2 )=0.1,0.15,0.21) for durations ranging from 58 to 1,008 h. Each yttria-stabilized zirconia (YSZ) electrolyte-supported “button” cell had a porous Ni/YSZ composite anode and a porous LSM/YSZ composite cathode. The cells’ output voltage versus time were recorded and electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) measurements were performed every 24 hours. The total area specific resistance (ASR) was calculated from these measurements. The values of ASR from both EIS and LSV were comparable between each other but lower than that from durability test. Distribution of relaxation times (DRT) analysis was performed to investigate the electrochemical processes and their corresponding relaxation frequencies as well as their attributions to the total ASR. The series resistance and parallel resistance that obtained from the equivalent circuit fit of the Nyquist plot were higher at low temperature and low p O 2 regardless of LSM compositions. The area of the peaks derived from DRT analysis increased with time during individual tests. The microstructures of the tested cells were examined using scanning electron microscopy and energy-dispersive x-ray spectroscopy (SEM/EDS). Manganese oxide particles were observed near the cathode-electrolyte interface after prolonged (1,008 h) testing in air of a cell with LSM of 11% manganese excess, and after a short test (58 h) under low oxygen (p O 2 = 0.10) in a cell with LSM of 5% manganese excess. However, the role of MnOx in cell degradation is still unknown.

08 HYDROGEN↗
DOE OSTI2024

Operando investigations of the solid electrolyte interphase in the lithium mediated nitrogen reduction reaction

The lithium-mediated nitrogen reduction reaction (Li-NRR) represents a promising approach for electrochemical nitrogen activation, in which the solid electrolyte interphase (SEI) layer formed on the electrochemically plated lithium plays a key role. Herein, we used time-resolved, operando, grazing incidence wide-angle X-ray scattering (GI WAXS) to identify SEI species and reaction intermediates in the Li-NRR, comparing LiBF 4 and LiClO 4 as electrolyte salts. In this study, we demonstrated how the SEI composition influences the Li-NRR performance by regulating proton transport to the plated Li. When LiBF 4 is used as the electrolyte salt, the formation of LiF and lithium ethoxide (LiEtO) is observed. Reaction intermediates such as LiH and LiN x H y species were found and provide insight into reaction pathways towards undesired and desired products, respectively. Observed restructuring of the Cu (111) single crystal substrate also indicates interaction with plated Li that could possibly influence the Li-NRR performance. Together, these experiments give molecular insight into how to design Li-NRR systems and their SEI layers for optimal performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Chemical Interplay of Silicon and Graphite in a Composite Electrode in SEI Formation

In this study, we investigated the effect of the Si/graphite weight ratio in half-cells on the solid electrolyte interphase (SEI) layer's chemistry. The nominal concentrations of active materials were (wt % Si/wt % Gr) 15/73, 30/58, 60/28, and 80/0. The electrolyte in the cells consisted of either 1.2 M LiPF 6 in ethylene carbonate/ethyl methyl carbonate (3:7 by wt) or 1.2 M LiPF 6 in ethylene carbonate:ethyl methyl carbonate (3:7 by wt) + 10 wt % fluoroethylene carbonate. These coin cells were cycled five times at the C/10 rate. As expected, the addition of silicon to the electrode significantly increased the measured capacity. Examination of the aged composite material showed that the electrolyte influenced the concentration of chemical environments on the surface. Depth profiling revealed that these concentrations of surface environments changed with sputtering time. A statistics-of-mixtures model was used to deconvolute how silicon and graphite interacted during the formation of these species and how the interaction changed with depth.

25 ENERGY STORAGE↗
DOE OSTI2023

Pitch Carbon-coated Ultrasmall Si Nanoparticle Lithium-ion Battery Anodes Exhibiting Reduced Reactivity with Carbonate-based Electrolyte

Silicon anodes for lithium-ion batteries (LIBs) have the potential for higher energy density compared to conventionally used graphite-based LIB anodes. However, silicon anodes exhibit poor cycle and calendar lifetimes due to mechanical instabilities and high chemical and electrochemical reactivity with the carbonate-based electrolytes that are typically used in LIBs. In this work, we synthesize a pitch carbon-coated silicon nanoparticle composite active material for LIB anodes that exhibits reduced chemical reactivity with carbonate-based electrolytes compared to an uncoated silicon anode. Silicon primary particle sizes less than 10 nm diameter minimize micro-scale mechanical degradation of the anode composite, while conformal coatings of pitch carbon minimize the parasitic reactions between the silicon and the electrolyte. When matched with a high voltage NMC622 (LiNi 0.6 Mn 0.2 Co 0.2 O 2 ) cathode, the pitch carbon-coated silicon anode retains approximately 75% of its initial capacity at the end of 1000 cycles. Increasing the areal loading of the pitch carbon-coated silicon anodes to realize energy density improvements over graphite anodes results in severe mechanical degradation on the electrode level, highlighting a remaining challenge to be addressed in future work.

25 ENERGY STORAGE↗
DOE OSTI2022

Co-intercalation-free ether electrolytes for graphitic anodes in lithium-ion batteries

Carbonate-based electrolytes are widely used in Li-ion batteries but are limited by a small operating temperature window and poor cycling with silicon-containing graphitic anodes. The lack of non-carbonate electrolyte alternatives such as ether-based electrolytes is due to undesired solvent co-intercalation that occurs with graphitic anodes. Here, we show that fluoroethers are the first class of ether solvents to intrinsically support reversible lithium-ion intercalation into graphite without solvent co-intercalation at conventional salt concentrations. In full cells using a graphite anode, they enable 10-fold higher energy densities compared to conventional ethers, and better thermal stability over carbonate electrolytes (operation up to 60 °C) by producing a robust solvent-derived solid electrolyte interphase (SEI). As single-solvent–single-salt electrolytes, they remarkably outperform carbonate electrolytes with fluoroethylene carbonate (FEC) and vinylene carbonate (VC) additives when cycled with graphite–silicon composite anodes. In conclusion, our molecular design strategy opens a new class of electrolytes that can enable next generation Li-ion batteries with higher energy density and a wider working temperature window.

25 ENERGY STORAGE↗
DOE OSTI2026

Understanding Discharge‐Driven Growth of Cathode Impedance in Ni‐Rich NMC Cathodes

Degradation of LiNi x Mn y Co 1-x-y O 2 (NMC)-based lithium-ion batteries depends strongly on cut-off voltage ranges. In addition to the high upper cut-off voltage, a high depth of discharge (i.e., lower cut-off voltage) significantly worsens cathode impedance growth and capacity fade during long-term cycling. However, there is currently no consensus on the mechanism behind the negative role of a deep discharge. Here, this phenomenon was investigated in graphite||NMC cells with single-crystal cathodes (LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC622) or LiNi 0.76 Co 0.14 Mn 0.10 O 2 (NMC76)) using targeted aging protocols (constant high-voltage holds vs. charge–discharge cycling), while monitoring transition-metal (TM) dissolution, cathode-electrolyte interface (CEI) impedance, and NMC surface composition. We demonstrate a correlation between discharge-driven CEI impedance growth and increased TM dissolution. Furthermore, this degradation pathway is more pronounced in lower-Ni NMC622 than in higher-Ni (NMC76) under comparable delithiation states at charge, with both compositions undergoing the H2→H3 phase transition. X-ray photoelectron spectroscopy (XPS) reveals NMC composition-dependent evolution of surface lattice oxygen and restructured surface layer composition between charged and discharged states. These findings add mechanistic depth to the role of discharge as an active driver of interfacial degradation and provide new insights into its composition dependence.

25 ENERGY STORAGE↗