Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “electrolyte additives”

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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Redesigning Photoelectrodes So They Can Work in the Light and Dark

Unassisted photoelectrochemical (PEC) reactions, such as H2 generation and CO2 reduction, are limited by the durability of the immersed photoelectrode. Small band gap semiconductors, like Si, are efficient at utilizing a large portion of the solar spectrum but are not stable in aqueous environments without protection. While great strides have been made to improve stability under constant illumination, dark stability remains relatively unexamined and presents great challenges for durable PEC systems. Cathodic protection is an established electrochemical method for preventing metal electrode degradation in harsh conditions. Similar protection strategies cannot be applied to traditional two-terminal (2T) semiconductor photoelectrodes because of their inability to pass reverse bias current in the dark. New, three-terminal (3T) photovoltaic (PV) architectures introduce additional degrees of freedom in traditional 2T PEC operations by adding an extra electrical contact for an alternative low resistance path to protect the photoelectrode and drive electrochemical reactions, even in the dark. Here, we investigate bare 3T Si PV devices operating as photocathodes in aqueous methyl viologen electrolyte. The 3T architecture provides additional capabilities to PEC systems such as cathodic protection, the ability to drive reactions with or without illumination, and in situ switching between different operational modes. We show that 3T-based Si photocathodes maintain PEC activity after several hours of light/dark cycling. This work helps advance PEC use in real-world conditions where variable illumination must be considered.

cathodic protection↗
DOE OSTI2024

Solid Electrolyte Interphase Formation at the Ionic Liquid Electrolyte—Lithium-Metal Interface Using an Ab Initio Molecular Dynamics Approach

An interfacial study is performed using ab initio molecular dynamics (AIMD) simulations to elucidate the electrochemical interfacial stability of an ionic liquid (IL) as component of an electrolyte in contact with a Li-metal anode when an additive, vinylene carbonate (VC), is added to the electrolyte. The IL electrolyte is composed of 1-butyl-1-methylpyrrolidinium bis(fluoro-sulfonyl)-imide (PYR14 + FSI − ) with lithium bis(trifluoromethane-sulfonyl)imide salt (Li + TFSI − ) in a 8:2 concentration ratio. Reactions observed at the interface electrolyte/Li-metal during the AIMD simulations are verified by electronic structure calculations using density functional theory calculations considering a continuum solvent model. We found that the addition of VC to the IL prevents further reduction of the counter-ion TFSI − and retards reduction of FSI − in comparison to the case when the additive VC is absent. The PYR14 + reduction is never observed with or without the additive. The 1st, 2nd, and 3rd electron affinities of the PYR14 + are −0.08, −0.36 and −3.65 eV, indicating little to large repulsive behavior against electrons. The opposite is observed for the two negative ions, FSI − and TFSI − , which yield 1st electron affinities of 1.73 and 1.83 eV, respectively. Reactions obtained under open circuit conditions. Dissociation mechanisms are presented for all IL components reduced at the IL/Li-metal interface.

Electrochemistry↗
DOE OSTI2024

The Impact of Lithium Anode Interface on Capacity Fade in Polymer Electrolyte-Based Solid-State Batteries

This study investigates the Li stripping-plating morphology and failure mechanisms in full cells consisting of a solid polymer electrolyte (SPE) with two commercial Li anodes: Li chip and Li foil. The primary identified failure mechanism of the SPE cell is capacity fade, regardless of the Li manufacturer. While the cathode’s role in capacity fade is evident, the Li anode significantly influences cycling performance, with Li foil cells cycling 50% longer than Li chip cells, a statistical difference. Further, post-mortem scanning electron microscopy and X-ray photoelectron spectroscopy results attribute the Li chip’s faster capacity fade to a loss of contact and continuous growth of the solid electrolyte interphase (SEI). Conversely, Li foil maintains consistent contact with the solid polymer, displaying a thin and stable SEI. Additionally, failure mechanisms between a gel electrolyte in previous work and the dry SPE are compared.

25 ENERGY STORAGE↗
DOE OSTI2021

Role of Electrolyte in Overcoming the Challenges of LiNiO 2 Cathode in Lithium Batteries

LiNiO 2 (LNO) is a high-capacity and model cathode first discovered in the 1980s that fell out of favor due to its intrinsic instabilities. However, research activities toward LNO are once again on the rise as the push for higher-energy-density cells marches on. Here we demonstrate here that with appropriate modern electrolytes, major performance improvements can be achieved with LNO with no additional modifications. Cells with a localized high concentration electrolyte (LHCE) deliver 92% capacity retention after 200 cycles compared with 56% capacity retention in a baseline carbonate electrolyte, maintain 94% capacity after high-voltage storage compared with 77% capacity, and display a higher onset temperature of thermal runaway of 244 °C compared with 188 °C. These improvements are attributed to the LHCE’s high oxidative stability and its formation of fluorine-rich interphases. Although further characterization of this new class of electrolyte is necessary, this work demonstrates that modern electrolytes can be drop-in enablers of high-capacity, long-cycle-life cells.

25 ENERGY STORAGE↗
DOE OSTI2022

Modeling Chemo-Mechanics with Electrolyte Infiltration to Quantify Degradation of Cathode Particles

One of the main goals in modeling lithium-ion batteries is to improve/predict longevity and resilience of new chemistries. To that end, this talk investigates the formation of stress-induced fracture within polycrystalline cathode particles and the impact on capacity loss. Physically based cathode aging dynamics is simulated in a 3D, continuum-level chemo-mechanical model. The model captures anisotropic Li diffusion within a single polycrystalline particle comprised of hundreds to thousands of randomly oriented grains. A recent addition to this model includes electrolyte infiltration, which occurs when the electrolyte seeps into surface cracks within the particle. The model predicts that particle fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. Essentially, when neighboring grains are misaligned, they expand a different rates relative to one another leading to high stresses and ultimately the formation of intraparticle cracks. The model predicts that small particles with large grains develop significantly less damage than larger particles with small grains. Finally, the model predicts most of the chemo-mechanical damage accumulates in the first charge after formation. This chemo-mechanical "damage saturation" effect indicates that initial particle fracture occurs within the first few cycles, while long-term cathode degradation is not solely chemo-mechanically induced. The principle contribution of this research is the use of an anisotropic chemo-mechanical model to test how particle geometry affect capacity fade, which predicts that particle size has a stronger effect on capacity fade than grain size and ultimately that small particles with large grains have the least capacity fade.

cathode↗
DOE OSTI2021

Mechanisms of Water-Stimulated Mg 2+ Intercalation in Vanadium Oxide: Toward the Development of Hydrated Vanadium Oxide Cathodes for Mg Batteries

As lithium-ion batteries approach their theoretical limits for energy density, magnesium-ion batteries are emerging as a promising next-generation energy storage technology. However, progress in magnesium-ion battery research has been stymied by a lack of available high capacity cathode materials that can reversibly insert magnesium ions. Vanadium Oxide (V 2 O 5 ) has emerged as one of the more promising candidate cathode materials, owing to its high theoretical capacity, facile synthesis methods, and relatively high operating voltage. This review focuses on the outlook of hydrated V 2 O 5 structures as a high capacity cathode material for magnesium-ion batteries. In general, V 2 O 5 structures exhibit poor experimental capacity for magnesium-ion insertion due to sluggish magnesium-ion insertion kinetics and poor electronic conductivity. However, several decades ago, it was discovered that the addition of water to organic electrolytes significantly improves magnesium-ion insertion into V 2 O 5 . This review clarifies the various mechanisms that have been used to explain this observation, from charge shielding to proton insertion, and offers an alternative explanation that examines the possible role of structural hydroxyl groups on the V 2 O 5 surface. While the mechanism still needs to be further studied, this discovery fueled new research into V 2 O 5 electrodes that incorporate water directly as a structural element. The most promising of these hydrated V 2 O 5 materials, many of which incorporate conductive additives, nanostructured architectures, and thin film morphologies, are discussed. Ultimately, however, these hydrated V 2 O 5 structures still face a significant barrier to potential applications in magnesium-ion batteries. During full cell electrochemical cycling, these hydrated structures tend to leach water into the electrolyte and passivate the surface of the magnesium anode, leading to poor cycle life and low capacity retention. Recently, some promising strides have been made to remedy this problem, including the use of artificial solid electrolyte interphase layers as an anode protection scheme, but a call to action for more anode protection strategies that are compatible with trace water and magnesium metal is required.

25 ENERGY STORAGE↗
DOE OSTI2024

Lithium-ion hopping weakens thermal stability of LiPF 6 carbonate electrolytes

Lithium hexafluorophosphate (LiPF 6 )-based carbonate electrolytes are widely used in commercial lithium-ion batteries (LIBs), but their thermal instability limits the cycle life and safety of LIBs at elevated temperatures. Few studies have yielded insight into the initial PF 6 — decomposition reaction that promotes thermal instability of LiPF6-based electrolytes. Here, we find that lithium-ion hopping assisted by the overall reorientational motion of propylene carbonate molecules facilitates PF 6 — decomposition at elevated temperatures in 1 M LiPF 6 /propylene carbonate electrolyte. Further, we demonstrate that urea additives, by preventing lithium-ion hopping, suppress the initial LiPF 6 decomposition reaction and enhance the thermal stability of the electrolyte. LIB cell tests with LiNi 0.6 Mn 0.2 Co 0.2 O 2 ||Li 4 Ti 5 O 12 show improved LIB performance at elevated temperatures with the thermally stabilized electrolyte. This study provides key insights into the design of thermally stable LiPF 6 -based carbonate electrolytes for improving the cycle life, calendar life, and safety of LIBs in elevated-temperature applications.

25 ENERGY STORAGE↗
DOE OSTI2025

Fast-Charging Li-Ion Battery Enabled by an Acetonitrile-Based Electrolyte

Fast charging remains a critical challenge for current-generation lithium-ion batteries (LIBs), particularly in electric vehicle applications. Here, in this study, we present a highly conductive electrolyte formulation based on a ternary solvent system consisting of acetonitrile (AN), fluoroethylene carbonate (FEC), and ethylene carbonate (EC), combined with a tailored additive, lithium difluoro­(oxalato)­borate (LiDFOB). This electrolyte demonstrates significantly enhanced ionic conductivity and a higher Li + transference number, enabling accelerated Li + transport kinetics. The synergistic effect of the solvents and the additive promotes the formation of a robust, low-resistance, inorganic-rich solid-electrolyte-interphase (SEI) that effectively passivates the graphite surface and suppresses AN decomposition. As a result, the electrolyte substantially reduces internal cell resistance and overpotential, both of which are critical for reliable fast charging. These findings highlight the essential role of rational electrolyte design in addressing the limitations of fast-charging LIBs.

Wu, Dezhen [Argonne National Laboratory (ANL), Arg↗
DOE OSTI2024

Weakly solvating ester electrolyte for high voltage sodium-ion batteries

Ethyl acetate (EA) was identified as a promising electrolyte solvent for sodium-ion batteries (SIBs), exhibiting low viscosity, cost-effectiveness, and low toxicity. Despite a significant portion of aggregation being linked to the weak solvation of Na + /EA as revealed by molecular dynamics (MD) simulations, pulsed-field gradient nuclear magnetic resonance (pfg-NMR) analysis identified a noteworthy Na+ diffusion coefficient of 3.95×10 -10 m 2 s -1 at 25°C in the presence of 1 m NaPF 6 salt. Employing fluoroethylene carbonate (FEC) as a film-forming additive to create electrode-electrolyte interphase, this electrolyte surprisingly made ~210 mAh Na 0.97 Ca 0.03 [Mn 0.39 Fe 0.31 Ni 0.22 Zn 0.08 ]O 2 (NCMFNZO)/hard carbon (HC) pouch cells achieve a lengthy cycling lifetime of 250 cycles with ~80 % capacity retention, cycled up to 4.0 V at 40°C. X-ray photoelectron spectroscopy (XPS) revealed increasing interphasial organic species over cycling, augmenting charge transfer resistance on both cathode and anode, particularly during fast charging or low temperatures (<10°C), promoting Na plating. Finally, gas chromatography-mass spectrometry combined with density functional theory identified CO 2 as the major gas generated from charged cathode/electrolyte interactions, exhibiting temperature/voltage dependence.

25 ENERGY STORAGE↗
DOE OSTI2022

Redox-homogeneous, gel electrolyte-embedded high-mass-loading cathodes for high-energy lithium metal batteries

Lithium metal batteries have higher theoretical energy than their Li-ion counterparts, where graphite is used at the anode. However, one of the main stumbling blocks in developing practical Li metal batteries is the lack of cathodes with high-mass-loading capable of delivering highly reversible redox reactions. To overcome this issue, here we report an electrode structure that incorporates a UV-cured non-aqueous gel electrolyte and a cathode where the LiNi 0.8 Co 0.1 Mn 0.1 O 2 active material is contained in an electron-conductive matrix produced via simultaneous electrospinning and electrospraying. This peculiar structure prevents the solvent-drying-triggered non-uniform distribution of electrode components and shortens the time for cell aging while improving the overall redox homogeneity. Moreover, the electron-conductive matrix eliminates the use of the metal current collector. When a cathode with a mass loading of 60 mg cm -2 is coupled with a 100 µm thick Li metal electrode using additional non-aqueous fluorinated electrolyte solution in lab-scale pouch cell configuration, a specific energy and energy density of 321 Wh kg -1 and 772 Wh L -1 (based on the total mass of the cell), respectively, can be delivered in the initial cycle at 0.1 C (i.e., 1.2 mA cm -2 ) and 25 °C.

25 ENERGY STORAGE↗
DOE OSTI2022

Enabling Non-Carbonate Electrolytes for Silicon Anode Batteries Using Fluoroethylene Carbonate

Silicon is considered as one of the most promising anodes for next generation lithium-ion batteries, due to its high theoretical capacity and energy density. However, many technical barriers remain to its implementation, due to its high chemical/electrochemical reactivities with standard electrolytes and incomplete passivation. In this work, we take the most effective passivating additive of fluoroethylene carbonate (FEC) and study its impact on non-carbonate electrolytes. Our results indicate that esters and ureas-based electrolytes are similarly stabilized by FEC, and have very similar capacity retentions and Coulombic efficiencies to the state-of-the-art carbonate electrolyte. This study indicates the discovery of more efficient additives other than FEC is vital in developing an electrolyte that can successfully enable a silicon-anode battery.

25 ENERGY STORAGE↗
DOE OSTI2022

Dynamic Structure Discovery Applied to the Ion Transport in the Ubiquitous Lithium-ion Battery Electrolyte LP30

The electrolytes of the today omnipresent lithium-ion batteries (LIBs) have for more than 25 years been based upon 1 M LiPF 6 in a 50:50 EC:DMC mixture—commonly known as LP30. The success of the basic design of the LP30 electrolyte, with many variations and additions made over the years, is unchallenged. Yet, some molecular level fundamentals of LP30 are surprisingly elusive: the structure of the first solvation shell of the Li + cation is still a topic of current debate; the details of the dynamics are not fully understood; the interpretation of structural and dynamic properties is highly dependent on the analysis methods used; the contributions by different species to the ion transport and the energetics involved are not established. We here apply dynamic structure discovery analysis as implemented in CHAMPION to molecular dynamics simulation trajectories to bring new light on the structure and dynamics within LP30 and especially the (Li + ) ion transport to rationalize further development of LIB electrolytes.

25 ENERGY STORAGE↗
NASA NTRS2007

Portable Apparatus for Electrochemical Sensing of Ethylene

A small, lightweight, portable apparatus based on an electrochemical sensing principle has been developed for monitoring low concentrations of ethylene in air. Ethylene has long been known to be produced by plants and to stimulate the growth and other aspects of the development of plants (including, notably, ripening of fruits and vegetables), even at concentrations as low as tens of parts per billion (ppb). The effects are magnified in plant-growth and -storage chambers wherein ethylene can accumulate. There is increasing recognition in agriculture and related industries that it is desirable to monitor and control ethylene concentrations in order to optimize the growth, storage, and ripening of plant products. Hence, there are numerous potential uses for the present apparatus in conjunction with equipment for controlling ethylene concentrations. The ethylene sensor is of a thick-film type with a design optimized for a low detection limit. The sensor includes a noble metal sensing electrode on a chip and a hydrated solid-electrolyte membrane that is held in contact with the chip. Also located on the sensor chip are a counter electrode and a reference electrode. The sensing electrode is held at a fixed potential versus the reference electrode. Detection takes place at active-triple-point areas where the sensing electrode, electrolyte, and sample gas meet. These areas are formed by cutting openings in the electrolyte membrane. The electrode current generated from electrochemical oxidation of ethylene at the active triple points is proportional to the concentration of ethylene. An additional film of the solid-electrolyte membrane material is deposited on the sensing electrode to increase the effective triple-point areas and thereby enhance the detection signal. The sensor chip is placed in a holder that is part of a polycarbonate housing. When fully assembled, the housing holds the solid-electrolyte membrane in contact with the chip (see figure). The housing includes a water reservoir for keeping the solid-electrolyte membrane hydrated. The housing also includes flow channels for circulating a sample stream of air over the chip: ethylene is brought to the sensing surface predominately by convection in this sample stream. The sample stream is generated by a built-in sampling pump. The forced circulation of sample air contributes to the attainment of a low detection limit.

Manoukian, Mourad↗
DOE OSTI2020

Femtosecond Laser Additive Manufacturing of Multi-Material Layered Structures

Laser additive manufacturing (LAM) of a multi-material multi-layer structure was investigated using femtosecond fiber lasers. A thin layer of yttria-stabilized zirconia (YSZ) and a Ni–YSZ layer were additively manufactured to form the electrolyte and anode support of a solid oxide fuel cell (SOFC). A lanthanum strontium manganite (LSM) layer was then added to form a basic three layer cell. This single step process eliminates the need for binders and post treatment. Parameters including laser power, scan speed, scan pattern, and hatching space were systematically evaluated to obtain optimal density and porosity. This is the first report to build a complete and functional fuel cell by using the LAM approach.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A high-performance organic cathode customized for sulfide-based all-solid-state batteries

All-solid-state batteries (ASSBs) have become increasingly attractive recently due to their better safety and prospective long-term stability compared with conventional liquid batteries. However, obtaining a sustainable cathode candidate to match the solid electrolyte with regards to operating potential, chemical compatibility, and mechanical property is still an open challenge. In this work, the chemical incompatibility of quinone-based active materials and sulfide-based electrolyte were unveiled for the first time through a heteroconjugate addition reaction mechanism. To develop a quinone cathode customized for sulfide-based ASSBs, poly-(anthraquinonyl sulfide)-graphene (PAQS-G) nanocomposite was reported. The stable polymer framework of PAQS can protect the quinone redox center by preventing nucleophilic attack from sulfide-based solid electrolytes. The graphene additives can ameliorate redox kinetics and improve active material utilization. The PAQS-G cathode exhibited a specific capacity of ~178 mAh g -1 and a high material utilization of ~79%. Excellent cycling stability was achieved with 94 % capacity after 200 cycles in lithium batteries and 95.5 % capacity after 300 cycles in sodium batteries at 0.1C rate, respectively. A promising potential for energy storage applications was demonstrated.

25 ENERGY STORAGE↗
DOE OSTI2021

Essential effect of the electrolyte on the mechanical and chemical degradation of LiNi 0.8 Co 0.15 Al 0.05 O 2 cathodes upon long-term cycling

Capacity fading during long-term cycling (>1500×) is still a critical challenge for Li-ion batteries that use Ni-rich layered oxides, e.g. LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA), as the cathode. Microcracks have been previously recognized as one of the primary reasons for the observed capacity fade. Although there exists a generally developed mechanical understanding of microcracks, the role of the electrolyte has not been clearly understood, especially after extended cycling and at the atomic scale. Here, we unveil the microstructural evolution of spherical NCA secondary particles after long-term cycling using scanning transmission electron microscopy accompanied with electron energy loss spectroscopy. In this work, we found that the microcracks initiated and grew through grain boundaries, which then serve as the pathway for electrolyte penetration into secondary NCA particles. Additionally, the rock-salt phase reconstruction is prone to occur at the (003) surfaces of the primary particles or the crack surfaces, largely due to electrolyte (LiPF 6 EC/EMC) corrosion. Crack propagation within the NCA grains is primarily a joint consequence from electrolyte corrosion and mechanical strain during lithiation/delithiation. During extended cycling, due to the distinctive surface facets, the primary grains located in the center of the secondary particles experience more intensive electrolyte corrosion, leading to a reduced contact with nearby particles, impairing the overall capacity. These results establish the initiation and growth mechanism of microcracks and voids in NCA-based cathodes during cycling and point out the role of the electrolyte in affecting the degradation of NCA-based cathodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Annulated tetra-substituted hydroquinone ether-based redox shuttle additives for lithium-ion batteries

An electrolyte for a lithium-ion electrochemical cell comprises a non-aqueous solution of a lithium salt and a redox shuttle compound, wherein the redox shuttle compound comprises —OR groups at carbons 1 and 4 of a benzene ring; a first hydrocarbon ring fused to carbons 2 and 3 of the benzene ring; and a second hydrocarbon ring fused to the carbons 5 and 6 of the benzene ring, wherein either (i) the first and second hydrocarbon rings together with the benzene ring constitute two fused benzobicyclo[2.2.2]octane ring systems sharing a common benzo core group; or (ii) the first and second hydrocarbon rings together with the benzene ring constitute two fused benzobicyclo[2.2.1]heptane ring systems sharing a common benzo core group.

25 ENERGY STORAGE↗