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Probing the Na metal solid electrolyte interphase via cryo-transmission electron microscopy.

ABSTRACT: Cryogenic transmission electron microscopy (cryo-TEM) is a valuable tool recently proposed to investigate battery electrodes. Despite being employed for Li-based battery materials, cryo-TEM measurements for Na-based electrochemical energy storage systems are not commonly reported. In particular, elucidating the chemical and morphological behavior of the Na-metal electrode in contact with a non-aqueous liquid electrolyte solution could provide useful insights that may lead to a better understanding of metal cells during operation. Here, using cryo-TEM, we investigate the effect of fluoroethylene carbonate (FEC) additive on the solid electrolyte interphase (SEI) structure of a Na-metal electrode. Without FEC, the NaPF₆-containing carbonate-based electrolyte reacts with the metal electrode to produce an unstable SEI, rich in Na₂CO₃ and Na₃PO₄, which constantly consumes the sodium reservoir of the cell during cycling. When FEC is used, the Na-metal electrode forms a multilayer SEI structure comprising an outer NaF-rich amorphous phase and an inner Na₃PO₄ phase. This layered structure stabilizes the SEI and prevents further reactions between the electrolyte and the Na metal.

SUBMITTER: Han B

PROVIDER: S-EPMC8144392 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Lithium metal stripping beneath the solid electrolyte interphase.

Project description:Lithium stripping is a crucial process coupled with lithium deposition during the cycling of Li metal batteries. Lithium deposition has been widely studied, whereas stripping as a subsurface process has rarely been investigated. Here we reveal the fundamental mechanism of stripping on lithium by visualizing the interface between stripped lithium and the solid electrolyte interphase (SEI). We observed nanovoids formed between lithium and the SEI layer after stripping, which are attributed to the accumulation of lithium metal vacancies. High-rate dissolution of lithium causes vigorous growth and subsequent aggregation of voids, followed by the collapse of the SEI layer, i.e., pitting. We systematically measured the lithium polarization behavior during stripping and find that the lithium cation diffusion through the SEI layer is the rate-determining step. Nonuniform sites on typical lithium surfaces, such as grain boundaries and slip lines, greatly accelerated the local dissolution of lithium. The deeper understanding of this buried interface stripping process provides beneficial clues for future lithium anode and electrolyte design.

| S-EPMC6112724 | biostudies-literature

Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery.

Project description:Solid-state electrolytes (SSEs) are receiving great interest because their high mechanical strength and transference number could potentially suppress Li dendrites and their high electrochemical stability allows the use of high-voltage cathodes, which enhances the energy density and safety of batteries. However, the much lower critical current density and easier Li dendrite propagation in SSEs than in nonaqueous liquid electrolytes hindered their possible applications. Herein, we successfully suppressed Li dendrite growth in SSEs by in situ forming an LiF-rich solid electrolyte interphase (SEI) between the SSEs and the Li metal. The LiF-rich SEI successfully suppresses the penetration of Li dendrites into SSEs, while the low electronic conductivity and the intrinsic electrochemical stability of LiF block side reactions between the SSEs and Li. The LiF-rich SEI enhances the room temperature critical current density of Li3PS4 to a record-high value of >2 mA cm-2. Moreover, the Li plating/stripping Coulombic efficiency was escalated from 88% of pristine Li3PS4 to more than 98% for LiF-coated Li3PS4. In situ formation of electronic insulating LiF-rich SEI provides an effective way to prevent Li dendrites in the SSEs, constituting a substantial leap toward the practical applications of next-generation high-energy solid-state Li metal batteries.

| S-EPMC6303121 | biostudies-other

Effective Solid Electrolyte Interphase Formation on Lithium Metal Anodes by Mechanochemical Modification.

Project description:Lithium metal batteries are gaining increasing attention due to their potential for significantly higher theoretical energy density than conventional lithium ion batteries. Here, we present a novel mechanochemical modification method for lithium metal anodes, involving roll-pressing the lithium metal foil in contact with ionic liquid-based solutions, enabling the formation of an artificial solid electrolyte interphase with favorable properties such as an improved lithium ion transport and, most importantly, the suppression of dendrite growth, allowing homogeneous electrodeposition/-dissolution using conventional and highly conductive room temperature alkyl carbonate-based electrolytes. As a result, stable cycling in symmetrical Li∥Li cells is achieved even at a high current density of 10 mA cm-2. Furthermore, the rate capability and the capacity retention in NMC∥Li cells are significantly improved.

| S-EPMC8397250 | biostudies-literature

Plating and Stripping Calcium Metal in Potassium Hexafluorophosphate Electrolyte toward a Stable Hybrid Solid Electrolyte Interphase

Project description:The use of calcium

| S-EPMC10091900 | biostudies-literature

Effects of Atmospheric Gases on Li Metal Cyclability and Solid-Electrolyte Interphase Formation.

Project description:For Li-air batteries, dissolved gas can cross over from the air electrode to the Li metal anode and affect the solid-electrolyte interphase (SEI) formation, a phenomenon that has not been fully characterized. In this work, the impact of atmospheric gases on the SEI properties is studied using electrochemical methods and ex situ characterization techniques, including X-ray photoelectron spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The presence of O2 significantly improved the lithium cyclability; less lithium is consumed to form the SEI or is lost because of electrical disconnects. However, the SEI resistivity and plating overpotentials increased. Lithium cycled in an "air-like" mixed O2/N2 environment also demonstrated improved cycling efficiency, suggesting that dissolved O2 participates in electrolyte reduction, forming a homogeneous SEI, even at low concentrations. The impact of gas environments on Li metal plating and SEI formation represents an additional parameter in designing future Li-metal batteries.

| S-EPMC7155172 | biostudies-literature

Bi-containing Electrolyte Enables Robust and Li Ion Conductive Solid Electrolyte Interphase for Advanced Lithium Metal Anodes.

Project description:The notorious lithium dendrite growth, causing the safety concern, hinders the practical application of high-capacity Li metal anodes for rechargeable batteries. Here, a robust and highly ionic conductive solid electrolyte interphase (SEI) layer to protect Li metal anode is in-situ constructed by introducing trace additive of tetrapotassium heptaiodobismuthate (K4BiI7) into electrolyte. The K4BiI7-added electrolyte enables Li metal anode to display a stable cycling for over 600 cycles at 1.0 mA cm-2/1.0 mAh cm-2 and over 400 cycles at 5.0 mA cm-2/5.0 mAh cm-2. In situ optical microscopy observations also conform the suppression of Li dendrites at high current density. Moreover, the in-situ SEI layer modified Li anode exhibits an average Coulombic efficiency of 99.57% and less Li dendrite growth. The Li-S full sells with the modified electrolyte also show improved electrochemical performance. This research provides a cost-efficient method to achieve a highly ionic conductive and stable SEI layer toward advanced Li metal anodes.

| S-EPMC6990125 | biostudies-literature

Cryo-electron microscopy structure of the Slo2.2 Na(+)-activated K(+) channel.

Project description:Na(+)-activated K(+) channels are members of the Slo family of large conductance K(+) channels that are widely expressed in the brain, where their opening regulates neuronal excitability. These channels fulfil a number of biological roles and have intriguing biophysical properties, including conductance levels that are ten times those of most other K(+) channels and gating sensitivity to intracellular Na(+). Here we present the structure of a complete Na(+)-activated K(+) channel, chicken Slo2.2, in the Na(+)-free state, determined by cryo-electron microscopy at a nominal resolution of 4.5 ångströms. The channel is composed of a large cytoplasmic gating ring, in which resides the Na(+)-binding site and a transmembrane domain that closely resembles voltage-gated K(+) channels. In the structure, the cytoplasmic domain adopts a closed conformation and the ion conduction pore is also closed. The structure reveals features that can explain the unusually high conductance of Slo channels and how contraction of the cytoplasmic gating ring closes the pore.

| S-EPMC4886347 | biostudies-literature

Tailoring the Preformed Solid Electrolyte Interphase in Lithium Metal Batteries: Impact of Fluoroethylene Carbonate.

Project description:The film-forming electrolyte additive/co-solvent fluoroethylene carbonate (FEC) can play a crucial role in enabling high-energy-density lithium metal batteries (LMBs). Its beneficial impact on homogeneous and compact lithium (Li) deposition morphology leads to improved Coulombic efficiency (CE) of the resulting cell chemistry during galvanostatic cycling and consequently an extended cell lifetime. Herein, the impact of this promising additive/co-solvent on selected properties of LMBs is systematically investigated by utilizing an in-house developed lithium pretreatment method. The results reveal that as long as FEC is present in the organic carbonate-based electrolyte, a dense mosaic-like lithium morphology of Li deposits with a reduced polarization of only 20 mV combined with a prolonged cycle life is achieved. When the pretreated Li electrodes with an FEC-derived preformed SEI (pSEI) are galvanostatically cycled with the FEC-free electrolyte, the described benefits induced by the additive are not observable. These results underline that the favorable properties of the FEC-derived SEI are beneficial only if there is unreacted FEC in the electrolyte formulation left to constantly reform the interphase layer, which is especially important for anodes with high-volume changes and dynamic surfaces like lithium metal and lithiated silicon.

| S-EPMC10685346 | biostudies-literature

Nanoarchitecture factors of solid electrolyte interphase formation via 3D nano-rheology microscopy and surface force-distance spectroscopy.

Project description:The solid electrolyte interphase in rechargeable Li-ion batteries, its dynamics and, significantly, its nanoscale structure and composition, hold clues to high-performing and safe energy storage. Unfortunately, knowledge of solid electrolyte interphase formation is limited due to the lack of in situ nano-characterization tools for probing solid-liquid interfaces. Here, we link electrochemical atomic force microscopy, three-dimensional nano-rheology microscopy and surface force-distance spectroscopy, to study, in situ and operando, the dynamic formation of the solid electrolyte interphase starting from a few 0.1 nm thick electrical double layer to the full three-dimensional nanostructured solid electrolyte interphase on the typical graphite basal and edge planes in a Li-ion battery negative electrode. By probing the arrangement of solvent molecules and ions within the electric double layer and quantifying the three-dimensional mechanical property distribution of organic and inorganic components in the as-formed solid electrolyte interphase layer, we reveal the nanoarchitecture factors and atomistic picture of initial solid electrolyte interphase formation on graphite-based negative electrodes in strongly and weakly solvating electrolytes.

| S-EPMC10006426 | biostudies-literature

Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries.

Project description:Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g-1) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as "plasticizer" in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% over 400 cycles at a current density of 2 mA cm-2). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes.The practical application of lithium metal anodes suffers from the poor Coulombic efficiency and growth of lithium dendrites. Here, the authors report an approach to enable the self-formation of stable and flexible solid-electrolyte interphase layers which serve to address both issues.

| S-EPMC5636837 | biostudies-literature

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