Browse
Submit Data
Databases
API
Help

Dataset Information

15 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries.

ABSTRACT: Many organic solvents have very desirable solution properties, such as wide temperature range, high solubility of Li salts and nonflammability, and should be able but fail in reality to serve as electrolyte solvents for Li-ion or -metal batteries due to their reduction instability. The origin of this interfacial instability remains unsolved and disputed so far. Here, we reveal for the first time the origin of the reduction stability of organic carbonate electrolytes by combining ab initio molecular dynamics (AIMD) simulations, density functional theory (DFT) calculations and electrochemical stability experiments. It is found that with the increase of the molar ratio (MR) of salt to solvent, the anion progressively enters into the solvation shell of Li⁺ to form an anion-induced ion-solvent-coordinated (AI-ISC) structure, leading to a "V-shaped" change of the LUMO energy level of coordinated solvent molecules, whose interfacial stability first decreases and then increases with the increased MRs of salt to solvent. This mechanism perfectly explains the long-standing puzzle about the interfacial compatibility of organic electrolytes with Li or similar low potential anodes and provides a basic understanding and new insights into the rational design of the advanced electrolytes for next generation lithium secondary batteries.

SUBMITTER: Shen X

PROVIDER: S-EPMC8261714 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Molecular regulation of electrolytes for enhancing anode interfacial stability in lithium-sulfur batteries.

Project description:We addressed the poor interfacial stability of the Li metal anode in Li-S batteries through molecular regulation of electrolytes using arylthiol additives with various numbers of anchoring sites. The dual functional tetrathiol additive markedly enhanced the Li anode interfacial stability, controlled the sulfur redox kinetics and suppressed side reactions towards polysulfides, thus leading to an improved capacity retention of 70% after 500 cycles at 1 C.

| S-EPMC10309021 | biostudies-literature

Nonflammable perfluoropolyether-based electrolytes for lithium batteries.

Project description:The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200 °C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi1/3Co1/3Mn1/3O2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity.

| S-EPMC3948224 | biostudies-literature

Highly Solvating Electrolytes for Lithium-Sulfur Batteries.

Project description:There is a critical need to evaluate lithium-sulfur (Li-S) batteries with practically relevant high sulfur loadings and minimal electrolyte. Under such conditions, the concentration of soluble polysulfide intermediates in the electrolyte drastically increases, which can alter the fundamental nature of the solution-mediated discharge and thereby the total sulfur utilization. In this work, we present an investigation into various high donor number (DN) electrolytes that allow for increased polysulfide dissolution, and demonstrate how this property may in fact be necessary for increasing sulfur utilization at low electrolyte and high loading conditions. The solvents dimethylacetamide, dimethyl sulfoxide, and 1-methylimidazole are holistically evaluated against dimethoxyethane as electrolyte co-solvents in Li-S cells, and they are used to investigate chemical and electrochemical properties of polysulfide species at both dilute and practically relevant conditions. The nature of speciation exhibited by lithium polysulfides is found to vary significantly between these concentrations, particularly in regards to the S3•- species. Furthermore, the extent of the instability in conventional electrolyte solvents and high DN solvents with both lithium metal and polysulfides is thoroughly investigated. These studies establish a basis for future efforts into rationally designing an optimal electrolyte for a lean electrolyte, high energy density Li-S battery.

| S-EPMC6894182 | biostudies-literature

High entropy liquid electrolytes for lithium batteries.

Project description:High-entropy alloys/compounds have large configurational entropy by introducing multiple components, showing improved functional properties that exceed those of conventional materials. However, how increasing entropy impacts the thermodynamic/kinetic properties in liquids that are ambiguous. Here we show this strategy in liquid electrolytes for rechargeable lithium batteries, demonstrating the substantial impact of raising the entropy of electrolytes by introducing multiple salts. Unlike all liquid electrolytes so far reported, the participation of several anionic groups in this electrolyte induces a larger diversity in solvation structures, unexpectedly decreasing solvation strengths between lithium ions and solvents/anions, facilitating lithium-ion diffusivity and the formation of stable interphase passivation layers. In comparison to the single-salt electrolytes, a low-concentration dimethyl ether electrolyte with four salts shows an enhanced cycling stability and rate capability. These findings, rationalized by the fundamental relationship between entropy-dominated solvation structures and ion transport, bring forward high-entropy electrolytes as a composition-rich and unexplored space for lithium batteries and beyond.

| S-EPMC9918526 | biostudies-literature

High-Entropy Electrolytes for Lithium-Ion Batteries.

Project description:One of the primary challenges to improving lithium-ion batteries lies in comprehending and controlling the intricate interphases. However, the complexity of interface reactions and the buried nature make it difficult to establish the relationship between the interphase characteristics and electrolyte chemistry. Herein, we employ diverse characterization techniques to investigate the progression of electrode-electrolyte interphases, bringing forward opportunities to improve the interphase properties by what we refer to as high-entropy solvation disordered electrolytes. Through formulating an electrolyte with a regular 1.0 M concentration that includes multiple commercial lithium salts, the solvation interaction with lithium ions alters fundamentally. The participation of several salts can result in a weaker solvation interaction, giving rise to an anion-rich and disordered solvation sheath despite the low salt concentration. This induces a conformal, inorganic-rich interphase that effectively passivates electrodes, preventing solvent co-intercalation. Remarkably, this electrolyte significantly enhances the performance of graphite-containing anodes paired with high-capacity cathodes, offering a promising avenue for tailoring interphase chemistries.

| S-EPMC11320655 | biostudies-literature

Stabilizing polymer electrolytes in high-voltage lithium batteries.

Project description:Electrochemical cells that utilize lithium and sodium anodes are under active study for their potential to enable high-energy batteries. Liquid and solid polymer electrolytes based on ether chemistry are among the most promising choices for rechargeable lithium and sodium batteries. However, uncontrolled anionic polymerization of these electrolytes at low anode potentials and oxidative degradation at working potentials of the most interesting cathode chemistries have led to a quite concession in the field that solid-state or flexible batteries based on polymer electrolytes can only be achieved in cells based on low- or moderate-voltage cathodes. Here, we show that cationic chain transfer agents can prevent degradation of ether electrolytes by arresting uncontrolled polymer growth at the anode. We also report that cathode electrolyte interphases composed of preformed anionic polymers and supramolecules provide a fundamental strategy for extending the high voltage stability of ether-based electrolytes to potentials well above conventionally accepted limits.

| S-EPMC6626095 | biostudies-literature

The solvation structure, transport properties and reduction behavior of carbonate-based electrolytes of lithium-ion batteries.

Project description:Despite the extensive employment of binary/ternary mixed-carbonate electrolytes (MCEs) for Li-ion batteries, the role of each ingredient with regards to the solvation structure, transport properties, and reduction behavior is not fully understood. Herein, we report the atomistic modeling and transport property measurements of the Gen2 (1.2 M LiPF6 in ethylene carbonate (EC) and ethyl methyl carbonate (EMC)) and EC-base (1.2 M LiPF6 in EC) electrolytes, as well as their mixtures with 10 mol% fluoroethylene carbonate (FEC). Due to the mixing of cyclic and linear carbonates, the Gen2 electrolyte is found to have a 60% lower ion dissociation rate and a 44% faster Li+ self-diffusion rate than the EC-base electrolyte, while the total ionic conductivities are similar. Moreover, we propose for the first time the anion-solvent exchange mechanism in MCEs with identified energetic and electrostatic origins. For electrolytes with additive, up to 25% FEC coordinates with Li+, which exhibits a preferential reduction that helps passivate the anode and facilitates an improved solid electrolyte interphase. The work provides a coherent computational framework for evaluating mixed electrolyte systems.

| S-EPMC8597828 | biostudies-literature

Monochromatic "Photoinitibitor"-Mediated Holographic Photopolymer Electrolytes for Lithium-Ion Batteries.

Project description:A new polymer electrolyte based on holographic photopolymer is designed and fabricated. Ethylene carbonate (EC) and propylene carbonate (PC) are introduced as the photoinert substances. Upon laser-interference-pattern illumination, photopolymerization occurs within the constructive regions which subsequently results in a phase separation between the photogenerated polymer and unreacted EC-PC, affording holographic photopolymer electrolytes (HPEs) with a pitch of ?740 nm. Interestingly, both diffraction efficiency and ionic conductivity increase with an augmentation of the EC-PC content. With 50 wt% of EC-PC, the diffraction efficiency and ionic conductivity are ?60% and 2.13 × 10-4 S cm-1 at 30 °C, respectively, which are 60 times and 5 orders of magnitude larger than the electrolyte without EC-PC. Notably, the HPEs afford better anisotropy and more stable electrochemical properties when incorporating N,N-dimethylacrylamide. The HPEs exhibit good toughness under bending, excellent optical transparency under ambient conditions, and astonishing capabilities of reconstructing colored images. The HPEs here open a door to design flexible and transparent electronics with good mechanical, electrical, and optical functions.

| S-EPMC6524123 | biostudies-literature

Ring-chain synergy in ionic liquid electrolytes for lithium batteries.

Project description:Lithium-ion batteries have been attracting much attention which enables the revolution of wireless global communication. Ionic liquids are regarded as promising candidates for lithium-ion battery electrolytes because they can overcome the limitations of high operating temperatures and flammability concerns of traditional electrolytes. However, at low temperatures they suffer from low ionic conductivity and phase transition. In this paper mixed electrolyte systems are described based on N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide (Pyr1,2O1TFSI) and lithium difluoro(oxalate)borate (LiODFB) lithium salt, with ethylene sulphite (ES) or dimethyl sulphite (DMS) as a cosolvent. The mixed electrolyte system exhibits good ion transport properties (a conductivity of 8.163 mS cm-1), a wide electrochemical window (5.2 V), non-flammability, the ability to form films to protect the anode and a large operating temperature range (-40 °C to 60 °C). We compare the performance and function of the new mixed electrolyte system with a variety of ionic liquid/cosolvent electrolyte systems developed in previous studies. The ring-chain synergy takes advantage of the availability of both high permittivities based on the ring-like components and low viscosities based on the chain-like components in the mixed electrolyte system and causes the electrolyte to exhibit a good overall performance in safety, ion transport and compatibility with electrodes.

| S-EPMC5950758 | biostudies-literature

Poly(ionic liquid) Based Composite Electrolytes for Lithium Ion Batteries.

Project description:Polymerized ionic liquids (PIL) are an interesting substance class, which is discussed to transfer the outstanding properties and tunability of ionic liquids into a solid material. In this study we extend our previous research on ammonium based PIL and discuss the influence of additives and their usability as polymer electrolyte membranes for lithium ion batteries. The polymer electrolyte is thereby used as replacement for the commercially widespread system of a separator that is soaked with liquid electrolyte. The influence of the material composition on the ionic conductivity (via electrochemical impedance spectroscopy) and the diffusion coefficients (via pulsed-field-gradient nuclear magnetic resonance spectroscopy) were studied and cell tests with adapted membrane materials were performed. High amounts of the additional ionic liquid (IL) MPPyrr-TFSI (1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide) increased the ionic conductivity of the materials up to 1.3·10-4 S·cm-1 but made the usage of a cross-linker necessary to obtain mechanically stable membranes. The application of liquid electrolyte mixtures with ethylene carbonate (EC) and MPPyrr-TFSI decreased ionic conductivity values down to the 10-9 S·cm-1 range, but increased 7Li diffusion coefficients with increasing amounts of EC up to 1.7·10-10 m2·s-1. Cell tests with two membrane mixtures proofed that it is possible to build electrolyte membranes on basis of the polymerized ionic liquids, but also showed that further research is necessary to ensure stable and efficient cell cycling.

| S-EPMC8707941 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data