High Electrolyte Concentrations Research Articles

Designing Localized High Concentration Electrolytes Based on Fluorinated Solvents for Lithium-Ion Batteries

Reduction at the anode can affect electrolyte decomposition, solid electrolyte interphase (SEI) formation and growth, and thus the lithium solvation/de-solvation near the SEI, and ultimately lead to various perilous side reactions such as inactive lithium formation. Lithium ions solvated in the electrolyte solution along with salt anions diffuse towards the surface of the electrode. At the charged surface, these solvated ions can undertake different pathways leading to various reductive decomposition products to subsequently form the SEI. The transfer of electrons from the electrode to the salt anions form inorganic SEI products. The SEI layer gradually thickens during repeated charge/discharge cycles due to electron exposure to electrolyte or electrolyte diffusion to the anode surface. This gradual thickening of SEI layer decreases active lithium ions, solvents, and salts and increases cell resistance and lowers the cell capacity and Coulombic efficiency. Essentially, the choice of electrolytes has a significant influence on the formation of an SEI and its underlying chemical and mechanical properties. Optimizing the electrolytes is crucial for an SEI formation since the properties of the SEI significantly affect the lithium-ion batteries’ cyclability, life time, capacity retention, high power density, rate capability, and safety. One approach of stabilizing the SEI is to utilize an electrolyte with high concentration of salt, also known as High-Concentration Electrolytes (HCEs). This approach modifies the Li+ solvation structure to form contact ion pairs (CIP) and aggregates (AGG) while decreasing solvent-separated ion pairs (SSIPs) so that the salt anion, such as FSI-, is preferentially decomposed to form a robust LiF-rich SEI. LiF is considered a beneficial SEI component to block electron transport. By introducing a diluent (a non-solvating solvent) in the HCE to form Localized High Concentration Electrolyte (LHCE), the disadvantages of the HCE, such as low ionic conductivity, high viscosity and high cost, can be minimized while retaining the highly concentrated salt-solvent clusters as they are in the HCE. LHCEs based on fluorinated solvents and diluents can further stabilize the electrode-electrolyte interface. Recent studies showed that the presence of fluorine in the SEI, either in the form of simple inorganic fluorides (LiF) or organofluoro-moieties, brought positive impacts such as expanded electrochemical stability window and high ionic transport. Fluorinated solvents can shift the oxidation stability to a higher voltage compared to their nonfluorinated counterparts. Fluorinated electrolytes enable a high lithium plating Coulombic efficiency and suppresses lithium dendrite formation to a greater extent. In this work we focused on identifying the selection rules for the diluent for designing LHCEs to preserve or improve the local high salt concentration clusters to facilitate the formation of an inorganic rich anion derivative film on the anode as well as to enhance ionic conductivity to enable fast charging. Some of the important properties to consider while selecting a diluent are: - diluent molecules must offer little or no solubility to the salt so that they have minimal participation in the solvation clusters, they must be readily miscible with the solvating solvent so that they dissolve and remove some solvent molecules from the clusters; effectively increasing the salt concentration in the solvation clusters, diluents should be distributed on the periphery of salt-solvent clusters, diluents should have low viscosity, to reduce the overall viscosity of the formulated electrolyte, which in turn improves the ionic conductivity since the low viscosity of diluents allow for higher mobility of the ionic clusters. We analyzed LHCEs consisting of different diluents and diluent molar ratios in a comparative fashion to understand their properties in retaining or improving the structures of the high concentration salt-solvent clusters and improving ionic conductivity. We varied the diluent molar ratio to understand its relationship to increasing salt concentration gradients in the center of the solvent-salt clusters. We also analyzed the relationship between diluent molar ratio and ionic conductivity and found that an optimum diluent molar ratio exists for which the ionic conductivity can be maximized. Our findings serve as design guidelines for practical applications of LHCEs.

(Invited) Modeling of the Bulk and Electrical Double-Layer Structures of Localized High-Concentration Electrolytes

A new class of electrolytes, localized high-concentration electrolytes (LHCE), have shown many benefits to high-capacity electrodes (lithium (Li)-metal, silicon, sodium, zinc, and potassium).[1] These electrolytes combine high-concentration electrolytes (HCE) with salt and solvent with low-viscosity diluents. The dilutes were added to increase ionic conductivity while the locally highly concentrated salt-solvent clusters will facilitate stable solid-electrolyte interphase (SEI) formation while preventing metallic-dendrite formation. For example, it was demonstrated that an LHCE based on lithium bis(fluorosulfonyl)imide (LiFSI) salt, Dimethoxyethane (DME) solvent, and tris(2,2,2-trifluoroethyl)orthoformate (TFEO) diluent (e.g., LiFSI-1.2DME-2TFEO by mol) forms inorganic-rich, monolithic SEI and shows excellent cycling performance for Li-metal batteries under practical conditions.[2] Here, the interactions among cations, anions, solvent molecules, and diluent molecules create a complex design space, making the trial-and-error empirical approach less efficient.Using density functional theory and classical molecular dynamics simulations, we reveal several important design principles:a) The dielectric constant of the pure solvent or diluent is not a good descriptor to describe the solubility of the salt in solvent and diluent.b) The single ion–solvent (diluent) binding energy is insufficient to predict the solubility, which also depends on the molecular structures and the corresponding solvation shell structure.c) The salt-solvent, salt-diluent, and diluent-solvent solubilities jointly determine the solvation structures in LHCE. For example, at certain concentrations, the Li+ solvation shells contain both anions and solvent molecules with minimal participation of the diluent molecules. The local salt concentration can be even higher than its counterpart in the HCE. These simulated solvation structures in bulk electrolytes compare well with Raman spectrum and SAXS data.d) Moreover, the solvation structures are temperature-sensitive. We revealed why the local salt concentration is higher at a certain temperature by MD simulations, which is further validated through Raman deconvolution analyses.e) The SEI formation is sensitive to the electrolyte structure near a charged surface. Therefore, the electrical double-layer (EDL) structure of LHCE needs to be resolved. Here we give a statistical representation of the LHCE in the EDL and show how it differs from the bulk structure and its impact on SEI formation.Reference:[1] J. Electrochem. Soc., 2021, 168, 010522[2] Nat. Energy 2019, 4, 796-805

Carbonate-Based Localized High Concentrated Electrolyte for Long-Cycle-Life Lithium Metal Batteries

Rechargeable Lithium Metal Batteries (LMBs) using high-voltage cathodes can deliver the highest possible energy densities among all electro-chemistries. However, the notorious reactivity of metallic lithium as well as the catalytic nature of the cathode materials largely prevent their practical application. Here, we demonstrate a formulated carbonate-based high concentrated electrolyte with LiPF6 that supports the most commercial aggressive and high-voltage cathode to realize a highly stable Li metal full-cell with limited metallic Li. The formation of stable Li2O/LiF-rich solid electrolyte interface (SEI) layers afforded stable operations of resultant LMBs under practical working conditions. Our electrolyte contributes to both high efficiency of 99.5% for Li||Cu half cell and ~100% for lithium full cells based on 4.3 V Ni-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Notably, at a loading of 4.0 mAh.cm−2, our full cells showed a capacity retention of ~80% over 280 cycles at lean electrolyte condition of 5 μL.mAh-1. The effective stabilization that inhibited the aggressive chemistries at extreme potentials in LMBs upon practical conditions by our electrolyte was determined to be the formation of the dense, inorganic-rich interphase.

Understanding Solvation Structures of Localized High-Concentration Electrolytes Used for Li-Metal Batteries

Liquid electrolytes in batteries are typically treated as macroscopically homogeneous ionic transport media, despite having complex chemical composition and atomistic solvation structures, thus leaving a knowledge gap of microstructural characteristics. A promising electrolyte system design has recently been developed with the title of a localized high-concentration electrolyte (LHCE). These electrolytes are a summation of three components – a charge-carrying salt, a solvent that solvates the salt, and a diluent that is highly immiscible with the salt. This creates the perception of a high-concentration electrolyte (HCE) with high anion-cation interactions that supports a salt-derived, stable solid-electrolyte interphase, while an LHCE improves bulk electrolyte properties, such as ionic conductivity and viscosity, when compared to an HCE. Much trial by error design of this LHCE concept has been supported by simulations to confirm ionic interactions, cycling data to confirm cell stability, and post-mortem analysis to provide evidence of mechanisms. However, a systematic design to extend the capabilities of LHCEs is still to be desired. Here, we analyzed a specific LHCE mixture with the use of a ternary phase diagram to dictate the best viable mixture to extend the localization of solvation structures while maintaining viable cell-level capabilities. It was seen that the electrolyte mixture has complex mechanisms from individual ion solvation up to the solution network scale, both of which are dictated by the interactions between the three electrolyte components. With the support of both experimental and computational analysis of different electrolyte features, we have begun a methodology of formulating the most ideal LHCE mixtures for improving the cyclability of high-capacity battery chemistries.

(Invited) Aemion+® AEM Water Electrolysis with Excellent Iridium-Free Performance and Industrially Relevant Stability in Hot, Caustic Electrolyte

Hydrogen has a unique ability to maximize the utility of and enable new business models for intermittent renewable deployment. It can be stored cost-effectively in geological storage, transported between regions to suit geographic needs and bridge Dunkelflautes. Global electrolysis capacity must increase from the current <2 GW to 850 GW in 2030 (IEA Net Zero 2050) and in excess of 3500 GW in 2050 to enable this transition.Both traditional Alkaline (AWE) and proton-exchange membrane electrolyzers (PEMWE) are mature technologies that are anticipated to split the overall market share. However, each of these technologies face fundamental challenges:AWE operate at low current density, requiring large and difficult to transport systems, require high concentration electrolytes (e.g. 30 wt% KOH) to conduct hydroxides and ensure low gas solubilities for safety, which necessitates the use of expensive and difficult to machine high-nickel steels, especially in advanced, pressurized designs. Additionally, the porous nature of the electrode separator (e.g. Zirfon) compromises the desired dynamic load for pairing with intermittent renewables.PEMWE use a proton-conductive membrane to enable high current densities, dynamic loads, and differential hydrogen pressures, however, the most efficient operation requires iridium catalyst, which presents a near-term challenges with scalability, together with Ti and PGM structural elements that further impede cost-effectiveness.Alkaline anion-exchange water electrolyzers (AEMWE) address both of these challenges by operating with a cohesive, hydroxide-transporting membrane together with alkaline electrolyte to enable high efficiency, high current density operation, without iridium electrocatalysts or other scarce or expensive components. The realization of capital cost-effectiveness, dynamic load, and compact systems in one technology enables the most cost-effective green hydrogen and represents a step-change in the trajectory towards the DOE Hydrogen Shot target of $1/kg.The instability of alkaline anion exchange membrane chemistries based on quaternary amines or pendant imidazolium groups in relevant temperatures and alkalinities to industrial operations have historically resulted in untenable compromises and too-short lifetimes for industrial-scale deployment. Ionomr's Aemion+® AF2-AWP8-75-X and AF3-HWK9-75-X membranes are based on a sterically-protected imidazolium chemistries that are chemically robust (e.g. 6 months, 1 M, 80 °C without alteration to chemical or mechanical properties), and additionally exhibit low swelling to provide mechanical integrity to electrodes and enable operation in low concentration electrolytes. These membranes are an enabling technology for long-duration AEM water electrolysis.This talk highlights how Ionomr's Aemion+® membranes demonstrate target performances (e.g. >2 A/cm² at 2 V) with non-PGM OER catalysts with no apparent losses to 1000 hours operation across several configurations at ≥70 °C and 1 M KOH operation, and several longer lifetime demonstrations including 1 year durability using AWE electrodes and >6 months including hydrogen crossover measurement. This talk further highlights the potential for the three-dimensionality of electrodes in alkaline AEMWE and the necessary processing and operational requirements to create reproducible and stable GDEs with catalyst ink-based deposition techniques. Figure 1

Pre-Treatment of Li-Metal Anode with Hydrohalic-Acid for Stable Cycling of Li-Metal Batteries Under Practical Conditions

Lithium (Li) metal anodes (LMAs) are considered as an ultimate choice for beyond Li-ion batteries because of their high capacity (3860 mAh g–1) and low working potential (–3.04 V vs. SHE). However, due to extremely high surface reactivity, uncontrollable dendritic plating, and infinite volume expansion, making Li-metal batteries (LMBs) has long encountered fatal challenges. Heterogeneous solid-electrolyte interphase (SEI) can be the main reason for Li dendrite growth, stemming from the electrolyte byproducts and native LMA surface. In this regard, uniform passivation of LMAs and homogenous SEI at the initial stage is necessary which can occur uniform Li+ ion flux. Furthermore, halogenated SEI is considered as promising component for achieving superior mechanical strength, insulating properties and thermodynamic stability.In this study, we present a simple LMA treatment using hydrohalic acids (HXs, X = F, Cl, Br, and I) to regenerate native passivation layer (NPL) of as-manufactured LMAs and evenly nourish halogenated compounds. The water molecules of aqueous HXs can dissolve the existing inorganic Li-compounds in the NPL, e.g., Li2O, LiOH, and Li2CO3, rendering the chemical reactions of HXs with pure Li, enriching the LiX compounds within the NPL. A comparative study was done to reveal which LiX compounds is beneficial to stabilize the LMA surface and to enhance the cycling stability of LMBs. Furthermore, it is elucidated that the pivotal role of LiX compounds was proved in the interfacial reaction when using localized high concentration electrolyte (LHCE) as an advanced electrolyte in LMBs. Through comparative study, building LiCl-rich SEI at the initial stage effectively reduces the energy barrier of Li nucleation and interfacial resistances, thereby enhancing the cycling performances in LMBs even under practical conditions.

(Invited) Improving Calendar Life of Si-Based Lithium-Ion Batteries By FEC/VC-Free Electrolytes

Silicon (Si) has been regarded as one of the most promising anode materials for the next generation lithium-ion batteries (LIBs) with high energy density because it has 10 times higher theoretical specific capacity (4200 mAh/g) than that of graphite. However, severe volume change (~300%) of Si during lithiation and delithiation hinders the practical application of Si anode. In the last decade, significant progresses have been made on the specific energy and cycle life of Si based LIBs. However, calendar-life of these batteries is still far less than 10-year target required by DOE’s electrical vehicle (EV) project.In the current work, the role of FEC/VC in conventional carbonate electrolytes has been investigated. It has been found that FEC/VC causes large impedance growth on both Si and graphite anodes at 55 oC. The cut-off voltage of NMC622 has been found to significantly affect its impedance. NMC622 at 4.2V shows no impedance growth at 55 °C for 8 days, while severe impedance growth is observed at 4.4V. To address the instability of both SEI and CEI at elevated temperature, a new Localized High Concentration Electrolyte (LHCE) has been developed to improve the calendar life of Si based LIBs by effectively limiting impedance growth of Si/NMC622 full cells. In addition, the cycle life of the full cell is improved. The mechanism of Si full cells with improved calendar life will also be discussed.

Non-Fluorinated Diluent in Localized High Concentration Electrolytes Enabling Superior Performance of Lithium Metal Negative Electrode Battery

Localized high-concentration electrolytes (LHCEs) are very promising strategies for the high-energy-density lithium (Li) metal batteries (LMBs). Nonsolvating diluents introduced in the LHCEs plays a critical role in physicochemical properties of LHCE and the overall LMB performance. However, there is a lack of design strategies for ideal nonsolvating diluents, and the reported cases are limited to fluorinated nonsolvating diluents (FNDs). FNDs suffer from accelerated decomposition at lithium metal, leading to electrolyte dry-up and ultimately battery failure. Furthermore, the high cost and potential environmental hazards of FNDs necessitate the development of non-fluorinated nonsolvating diluents (NFNDs). Here, we present a design rule for the ideal NFNDs by spectroscopically characterizing the Li+ solvation ability and miscibility. Our design rule identifies the ideal NFNDs, based on the superior cycling performane of candidate diluents over 350 cycles (99.0% ethoxybezene), 500 cycles (98.5% anisole), and 1400 cycles (99.0%, furan). NMR spectra revealed that the designed NFNDs were highly stable in electrolytes during extended cycles. Raman spectroscopy and theoretical calculation reveal that resonance of an electron pair on the oxygen atom of NFND molecules decreases the lithium-ion solvation ability, thereby achieving desirable non-solvating characteristics while maintaining good miscibility, superior cathodic stability, and low prices. Figure 1

(Invited) Important Factors Affecting Calendar Life of Lithium Metal Batteries

With the growing maturity of lithium (Li) ion battery technologies, Li metal battery (LMB) is being revitalized in recent years to achieve high energy density. Great progress has been made in understanding the Li utilization and extending the cycle life of LMBs. However, the study of calendar life of LMBs is still limited, although the calendar life of the battery is also critical for application of LMBs. Therefore, there is an urgent need to investigate the calendar life of LMBs systematically and extend their calendar life. In this work, we will report our recent works on investigation of the calendar life of LMBs based on Li||NMC811 cells using advanced localized high concentration electrolyte, which has already demonstrated excellent cycling stability. Two key criteria, self-discharge rate (percentage of capacity loss per day at open circuit) and recoverable capacity after long-term storage, are used to quantify the calendar aging at different states of charge (SOCs) and temperatures. Together with the postern mortem analysis of Li metal anode and NMC811 cathode retrieved from the long-term stored cells, this work provided an in depth understanding on the important factors affecting calendar aging of LMBs. These findings can guide the storage of LMBs and shed light on the further development of LMBs. Figure 1

Ultrathin, Smooth Li-Metal Anode Via Electrodeposition for Stable Cycling of Li-Betal Batteries Under Practical Conditions

Lithium (Li) metal anodes (LMAs) with high specific capacity (3860 mAh g–1) and lowest redox voltage (–3.04 V vs SHE) are considered superlative candidates for high energy batteries. Ultra-thin, large-area LMA is crucial for building Li-metal batteries (LMBs) that can deliver high volumetric and gravimetric energy density in practice. As the charging and discharging continue, the growth of Li dendrite is regarded as one of the significant challenges. The surface nature of LMAs is the main aspect of Li dendrite formation and interface reaction. However, most studies overlooked the initial condition of LMA surface. Native passivation layer (NPL) of commercial Li foils is inherently uneven composed of Li2CO3, LiOH, and Li2O, and its chemical nature is mostly determined under manufacturing conditions. Incomplete passivation at an initial stage can trigger sporadic Li dendrite growth and chemical/structural deterioration of LMAs, adversely affecting the cycling stability of LMBs.This work presents the electrochemical pre-passivation to build an electrolyte-derived native layer (electro-native layer, E-NPL) through Li electrodeposition method. Electrodeposited LMA (ed-LMA) was prepared by pre-deposition at the Cu foil using localized high-concentration electrolyte (LHCE) and post calendaring for smooth LMA surface. As-prepared ed-LMA has 4.13 mAh cm-2 of areal capacity with ~22 µm, and reduced roughness, which is much lower than that of manufactured LMA (m-LMA). Particularly, the E-NPL derived by LHCE can tailor the LMA surface by enriching the inorganic SEI compounds such as LiF, and N-SOx. In addition, decreased amount of passivated components such as Li2CO3, LiOH, and hydroxide were found in XPS analysis of the anodes. Compared to manufactured LMA (m-LMA), the ed-LMA exhibited lower overpotential for Li plating/stripping cycles and enhanced capacity retention. Benefiting from better compatibility with newly plated Li, it showed higher plating density without electric isolation from beneath Li surface, mitigating the anode swelling during subsequent cycling. We successfully demonstrated battery cycling stability of Li||NMC622 cells exploiting ed-LMA (195 cycle at 80% retention), superior to m-LMA (110 cycle at 80% retention) under stringent conditions.

The Relationship between Ionic Conductivity and Solvation Structures of Localized High-Concentration Fluorinated Electrolytes for Lithium-Ion Batteries.

Localized high-concentration electrolytes (LHCEs) combine a diluent with a high-concentration electrolyte, offering promising properties. The ions, solvent, and diluent interact to form complex heterogeneous liquid structures, where high salt concentration clusters are embedded in the diluent. Optimizing LHCEs for desired electrolyte properties like high ionic conductivity, low viscosity, and effective solid electrolyte interphase (SEI) formation ability within the vast chemical and compositional design space requires deeper understanding and theoretical guidance. We investigated the structures and conductivities of LHCEs based on a fluorinated solvent with two different diluents at varying concentrations. 2,2,3,3-Tetrafluoropropyl trifluoroacetate (TFPTFA) enters the solvation cluster due to its stronger Li-ion interactions, whereas 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFETFE) enters only at extremely high diluent concentrations. The ionic conductivity increases with decreasing diluent concentrations, with a slope change during cluster percolation. Overall, TFETFE demonstrates higher effectiveness than TFPTFA, forming higher local salt concentration clusters and resulting in higher ionic conductivity.

Particle Network Self-Assembly of Similar Size Sub-Micron Calcium Alginate and Polystyrene Particles Atop Glass.

Particle-mediated self-assembly, such as nanocomposites, microstructure formation in materials, and core-shell coating of biological particles, offers precise control over the properties of biological materials for applications in drug delivery, tissue engineering, and biosensing. The assembly of similar-sized calcium alginate (CAG) and polystyrene sub-micron particles is studied in an aqueous sodium nitrate solution as a model for particle-mediated self-assembly of biological and synthetic mixed particle species. The objective is to reinforce biological matrices by incorporating synthetic particles to form hybrid particulate networks with tailored properties. By varying the ionic strength of the suspension, the authorsalter the energy barriers for particle attachment to each other and to a glass substrate that result from colloidal surface forces. The particles do not show monotonic adsorption trend to glass with ionic strength. Hence, apart from DLVO theory-van der Waals and electrostatic interactions-the authors further consider solvation and bridging interactions in the analysis of the particulate adsorption-coagulation system. CAG particles, which support lower energy barriers to attachment relative to their counterpart polystyrene particles, accumulate as dense aggregates on the glass substrate. Polystyrene particles adsorb simultaneously as detached particles. At high electrolyte concentrations, where electrostatic repulsion is largely screened, the mixture of particles covers most of the glass substrate; the CAG particles form a continuous network throughout the glass substrate with pockets of polystyrene particles. The particulate structure is correlated with the adjustable energy barriers for particle attachment in thesuspension.

Solvent modulation strategy for Sb-based anode to achieve stable potassium storage

High-concentration electrolyte (HCE) and localized high-concentration electrolyte (LHCE) strategies have been successfully developed for potassium-ion batteries (PIBs) to address the interface incompatibility issue, especially for the high-theoretical-capacity antimony (Sb)-based alloy-typed anode suffering from the drastic volume expansion problem. However, the high costs along with special solvents for these electrolytes significantly limits their widespread applications in PIBs. Herein, a new dilute electrolyte of 1 M KFSI in a mixed solvent of ethylene carbonate (EC) and 1, 2-dimethoxyethane (DME) (1:1 v/v) is developed to stabilize the K-storage kinetics of Sb anodes. The mixed solvent of common ester and ether promotes the formation of stable K+-EC solvent pair and thus generates a robust solid-electrolyte-interphase (SEI) for stable K-storage. As a result, the fabricated Sb@NC anode exhibits a stable capacity of 376 mAh/g after 100 cycles at 100 mA g−1, which is comparable to that in the HCE of 5 M KFSI/DME. These results demonstrated that low-cost and high-compatibility electrolytes for alloy-typed anodes can be achieved via rational design of the solvation structures for dilute electrolytes, resulting into stable K-storage properties and huge prospects of commercialized applications.

Localized High-Concentration Electrolytes with Low-Cost Diluents Compatible with Both Cobalt-Free LiNiO2 Cathode and Lithium-Metal Anode.

High-nickel layered oxide cathodes and lithium-metal anode are promising candidates for next-generation battery systems due to their high energy density. Nevertheless, the instability of the electrode-electrolyte interphase is hindering their practical application. Localized high-concentration electrolytes (LHCEs) present a promising solution for achieving uniform lithium deposition and a stable cathode-electrolyte interphase. However, the limited choice of diluents and their high cost are restricting their implementation. Four novel cost-effective diluents and their performance with highly reactive LiNiO2 cathode and Li-metal anode are reported here. The results show that all the LHCE cells exhibit a Coulombic efficiency of >99.38% in Li | Cu cells and a capacity retention of >85% in Li | LiNiO2 cells after 250 cycles. Advanced characterizations unveil that the stable cell operation is due to well-tuned electrode-electrolyte interphases and Li deposition morphology. In addition, online electrochemical mass spectroscopy and differential scanning calorimetry reveal that the gas generation and heat-release are greatly reduced with the LHCEs presented. Overall, the study provides new insights into the role of diluents in LHCEs and offers valuable guidance for further optimization of LHCEs for high energy density lithium-metal batteries.

Tunning solvation structure in non-flammable, localized high-concentration electrolytes with enhanced stability towards all aluminum substrate-based K batteries

Although metallic potassium or graphite anode with low redox potentials are desirable for potassium-ion batteries (PIBs), the severe capacity decay caused by consecutive reduction reactions on the aggressively reactive anode surface is inevitable because of the scarcity of an effective passivation layer. Additionally, the development of PIBs faces potential safety hazards due to the usage of reactive anodes with flammable electrolytes. Herein, a fire-retardant localized high-concentration electrolyte (LHCE) is formulated by adding a low-polarity co-solvent of highly fluorinated ether into the concentrated potassium bis(fluorosulfonyl)imide/trimethyl phosphate. A unique electrolyte solvation environment with the enhanced anion-cation interaction in an LHCE facilitates a durable anion-derived solid electrolyte interphase (SEI) with self-accelerated interfacial kinetics and minimizes the SEI dissolution compared to the conventional carbonate-based electrolyte. Consequently, the unmodified Al substrate could sustain stable potassium metal cycling above 3400 h (over 800 cycles) with high reversibility (98%), and the graphite anode retains prolonged cyclic stability (over 300 cycles) with a high reversible capacity (257.6 mAh g−1) and capacity retention (92.6 % at 0.2 C). Meanwhile, Al corrosion at high voltage is significantly suppressed, and the electrochemical window is extended due to less free solvents in an LHCE, enabling good electrolyte compatibility with high-voltage cathodes. Coupling non-flammable solvents and the concept of LHCE could facilitate a better understanding of electrolyte chemistry and offer more opportunities to use K or graphite anode for all Al substrate-based PIBs highlighted with high performance and superb safety.

Reforming the Uniformity of Solid Electrolyte Interphase by Nanoscale Structure Regulation for Stable Lithium Metal Batteries.

The stability of high-energy-density lithium metal batteries depends on the uniformity of solid electrolyte interphase (SEI) on lithium metal anodes. Rationally improving SEI uniformity is hindered by poorly understanding the effect of structure and components of SEI on its uniformity. Herein, a bilayer structure of SEI formed by isosorbide dinitrate (ISDN) additives in localized high-concentration electrolytes was demonstrated to improve SEI uniformity. In the bilayer SEI, LiNx Oy generated by ISDN occupies top layer and LiF dominates bottom layer next to anode. The uniformity of lithium deposition is remarkably improved with the bilayer SEI, mitigating the consumption rate of active lithium and electrolytes. The cycle life of lithium metal batteries with bilayer SEI is three times as that with common anion-derived SEI under practical conditions. A prototype lithium metal pouch cell of 430 Wh kg-1 undergoes 173 cycles. This work demonstrates the effect of a reasonable structure of SEI on reforming SEI uniformity.

Concentration induced modulation of solvation structure for efficient lithium metal battery by regulating energy level of LUMO orbital

Nitrile electrolytes have attracted extensive attention for achieving high-voltage lithium metal batteries. However, the poor compatibility of nitrile electrolyte with Li anode remains a huge challenge owing to severe side reactions. Herein, changing concentration of LiTFSI in succinonitrile (SN) is proposed to improve interface compatibility by regulating the solvation structure. The higher coordination number (1.3) of TFSI− in high concentration electrolytes results in a LiF-rich SEI film, accounting for the superior performance of LiNi0.8Co0.1Mn0.1O2|Li cell with negligible capacity fade after 100 cycles at 0.5 C. Density functional theory (DFT) suggests that the solvation structure with a high coordination number of TFSI− towards Li+ leads to a reduced Lowest Unoccupied Molecular Orbital (LUMO) energy level, which promotes the decomposition of TFSI− to form LiF-rich film. Also, a reduced decomposition energy barrier of anion is demonstrated. This work provides an encouraging way to enhance interface stability via modulating the solvation structure achieved by regulating concentration.

Interaction of Nanoparticles in Electrolyte Solutions.

The interaction between nanoparticles includes several components; however, the most frequently used are electrostatic, caused by overlapping double electrical layers, and London-van der Waals interactions, caused by quantum and thermodynamic fluctuations of electromagnetic fields. Only these two kinds of interaction are considered below. The electrostatic interaction is calculated based on the linearized Poisson-Boltzmann equation for particles with constant electrical potential of the surfaces (constant ζ potentials). An exact solution of the problem is obtained for both identical particles and particles of different sizes. For the London-van der Waals interaction, the screening of static fluctuations and the retardation of electromagnetic fields for the dispersive part of the interaction are taken into account. The total interaction energy for two particles was calculated for a range of possible nanoparticle sizes from 1 to 103 nm and electrolyte concentration from 10-2 to 10-6 mol/L. The predominance of the London-van der Waals force over the shielded electrostatic repulsion force was found at high electrolyte concentrations in the range from 10-2 to 10-3 mol/L at large interparticle distances.

High electrolyte concentration effect on enzymatic oxygen reduction

The nature, the composition and the concentration of electrolytes is essential for electrocatalysis involving redox enzymes. Here, we discuss the effect of various electrolyte compositions with increasing ionic strengths on the stability and activity towards O2 reduction of the bilirubin oxidase from Myrothecium verrucaria (Mv BOD). Different salts, Na2SO4, (NH4)2SO4, NaCl, NaClO4, added to a phosphate buffer (PB) were evaluated with concentrations ranging from 100 mM up to 1.7 M. On functionalized carbon nanotube-modified electrodes, it was shown that the catalytic current progressively decreased with increasing salt concentrations. The process was reversible suggesting it was not related to enzyme leakage. The enzyme was then immobilized on gold electrodes modified by self-assembling of thiols. When the enzyme was simply adsorbed, the catalytic current decreased in a reversible way, thus behaving similarly as on carbon nanotubes. Enzyme mobility at the interface induced by a modification in the interactions between the protein and the electrode upon salt addition may account for this behavior. When the enzyme was covalently attached, the catalytic current increased. Enzyme compaction is proposed to be at the origin of such catalytic current increase because of shorter distances between the first copper site electron acceptor and the electrode.

Industrial wastewater treatment using batch recirculation electrocoagulation (BRE) process: Studies on operating parameters

The environmental industry has demonstrated an increasing interest in employing electrocoagulation (EC) process to treat industrial wastewater/effluent for recycling/drinking purposes. An iron (Fe)/aluminum (Al) plate-based batch recirculation electrocoagulation technology for wastewater treatment in the distillery industry is discussed in this work. The impact of different operational parameters, including COD, wastewater pH, current, inter-electrode spacing, combination of electrodes, recirculation flow rate, concentration of electrolytes, and treatment duration on % color, % COD reduction efficiency, and energy consumption was examined. The experimental outcomes demonstrated that, the color removal was 100 %, COD removal was 99.90 %, and energy consumption was 7.73 kWh m−3 for COD of 3600 mg L−1, current of 0.56 Amp, combination of electrodes of Fe/Fe, inter-electrode spacing of 1 cm, wastewater pH of 7, flow rate of 15 L h−1, concentration of electrolytes of 5 g L−1, and treatment time of 180 min, respectively. It was found that, a longer treatment period, higher electrolyte concentrations and current, lower COD concentrations and recirculation flow rates, Fe/Fe electrode pairings, a pH of 7, and a smaller inter-electrode spacing all contributed to increased % COD reduction efficiency. The quantity of solid sludge formed were studied with the help of operational parameters, and the results were reported. Under the optimized process conditions, the wastewater treated can be fully recovered as clean water. As a consequence of this, the results of the experiments have shown that the batch recirculation electrocoagulation process has the potential to be a more promising solution to the problem of eliminating contaminants from wastewater and industrial effluent.