High Electrolyte Concentrations Research Articles

Anionic Effects on Li-Ion Activity and Intercalation Kinetics in Highly Concentrated Electrolytes

Certain highly concentrated electrolytes (HCEs) enhance the charge-transfer reaction rate at the electrode/electrolyte interface in Li-ion batteries. The solvation structure of Li+ in HCEs significantly affects the electrochemical interfacial reaction kinetics.1 However, the effects of different anions on these kinetics have not yet been fully understood. In this study, we investigated the effects of anionic species on the liquid structure and electrochemical reactions of HCEs composed of various Li salts and propylene carbonate (PC).2 Raman spectra revealed that both PC and anions were coordinated to Li+ ions in HCEs and that the concentration of uncoordinated (free) PC changed depending on the anionic species. Consequently, the activity of Li+ in the electrolyte changed depending on the anionic species. The use of Li salts with weakly Lewis basic anions increased the activity of Li+ and decreased the concentration of free PC in HCEs.The activity of Li+ in the electrolyte significantly affected the Li+ intercalation/deintercalation reaction rate of the LiCoO2 thin-film electrode. Electrochemical impedance spectroscopy revealed that the interfacial reaction rate of LiCoO2 was enhanced in the HCEs with anions having weaker Lewis basicity owing to the higher Li+ ion activity. In addition to the Li+ ion activity, the electrolyte viscosity also gives a significant effect on the charge-transfer kinetics at the electrode/electrolyte interface. The effects of salt concentration and anionic species on Li+ ion activity, electrolyte viscosity, and reaction kinetics in the HCEs will be discussed in detail. Acknowledgements : This study was partially supported by the JSPS KAKENHI (Grant No. JP19H05813, JP21H04697, and JP22H00340). References Y. Kondo et al., ACS Appl. Mater. Interfaces 2022, 14, 22706-22718.Y. Ugata et. al., J. Phys. Chem. C 2023, 127, 3977-3987.

Highly Concentration Aqueous Electrolytes for Zinc Metal Batteries

Aqueous zinc batteries (AZB) emerged as a promising technology for renewable and low-cost storage devices.[1] Zinc (Zn) metal features high abundance, intrinsic safety, low cost (~USD $2 kg-1) and high theoretical capacity (820 mA h g-1).[2,3] However, AZBs do suffer from low Coulombic efficiency, dendrite growth and parasitic hydrogen evolution reaction (HER), which restrict their practical applications.[4] To combat this problem, highly concentrated electrolytes (HCEs) are employed to improve the cycling stability of AZBs.[5] In this work, we demonstrate that aqueous HCEs based on Zn and organic salts are a very effective way to address these issues. Aqueous eutectic electrolytes were obtained by simply optimizing the salt ratio, as evidenced by the low liquid-to-solid transition temperature. These unique HCEs feature a wider electrochemical stability window and an improved ionic conductivity. Additionally, the high-density of Zn cations near the electrode surface results in reversible and stable Zn electrodeposition - with relatively low overpotentials in comparison to other reported hybrid Zn electrolytes. Thus, this work presents an efficient, economically attractive and simple approach for the development of HCEs for practical applications of AZBs.

Eutectic Mixtures As Highly Concentrated and Molten Electrolytes with Nearly Single-Ion Conducting Behavior

Today's state-of-the-art liquid electrolytes in lithium ion batteries (LIBs) have a high ionic conductivity and good performance regarding their cycle life. (1) However, they pose a safety risk due to their high vapor pressures and low thermal stability. (1) Furthermore, due to the limited electrochemical stability of the solvent, liquid electrolytes are not suitable for the application in high-voltage LIBs. (2) Molten salts, also called ionic liquids (IL), or highly concentrated electrolytes (HCE) have high lithium ion concentrations, where nearly every solvent molecule is coordinated. Due to this, there are strong ion interactions and the formation of ion clusters that lead to an increased lithium ion transference number of >0.5. (3) Therefore, they can represent an alternative in the field of liquid electrolytes. Additionally, HCE exhibit a higher thermal and electrochemical stability compared to dilute electrolytes and can improve the cycle performance in lithium metal batteries. (4, 5)McOwen et al. reported the coordination of lithium ions and crystalline structures in HCE of the binary mixtures of ethylene carbonate (EC) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) with molar ratio up to 1:1. (6) Based on the concept of melting point depression as known from thermodynamics, room-temperature molten, highly concentrated electrolytes of a carbonate-based solvent with lithium sulfonyl imides were investigated. Instead of EC, the solvent pinacol carbonate (PIC) without acidic α-hydrogen atoms, but four bulky methyl groups was synthesized and used for eutectic mixtures, as the melting point of PIC is with 187 °C far above room-temperature. The physicochemical properties of these electrolytes are studied with respect to the different influence of lithium bis(fluorosulfonyl)imide and LiTFSI despite their same basic molecule structure. The focus will be on the electrochemical analysis by the means of the ionic conductivity, transference number and the electrochemical stability.In comparison to dilute liquid electrolytes the molten electrolytes show extremely high transference numbers, especially for the PIC-LiTFSI mixtures nearly a single-ion conducting behavior (0.9) is observed. This behavior can be explained by the formation of a 2D polymeric network within the HCE electrolyte as determined by crystallographic measurements in the solid state. Combined with the high electrochemical stability, a stable long-term cycling and dendrite suppression in symmetric lithium cells could be shown. Cycling in full cells with high-voltage cathode materials such as LiNi0.6Mn0.2Co0.2O2 (NMC622) or LiMn4O2 (LMO) against lithium metal anodes is applicable. References K. Xu, Chemical Reviews, 104(10), 4303–4417 (2004).J. Li, C. Ma, M. Chi, C. Liang and N. J. Dudney, Advanced Energy Materials, 5(4) (2015).K. M. Diederichsen, E. J. McShane and B. D. McCloskey, ACS ENERGY LETTERS, 2(11), 2563–2575 (2017).G. Jiang, F. Li, H. Wang, M. Wu, S. Qi, X. Liu, S. Yang and J. Ma, Small Struct., 2(5), 2000122 (2021).V. Nilsson, A. Kotronia, M. Lacey, K. Edstrom and P. Johansson, ACS Applied Energy Materials, 3(1), 200–207 (2020).D. W. McOwen, D. M. Seo, O. Borodin, J. Vatamanu, P. D. Boyle and W. A. Henderson, Energy & Environmental science, 7(1), 416–426 (2014).

Investigation of Heteroatom Doped Graphene Anode for High-Capacity Alkali Metal-Ion Batteries

The drastic growth of Li-ion batteries (LIBs) in global electronic market and low crustal abundance of Li demands for more abundant alternatives such as sodium and potassium having similar electrochemical properties. Sodium-ion battery (SIB) and potassium-ion battery (PIB) can be used “side-by-side” to LIB which can help battery technology progress efficiently. 1Graphite has been a commercial anode in LIB due to its low cost, high abundance, high electrical conductivity, with a theoretical storage capacity (LiC6) of 372 mAh g-1. In contrast the utilization of graphite in SIBs and PIBs is challenging. This is due to the large radius and unstable graphite-intercalation compounds (NaC64) giving very low theoretical capacity of 30 mAh g-1. In PIBs, graphite exhibits a theoretical capacity of 279 mAh g-1 but suffers from poor stability due to huge volume expansion (60%) in fully potassiated state (KC8). Thus, focus is now shifted on to class of amorphous carbon materials such as hard carbon, soft carbon, graphene etc. with variations in micro-structures, larger interlayer spacing, and defect rich sites promoting enhanced capacity and stability even at high current densities. 2 In my presentation I will be discussing about the synthesis of heteroatom doped graphene with high charge storage and stability for LIB, SIB and PIB compared to graphite. The heteroatom doped graphene exhibits nearly 1000 mAh g-1 (LIB), 380 mAh g-1 (SIB) and 379 mAh g-1 (PIB) at a low current density of 25 mAg-1. Additionally, the elastic nature of ultrathin graphene nanosheets aids in attaining long term cyclability at 1 A g-1 with high-capacity retention of 83% for 300 cycles (LIB), 73% for 400 cycles (SIB) and 91% for 600 cycles (PIB). The enhanced stability in case of PIB, is attributed to optimizing solid electrolyte interphase (SEI) components and improving interfacial reaction kinetics at high current densities. Choice of high concentrated electrolyte (HCE) over conventional KPF6 in EC:DEC determines the nature of SEI and thereby helps in achieving cycling stability. The stability in SEI is characterized via voltage profile and understanding chemical composition by ex-situ X-ray photoelectron spectroscopy. Robust SEI in HCE is due to difference in anion structure studied by Raman spectroscopy.Furthermore, the charge-discharge mechanism, alkali ion diffusion kinetics and structure-activity relationship of electrode materials was investigated using various techniques like cyclic voltammetry profiles at different scan rates and Galvanostatic intermittent titration technique (GITT). Additionally, deeper insights into the fundamental understanding of interfacial and bulk behavior were provided with the help of in-situ Raman spectroscopy and in-situ potentiostatic electrochemical impedance spectroscopy (PEIS) analysis. The investigation of peak area and shift in D (defect) and G (graphitic) band analyzed from in-situ Raman studies helped in understanding the evolution and reversibility of alkali ion storage behavior during charging and discharging. PEIS analysis gave us a thorough understanding of the evolution of stable SEI on charging-discharging and after cycling, which helps us to understand the long-term stability in LIB, SIB and PIB.

Highly Concentrated Electrolytes for Lithium Sulfur Batteries – the Role of the Anion(s)

Lithium-sulfur batteries (Li-S) have attracted a lot of attention as a alternative/complement to lithium-ion batteries (LIBs) – due to both high energy density, availability, and inexpensive materials used.[1]Yet, dissolution of sulfur from the C/S cathode and subsequent shuttling of lithium polysulfides (LiPS) to the anode as well as the instability of the Li metal anode itself are true scientific and technological challenges. Advancing in the field of electrolytes is one promising way to overcome both issues.Switching from the standard 1 M electrolyte design of LIBs to highly concentrated electrolytes (HCEs) may both prevent the dissolution of LiPSs and hinder dendrite formation at the lithium metal anode.[2]Here we combine experimental methods and computational approaches to investigate several HCEs based on various Li-salts in several standard organic solvents. Experimentally we targeted electrochemical properties, local electrolyte structure, and physico-chemical properties, with focus on the role(s) of the Li-salt anions. Furthermore, to predict the solubility of sulfur the conductor like screening model for real solvents (COSMO-RS), a computational fluid phase thermodynamic approach, was used.[3] Overall, the challenges and opportunities associated with the use of HCEs in Li-S batteries will be addressed, also highlighting potential areas for future research and development.References Peng et al., "Drastic effect of salt concentration in ionic liquid on performance of lithium sulfur battery." Journal of the Electrochemical Society 169.5 (2022): 050515.Suo et al., "A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries." Nature communications 4.1 (2013): 1481.Jeschke and P. Johansson, "Predicting the Solubility of Sulfur: A COSMO‐RS‐Based Approach to Investigate Electrolytes for Li–S Batteries." Chemistry–A European Journal 23.38 (2017): 9130-9136.

A Glass-Interphase for Highly Reversible and Stable RT-Na/S Batteries

Owing to the high theoretical specific capacity (1165 mA h g-1), high natural abundance, and low redox potential (-2.71 V vs standard hydrogen electrode), sodium metal is considered as an ideal anode material for the next-generation high-energy batteries. Though, a high-temperature variant of the sodium-sulfur batteries has already been commercialized, its compromised safety (due to high-temperature operation, 250 – 300 ⁰C) has triggered the research interest in developing its room-temperature analogue. At room-temperature, the thermodynamic instability of Na metal with the liquid electrolytes often leads to develop a thick and chemically unstable interphase, often called the solid electrolyte interphase (SEI). Upon Na plating/stripping, the SEI grows and dissolves repeatedly, results in consuming both the Na anode and the electrolyte inventory. The Na dendrites, the primary unknown risk associated with Na metal-based batteries, are inclined to develop from the fractured sites of the SEI. The SEI exfoliation can be attributed to weak chemical adhesion between the SEI and the Na metal anode. Functional additives, engineered solvents, and the high concentration electrolytes have often been used to alter the mechanical and electrochemical properties of the SEI. It is apparent that, a stable and durable SEI is the key to creating a secure, dendrite-free, and long-lasting RT-Na/S batteries.More recently, the idea of glass-electrolytes to stabilize the metal anodes is disclosed by the Nobel laureate Prof. J. Goodenough. The glass-electrolyte is used to suppress the dendrite growth and ensured improved safety of the high-energy metal-sulfur batteries. However, the cell experiences a huge interfacial resistance due to metal anode/glass-electrolyte interface.The present work relates to the development of a glass-interphase for RT-Na/S batteries. The interphase is grown directly over the sodium metal anode through a simple and scalable approach. To growth the interphase, a novel organic molecule is used to facilitate the formation of the glass-interphase, and called as “glass-interphase forming additive (GIFA). In general, GIFAs contains the hydrolysable group, which is commonly an amine, acyloxy, alkoxy, or halogen on one side, and one Si atom. It contains organo-functional group, such as epoxide, on other side. The presence of oxide or hydroxide is essential in realizing interaction of GIFA with the sodium metal surface.

Snsb Film As a Long Cycle Life Binder Free Anode Material for Sodium-Ion Batteries Facilitated By High Concentration Electrolyte

With demand for battery devices projected to grow substantially over the coming decades the cost of lithium is expected to increase proportionally[1]. Li mining is an unsustainable process and developing post lithium-ion battery technology will be a critical step in accommodating the increasing demand for energy storage.[2] At the forefront of post-Li battery technology are sodium ion batteries (SIBs). SIBs are not only inherently more sustainable due to avoiding the use of Li but can potentially be more cost efficient. Sodium precursors, such as Na2CO3 and NaCl, are low cost and can be sourced globally. Furthermore, aluminium can be used as the anode current collector instead of copper, significantly reducing costs[1]. However, LIBs are still superior in terms of energy density, and SIB will require much progress to be competitive in that respect. To date, the most widely used anode material in SIBs is hard carbon. Although there are many advantages to using this carbonaceous anode material, it has several limitations, such as limited capacity and some uncertainty surrounding the sodiation mechanism.[3,4] Na-alloying metals are an interesting alternative to hard carbon with some key advantages. Group 14 and 15 metals such as Sn, Sb, and Bi have received much attention recently as potential anode materials because of their high theoretical capacities. However, application of these materials has been limited due to pulverization caused by large volume change during cycling. Nano-structuring alloying materials has been established as a key step in mitigating this issue as the nano-dimensions can accommodate the volume change without pulverization.[5][6]Forming composites of Na-alloying metals is another method that has been successful in extending anode cycle life. One such material is SnSb, which is a promising anode material for sodium-ion batteries due its high theoretical capacity of 751 mAh g-1 while a buffering effect between Sn and Sb during sodiation reduces pulverization.[7] Depositing SnSb directly onto the current collector via physical vapor deposition yields a conductive additive and binder free anode. The resulting layer, being both a composite and nanosized, benefits from the aforementioned advantages. The absence of conductive additives, binders and the need for solvents results in an increased energy density and reduced cost. When tested with a bespoke high concentration electrolyte consisting of NaClO4 in dimethoxyethane and fluoroethylene carbonate additive this anode can achieve capacities exceeding 390 mAh/g after 1500 cycles. The material was tested versus Na foil in a half-cell configuration using 2032 coin-cells.

(Invited) Modeling of the Electric Double Layer (EDL) at Li/SEI/Electrolyte Interfaces

Liquid electrolytes, consisting of salts, solvents, and additives, must form a stable solid electrolyte interphase (SEI) to ensure the performance and durability of lithium(Li)-ion batteries. However, the electric double layer (EDL) structure near charged surfaces is still unsolved, despite its importance in dictating the species being reduced for SEI formation near a negative electrode. Recently, we have developed an interactive Molecular Dynamics -Density Functional Theory -data statistics (MD-DFT-data) model to investigate the reduction reactions of multicomponent electrolytes within the EDL. We will illustrate the effect of EDL on SEI formation in two essential electrolytes, the carbonate-based electrolyte for Li-ion batteries and the ether-based electrolyte for batteries with Li-metal anodes. Our results reveal that the role of fluoroethylene carbonate (FEC) additive differs drastically in the two electrolytes as an SEI modifier to form the beneficial F-containing SEI component (e.g., LiF). The competition among the cations, anions, and various species in the solvents with a charged surface at different temperatures can all jointly determine the EDL structure and therefore the SEI compositions. [1]While the classical Poisson–Boltzmann EDL model developed for fully solvated ions face new challenges in high-concentration liquid electrolytes (HCE), localized high-concentration liquid electrolytes (LHCE) as well as solid electrolytes (SE), new theoretical developments are required. We will introduce a new DEL model in SE and SEI by solving the DFT-informed Poisson–Fermi–Dirac equation and demonstrate how it can be used for interlayer thickness design. [2][1] Wu, Q.S, McDowell, M.T., & Qi, Y., Journal of the American Chemical Society 145 (4), 2473-2484 (2023)[2] Swift, M.W., Swift, J.W. & Qi, Y. Modeling the electrical double layer at solid-state electrochemical interfaces. Nat Comput Sci 1, 212–220 (2021)

Intercalated Redox-Active Anions in Layered Double Hydroxides: Toward New Electrode Designs

Layered Double Hydroxides (LDHs) are a versatile class of 2D materials, which consist of layered di- and trivalent metal cation hydroxides with intercalated anions (1). They are used in many applications including energy storage electrodes, water purification or drug delivery (2, 3).In this new study, Anthraquinone-2-sulfonate (AQS) intercalated in the LDH structure of Mg2Al(OH)6, has been investigated and a charge capacity of 100 mAh g-1 has been measured. However, the dissolution of reduced AQS into the aqueous electrolyte occurs from the first reduction leading to a drastic capacity fade upon cycling.To get around the dissolution issue, we synthesize a new intercalated LDH using ferrocene as the redox active moiety. Electrodes with this new LDH material Mg2Al(OH)6-Fc (Figure 1A) showed more stable cycling when used in combination with aqueous or organic electrolytes. However, the most significant increase in cycle life was achieved by operating this electrode in highly concentrated, highly viscous ionic liquid based electrolytes such as Pyr13TFSI. Over 97 % capacity retention was achieved after 200 cycles with a coulombic efficiency close to 100 % (Figure 1B). The higher stability of redox active anions working at positive redox potentials like ferrocene in the LDH structure is a key parameter to improve cycling ability. Moreover, the limited solubility of the intercalated redox anions into the high concentrated ionic liquid electrolyte is also a key factor for improving cycle life of this new electrode.Figure 1: A) Schematic structure of Mg2Al(OH)6-Fc, C) Improved cycling stability of Mg2Al(OH)6-Fc based electrodes in ionic liquid electrolyte Pyr13TFSI. Figure 1

Investigations on the Initial-Stages of Lithium Deposition/Dissolution Processes in Sulfolane Based Electrolytes

Li metal could be the ideal anode for rechargeable battery technologies, due to its negative redox potential (ca. -3 V vs. SHE), high specific capacity (3860 mAh g−1), and low density (0.534 g cm−3) [1-3]. Recent advances show a new design concept where there are no initial active materials in the anode (no carbon, Si, or Li metal) and the corresponding Li quantity is directly deposited on the current collector during charging. This approach will result in important practical advantages such as enhanced volumetric and gravimetric specific energies, ease of manufacturing and reduced complexity/safety concerns of the recycling process (ideally Li is completely removed in the discharged state). However, the applicability of the Li-metal batteries is constrained by the nonuniform lithium deposition, accompanied by dendrite growth and the formation of dead lithium during long-term cycling, which lead to low Coulombic efficiency and even cell failure [2]. The initial structure and morphology of the Li deposit has a vital influence on the later progression of the Li layer [4]. This underpins the importance of a fundamental understanding of the electrodeposition process. However, the presence of a solid-electrolyte interphase (SEI) makes such investigations difficult, since after the transport of the Li ions through the SEI, a subsequent charge transfer and nucleation growth process at the substrate-SEI interface, instead of substrate-liquid electrolyte interface occurs. This contribution will discuss lithium electrodeposition in a sulfolane based, localized high concentrated electrolyte system. Possible phase formation mechanisms as well as kinetic and thermodynamic aspects during the initial stages of the process are studied by classical electrochemical methods (Fig. 1, left). Furthermore, the mass-charge balance during deposition and stripping was monitored (Fig. 1, right) via in-situ microgravimetry (electrochemical quartz crystal microbalance). In the contribution we will discuss these transients in terms of lithium layer growth and SEI formation.

(Invited) Extending Cycle and Calendar Life of Si Based Li-Ion Batteries By Localized High Concentration Electrolytes

Si is one of the most promising anode materials for the next generation of lithium (Li) ion batteries (LIBs). Recently, we have developed a porous Si with a unique carbon coating structure (“carbon on Si” instead of “Si on carbon”). The nano-porosity of the materials absorbed most of volume expansion so the particles (between 3-5 mm) can retain their integrity during cycling instead of breakdown observed in bulk Si particles. Although single layer pouch cells (Si/NMC622, 62 mAh) with this porous Si anode and baseline electrolyte (1.2 M LiPF6 in EC-EMC (3:7 by wt.) +10 wt.% FEC) can retain 91% capacity after 800 cycles, their calendar life is still far shorter from 10-year target required by electrical vehicles.In this work, we present a systematic investigation of the application of localized high concentration electrolyte (LHCE) to extend the cycle life and calendar life of Si-LIBs. A typical LHCE contains a Li salt (typically LiFSI) with high solubility in a common solvent (such as DMC), and a diluent (such as TTE) with minimal solubility of the Li salt. Compared with other electrolyte design, one distinct advantage of LHCE is that solvent and diluent in LHCE can be largely decoupled from each other: change in once components will have not significantly affect the functionality of other components. This characteristic of LHCE enables much more freedom in the electrolyte designs to satisfy different practical application needs (such as long cycle life, long calendar life, high rate, high temperature, and high voltage). For example, Si/NMC622 cells with a composition of LiFSI-2.15DMC-0.17VC-0.69FEC-4.31TTE (in molar ratio) have increased cycle life of Si/NMC622 pouch cells to 2000 cycles with 80% capacity retention at 25°C as compared with 1000 cycles when baseline electrolyte was used. However, this electrolyte is less stable when LiCoO2 is used as the cathode, leading to rapid capacity loss at elevated temperatures (45°C). One possible reason for this is that cobalt in the cathode leads to more rapid decomposition of FEC than in the case of NMC622 at 45°C. On the other hand, the stability of LHCE is significantly affected by the amount of free (unbound) solvent (including DMC, VC, and FEC in the above example) in the electrolyte. By minimizing the amount of total free solvents, an electrolyte with a composition of LiFSI-2DMC-0.1EC-0.1FEC-3TTE has led to a long cycle life of Si/NMC622 cells at 25°C. Increasing the amount of main solvent in the electrolyte can further increase the conductivity of the electrolyte and significantly increase the charge/discharge rate of the cells.The long calendar life of Si-LIBs can be measured by accelerated tests at elevated temperatures (up to 55°C). Although FEC-containing electrolytes can increase the cycle life of Si-LIBs at room temperature, most Si-LIBs with FEC-containing electrolytes exhibit a rapid increase in impedance at elevated temperature, leading to a short projected-calendar-life. We designed a series of experiments to investigate the effect of FEC on the calendar life of Si-LIBs. The results clearly indicate that the formation of a high impedance interphase layer on the anode and cathode surfaces due to the decomposition of FEC at high temperatures is one of the fundamental reasons for the short calendar life of Si-LIBs. By replacing FEC with an alternative additive, a new LHCE electrolyte has been designed that led to much better cycling stability of Si-LIBs at 45°C (less than 5% capacity loss in 500 cycles) and much longer calendar life. More details of these investigations will be reported in this presentation.

Enhancing Cycle Life of Lithium Metal Batteries By Regulating Solid-Electrolyte Interphase Using Gel Polymer Electrolyte

Lithium metal with high theoretical capacity and low redox potential is one of the promising anode materials for high energy density batteries. However, the lithium metal has safety problems and poor cycling performance, due to the growth of Li dendrite and side reactions between Li and electrolytes. One of the most effective strategies to stabilize Li metal is forming robust solid-electrolyte interphase (SEI). Recently, anion-derived and inorganic-rich SEI is known to be stable and ionic conductive, leading to good cycling stability. One of the most popular strategies to form durable SEI is to use the localized high-concentration electrolytes (LHCE) which construct an anion-derived SEI layer on Li metal. In this work, we synthesized LHCE-based gel polymer electrolytes to form a stable SEI layer and enhance cycling stability. Small amount of cross-linking agent was added into dimethoxyethane (DME)-based LHCE when synthesizing gel polymer electrolyte. The functional groups in cross-linking agents increase Li+ and anion interaction in the gel polymer electrolytes, resulting in formation of the stable SEI layer. The solvation structure and chemical composition of the SEI layer were investigated by density functional theory (DFT) calculation and spectroscopic analyses such as FT-IR, Raman, and XPS. The Li/NCM811 cells with LHCE-based gel polymer electrolyte were assembled for the cycling test, and they exhibited superior cycling performance than liquid electrolyte-based cells.

Flame-Retardant Nonaqueous Electrolytes for High-Safety Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) with conventional organic-based flammable electrolytes suffer from serious safety issues with a high risk of ignition and burning especially under harsh conditions, which significantly limits their widespread applications. Flame-retardant electrolytes (FREs) are considered as one of the most effective strategies to address these safety issues. Therefore, it's much necessary to summarize the challenges, recent progress, and design principles of flame-retardant nonaqueous electrolytes for PIBs to guide their development and future applications. In this review, an in-depth introduction and explanation of the origins of electrolyte flammability are first presented. Particularly, the state-of-the-art design principles of FREs for PIBs are extensively summarized and emphasized, including the electrolyte flame-retardant solvents/additives, highly concentrated electrolytes (HCEs), localized high-concentration electrolytes (LHCEs), ionic liquids-based electrolytes and solid-state electrolytes. Moreover, the advantages and drawbacks of each approach are systematically presented and discussed, following by proposed perspectives to guide the rational development of next-generation high-safety PIBs for practical applications.

Performance analysis and gradient-porosity electrode design of vanadium redox flow batteries based on CFD simulations under open-source environment

As a promising large-scale energy storage device, the vanadium redox flow battery (VRFB) has attracted attention due to its excellent safety, the independence between energy capacity and power capacity, the suitable polarization potential, and the ability to avoid cross-contamination. In this work, a 3D model of VRFB is developed based on the open-source computational fluid dynamics (CFD) platform OpenFOAM, which is well-validated. Then, the effect of operating conditions is studied, which shows that a higher electrolyte concentration can reduce the overpotential and increase the discharge voltage. Reducing the current density can increase the deepness of charge and discharge, reduce the electrolyte concentration gradient, the mass transfer loss and the activation loss. In addition, the effect of electrode porosity is studied that the overpotential decreases near the membrane and increases near the current collector with increasing porosity. Finally, the effect of porosity changes in different directions is studied, and an attempt is made to utilize this overpotential distribution by introducing the gradient-porosity electrode to reduce the non-uniformity of overpotential. The gradient-porosity electrode design using higher porosity near the membrane and lower porosity near the current collector can effectively improve the distribution of overpotential and increase battery performance by 1.67 mV.

An Electrolyte with Less Space-Occupying Diluent at Cathode Inner Helmholtz Plane for Stable 4.6 V Lithium-Ion Batteries.

Reasonably elevating the working voltage (≥4.4 V vs. Li/Li+ ) of the cathode is one of the efficient approaches to maximize the energy density of lithium-ion batteries (LIBs). As a preferred partner for high-voltage LIB systems, localized high-concentration electrolyte (LHCE), characterized by a stronger Li solvation structure, less free solvent, and robust electrode/electrolyte interphase has attracted much attention in academic circles. Herein, we systematically studied the role of the diluent in LHCE on the formation of the cathode electrolyte interphase (CEI) and elucidated that the existing anion-diluent pairing in the inner Helmholtz plane (IHP) results in an uneven CEI and subsequent battery degradation under high voltage. A m-fluorotoluene (mFT) diluent was further employed in the LHCE containing lithium difluoro(oxalato)borate (LiDFOB) to facilitate a uniform and rich-anion-derived CEI, since the weaker interaction of HmFT -BDFOB - , as compared to the HHhydrofluoroether -BDFOB - , reduces the influence of mFT in IHP or initial CEI formation. Consequently, the mFT-dominated LHCE propels the high-voltage performance of LIBs one step forward, endowing a 4.6 V-class 1.2-Ah graphite||LiNi0.8 Co0.1 Mn0.1 O2 pouch cells a 90.4 % capacity retention after 130 cycles. Our study thus describes a new index affecting the CEI formation and proposes novel strategies to deeply optimize the high-voltage LIBs.

Understanding steric hindrance effect of solvent molecule in localized high-concentration electrolyte for lithium metal batteries

High energy density lithium metal batteries (LMBs) have garnered significant research interests in the past decades. However, the growth of lithium dendrites and the low Coulombic efficiency (CE) of Li metal anode pose significant challenges for the development of LMBs. Herein, we report a triethyl orthoformate (TEOF)-based localized high-concentration electrolyte (LHCE) that facilitates a highly reversible Li metal anode with dendrite-free deposition morphologies and an average Coulombic efficiency of 99.1% for 450 cycles. Mechanistic study reveal that the steric hindrance caused by the terminal ethyl groups in the TEOF solvent molecule results in a weak solvating ability, leading to the formation of anion-dominant solvation structures. The anion-dominant solvation sheaths play an essential role in the formation of a LiF-rich solid-electrolyte interphase (SEI), which effectively suppresses the growth of Li dendrites. Furthermore, the TEOF-based electrolyte demonstrates the stable cycling of high-voltage Li||NMC811 cells. These results provide insights into understanding of steric hindrance effect on electrolyte solvation structure and offer valuable guidance for the design of electrolyte solvents in the development of lithium metal batteries.

Diluents Effect on Inhibiting Dissolution of Organic Electrode for Highly Reversible Li‐Ion Batteries

AbstractThe potential of organic electrodes in lithium‐ion batteries (LIBs) is highlighted by their cost‐effectiveness and natural abundance. However, the dissolution of the active material in the electrolyte is a major obstacle to their use in LIBs. Although high‐concentration electrolytes (HCEs) have been proposed to address this issue, they face challenges such as high viscosity, poor wettability, and suboptimal ion conductivity. Hence, this study introduces diluted electrolytes as non‐solvating electrolytes to offset the physical limitations of HCEs and suppress the dissolution of organic electrodes. When a diluted electrolyte is used, perylene‐3,4,9,10‐tetracarboxylic dianhydride (PTCDA)—a notable organic electrode material—demonstrates superior capacity retention and rate performance, achieving 91% of capacity retained at 1000 mA g−1 over 1000 cycles. Through electrochemical and spectroscopic measurements and molecular dynamics simulations, the diluted electrolyte successfully inhibits and demonstrates the dissolution of the active material, preventing capacity loss and the detrimental shuttle effect. This study presents a promising strategy for achieving highly reversible organic electrode‐based LIBs through the development of nonsolvating electrolytes.

A flexible supercapacitor with high energy density and wide range of temperature tolerance using a high-concentration aqueous gel electrolyte

As the demand for a wide range of wearable devices increases, extensive effort is devoted to developing high-performance flexible energy storage devices such as batteries and supercapacitors. Of particular interest, flexible supercapacitors using aqueous electrolytes have high application potential owing to their many advantages including low cost, harmlessness to the human, and environmental safety compared to others using electrolytes such as ionic liquids and organic electrolytes. However, poor temperature tolerance and narrow operation voltage window have hindered the practical application of aqueous supercapacitors. In this study, we report on a wide temperature-tolerant flexible aqueous supercapacitor featuring high electrochemical performance designed by a deliberate selection of electrode materials and electrolytes. As a flexible electrode, three-dimensional microporous graphene foam coated with conducting polymer Polypyrrole (PPy) is used to enhance capacitance up -to 90.0 F/g by increasing the surface area and inducing the pseudo-capacitance of PPy. As a gel-type electrolyte, a high-concentration NaClO4 is mixed with Polyvinyl alcohol to enlarge the voltage window to 1.8 V and a stable temperature range from -25 to 80°C, even under repetitive bending deformation. The fabricated supercapacitor exhibits a superior energy density of 37.4 Wh kg−1 and maintains 92.0% of initial capacitance at room temperature after three repeated cycles of cooling/heating across a wide temperature range over 100°C. This work suggests a high potential application of the fabricated supercapacitor as an eco-friendly and stable energy storage system for powering diverse wearable devices under various conditions.

Electrochemical degradation of ciprofloxacin from water: Modeling and prediction using ANN and LSSVM

Ciprofloxacin is a widely used antibiotic that is also a persistent contamination that causes major health and environmental risks. This study investigated the electrochemical removal of ciprofloxacin using a boron-doped diamond anode and a non-supportive electrode to get an accurate understanding of the anode's performance. The effects of current density, initial ciprofloxacin concentration, time, pH, and electrolyte concentration on the removal efficiency of ciprofloxacin were investigated. Additionally, ANN and LSSVM models were used to predict ciprofloxacin removal. The results showed that the BDD anode was effective in removing ciprofloxacin from water, with complete removal of 10 mg L−1 CIP in less than 45 min with electrolyte concentration of 25 g L−1, a current density of 20 mA cm−2, and a pH value of 3. The removal efficiency was found to increase with increasing current density and time because it increases the concentration of active species. The removal efficiency was also found to be higher at acidic pH values and higher electrolyte concentrations. The ANN model was found to be more accurate in predicting ciprofloxacin removal than the LSSVM model, with an R2 of 0.9982 and an AARE% of 2.68%, compared to R2 of 0.9978 and an AARE% of 3.85%. The models were validated using a new set of data, and the results showed that the ANN model was able to accurately predict ciprofloxacin removal under a variety of conditions.

Loosely coordinating diluted highly concentrated electrolyte toward −60 °C Li metal batteries

Lithium metal batteries (LMBs) promise energy density over 400 Wh kg−1. However, they suffer severe electrochemical performance deterioration at sub-zero temperatures. Such failure behavior highly correlates to inferior lithium metal anode (LMA) compatibility and sluggish Li+ desolvation. Here, we demonstrate that cyclopentylmethyl ether (CPME) based diluted high-concentration electrolyte (DHCE) enables −60 °C LMBs operation. By leveraging the loose coordination between Li+ and CPME, such developed electrolyte boosts the formation of ion clusters to derive anion-dominant interfacial chemistry for enhancing LMA compatibility and greatly accelerates Li+ desolvation kinetics. The resulting electrolyte demonstrates high Coulombic efficiencies (CE), providing over 99.5%, 99.1%, 98.5% and 95% at 25, −20, −40, and −60 °C, respectively. The assembled Li-S battery exhibits remarkable cyclic stability in −20, and −40 °C at 0.2 C charging and 0.5 C discharging. Even at −60 °C, Li-S cell with this designed electrolyte retains > 70% of the initial capacity over 170 cycles. Besides, lithium metal coin cell and pouch cell with 10 mg cm−2 high S cathode loading exhibit cycling stability at −20 °C. This work offers an opportunity for rational designing electrolytes toward low temperature LMBs.