Conductivity Of Electrolyte Research Articles

High ionic conductive Sodium β-alumina (SBA) and SBA-NaPF6 composite solid electrolytes prepared by cold sintering process

Sodium β-alumina (SBA) electrolytes are among the most excellent candidates for all-solid-state batteries due to their high electrochemical performances and low cost of sodium resources. However, thermally sintering at above 1400 °C is required to fabricate high dense SBA electrolytes, thus giving rise to a huge energy consumption. Here, dense SBA electrolytes and (1-x)SBA-xNaPF6 (x=5, 10, 15, 20 wt%) composites were fabricated using cold sintering process (CSP) below 300 °C with 2 mol/L NaOH solution as transient chemistry. The ionic conductivity of SBA electrolytes is significantly enhanced from 5.53×10-6 S·cm-1 to 5.91 × 10−4 S·cm−1 as 15 wt% NaPF6 was introduced to the composite, which is comparable with the SBA sintered above 1400 °C. CSP may provide a promising approach for the fabrication of solid-state electrolytes by avoiding the detrimental impact of high temperature heat treatment.

Influence of calcium-doped on the conductivity of NASICON-type Na3Zr2Si2PO4 solid electrolyte

Sodium-ion solid electrolyte has many advantages such as high safety, good ionic conductivity, and strong chemical stability. NASICON-type Na3Zr2Si2PO4 solid electrolyte was prepared by high-temperature Solid State Reaction (SSR). X-ray Diffraction (XRD) show that the 20% excess addition of Na and P elements will reduce the formation of ZrO2 impurity phase and increase the ionic conductivity to 1.01×10−4 S cm−1. On the basis of this experiment, Ca was added to dope the Na site in Na3Zr2Si2PO4 with different contents. Electrochemical impedance spectroscopy (EIS) results show that the conductivity of Ca2+ doped Na2.7Ca0.15Zr2Si2PO4 is significantly increased to 1.53×10−4 S cm−1, the electronic conductivity is 3.99×10−8 S cm−1, and the activation energy is 0.32 eV. Cyclic voltammetry testing demonstrated stable chemical properties below to 5 V. Na | Na2.7Ca0.15Zr2Si2PO4 | Na3V2(PO4)3 battery still maintains a high capacity retention rate of 98.76% after 200 cycles at 25oC-0.2C. It indicating that the new 0.15molCa-doped Na2.7Ca0.15Zr2Si2PO4 has the highest electrical conductivity, which provides a new research idea for sodium-ion solid-state batteries and has great potential in solid-state battery applications.

Na3Zr2Si2PO12-Polymer Composite Electrolyte for Solid State Sodium Batteries.

The integration of the flexibility of organic polymer electrolyte and high ionic conductivity of the ceramic electrolyte is attempted in search of efficient and safer battery. Composite solid polymer electrolyte (CSPE) provides high ionic conductivity with a sustainable thin film of electrolyte having the synergistic effect of ionic liquid and active inorganic filler. The CSPE is synthesized by the solution cast technique using Na3Zr2Si2PO12 (NZSP) as ceramic and poly(vinylidene fluoride-hexafluoropropylene) with Salt-Ionic liquid as polymer electrolyte. X-ray diffraction (XRD) of CSPE includes amorphous nature due to the polymer part as well as crystalline peaks of ceramic NZSP, simultaneously. The prepared CSPE sample shows homogeneous and interconnected surface morphology is observed by Scanning electron microscopy (SEM) image. Thermogravimetric analysis (TGA) shows electrolyte is thermally stable up to 200 °C and differential scanning calorimetry (DSC) reveals decrease in degree of crystallinity due to NZSP addition in the CSPE. By complex impedance spectroscopy (CIS), room temperature ionic conductivity of the prepared CSPE is found ~1.03 mS/cm. The dielectric behaviour of the prepared electrolyte is also studied to investigate the ion dynamics within the sample. The cationic transference number is 0.53 and the electrochemical stability window (ESW) of the CSPE is 4.9 V which is suitable for sodium solid-state batteries applications.

Liquid-phase synthesis of a Li3PS4 solid electrolyte using ethyl isobutyrate as a synthetic medium

A β-Li3PS4 solid electrolyte was prepared via liquid-phase synthesis using ethyl isobutyrate as a synthetic medium. The precursor and solid electrolyte structures were characterized using thermogravimetry–differential thermal analysis and X-ray diffraction techniques. The dielectric relaxation analysis showed two relaxation regions, which revealed a bulk and grain boundary ionic migration process. At a temperature lower than 90°C, the frequency dependence of the dielectric constant of the prepared sample was different from that of glassy Li3PS4, indicating that the motion of the PS4 unit enhances the ionic conductivity of the Li3PS4 solid electrolyte. The ionic conductivities of the cold-pressed and warm-pressed pellets at 25°C were 6.8 × 10−5 Scm−1 and 3.6 × 10−4 Scm−1, respectively.

Photoexcitation‐Enhanced High‐Ionic Conductivity in Polymer Electrolytes for Flexible, All‐Solid‐State Lithium‐Metal Batteries Operating at Room Temperature

Designing solid polymer electrolytes (SPEs) with high ionic conductivity for room‐temperature operation is essential for advancing flexible all‐solid‐state energy storage devices. Innovative strategies are urgently required to develop SPEs that are safe, stable, and high‐performing. In this work, we introduce photoexcitation‐modulated heterojunctions as catalytically active fillers within SPEs, guided by photocatalytic design principles, and employ natural bacterial cellulose to enhance the mechanical properties of the inorganic‐filled SPEs. In‐situ photothermal experiments and theoretical calculations reveal that the strong photogenerated electric field produced by trace heterojunctions within poly(ethylene oxide) electrolytes under photoexcitation significantly enhances lithium salt dissociation, increasing the concentration of mobile Li+. This results in a substantial increase in ionic conductivity, reaching 0.135 mS cm−1 at 25 °C, with a Li+ transference number as high as 0.46. The flexible all‐solid‐state lithium‐metal pouch cells exhibit an impressive discharge capacity of 178.8 mAh g−1 even after repeated bending and folding, and demonstrate exceptional long‐term cycling stability, retaining 86.7% of their initial capacity after 250 cycles at 1 C (25 °C). This research offers a novel approach to developing high‐performance flexible lithium‐metal batteries.

Enhancing the performance of ionic conductivity for solid-state electrolytes: an effective strategy of injecting lithium ions within anionic metal-organic frameworks.

Metal-organic frameworks (MOFs) are considered as potential solid-state electrolyte (SSE) materials due to their structural diversity and porosity. Adding lithium ions into the anionic frameworks of MOFs and then realizing single-ion transport is an efficient way to enhance the performance of ionic conductivity of SSE materials. Herein, an ionotropic MOF (Li+[Cu-BTC]-) with lithium ions in the pores of the lattice was synthesized through an ion exchange strategy, which exhibits outstanding lithium ionic conducting properties over a wide temperature range (ionic conductivity: 0.11-2.96 × 10-3 S cm-1 in the temperature range of -40 to 100 °C). The strategy of injecting Li+ within anionic metal-organic frameworks provides a new opportunity for exploring advanced SSEs.

Thermodynamic study of pyridoxine in different solvents and temperatures: DFT study

The equivalent conductivities (Λ) of B6 vitamin (pyridoxine) in HշՕ and MeOH were measured at different temperatures between 293 to 313 K, as well as in mixtures of H₂O and MeOH at percentages of 10, 20, 30, 40, and, 50% MeOH at 310 K. All the practical results were mathematically processed using the Lee Wheaton equation, which is applied to the derived conductivity of electrolytes with a similar composition (1:1). This equation calculates various conductivity components, including the equivalent conductance at infinite dilution (Λₒ), the ionic conductivity, the distance between ions (R), and also the constant of ionic aggregation (Ka) at best-fit values of (ϬΛ). The values of these parameters differed from one solvent to another depending on the molecular interactions in the solution and the physical properties of the solvents, such as viscosity and dielectric constant. Finally, thermodynamic quantities for the ion association reaction (ΔG°, ΔH°, and ΔS°) were also studied. Density functional theory (DFT) calculations (B3LYP/6-31G (d,p)) were employed to analyze vitamin B6 in the gas phase and diverse solvents. Three different continuum methods, namely AM1, PM3, and HF, were utilized, followed by DFT. The final method was utilized to explore the effects on its characteristics. KEY WORDS: Electrical conductivity, Lee-Wheaton equation, Theoretical chemistry, DFT. Bull. Chem. Soc. Ethiop. 2025, 39(1), 165-176. DOI: https://dx.doi.org/10.4314/bcse.v39i1.14

Tuning the Nucleophilicity of Anion in Lithium Salt to Enable an Anion‐Rich Solvation Sheath for Stable Lithium Metal Batteries

AbstractTraditional lithium salts typically adhere to the designing principles of enhancing cation‐anion dissociation degree to obtain a high electrolyte conductivity. This promotes the invention of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), where the symmetric electron‐withdrawing trifluoromethanesulfonyl groups significantly delocalize the negative charge density around the nitrogen atom, thereby weakening the electrostatic interaction between Li+ and the anion. Herein, deviating from the general principle, lithium (methanesulfonyl)(trifluoromethanesulfonyl) imide (LiMTFSI) is deliberately designed by substituting a unilateral electron‐withdrawing trifluoromethyl (─CF3) group of LiTFSI with an electron‐donating methyl (─CH3) group, to tune the nucleophilicity of the anion. This modification enhances Li‐anion interaction, causing the anion to replace the solvent molecules in the Li+ solvation shell. Additionally, the MTFSI− anion exhibits an elevated donor number to facilitate the solubility of LiNO3 in carbonate‐based electrolytes. The synergistic effect of these changes suppresses the decomposition of solvent and helps construct a stable solid electrolyte interphase (SEI) enriched with multiple inorganic lithium salts (e.g., Li2S, Li3N, and LiNxOy) on the Li metal anode, which enables the 500 mAh Li||LiNi0.5Co0.2Mn0.3O2 pouch cell to operate steadily for 150 cycles. It is believed this work would provide new insights and another dimension for designing functional anions beyond their role as charge carriers.

Halogen-Bonding Nanoarchitectonics in Supramolecular Plasticizers for Breaking the Trade-Off between Ion Transport and Mechanical Strength of Polymer Electrolytes for High-Voltage Li-Metal Batteries.

The low ionic conductivity of poly(ethylene oxide) (PEO)-based polymer electrolytes at room temperature impedes their practical applications. The addition of a plasticizer into polymer electrolytes could significantly promote ion transport while inevitably decreasing their mechanical strength. Herein, we report a supramolecular plasticizer (SMP) to break the trade-off effect between ionic conductivity and mechanical properties in PEO-based polymer electrolytes. Accordingly, the SMP is constructed by tetraethylene glycol dimethyl ether (G4) and SbF3 through halogen bonds. The SMP-plasticized PEO electrolyte (PEO/SMP) presents a simultaneously enhanced ionic conductivity of 2.4 × 10-4 S cm-1 (25 °C) and a high mechanical strength of 8.1 MPa, compared to those of pristine PEO-based electrolytes. Benefiting from the halogen bonds between G4 and SbF3, the Li-O coordination in PEO/SMP is evidently weakened, and thus rapid Li+ transport is achieved. Furthermore, the PEO/SMP electrolyte possesses a wide electrochemical stability window of 4.5 V and, importantly, derives an inorganic-rich SEI with a low interfacial resistance on a lithium metal surface. By using PEO/SMP, the lithium-metal battery with the LiNi0.5Co0.2Mn0.3O2 cathode exhibits a good rate and long-term cycling performance with a capacity retention of 75.3% (500 cycles). This work offers a rational guideline for the design of polymer electrolytes suitable for high-performance lithium-metal batteries.

Soft Matter Electrolytes: Mechanism of Ionic Conduction Compared to Liquid or Solid Electrolytes

Soft matter electrolytes could solve the safety problem of widely used liquid electrolytes in Li-ion batteries which are burnable upon heating. Simultaneously, they could solve the problem of poor contact between electrodes and solid electrolytes. However, the ionic conductivity of soft matter electrolytes is relatively low when mechanical properties are relatively good. In the present review, mechanisms of ionic conduction in soft matter electrolytes are discussed in order to achieve higher ionic conductivity with sufficient mechanical properties where soft matter electrolytes are defined as polymer electrolytes and polymeric or inorganic gel electrolytes. They could also be defined by Young’s modulus from about Pa to Pa. Many soft matter electrolytes exhibit VFT (Vogel–Fulcher–Tammann) type temperature dependence of ionic conductivity. VFT behavior is explained by the free volume model or the configurational entropy model, which is discussed in detail. Mostly, the amorphous phase of polymer is a better ionic conductor compared to the crystalline phase. There are, however, some experimental and theoretical reports that the crystalline phase is a better ionic conductor. Some methods to increase the ionic conductivity of polymer electrolytes are discussed, such as cavitation under tensile deformation and the microporous structure of polymer electrolytes, which could be explained by the conduction mechanism of soft matter electrolytes.

Borophosphate glass based electrolyte composite for high lithium ionic conductivity

The application requirements of solid-state lithium (Li) metal batteries are satisfied by the ionic conductivity of composite solid-state electrolytes, attributed to their minimal interfacial resistance. Herein, composite solid electrolytes were obtained by mixing a crystalline Li0.5La0.5TiO3 (LLTO) perovskite with different amount of 47Li2O-30B2O3-23P2O5 (LBP) glass phase. The results show that the crystal phase of the composite samples exhibit a tetragonal perovskite structure with a P4/mmm space group. Frequency dependent AC conductivity shows that composite containing 1 % LBP glass avoids the phenomenon of charge carrier blocking at low frequency and low temperature at the same time. The room temperature maximum total ionic conductivity was obtained for sample with 0.5 % LBP glass presenting a conductivity that is almost three times higher than that of pure LLTO. The factors influencing ionic conductivity are not only grain morphology and size, and activation energy, but also lithium content, and entropic effects contribute to the facility or difficulty with which Li+ can migrate into the LLTO solid electrolyte.

Autonomous Battery Optimization by Deploying Distributed Experiments and Simulations

AbstractNon‐trivial relationships link individual materials properties to device‐level performance. Device optimization therefore calls for new automation approaches beyond the laboratory bench with tight integration of different research methods. This study demonstrates a Materials Acceleration Platform (MAP) in the field of battery research based on the problem‐agnostic Fast INtention‐Agnostic LEarning Server (FINALES) framework, which integrates simulations and physical experiments while leaving the active control of the hardware and software resources executing experiments or simulations with the partners running the respective units. This decentralization of control is a distinctive feature of MAPs using the FINALES framework. The connected capabilities entail the formulation and characterization of electrolytes, cell assembly and testing, early lifetime prediction, and ontology‐mapped data storage provided by institutions distributed across Europe. The infrastructure is used to optimize the ionic conductivity of electrolytes and the End Of Life (EOL) of lithium‐ion coin cells by varying the electrolyte formulation. Trends in ionic conductivity are rediscovered and the effect of the electrolyte formulation on the EOL is investigated. Further, the capability of this MAP to bridge diverse research modalities, scales, and institutions enabling system‐level investigations under asynchronous conditions while handling concurrent workflows on the material‐ and system‐level is shown, demonstrating true intention‐agnosticism.

Enhancement of Low-Temperature Cycling Performance of Lithium-Ion Batteries by use of Dual Cosolvent

Abstract Lithium-ion batteries (LIBs) based on conventional electrolyte suffer from poor cycling performance at low temperatures due to the reduced ionic conductivity of electrolytes, sluggish charge transfer reaction, and Li plating during the charging process. Herein, we propose a dual cosolvent composed of methyl acetate (MA) and ethyl fluoroacetate (EFA). MA effectively reduced the viscosity of the electrolyte, improving the ionic conductivity at low temperatures. EFA facilitated the de-solvation of Li+ ions and formed an anion-derived solvation structure, enabling the formation of an inorganic-rich solid electrolyte interphase on the graphite anode. Due to the synergistic effect of MA and EFA, the graphite/LiFePO4 cell employing a dual cosolvent exhibited good cycling performance at low temperatures, delivering a discharge capacity of 68.7 mAh g-1 at -20 °C and 0.2 C and showing a capacity retention of 99.7% after 100 cycles at -20 °C and 0.33 C. Additionally, the cell exhibited an initial discharge capacity of 131.2 mAh g-1 at 25 °C and 1.0 C, with a capacity retention of 99.4% after 300 cycles. Our results demonstrate that liquid electrolytes containing dual cosolvent with various beneficial roles can be a promising solution for improving the low-temperature cycling performance of LIBs.

DNA: Novel Crystallization Regulator for Solid Polymer Electrolytes in High-Performance Lithium-Ion Batteries.

In this work, we designed a novel polyvinylidene fluoride (PVDF)@DNA solid polymer electrolyte, wherein DNA, as a plasticizer-like additive, reduced the crystallinity of the solid polymer electrolyte and improved its ionic conductivity. At the same time, due to its Lewis acid effect, DNA promotes the dissociation of lithium salts when interacting with lithium salt anions and can also fix the anions, creating more free lithium ions in the electrolyte and thus improving its ionic conductivity. However, owing to hydrogen bonding between DNA and PVDF, excess DNA occupies the lone pairs of electrons of the fluorine atoms on the PVDF molecular chains, affecting the conduction of lithium ions and the conductivity of the solid electrolyte. Hence, in this study, we investigated the effects of adding different DNA amounts to solid polymer electrolytes. The results show that 1% DNA addition resulted in the best improvement in the electrochemical performance of the electrolyte, demonstrating a high ionic conductivity of 3.74 × 10-5 S/cm (25 °C). The initial capacity reached 120 mAh/g; moreover, after 500 cycles, the all-solid-state batteries exhibited a capacity retention of approximately 71%, showing an outstanding cycling performance.

Synergistic effect of ceramic filler in polymer salt complex for improved ion dissociation and migration mechanism

Abstract Use of Ceramic filler is one of the most common approaches to improve the conductivity and stability properties of a solid polymer electrolyte (SPE) cum separator. Among them, active fillers like Garnet have been extensively used to enhance the stability and conductivity of SPE. However, SPE suffers from limited ion migration at room temperature acting as a bottleneck for their application in all solid-state batteries. An extensive study on these fillers' role in ion dissociation and migration can be a stepping stone for advanced SPE. In the present work, an FTIR analysis has primarily been used to identify and evaluate cation coordinate site-cation, and ion pair interactions in a Li6.5La3Zr1.75Te0.25O12 loaded polyethylene oxide-LiCF3SO3 matrix with varying ceramic concentrations. Further, the Trukhan model has been used to calculate diffusion coefficient, mobility, and charge carrier density to interpret relaxation parameters, conductivity, and FTIR results in the SPE samples. Finally, an ion migration model has been proposed based on the results obtained in experimental studies.

Scaling the ionic conductivity and electrochemical properties of bio-based gel polymer electrolytes reinforced with Al2O3 nanofibers for energy storage applications

Scaling the ionic conductivity and electrochemical properties of bio-based gel polymer electrolytes reinforced with Al2O3 nanofibers for energy storage applications

Fabrication of Scalable Covalent Organic Framework Membrane-based Electrolytes for Solid-State Lithium Metal Batteries.

The conventional covalent organic framework (COF)-based electrolytes with tailored ionic conducting behaviors are typically fabricated in the powder morphology, requiring further compaction procedures to operate as solid electrolyte tablets, which hinders the large-scale manufacturing of COF materials. In this study, we present a feasible electrospinning strategy to prepare scalable, self-supporting COF membranes (COMs) that feature a rigid COF skeleton bonded with flexible, lithiophilic polyethylene glycol (PEG) chains, forming an ion conduction network for Li+ transport. The resulting PEG-COM electrolytes exhibit enhanced dendrite inhibition and high ionic conductivity of 0.153 mS cm-1 at 30 °C. The improved Li+ conduction in PEG-COM electrolytes stems from the loose ion pairing in the structure and the production of higher free Li+ content, as confirmed by solid-state 7Li NMR experiments. These changes in the local microenvironment of Li+ facilitate its directional movement within the COM pores. Consequently, solid-state symmetrical Li|Li, Li|LFP, and pouch cells demonstrate excellent electrochemical performance at 60 °C. This strategy offers a universal approach for constructing scalable COM-based electrolytes, thereby broadening the practical applications of COFs in solid-state lithium metal batteries.

Effects of a Mechanically Interlocked Structure on Ionic Conductivity in Polyrotaxane-Based Polymer Electrolytes.

Polyrotaxane (PR) is a mechanically interlocked polymer (MIP) utilized as an electrolyte because of its distinctive property of dynamic molecular mobility. While numerous studies have concentrated on modifying external properties to decrease high crystallinity, few have explored the control of intrinsic properties. This study examines the crystalline properties and molecular mobility of PR-based electrolytes, along with their effects on ionic conductivity, by manipulating intrinsic properties. By systematically varying the inclusion ratio, we demonstrate that lower inclusion ratios lead to reduced crystallinity, enhancing molecular mobility. Consequently, 100PRE exhibits decreased crystallinity due to lower aggregation probabilities of α-cyclodextrins (α-CDs), longer T2 relaxation times (0.215 s), and higher ionic conductivity (3.4 × 10-3 S cm-1 at 25 °C).

Boosting Li-Ion Conductivity of Fluoride Solid Electrolyte by Low-Temperature Molten Salt Ablation and Particle Boundary Doping.

Halide solid electrolytes (SEs) are attracting great attention, owing to their high ionic conductivity and excellent high-voltage compatibility. However, severe moisture sensitivity, poor thermal stability, and instability at the lithium metal anode interface with chloride and bromide SEs retard their applications in solid-state lithium metal batteries. Fluoride SEs are expected to solve these problems, but they are now plagued by inadequate room-temperature (RT) ionic conductivity. Herein, a low-temperature molten salt (LiCl+1.33AlCl3) ablation method is proposed to enhance the ionic conductivity of monoclinic Li3GaF6 by particle boundary doping. The RT ionic conductivity of Li3GaF6 is correspondingly increased by 2 orders of magnitude, and the conductivity reaches 10-4 S cm-1 at 60 °C. The improved ionic conductivity benefits from the enhancement of interfacial ion transport, with the formation of more conductive chlorine-doped Li3GaF6-xClx and in situ binder LiAlCl4 to cement surrounding nanoparticles. The as-synthesized Li3GaF6 demonstrates outstanding humidity tolerance without conductivity degradation after exposure to a relative humidity of up to 35%. It also exhibits the widest electrochemical stability window experimentally (close to 6 V) compared with other state-of-the-art SEs. The solid-state Li/Li3GaF6/LiFePO4 cell with a stable Li+-conductive polymer interface is successfully driven for at least 200 cycles at 0.5C. Our study provides a solution to various chemical and electrochemical stability issues encountered by the halide SE family.

Ionic Covalent Organic Frameworks Consisting of Tetraborate Nodes and Flexible Linkers.

Covalent organic frameworks (COFs) have emerged as versatile materials with many applications, such as carbon capture, molecular separation, catalysis, and energy storage. Traditionally, flexible building blocks have been avoided due to their potential to disrupt ordered structures. Recent studies have demonstrated the intriguing properties and enhanced structural diversity achievable with flexible components by judicious selection of building blocks. This study presents a novel series of ionic COFs (ICOFs) consisting of tetraborate nodes and flexible linkers. These ICOFs use borohydrides to irreversibly deprotonate the alcohol monomers to achieve a high degree of polymerization. Structural analysis confirms the dia topologies. Reticulation is explored using various monomers and metal counterions. Also, these frameworks exhibit excellent stability in alcohols and coordinating solvents. The materials have been tested as single-ion conductive solid-state electrolytes. ICOF-203-Li displays one of the lowest activation energies reported for ion conduction. This tetraborate chemistry is anticipated to facilitate further structural diversity and functionality in crystalline polymers.