Ionic Transference Number Research Articles

Ionic liquid supported chitosan-g-SPA as a biopolymer-based single ion conducting solid polymer electrolyte for energy storage devices

This article discusses the preparation of different grades of single-ion conducting quasi-solid polymer electrolytes (q-SPE) material (Chit-g-SPA-IL) based on biopolymer (chitosan), polyacrylic acid and DBU-acetate (DBUH+ AcO−) ionic liquid. Chit-SPA-60 %-IL exhibited the highest conductivity within the range of 10−4 S/cm. TGA analysis demonstrated the stability of electrolytes up to a temperature of 120 °C. SEM-EDS analysis unveiled the porous nature of the electrolyte and even distribution of ions throughout the matrix. It exhibited an electrochemical stability window (EWS) of 2.53 V with significant current density and an ionic transference number (ITN) of ~99.9 %. The temperature-dependent conductivity established an Arrhenius-type conduction mechanism with an activation energy of 0.149 eV for ion movement within the electrolyte matrix. The AC conductivity analysis emphasized the time-temperature independence of the ionic conduction mechanism. Dielectric analysis highlighted the capacitive nature of the electrolyte, underlining its substantial capacitance, while modulus studies indicated minimal influence from the electrode-electrolyte interface. Chit-SPA-60 %-IL at 30 °C included a self-diffusion coefficient of 4.57 × 10−5 m2/s, ionic mobility of 1.75 × 10−3 m2/Vs, and drift ionic velocity of 0.44 m/s. These findings makes SPE as a promising candidate for sodium-ion-based energy storage devices.

Experimental investigation of the impact of additives in low clinker cementitious materials on multi-ion transference numbers and diffusion coefficients

In this paper, multi-ion transference numbers were determined throughout the chloride migration testing of low clinker cement-based materials. For this purpose, five cement pastes were studied: pure Portland paste (as a reference) and four other pastes, based on limestone filler, fly ash, slag or silica fume. The transference numbers were calculated from the concentration evolution in the three zones of the migration cell (catholyte, anolyte and sample), considering that: (i) ions moved in the catholyte and anolyte; (ii) ions leached from the sample; (iii) ions were generated from the electrode processes, and (iv) the pore solution of the sample evolved during the test. The chloride transference numbers of pastes with pure Portland cement, limestone filler, fly ash, slag or silica fume are almost zero at the beginning of the migration test but 0.23; 0.18; 0.06; 0.05 and 0.20 at the end of the test, respectively. The ion transference numbers obtained were used for the calculation of diffusion coefficients of chlorides, sodium and potassium using the Nernst-Einstein equation.

FFF/FDM 3D-Printed Solid Polymer Electrolytes Based on Acrylonitrile Copolymers for Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) are essential in modern electronics, particularly in portable devices and electric vehicles. However, the limited design flexibility of current battery shapes constrains the development of custom-sized power sources for advanced applications like wearable electronics and medical devices. Additive manufacturing (AM), specifically Fused Filament Fabrication (FFF), presents a promising solution by enabling the creation of batteries with customized shapes. This study explores the use of novel poly(acrylonitrile-co-polyethylene glycol methyl ether acrylate) (poly(AN-co-PEGMEA)) copolymers as solid polymer electrolytes for lithium-ion batteries, optimized for 3D printing using FFF. The copolymers were synthesized with varying AN:PEGMEA ratios, and their physical, thermal, and electrochemical properties were systematically characterized. The study found that a poly(AN-co-PEGMEA) 6:1 copolymer ratio offers an optimal balance between printability and ionic conductivity. The successful extrusion of filaments and subsequent 3D printing of complex shapes demonstrate the potential of these materials for next-generation battery designs. The addition of succinonitrile (SCN) as a plasticizer significantly improved ionic conductivity and lithium cation transference numbers, making these copolymers viable for practical applications. This work highlights the potential of combining polymer chemistry with additive manufacturing to provide new opportunities in lithium-ion battery design and function.

Stable Efficient Solid-State Supercapacitors and Dye-Sensitized Solar Cells Using Ionic Liquid-Doped Solid Biopolymer Electrolyte.

As synthetic and nonbiodegradable compounds are becoming a great challenge for the environment, developing polymer electrolytes using naturally occurring biodegradable polymers has drawn considerable research interest to replace traditional aqueous electrolytes and synthetic polymer-based polymer electrolytes. This study shows the development of a highly conducting ionic liquid (1-hexyl-3-methylimidazolium iodide)-doped corn starch-based polymer electrolyte. A simple solution cast method is used to prepare biopolymer-based polymer electrolytes and characterized using different electrical, structural, and photoelectrochemical studies. Prepared polymer electrolytes are optimized based on ionic conductivity, which shows an ionic conductivity as high as 1.90 × 10-3 S/cm. Fourier transform infrared spectroscopy (FTIR) confirms the complexation and composite nature, while X-ray diffraction (XRD) and polarized optical microscopy (POM) affirm the reduction of crystallinity in biopolymer electrolytes after doping with ionic liquid (IL). Thermal and photoelectrochemical studies further affirm that synthesized material is well stable above 200 °C and shows a wide electrochemical window of 3.91 V. The ionic transference number measurement (t ion) confirms the predominance of ionic charge carriers in the present system. An electric double-layer capacitor (EDLC) and a dye-sensitized solar cell (DSSC) were fabricated by using the highest conducting corn starch polymer electrolyte. The fabricated EDLC and DSSC delivered an average specific capacitance of 130 F/g and an efficiency of 1.73% in one sun condition, respectively.

Compositional dependence of electrochemical properties in biopolymer blend-based solid electrolytes doped with sodium perchlorate for EDLC applications

Biopolymer-based blends of solid electrolytes capable of conducting sodium ions were prepared via solution casting by incorporating sodium carboxymethyl cellulose (NaCMC) and polyvinyl alcohol (PVA) with varying concentrations of sodium perchlorate monohydrate (NaClO4.H2O), which was used as the dopant. The prepared electrolytes were characterized to reveal their structural, vibrational, electrical, and electrochemical properties that make them promising as solid polymer electrolytes (SPEs). X-ray diffraction (XRD) analysis showed that the amorphous nature of the sample increased with the addition of NaClO4.H2O salt concentrations of up to 30 wt.%. The complexation between the polymers and salt was confirmed by Fourier-Transform Infrared (FTIR) analysis. The SPE exhibited an optimal ionic conductivity of (1.90 ± 0.05) ×10−5 S cm−1, which is three orders higher than that of the pristine polymer blend with (5.31 ± 0.61) ×10−8 S cm−1, as determined by electrochemical impedance spectroscopy (EIS) analysis. Scaling studies conducted based on AC conductivity and tangent loss revealed that these measurements could be represented by a single master curve, which suggests that the optimal sample adheres to the time-temperature superposition principle (TTSP). The temperature dependence of Jonscher's exponent indicates that the conduction mechanism can be effectively represented by the Quantum Mechanical Tunneling model (QMT). Both transference number measurement (TNM) and linear sweep voltammetry (LSV) analyses validated the electrolyte's suitability for energy device applications by demonstrating its high ion transference number and electrochemical potential window of 3.93 V. The optimized SPE film was subsequently utilized in an electrochemical double-layer capacitor (EDLC) device to evaluate its performance as both an electrolyte and separator. The supercapacitor exhibited an impressive energy density of 15.18 Wh kg−1 and a power density of 4512.5 W kg−1, along with remarkable stability in terms of cycle life.

Leveraging Ion Pairing and Transport in Localized High-Concentration Electrolytes for Reversible Lithium Metal Anodes at Low Temperatures.

Coulombic efficiency of over 99% is rarely achieved for Li metal anode below -40°C, hindering the practical application of high-energy-density Li metal batteries under extreme conditions. Herein, limiting factors for Li metal reversibility are investigated utilizing ether-based localized high-concentration electrolytes of different solvent-diluent combinations. We find that along with the desolvation barrier, bulk ion transport properties including ionic conductivity, transference number, and diffusivity are also crucial factors for low-temperature Li deposition behavior. Superior Li metal reversibility was observed within the combination of the solvent with moderately weak solvating power and the diluent with minimal viscosity, highlighting the role of ion transport and the necessity for a trade-off with desolvation. The optimized electrolyte composed of lithium bis(fluorosulfonyl)imide, methyl n-propyl ether, and 1,1,2,2-tetrafluoroethyl methyl ether delivers exceptional Coulombic efficiency of 99.34% at -40°C and 98.96% at -60°C under a current density of 0.5 mA cm-2. Furthermore, Li||LiCoO2 (2.7 mAh cm-2) cells demonstrate impressive reversible capacity and cycling stability at these temperatures. This work sheds light on the less-recognized relevance of bulk ion transport to low-temperature performance and provides guidelines for the electrolyte design of Li metal batteries operating in cold environments.

Boron Surface Treatment of Li7La3Zr2O12 Enabling Solid Composite Electrolytes for Li-Metal Battery Applications.

Despite being promoted as a superior Li-ion conductor, lithium lanthanum zirconium oxide (LLZO) still suffers from a number of shortcomings when employed as an active ceramic filler in composite polymer-ceramic solid electrolytes for rechargeable all-solid-state lithium metal batteries. One of the main limitations is the detrimental presence of Li2CO3 on the surface of LLZO particles, restricting Li-ion transport at the polymer-ceramic interfaces. In this work, a facile way to improve this interface is presented, by purposely engineering the LLZO particle surfaces for a better compatibility with a PEO:LiTFSI solid polymer electrolyte matrix. It is shown that a surface treatment based on immersing LLZO particles in a boric acid solution can improve the LLZO surface chemistry, resulting in an enhancement in the ionic conductivity and cation transference number of the CPE with 20 wt % of boron-treated LLZO particles compared to the analogous CPE with non-treated LLZO. Ultimately, an improved cycling performance and stability in Li//LiFePO4 cells was also demonstrated for the modified material.

Flexible magnesium-ion-conducting solid poly-blend electrolyte films for magnesium-ion batteries

Solid biodegradable polymer electrolyte systems are considered the optimal choice for energy storage devices because they are both cost-effective and energy-efficient. A solid blend polymer electrolyte (SBPE) membrane capable of transporting magnesium ions was prepared using a mixture of 70 wt% methylcellulose, 30 wt% chitosan, and varying wt% magnesium perchlorate salt. X-ray diffraction analysis revealed an increase in the amorphous nature caused by the inclusion of Mg(ClO4)2 salt in the polymer blend matrix. A Fourier transform infrared spectroscopy study of samples containing varying salt concentrations revealed secondary interactions between polymer segments and salt, which provides the basis for energy density. Moreover, through impedance analysis, it was determined that the bulk resistance decreased with increasing salt concentration. The SBPE containing 30 wt% magnesium perchlorate exhibited the highest ionic conductivity, with a value of 2.49 × 10–6 S cm−1. A comprehensive evaluation of the ion transport parameters, including mobility, carrier density, and diffusion, was conducted for the prepared electrolyte samples. Notably, an ionic transference number (tion) of approximately 0.83 was observed for the SBPE sample with 30 wt% magnesium salt, indicating ions’ prevalence as the system’s primary charge carriers. Electrochemical analyses demonstrated that the SBPE with the highest ion conductivity possessed an electrochemical stability window (ESW) of 1.92 V. Additionally, the thermal characteristics of the samples were evaluated using thermogravimetric analysis (TGA) to assess the thermal stability of the electrolyte. Finally, the highest conducting polymer electrolyte was employed to construct a primary magnesium battery, and its discharge profile with different cathode materials was studied. Based on these findings, the current study suggests an environmentally friendly, biodegradable, and economically viable electrolyte option suitable for separator cum electrolytes in magnesium-ion batteries.

Highly Anion‐Conductive Viologen‐Based Two‐Dimensional Polymer Membranes as Nanopower Generators

AbstractTwo‐dimensional polymers (2DPs) and their layer‐stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (<3 nm), much smaller than the duple Debye length in the diluted electrolyte (6–20 nm), as well as low charge density (<4.5 mC m−2). Here, we introduce a π‐conjugated viologen‐based 2DP (V2DP) membrane possessing a large pore size of 4.5 nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6 mC m−2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103 A m−2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl−, contributing to an outstanding power density of ~55 W m−2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N‐containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl− ion transport pathway. This work demonstrates the great promise of large‐area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.

Metal-organic frameworks Derived frustrated Lewis acid-base pairs accelerate ion dynamics to dendrite-free solid-state lithium batteries

The Poly(ethylene oxide) (PEO)-based polymer electrolytes exhibit the drawbacks of high crystallinity and low ionic conductivity (<10−5 S m−1), which significantly restrict their application in solid-state lithium metal batteries. This study presents the bismuth metal-organic frameworks (MOFs) as a PEO-based electrolyte filler, incorporating frustrated Lewis acid-base pairs, which is formed in-situ through the coordination of ellagic acid (EA) and bismuth ions (Bi3+). The simultaneous presence of Lewis acids (unsaturated Bi3+) and bases (free nitrate, NO3−) in the MOFs, which effectively transfers and transports the lithium ions through the synergistic interaction based on the polymer matrix and the lithium salts, resulting in the high durable solid-state lithium batteries. Meanwhile, NO3− can further promote the dissociation of lithium ion (Li+) and the formation of inorganic solid electrolyte interfaces (SEIs) with lithium metal, which is conducive to the dynamic repair of SEIs. Characterizations and calculations show that Bi-MOFs promote the increase of composite ionic conductivity (6.4 × 10−4 S cm−1, 60 °C) and lithium transference number (0.52, 60 °C). At a current density of 0.4 mA cm−2, the assembled Li–Li symmetric battery can be continuously cycled for more than 500 h. This strategy opens a new window for improvement of solid-state electrolyte performance.

Enhancing Cycle Life of Rechargeable Zinc Hybrid Batteries in a Low-Cost, Nonfluorinated Dual-Cation Electrolyte.

Rechargeable zinc batteries (RZBs) are highly attractive as energy storage solutions due to their low cost and sustainability. Nevertheless, the use of fluorine-free zinc electrolyte systems to create affordable, ecofriendly, and safe RZBs has been largely overlooked in the battery community. Previously, we showcased the utilization of a fluorine-free, nonaqueous electrolyte comprising zinc dicyanamide (Zn(dca)2) in dimethyl sulfoxide (DMSO) to enable the electrochemical cycling of zinc. Herein we present a dual-cation-based electrolyte, [1.0 M Na(dca) +1.0 M Zn(dca)2]/DMSO, in pursuit of a rechargeable zinc hybrid battery. Fourier-transform infrared spectroscopy and molecular dynamics simulation studies indicate that the presence of Na(dca) diminishes ion-pairing in Zn(dca)2 through [dca]- anion bridging between Zn2+ and Na+ ions, thereby enhancing Zn2+ ion transport in the electrolyte. Thus, the electrolyte exhibits high ionic conductivity and transference numbers (tZn2+) of 7.9 mS cm-1 and 0.83, respectively, at 50 °C, making it particularly suitable for high-temperature battery applications. Furthermore, we demonstrate, for the first time, the cycling of a full cell with a zinc anode and triphylite sodium iron phosphate cathode (NFP) in an organic electrolyte, showcasing stable performance over 100 cycles at 0.1C rate. These encouraging findings pave the way for affordable battery technologies using, fluorine-free electrolyte.

Garnet and Li29Zr9Nb3O40 Modified PEO‐Based Hybrid Solid Electrolytes for All‐Solid‐State Lithium Metal Batteries

AbstractInorganic‐organic hybrid solid electrolytes (HSEs) are an important category of electrolyte materials for solid‐state batterie. It is of interest and importance to investigate the influence of composition and content of inorganic fillers on the electrochemical performance of HSEs. In this paper, we fabricated HSEs using polyethylene oxide (PEO) as matrix and incorporating different inorganic powders as active fillers. A series of HSEs with different contents of Ga/Nb co‐substituted garnet oxide (Li6.35Ga0.15La3Zr1.8Nb0.2O12, GN‐LLZO) and Y‐doped Li29Zr9Nb3O40 (Li29.3Zr8.7Y0.3Nb3O40, 0.3Y‐LZNO) were carefully designed. The ionic conductivity of these PEO‐based HSEs were studied, and their performance in solid‐state lithium‐ion batteries with LiFePO4 (LFP) as cathode material and Li metal as anode were evaluated. The results showed that the HSE with addition content of inorganic powders, namely PEOLiTFSI@5 % GN‐LLZO +5 %0.3Y‐LZNO (noted as PL3) showed the optimized ionic conductivity of 2.9×10−4 S cm−1 at room temperature with an activation energy Ea of 0.21 eV. It has an electrochemical stability window of 4.65 V and ionic transfer number of 0.242. The addition of inorganic powders not only enhanced the ionic conductivities of PEO‐based HSEs, but also exhibited superior stability and interfacial compatibility with electrodes, leading to the improved cycle stability in the LFP/PL3/Li solid‐state battery configuration.

In situ construction of 3D crossing-linked gel polymer electrolyte toward high performance and safety lithium metal batteries

Our study focuses on developing high-performance gel polymer electrolytes (GPEs) tailored for lithium metal batteries (LMBs), harnessing the combined benefits of high conductivity of liquid electrolytes and the enhanced safety of solid electrolytes. To this end, we engineered an in situ polymerized GPE (PMIA- TP) that integrates trifluoroethyl methacrylate (TFMA) and pentaerythritol triacrylate (PETA) monomers within an electrospun poly (m-phthaloyl-m-phenylenediamine) (PMIA) supporting membrane. In addition to high ionic conductivity, high lithium ion transference number, enhanced tensile strength and good thermal stability, the resulting PMIA-TP GPE exhibits satisfactory electrochemical stability against lithium electrodes, enabling long-term and stable lithium plating/stripping in symmetric Li//Li cells, and good rate capability and prolonged cycle life for LiFePO4//Li cells. Further X-ray photoelectron spectroscopy analysis and density functional theory calculations revealed that the electrochemical stability of the PMIA-TP GPE towards lithium metal electrode is due to the formation of a fluorine-rich solid electrolyte interphase (SEI) layer facilitated by reactions involving the –CF3 groups in TFMA, which is beneficial for the effective Li+ transport and lithium dendrite suppression. In summary, our study offers a promising approach to fabricating GPEs that offer high safety and high performance for LMBs.

Synthesis and Characterizations of Novel Copolymers with Zwitterionic Moiety-Based Solid Polymer Electrolytes for Solid-State Lithium Metal Battery

Electric vehicles (EVs) have become the dominant choice in the automotive industry, displacing internal combustion engine vehicles (ICEVs) to some extent. The development of high-efficiency batteries is essential to meet these market demands. Conventional lithium-ion batteries (LIBs), which consist of a cathode, anode, separator, and liquid electrolyte (such as 1M LiPF6 in carbonate solvents), have been widely utilized in portable electronic devices, hybrid electric vehicles (HEVs), and EVs. This popularity is attributed to their relatively high energy density and extended cycle life [1]. However, LIBs with energy density exceeding 240 Wh kg-1 face challenges in terms of thermal stability, potentially leading to fire and explosions by overcharging or accidental cell penetration. This drawback significantly hinders their application in automotive settings [2, 3]. In response to these safety concerns, there is a shift towards incorporating solid-state electrolytes (SSEs) as a replacement for liquid electrolytes. SSEs include solid polymer electrolyte (SPE), inorganic solid electrolyte (ISE), and composite polymer electrolyte (CPE).Solid-state lithium metal batteries (SSLMBs) incorporating SPE hold significant promise for advancing energy storage technologies due to their high energy density and improved safety features. However, the low ionic conductivity and ionic transference number of SPEs present challenges in their application for solid-state batteries. This work focuses on designing novel copolymers with polar soft unit and zwitterionic unit to address these challenges.In this study, poly(ethylene glycol) methyl ether acrylate (PEGMEA) and sulfobetaine methacrylate (SBMA) were selected as the polar soft segment and zwitterionic unit, respectively. Various ratios of PEGMEA/SBMA in copolymers were synthesized and characterized, and the resultant SPEs consisting of resultant copolymers and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared. Subsequently, their electrochemical, thermal, mechanical, and morphological properties were systematically investigated. The copolymers-based SPEs exhibited improved electrochemical properties. The optimized SPE comprising the copolymer with the molar ratio of PEGMEA/SBMA = 1/3 and 50 wt% LiTFSI exhibited the ionic conductivity of approx. 2×10–4 S cm–1, lithium-ion transference number of approx. 0.3, Li+ diffusion coefficient of 15×10-12 cm² s-1, and oxidation stability of 5.2 V (vs. Li/Li+) at 25 oC. Additionally, the mechanical properties of such SPEs were assessed, showing improved tensile strength (up to approx. 6 MPa) and Young’s modulus (up to approx. 83 MPa) with increasing SBMA content. The selected SPE with the best electrochemical properties was sandwiched between a Li metal electrode and a LiFePO4 electrode to assemble a SSLMB. As a result, the discharge capacity (DC) at 0.1 C-rate and room temperature was approx. 170 mA h g–1. Furthermore, the DC at a 0.5 C-rate was approx. 146 mA h g–1, and the capacity retention of 70% obtained after 470 cycles. In summary, this work demonstrates the potential of tailored copolymers with zwitterionic moiety-based SPEs for SSLMB. The comprehensive characterization and performance assessments provide valuable insights into the design and optimization of polymer electrolytes for next-generation energy storage systems.The copolymers and corresponding SPEs underwent characterization through various techniques such as DSC, SEM, XRD, and FTIR. The Ionic conductivity of the SPEs was determined by analyzing the results obtained from EIS measurement. The lithium-ion diffusion coefficient (DLi+) for SPE in a symmetric SSLMB cell, Li/SPE/Li, was also calculated based on the EIS results [4]. The oxidation stability window of the SPE was measured using the linear sweep voltammetry technique, and the ion transfer number was determined using the Evans-Vincent-Bruce method [5].

Influence of Microstructure on Defect Chemistry - Transport - Chemical Strain Coupling of (Pr,Ce)O2-δ Nanoparticles

Solid oxide fuel/electrolysis cells (SOFC/SOECs) are promising and environmentally-friendly technologies for meeting ever-increasing electricity and energy storage demands. Nanostructuring of SOFC/SOEC electrodes can enable improvement of the reaction kinetics and reduction of the operating temperature, owing to factors including the enlarged surface area, short diffusion lengths, and unique surface & interface properties. While the kinetic benefit is apparent, the effect of nanostructuring on other device-relevant physico-chemical properties cannot be neglected. Especially, the coefficients of chemical expansion (CCEs) are an important metric for mixed ionic-electronic conductors that can undergo changes in oxygen stoichiometry with variations in the surrounding atmosphere, temperature, and voltages during processing/operation. Chemical strains can cause cracking of monolithic parts during fabrication and delamination of electrodes from electrolytes in operation. CCEs are typically measured on bulk, polycrystalline materials with large particle or grain sizes. Therefore, it is important to understand the coupled transport and chemical expansion behavior in nano-ionic materials with large interface/surface density. This work aims to uncover the role of microstructure and nanoscale effects on the chemical strain and transport properties, through the lens of defect chemistry, with the goal of ultimately developing design principles for zero-strain materials with improved device lifetime and performance.Pr0.2Ce0.8O2- δ (PCO20) was selected as a model system and prepared as nanoparticles by a surfactant-free, low temperature co-precipitation method. (Pr,Ce)O2-δ compositions are valuable model oxide ion conductors to study, since both Pr and Ce can undergo changes of valence states under different temperature and pO2 regimes to accommodate oxygen stoichiometry excursions. Prepared nanoparticle samples were first in-situ sintered in the dilatometer at three different temperatures (600 ⁰C, 725 ⁰C, 850 ⁰C) to induce and evaluate microstructure evolution. The chemical strain and electronic/ionic conductivity were then studied on stable microstructures with different average particle sizes at lower temperatures by simultaneous in-situ dilatometry and electrochemical impedance measurement (EIS) upon changing pO2 at different isotherms (550 to 400 ⁰C). At each isotherm, all the samples expand as pO2 decreases. From the conductivity vs. pO2 measurements, the maxima at certain pO2 indicate the dominant polaron mechanism of the electronic transport, consistent with the measured conductivity activation energy. However, samples with lower sintering temperatures exhibit less pO2 dependence of the conductivity, which implies a transition in the mixed ionic/electronic conduction behavior toward higher ionic transference numbers as particle size decreases. Correspondingly, the chemical strains associated with losing oxygen monotonically decrease with the decrease of the sintering temperature, and hence the particle size. The chemical strain vs. oxygen stoichiometry dependence and corresponding CCEs were quantified as function of particle size and temperature by combining thermogravimetric analysis (TGA) with the dilatometry results and in-situ X-ray diffraction. The particle size, chemical composition, valence states, and morphology of samples after CCEs measurements were also compared using XRD, SEM, and S/TEM-EELS, with the latter indicating the expected differences between bulk and surface defect chemistry. Implications of the results for size-dependent defect chemistry and its influence on chemical strains and redox CCEs will be further discussed. Keywords: redox, chemical expansion, defect chemistry, mixed ionic electronic conduction, ceria, chemo-mechanics, nanoparticle, thermogravimetric analysis, dilatometry, impedance

Recent Advancements in Materials for Proton-Conducting Reversible Solid Oxide Cells

The escalating threats posed by climate change and environmental issues underscore the need for urgent exploration of clean energy technologies. In this context, proton-conducting reversible solid oxide cells (P-RSOCs) have emerged as promising contenders for large-scale energy storage and conversion. Their efficacy at intermediate temperatures (400 - 600 °C) is a distinctive advantage, attributed to the remarkable ionic conductivity of proton conductors within this temperature range. This feature positions P-RSOCs favorably for the efficient, cost-effective, and enduring conversion between clean electricity and green hydrogen.However, the successful commercialization of P-RSOCs hinges on the rational design of novel materials and meticulous surface/interface modifications to significantly enhance performance and durability. Achieving prolonged durability during cycling between fuel cell and electrolysis modes while maintaining high Faraday efficiency and roundtrip energy efficiency is of paramount importance. A central challenge involves the development of electrolyte materials exhibiting exceptional stability and a high ionic transference number under operating conditions. Additionally, bifunctional electrodes/catalysts, particularly for the oxygen electrode, must demonstrate elevated activity for efficient dual-mode operation.To effectively tackle these challenges, it is imperative to devise new protocols for controlling the structure, composition, and morphology of materials across multiple length scales. Equally crucial is gaining a fundamental understanding of degradation mechanisms and electrode processes. This presentation will illuminate the critical scientific challenges inherent in developing a new generation of P-RSOCs, providing insights into the latest advancements in electrolyte materials and bifunctional electrodes/catalysts. Furthermore, it will highlight strategies for enhancing durability and electrode activity through surface/interface modification, along with the latest developments in modeling, simulation, and in situ characterization techniques to deepen our understanding of the underlying mechanisms. The presentation will conclude prospects for achieving low-cost, highly efficient, and durable P-RSOCs through innovative material-based solutions.

Development of Eco‐Friendly Chitosan‐Dextran Polyblend Electrolyte for Enhanced Performance in Primary Magnesium Batteries

The potential of next‐generation batteries lies in solid biodegradable polymer electrolytes. This research delves into a solid blend polymer electrolyte (SBPE) for magnesium conduction, utilizing a chitosan‐dextran blend matrix doped with magnesium perchlorate (Mg(ClO4)2) salt. The electrolyte films are prepared using a conventional solution casting technique. Through techniques like X‐ray diffraction and Fourier transform infrared spectroscopy, the successful incorporation of Mg(ClO4)2 into the blend matrix is confirmed. Notably, the SBPE containing 30 wt% of Mg(ClO4)2 demonstrates the highest ionic conductivity of 6.99 × 10−4 S cm−1 and a prominent ionic transference number of 0.84. Thermogravimetric analysis is carried out to study thermal stability. Differential scanning calorimetry analysis of the electrolyte systems gives insight into their thermal properties. Additionally, it showcases favorable electrochemical stability of 2.66 V. The oxidation and reduction peaks are observed in the cyclic voltammetry curve of the highest conducting sample. Furthermore, the discharge performance of Mg/(CS + DN + Mg(ClO4)2)/cathode cells is explored with varied cathode materials, illustrating the SBPE's potential for magnesium‐ion batteries. This study unveils a sustainable, biodegradable, and economical electrolyte solution for advanced energy storage systems.

Highly Ionic Conductive, Self-Healing, Li10GeP2S12-Filled Composite Solid Electrolytes Based on Reversibly Interlocked Macromolecule Networks for Lithium Metal Batteries with Improved Cycling Stability.

Ceramic-polymer composite solid electrolytes (CSEs) have attracted great attention by combining the advantages of polymer electrolytes and inorganic ceramic electrolytes. Herein, Li10GeP2S12 (LGPS) particles are incorporated into poly(ethylene oxide) (PEO)-based reversibly interlocked polymer networks (RILNs) derived from the topological rearrangement of two PEO networks cross-linked by reversible imine bonds and disulfide linkages. A series of highly ionic conductive, self-healing CSEs are obtained accordingly. The interlocking architecture successfully inhibits PEO crystallization, increasing the amorphous phase for Li ion transportation, and stabilizes the conductive pathways of LGPS particles by its unique confinement effect. Meanwhile, the LGPS particles cooperate with the RILN matrix, forming a filler-polymer interfacial phase for additional Li ion transportation and strengthening and toughening the resultant CSEs via the strong intermolecular Li+-O2- interactions. Furthermore, the dynamic characteristics of the included reversible bonds ensure a multiple intrinsic self-healing capability. Consequently, the CSEs containing 15 wt % LGPS deliver a high ionic conductivity (1.06 × 10-3 S cm-1) and high Li ion transference number (∼0.6) at 25 °C, a wide electrochemical stability window (>4.9 V), good mechanical properties (0.63 MPa, 377%), and a stable CSE/Li anode interface. The integrated Li/CSE/LiFePO4 battery exhibits a specific discharge capacity of 110.8 mAh g-1 at 1 C (25 °C) and a capacity retention of 76.9% after 200 cycles. Thanks to the healability, the damaged CSEs can regain the structural integrity, ion conductive capability, and cycling performance of the assembled cells. The present work provides an effective strategy to fabricate CSEs for lithium metal batteries that are workable at ambient temperature.

PVDF/lithiated sulfonated poly (ether ether ketone) blend coated PE separators for high-performance lithium metal batteries

Ionic conductivity and lithium ion transference number (tLi+) of electrolytes are essential parameters governing the performances of high energy density lithium metal batteries. Although the importance of tLi+versus ionic conductivity has been theorized by simulation, the systematically experimental study of their respective effects on lithium dendrite suppression and battery performances is rarely carried out. Here, a series of polyvinylidene fluoride and lithated sulfonated poly (ether ether ketone) blend (PVDF/SPEEK-Li) coated polyethylene (PE) separators with exactly the same composition but different pore morphologies are fabricated by vapor and non-solvent induced phase separation. The effects of sulfonate group–ion interaction and pore morphologies on ionic conductivity and tLi+ of the electrolytes are studied. The performances of lithium metal batteries can be obviously improved by subtle increase of the tLi+, especially at high charge rates and even with a decrease in conductivity. Even at a high current density of 3 C, the PVDF/SPEEK-Li coated PE separator assembled lithium metal battery using a LiFePO4 cathode with a mass loading of 10.5 mg cm−2 can run stably for 200 cycles with a capacity retention of 79 %, which is superior to the PE separator assembled battery with a life of only 55 cycles.

Constructing efficient lithium salt dissociation solid-state electrolytes with high conductivity and transference number of Li ions for stable all-solid-state lithium batteries

The broad application of solid-state polymer electrolytes (SPEs) has been hindered by the extremely low transference number of lithium ions and ionic conductivities. This study innovatively introduces Co-doped Li4Ti5O12 (CLTO) into poly(ethylene oxide) (PEO) matrix, CLTO not only brings a stronger interaction with TFSI−, but also weakens the Li-O bond in Li4Ti5O12 and reduces the diffusion activation energy of Li+. Thus, CLTO introducing PEO-based polymer solid electrolytes could simultaneously promote the dissociation of Li+ from LiTFSI and Li4Ti5O12, constructing efficient dual lithium salt dissociation regions and rapid Li+ conduction channels. The experimental tests and density functional theory calculations have confirmed the operational mechanisms of CLTO within the polymer matrix. As a result, the obtained SPEs exhibit a high ionic conductivity (1.09 × 10−4 S cm−1) and a quite large tLi+ of 0.83 at 60 °C. Moreover, the low (Highest Occupied Molecular Orbital) HOMO energy (−7.25 eV) of the CLTO-LiTFSI-PEO-10 (CLP-10) endow it can accommodate both the Li-metal anode and high-voltage cathodes. The all-solid-state LiFePO4||Li and NCM811|| Li batteries offer exceptional specific capacities of 164.61 and 194.95 mAh/g at 60 °C, respectively. In addition, the pouch cell assembled with CLP-10 works stably under extreme conditions such as bending and shearing.