Ionic Conductivity Research Articles

Cutting-Edge Progress in Aqueous Zn-S Batteries: Innovations in Cathodes, Electrolytes, and Mediators.

Rechargeable aqueous zinc-sulfur batteries (AZSBs) are emerging as prominent candidates for next-generation energy storage devices owing to their affordability, non-toxicity, environmental friendliness, non-flammability, and use of earth-abundant electrodes and aqueous electrolytes. However, AZSBs currently face challenges in achieving satisfied electrochemical performance due to slow kinetic reactions and limited stability. Therefore, further research and improvement efforts are crucial for advancing AZSBs technology. In this comprehensive review, it is delved into the primary mechanisms governing AZSBs, assess recent advancements in the field, and analyse pivotal modifications made to electrodes and electrolytes to enhance AZSBs performance. This includes the development of novel host materials for sulfur (S) cathodes, which are capable of supporting higher S loading capacities and the refinement of electrolyte compositions to improve ionic conductivity and stability. Moreover, the potential applications of AZSBs across various energy platforms and evaluate their market viability based on recent scholarly contributions is explored. By doing so, this review provides a visionary outlook on future research directions for AZSBs, driving continuous advancements in stable AZSBs technology and deepening the understanding of their charge-discharge dynamics. The insights presented in this review signify a significant step toward a sustainable energy future powered by renewable sources.

Surface Coordination of Garnet Fillers Improves the Organic-Inorganic Interfacial Compatibility of Composite Solid Electrolyte.

Composite solid electrolytes (CSEs) have become one of the most promising solid-state electrolytes due to their favorable safety and flexibility. However, the weak interaction between inorganic fillers and polymer matrix leads to poor organic-inorganic interfacial compatibility, which degrades the electrochemical performance of CSEs. Herein, it is demonstrated that Li6.4La3Zr1.4Ta0.6O12 (LLZTO) can be chemically bonded to the polymer matrix by surface coordination of the 1,2-dithiolane group of lipoic acid (LA) with metal atoms on the surface of LLZTO through a combination of experimental investigations and theoretical calculations. The surface coordination not only enhances the interfacial compatibility between LLZTO and the polymer matrix, but also facilitates rapid Li+ transport, which leads to the ionic conductivity of the prepared CSE (P-V-M@LLZTO) as high as 6.1×10-4Scm-1 at 30°C. The excellent interface compatibility ensures a stable cycle of Li/P-V-M@LLZTO/Li symmetrical cell for more than 3500h. As a result, LiFePO4/P-V-M@LLZTO/Li cell delivers the discharge capacity of 161mAhg-1 after 5 cycles with a capacity retention of 81% after 500 cycles at 0.5C under 30°C. This work demonstrates that surface coordination is an effective strategy to solve the inherent interfacial incompatibility problem in CSEs.

Li-Ga Alloy-Contained Hybrid Solid Electrolyte Interphase Induced by In Situ Polymerization for High-Performance Lithium Metal Batteries.

Construction of quasi-solid-state lithium metal batteries (LMBs) by in situ polymerization is considered a key strategy for the next generation of energy storage systems with high specific energy and safety. Poly(1,3-dioxolane) (PDOL)-based electrolytes have attracted wide attention among researchers, benefiting from the low cost and high ionic conductivity. However, interfacial deterioration and uncontrollable growth of lithium dendrites easily appeared in LMBs due to the high reactivity of lithium metal, resulting in the failure of LMBs. In this work, a strategy is developed of using Ga(OTF)3 as the initiator to obtain a PDOL-based gel electrolyte (GaPD). In addition, a hybrid stable solid electrolyte interphase (SEI) of lithium fluoride/Li2O/Li-Ga alloys is observed on the surface of lithium metal. Combined with density functional theory calculations, the hybrid SEI shows high affinity toward Li+, indicating that a uniform deposition of Li+ could be achieved. Therefore, the Li/GaPD/Li cell operates stably for 1600 h at room temperature. In addition, the LiFePO4/GaPD/Li cell retains a capacity retention rate of 90.2% over 200 cycles at 1 C. This work provides a reference for the practical application of in situ polymerization technology in high-performance and safe LMBs.

Hybrid Screen Printable Electrolyte for Large‐Scale Flexible Electrochromic Display Production

AbstractThis study presents the development of a novel screen printable quasi‐solid polymer electrolyte (p‐QSPE) for Electrochromic Displays (ECDs) applications. p‐QSPE is composed of three key components: polyvinylidene fluoride (PVDF), a high‐dielectric constant polymer that ensures high ionic conductivity in solid‐state; glyceril propoxy triacrylate (GPTA), a UV‐cross‐linkable monomer that provides structure and durability for overprinting; titanium dioxide (TiO₂) nanoparticles, which modulate the electrolyte's rheological properties for screen printing; reducing the solvent (PC:EC) content to only 35.90 wt.%. Electrochemical Impedance Spectroscopy (EIS) revealed that this well‐designed formulation achieved an ionic conductivity of 1.17 × 10−3 S cm−1 at room temperature, surpassing the threshold required for commercial applications. Moreover, p‐QSPE facilitated the production of fully screen printed ECDs in an industrial printing line, streamlining their production process and achieving an optimal balance between printability, overprint resilience, and device performance. Operational tests for the ECDs showed fast switching times (<6 s for t90 and <2 s for t75) across a wide temperature range (−20 °C to 80 °C). Additionally, the electrolyte demonstrated low charge consumption (2.10 ± 0.11 mC cm−2) and a lifespan exceeding 10 000 cycles. These results highlight the potential of p‐QSPE as a screen printable, high‐performance electrolyte, capable of advancing ECD manufacturing by enabling the production of fully screen‐printed, performing ECDs.

An artificial layer enables in situ generation of a homogeneous inorganic/organic composite solid electrolyte interphase for stable lithium metal batteries.

Lithium (Li) metal anodes are considered one of the most promising anodes for high-performance batteries with ultra-high specific energy density. However, uncontrolled dendrite growth and the unsuitability of common systems for high voltage hinder the development of Li metal batteries with long cycle life. Herein, we report a rationally designed artificial solid electrolyte interphase (SEI) for Li metal anodes, incorporating LiNO3 and lithium difluoro(oxalato)borate (LiDFOB) as additives within a porous poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer skeleton (referred to as PNF). LiNO3 and LiDFOB can release and synergistically react at the electrode surface, leading to the in situ generation of a homogeneously distributed inorganic/organic SEI during the electrochemical process. This SEI improves homogeneity, ionic conductivity and mechanical stability, contributing to the suppression of electrolyte side reactions and Li dendrite growth. Moreover, a uniform CEI with high Li+ conductivity can be constructed on the NCM811 particles, further enhancing the structural integrity of the NCM811 cathode. As a result, the artificial SEI layer on Li metal anodes enables stable cycling of Li-Cu half cells in an ester-based electrolyte and Li-LiNi0.8Mn0.1Co0.1O2 full cell even at a high voltage of 4.5 V. This work provides new insights into designing homogeneous SEIs for Li metal batteries.

Hygroscopic Nature of Lithium Ions: A Simple Key to Super Tough Atmosphere-Stable Hydrogel Electrolytes.

Gel electrolytes have emerged as a versatile solution to address numerous limitations associated with liquid electrolytes in electrical energy storage (EES) devices, in terms of safety, flexibility, and affordability. Aqueous gel electrolytes, in particular, exhibit exceptional features by offering one of the highest ion solvation capacities and ionic conductivities. The two main challenges with hydrogel electrolytes are their easy freezing at subzero temperatures and rapid dehydration under open conditions, leading to the failure of the EES device. In response, we present an uncomplicated and quick-to-make hydrogel electrolyte system offering impressive mechanical properties (205.5 kPa tensile strength, 2880 kJ/m3 toughness, and 3030% strain at the break), along with antifreezing and antiflammability attributes. Notably, the hydrogel electrolyte demonstrates high ionic conductivity and superior performance in supercapacitor cells over a wide range of temperatures (-40 to 80 °C) and under various deformations. The hydrogel electrolyte maintains its capabilities under open conditions over an extended period of time, even at 50 °C, showcased by powering a wristwatch. The atmospheric stability of the hydrogel electrolyte demonstrated in this study introduces promising prospects for the future of EES devices spanning from production to end-user consumption.

Characterization and properties of solid-state nanocomposite Acacia gum electrolytes with emphasis on diverse applications

A novel, natural, eco-friendly, solid-state Acacia gum nanocomposite electrolyte has been prepared with different weight ratios of nanoparticle ZrO2 introduced to the standard composition of 70% Acacia gum and 30% ZnSO4·7H2O. Sequential examinations, encompassing XRD, and FTIR, were conducted to evaluate the amorphous characteristics, complexation nature, and interaction of dopant nanoparticles within the acacia-salt electrolyte matrix network. The optimum ionic conductivity of nanocomposite electrolytes was found using electrochemical impedance analysis. The remarkable ionic conductivity was achieved for the electrolyte sample consisting of 10% nanoparticle ZrO2 introduced to the standard composition of 70% of Acacia gum and 30% of ZnSO4·7H2O(AZR4) at 100 °C, 6.1×10−3S/cm, at room temperature (RT) the electrolyte sample exhibited conductivity value of 1.13×10−3 S/cm. Additionally, an examination of the dielectric characteristics dependent on frequency demonstrated the existence of space charge polarization in the electrolyte and a notable tail in the low-frequency area. Through the parameters of the dielectric modulus, the research also investigated the hopping mechanism and relaxation time. Furthermore, nano-composite electrolytes were employed in the construction of solar cell devices. The outstanding results were obtained for electrolyte upon (10 wt%) nanoparticle-introduced, overall power conversion efficiency (ƞ) reached 5.38%, short-circuit photocurrent density (Jsc) 10.92 mA/cm2, open-circuit voltage (Voc) at 735 mV, and fill factor (FF) at 0.63.

Li-Fe-Cl Families as Novel Solid Electrolytes for All-Solid-State Batteries.

The halides have attracted much attention as novel solid electrolytes because of their easy synthesis, high electrochemical stability, and high ionic conductivities. However, the reported halides for solid electrolytes are still understudied compared with the oxides and sulfides. Here, we studied the Li-Fe-Cl phases that include Li2FeCl4 and Li6FeCl8. Using the self-doping approach, a maximum ionic conductivity of 2.0 × 10-4 S cm-1 at 50 °C was achieved for Li1.8Fe1.1Cl4. It was improved by 3 orders of magnitude compared with that of Li2FeCl4 (8.27 × 10-7 S cm-1 at 50 °C). For the Li|Li1.8Fe1.1Cl4|Li half-cell, it cycled for 2000 h at 50 °C under a current density of 0.01 mA cm-2, indicating an acceptable compatibility between Li2FeCl4 and Li. Finally, an all-solid-state battery was successfully assembled with Li1.8Fe1.1Cl4@LFP as the cathode, Li1.8Fe1.1Cl4 as the electrolyte, and a Li sheet as the anode. The initial specific charge capacity of the battery was 76.36 mAh g-1 at 0.1C and 50 °C. The initial Coulombic efficiency was 73.06%. This study suggests Li2FeCl4 as a new solid electrolyte, and the introduction of Li vacancies into the Li site is an efficient way to improve the electrochemical properties of halides.

Phonon-Lithium Ion Interactions: A Case Study of LiM(SeO3)2 (M = Al, Ga, In, Sc, Y, and La).

Li ion diffusion is fundamentally a thermally activated ion hopping process. Recently, soft lattice, anharmonic phonon, and paddlewheel mechanism have been proposed to potentially benefit the ion transport, while the understanding of vibrational couplings of mobile ions and anions is still very limited but essential. Herein, we accessed the ionic conductivity, stability, and especially, lattice dynamics in LiM(SeO3)2 (M = Al, Ga, In, Sc, Y, and La) with two different types of oxygen anions within a LiO4 polyhedron, namely, edge-shared and corner-shared with MO6 polyhedra, the prototype of which, LiGa(SeO3)2, has been theoretically reported before with the similar structural features to NASICON and later experimentally synthesized with the room temperature conductivity ∼0.11 mS cm-1. It is interesting to note that LiM(SeO3)2 with a higher Li phonon band center shows higher Li conductivity, which is in contradiction to the conventional understanding of the importance for soft lattice to superionic conductors. The anharmonic and harmonic phonon interactions as well as the couplings between the vibration of the edge-bonded or corner-bonded anion in Li polyanions and the Li ion diffusion have been studied in detail. With transition metal M changing from La, Y, In, Ga, Al, and Sc, anharmonic phonons increase with reduced activation energy for Li diffusion. The phonon modes dominated by the edge-bonded oxygen anions contribute more to the migration of the Li ion than those dominated by the corner-bonded oxygen anions because of the greater atomic interaction between the Li ion and the edge-bonded anions. Thus, rather than the overall lattice softness, attention shall be given to reduce the frequency of the critical phonons contributing to Li ion diffusion as well as to increase the anharmonicity, i.e., through asymmetric Li polyhedra, for the design of Li ion superionic conductors for all-solid-state batteries.

Flexible high electrochemical collagen/lignin composite hydrogel for sensing and supercapacitor applications

Synthesis of polymer-based highly conductive hydrogels from natural and renewable sources with robust mechanical performances in flexible electronics remains a great challenge. In this research, a dynamic redox system is designed by using collagen (CL), sulfonate lignin (SL), acrylic acid (AA), and Al3+ to synthesize CL/PAA/SL/Al hydrogels. The formation of effective complexes of Al3+ with the abundant functional groups of CL, SL and PAA, the prepared hydrogel delivers various specific properties, for example, excellent ionic conductivity (4.61 S·m−1), stretchability and antimicrobial performance. The CL/PAA/SL/Al hydrogel demonstrates good mechanical strength, while the maximum tensile strength of the hydrogels is ∼604 kPa at a stretching of 1254 %, and the maximum compressive strength is ∼0.45 MPa, with the maximum stretching of 59.6 %. The CL/PAA/SL/Al hydrogel acts as a flexible strain sensor with high sensitivity. Enough hydroxyl and carboxyl groups in the hydrogels are essential for delivering the maximum 191 mV of open circuit voltage (Voc) rendered during moisture spraying. The supercapacitor assembled from CL/PAA/SL/Al hydrogel manifests specific capacitance (Cs), maximum energy density (Ed) and power density (Pd) of 268.75 F·g−1, 23.89 Wh·kg−1 and 2.4 kW·kg−1, respectively. The supercapacitor can retain its capacitance of 95.8 % after 5000 consecutive charge-discharge cycles.

Design and Characterization of Poly(ethylene oxide)-Based Multifunctional Composites with Succinonitrile Fillers for Ambient-Temperature Structural Sodium-Ion Batteries.

A new approach to developing structural sodium batteries capable of operating in ambient-temperature conditions has been successfully achieved. The developed multifunctional structural electrolyte (SE) using poly(ethylene oxide) (PEO) as a matrix integrated with succinonitrile (SN) plasticizers and glass-fiber (GF) reinforcements identified as GF_PEO-SN-NaClO4 showed a tensile strength of 32.1 MPa and an ionic conductivity of 1.01 × 10-4 S cm-1 at room temperature. It displayed a wide electrochemical stability window of 0 to 4.9 V and a high sodium-ion transference number of 0.51 at room temperature. The structural electrode (CF|SE) was fabricated by pressing the structural electrolyte with carbon fibers (CFs), and it showed a tensile strength of 72.3 MPa. The fabricated structural battery half-cell (CF||SE||Na) demonstrated good cycling stability and an energy density of 14.2 Wh kg-1, and it retained 80% capacity at the end of the 200th cycle. The cycled electrodes were observed using scanning electron microscopy, which revealed small dendrite formation and dense albeit uniform deposition of the sodium metal, helping to avoid a short-circuit of the cell and providing more cycling stability. The developed multifunctional matrix composites demonstrate promising potential for developing ambient-temperature sodium structural batteries.

Nonflammable Ether and Phosphate-Based Liquid Electrolytes for Sodium-Ion Batteries.

This study investigates a group of electrolytes containing NaPF6 or NaBF4 salts in phosphate- and ether-based solvents for high-mass loading sodium-ion batteries. It explores physicochemical properties such as ionic conductivity, dynamic viscosities, and nonflammability. The combination of experimental with computational studies reveals detailed insights into the physicochemical properties of the nonflammable liquid electrolytes. Diglyme-based electrolytes become nonflammable with 50 vol % phosphate solvents, while tetraglyme-based electrolytes require 70 vol %. The solvation structure has been investigated using NMR and is combined with computational studies to provide information about properties such as solvation structure, ionic conductivity, and viscosity. The molecular dynamic simulations confirm the enhanced solvation in diglyme-based liquid electrolytes observed experimentally by 23Na-NMR. Despite lacking sufficient electrochemical stability, this work provides a fundamental understanding of the solvation structure and physicochemical properties of a novel electrolyte system. This is an important contribution to be applied in future electrolyte design rationale.

Enhancing polypropylene-based separator efficiency in lithium-ion batteries through maleic anhydride addition and corona radiation modification

Polypropylene-grafted-maleic anhydride (PPMA) as a modifier of polypropylene (PP) at different contents and the corona radiation for surface ionization at various modification times were applied to promote the PP-based separator efficiency. The determined microstructural characteristics showed an improvement in the separator's porosity of 6–139 % at the tension amounts of 700–900 %, however, more stretching hurts the mechanical properties. The electrostatic interactions formed between the electrolytes and anhydrides increased the electrolyte sorption capacity in the samples and the surface wettability by 740 % and 25 %, respectively. The electrical test results indicated that the anhydrides led to capturing the electrolytes in the separator and created a resistance against the ion diffusion. This phenomenon reduced the separator resistance from 475 to 165 Ω, and enhanced the charge capacity and ion conductivity from 585 to 871 mAh/g and 0.29 to 0.34 S cm−1, respectively, while the PPMA content increased from 20 to 60 wt.%. The achieved FT-IR illustrated that the ionization caused the creation of more polar groups in the LIB separator, which increased the bulk and surface wettability by 420 % and 21 %, respectively, without any change in the microstructure of the separator. However, raising the exposure time in the radiation process decomposed the sample surface and led to damage in the separator microstructure. This issue reduced the separator porosity as well as the electrolyte absorption amount and ion conductivity.

Guiding nitrogen doped vanadium pentoxide nanoclusters on cobalt sulfide nano-flakiness as stable seamless interface anode toward highly energy density and durable asymmetric supercapacitors

Interaction of the interface-heterostructures is crucial to rapid ionic conductivity and highly energy density of electrode materials toward supercapacitors. Herein, a novel anode heterostructure is synthesized using cobalt sulfide (CoS) nanoflowers as a substrate for composite nitrogen doped vanadium pentoxide (denoted as N-V2O5@CoS) by combination of hydrothermal and calcination method. As expected, the N-V2O5@CoS electrode possesses superhigh specific surface area that significantly enhances the specific capacitance, and its unique porous interconnected structure not only reduces the volume effect during the cycles, but also greatly enhances the conductivity of electron transfer. The as-prepared N-V2O5@CoS electrode has a specific capacitance of up to 2413.6F/g at a current density of 1 A/g, and can still maintain 87.51 % of the initial capacitance after 5,000 cycles at a high current density of 10 A/g. More importantly, the partial density of states (PDOS) ares obtained through theoretical calculations reveal that the interaction of heterogeneous interfaces is contributed by the p-orbitals of C, O and S and d-orbitals of V and Co. In addition, asymmetric supercapacitor (ASC) with N-V2O5@CoS as the positive electrode and activated carbon (AC) as the negative electrode has a high voltage of 1.7 V, which achieves an outstanding energy density of 71.6 W h kg−1 at a power density of 849.8 W kg−1, showing excellent cycle stability (retain 90.6 % of the initial capacitance after 10,000 charge/discharge cycles). This paper offers novel paradigm for the doping of metal oxides and the development of heterostructures, which provides support for their use as advanced energy storage materials.

Confined Polyethylene Glycol Anchored in Kaolinite as High Ionic Conductivity Solid-State Electrolyte for Lithium Batteries.

Solid-state electrolytes (SSEs) have garnered significant attention as critical materials for enabling safer, energy-dense, and reversible electrochemical energy storage in batteries. Among the various types of solid electrolytes developed, composite polymer electrolytes (CPEs) have stood out as some of the most promising candidates due to their well-rounded performance. In this study, we choose polyethylene glycol (PEG) as the covalent grafting intercalant and lithium perchlorate as carrier source to prepare a fast lithium ion conductor, K-PEG-Li doped with clay-based active filler as a CPE. The CPE exhibits excellent lithium conduction (4.36 × 10-3 S cm-1 at 25 °C and 3.32 × 10-2 S cm-1 at 115 °C), great mechanical performance with good tensile strength (6.07 MPa) and toughness (strain 313%), and convincing flame-retardancy. These outstanding conducting and mechanical functionalities indicate that such a clay-based active filler doped composite polymer electrolyte will find promising application in solid-state lithium batteries.

Bio-derived gel polymer electrolytes from zein and honey blends integrated with ammonium nitrate for electrical double layer capacitors

Although electrical double layer capacitors (EDLCs) are known to exhibit impressive power density, rapid charging/discharging, and long cycle life, their energy density remains a hurdle for broader use. Gel polymer electrolytes (GPEs) offer an interesting approach to improve the energy density of EDLCs while maintaining their other desirable characteristics. This study investigates the development of novel GPEs based on zein, honey, and ammonium nitrate (NH4NO3) for EDLC applications. The GPEs are prepared by incorporating zein, honey, and NH4NO3 in a dimethyl sulfoxide (DMSO) solvent system through a solution casting method. The degree of crystallinity of zein successfully reduced from 33.0 % to 15.71 % with the addition of 20 wt% NH4NO3. The interaction between zein, honey and NH4NO3 is confirmed by observing the shifting of the hydroxyl band. The ambient ionic conductivity of zein-honey increases from (4.86 ± 0.36) × 10−4 S cm−1 to (4.19 ± 0.40) × 10−3 S cm−1 with the incorporation of 20 wt% NH4NO3 (ZH20), exhibiting the significantly lowest Tg value (77.53 °C). Linear sweep voltammetry (LSV) demonstrates high electrochemical stability up to 2.6 V of ZH20. Additionally, the transference number (tion) of 0.989 indicates a dominant role of ionic charge carriers in this work. Finally, the ZH20-based GPE is used as both an electrolyte and separator to fabricate EDLC. Its electrochemical behavior has demonstrated stable results in terms of specific capacitance, energy, and power density, with fast rate performance observed through cyclic voltammetry and galvanostatic charge-discharge techniques.

Biomimetic Aramid Nanofiber/β-FeOOH Composite Coating for Polypropylene Separators in Lithium-Sulfur Batteries.

Aramid nanofibers (ANFs), with attractive mechanical and thermal properties, have attracted much attention as key building units for the design of high-performance composite materials. Although great progress has been made, the potential of ANFs as fibrous protein mimetics for controlling the growth of inorganic materials has not been fully revealed, which is critical for avoiding phase separation associated with typical solution blending. In this work, we show that ANFs could template the oriented growth of β-FeOOH nanowhiskers, which enables the synthesis of ANFs/β-FeOOH hybrids as composite coatings for polypropylene (PP) separators in Li-S batteries. The modified PP separator exhibits enhanced mechanical properties, heightened thermal performance, optimized electrolyte wettability, and improved ion conductivity, leading to superior electrochemical properties, including high initial specific capacity, better rate capability, and long cycling stability, which are superior to those of the commercial PP separators. Importantly, the addition of β-FeOOH to ANFs could further contribute to the suppression of lithium polysulfide shuttling by chemical immobilization, inhibition of the growth of lithium dendrites because of the intrinsic high modulus and hardness, and promotion of reaction dynamics due to the catalytic effect. We believe that our work may provide a potent biomimetic pathway for the development of advanced battery separators based on ANFs.

Preparation and Conductivity Analysis of LLTO Nanofiber‐Incorporated PEO‐PVDF‐HFP‐LiClO4 Solid Polymer Electrolytes for High‐Voltage Lithium Metal Batteries

ABSTRACTThis work focuses on the development of a composite polymer electrolyte (CPE) for all‐solid‐state lithium metal batteries (ASSLMBs), integrating LLTO nanofibers into a PEO (polyethylene oxide)‐PVDF‐HFP (poly(vinylidene fluoride‐cohexafluoropropylene)) matrix with LiClO4 as the lithium salt. The PEO has high ionic conductivity and flexibility, and the PVDF‐HFP has high mechanical strength and electrochemical stability. Therefore, the resulting composite has improved electrochemical performance and mechanical properties. Incorporating LLTO nanofibers enhances ionic conductivity due to the one‐dimensional ion transport pathways provided by the nanofibers while maintaining mechanical integrity and air stability, overcoming the challenges associated with conventional fillers. The prepared CPE demonstrates exceptional electrochemical stability up to 5.1 V versus Li/Li+, making it suitable for high‐voltage applications over traditional polymer electrolytes. The optimized CPE with 15 wt% LLTO provides the ionic conductivity of 1.1 × 10−5 S cm−1 at room temperature and reaches 1.46 × 10−4 S cm−1 at 80°C. The assembled LiNi1/3Mn1/3Co1/3PO4||PEO‐PVDF‐HFP‐LiClO₄‐LLTO||Li based 2032 coin cell worked in between 3 and 4.8 V versus Li/Li+ potential window without any electrolyte decomposition from 0.5 to 5 mV/s scan rates. Similarly, the fabricated LiFePO₄||PEO‐PVDF‐HFP (1:2)‐LiClO4‐LLTO (15 wt%)||Li cell provides an initial capacity of 149 mAh g−1 at 0.1 C and 85 mAh g−1 at 0.5 C, exploring its potential for lithium metal batteries. Overall, this work offers a promising pathway for developing advanced solid polymer electrolytes for next‐generation lithium metal batteries, which combine high ionic conductivity, excellent electrochemical performances, and robust mechanical properties.

Boosting electrochemical performance by regulating rigid-flexible microphase separation of multiblock copolymers

The growth of lithium dendrites and associated safety issues hinder the further development of liquid lithium metal batteries. A novel rigid-flexible multiblock copolymer PBC-mb-PBS was successfully synthesized based on molecular design. Incorporating crystalline rigid phase polybutylene succinate (PBS) into PBC-mb-PBS significantly enhances its tensile strength and low-temperature toughness through physical crosslinking. The flexible polydibutyl 2-(2-cyanoethyl)malonate (PBC) phase with side-chain cyano groups facilitate ionic conduction, forming a LiN-rich stabilized interfacial layer, thereby improving oxidative stability and high-voltage cathode compatibility. A series of multiblock copolymers with varying segment lengths were synthesized to balance mechanical properties and ionic conductivity by adjusting microphase separation. The quasi-solid-state polymer electrolyte (QSPE), derived from PBC-mb-PBS with the molar block ratio of 0.42, exhibits optimal electrochemical performance with ionic conductivity of 6.20 × 10−5 S cm−1 at 30 °C and 4.22 × 10−4 S cm−1 at 60 °C. Due to its bicontinuous microphase structure, it also shows excellent mechanical strength and promotes uniform lithium deposition at high current densities. Li//LiFePO4 and Li//LiNi0.83Co0.05Mn0.12O2 cells demonstrate high capacity retention, confirming the potential of this polymer electrolyte in high-voltage applications. This design strategy offers insights for developing quasi-solid-state lithium metal batteries with superior overall performance.

Electrochemical performance enhancement of perovskite-type Li0.3La0.57TiO3 ceramic electrolyte by controlling synthesis parameters

This study investigates the enhancement of the electrochemical performance of perovskite-type Li0.3La0.57TiO3 (LLTO) solid electrolytes through the optimization of synthesis parameters of a sol-gel process. The primary focus lies in examining the impact of calcination temperature on the structural, morphological, and electrochemical properties of LLTO. Our findings reveal that controlling the calcination temperature significantly influences the grain boundary resistance and overall ionic conductivity. The optimal calcination temperature was identified to be 800 °C, yielding a remarkable improvement in ionic conductivity at grain boundaries (0.88 mS/cm), and total ionic conductivity (0.54 mS/cm), at 30 °C. This enhancement is attributed to the refined microstructure, increased density, and reduced porosity, which collectively facilitate lithium-ion diffusion. These advancements in LLTO electrolytes present promising implications for their application in all-solid-state lithium-ion batteries, offering a safer and more efficient alternative to conventional liquid electrolyte systems.