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The fundamental understanding of the relationship between ion transport and segmental dynamics of polymer chains in polymer electrolytes is crucial for achieving high ionic conductivity at room temperature for technological applications in supercapacitors, batteries, etc. In this work, the ion dynamics and relaxation have been studied for gel polymer electrolytes (GPEs) containing P(VdF-HFP) as host polymer, adiponitrile as a plasticizer, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide as ionic liquid, and diphenylamine and copper iodide redox additives as fillers. The crystallization temperature of the ionic liquid and the melting temperature of the plasticizer play important roles in ion dynamics. The highest room-temperature ionic conductivity (3.3 × 10−3 S/cm) was obtained for the GPE filled with dual redox additives. The broadband ac conductivity spectra have been analyzed by using the Universal Power law model coupled with the Poisson–Nernst–Planck (PNP) model. The solid–solid phase transition of the ionic liquid affects the grain and grain boundary regions of the GPEs due to the presence of redox fillers. The temperature dependence of the dielectric spectra of the GPEs containing redox fillers confirms the phase transition at the crystallization temperature. The electric modulus and dielectric spectra have been analyzed by using the Havrilliak–Nigami, Kohlrausch–Williams–Watts, and derivative dielectric constant functions. The scaling of ac conductivity and modulus spectra confirms a common ion conduction and relaxation mechanism for the GPEs. The influence of dual redox additives is clearly observed in the values of ionic conductivity, ion diffusivity, and relaxation time. [ABSTRACT FROM AUTHOR]

Recent experimental results have demonstrated that zwitterionic ionogel comprised of polyzwitterion (polyZI)-supported lithium salt-doped ionic liquid exhibits improved conductivities and lithium transference numbers than the salt-doped base ionic liquid electrolyte (ILE). However, the underlying mechanisms of such observations remain unresolved. In this work, we pursued a systematic investigation to understand the impact of the polyZI content and salt concentration on the structural and dynamic properties of the poly(MPC) ionogel of our model polyZI ionogel, poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] supported LiTFSI/N-butyl-N-methylpyrrolidinium TFSI base ionic liquid electrolyte. Our structural analyses show strong lithium–ZI interaction consistent with the physical network characteristic observed in the experiments. An increase in polyZI content leads to an increased fraction of Li+ ions coordinated with the polyZI. In contrast, an increase in salt concentration leads to a decreased fraction of Li+ ions coordinated with the polyZI. The diffusivities of the mobile ions in the poly(MPC) ionogel were found to be lower than the base ILE in agreement with experiments at T > 300 K. Analysis of ion transport mechanisms shows that lithium ions within the poly(MPC) ionogel travel via a combination of structural, vehicular diffusion, as well as hopping mechanism. Finally, the conductivity trend crossover between the poly(MPC) ionogel and the base ILE was rationalized via a temperature study that showed that the base ILE ions are influenced more by the variation of temperature when compared to the poly(MPC) ions. [ABSTRACT FROM AUTHOR]

We present a strategic approach for enhancing the ionic conductivity of block copolymer electrolytes. This was achieved by introducing mixed ionic liquids (ILs) with varying molar ratios, wherein the imidazolium cation was paired with either tetrafluoroborate (BF4) anion or bis(trifluoromethylsulfonyl)imide (TFSI) anion. Two polymer matrices, poly(4-styrenesulfonate)-b-polymethylbutylene (SSMB) and poly(4-styrenesulfonyl (trifluoromethanesulfonyl)imide)-b-polymethylbutylene (STMB), were synthesized for this purpose. All the SSMB and STMB containing mixed ILs showed hexagonal cylindrical structures, but the type of tethered acid group significantly influenced the interfacial properties. STMB electrolytes demonstrated enhanced segregation strength, which was attributed to strengthened Coulomb and hydrogen bonding interactions in the ionic domains, where the ILs were uniformly distributed. In contrast, the SSMB electrolytes exhibited increased concentration fluctuations because the BF4 anions were selectively sequestered at the block interfaces. This resulted in the effective confinement of imidazolium TFSI along the ionic domains, thereby preventing ion trapping in dead zones and facilitating rapid ion diffusion. Consequently, the SSMB electrolytes with mixed ILs demonstrated significantly improved ionic conductivities, surpassing the expected values based on the arithmetic average of the conductivities of each IL, whereas the ionic conductivity of the STMB was aligned with the expected average. The methodology explored in this study holds great promise for the development of solid-state polymer electrolytes. [ABSTRACT FROM AUTHOR]

[Display omitted] • Well-complexed PEGDA generates extra Na+ transport pathways. • The optimized quasi-solid PPE-50 exhibits a high ionic conductivity of 3.42 × 10–4 S cm−1. • PPE-50 displays high electrochemical oxidation stability and mechanical strength. • PPE-50 guides the formation of flexible and rigid SEI and dense and homogeneous CEI. • Na|PPE-50|Na and Na 3 V 2 (PO 4) 3 |PPE-50|Na cells demonstrate excellent long-term cyclability and capacity. Sodium-metal batteries (SMBs) are ideal for large-scale energy storage due to their stable operation and high capacity. However, they have safety issues caused by severe dendrite growth and side reactions, particularly when using liquid electrolytes. Therefore, it is critically important to develop electrolytes with high ionic conductivity and improved safety that are non-flammable and resistant to dendrites. Here, we developed polymerized polyethylene glycol diacrylate (PEGDA)-modified poly(vinylidene fluoride- co -hexafluoropropylene) (PVDF-HFP) electrolytes (PPEs) with highly conductive sodium bis(trifluoromethanesulfonyl)imide and corrosion-inhibitive sodium bis(oxalato)borate salts for SMBs. Well-complexed PEGDA not only increases the amorphicity of the PVDF matrix, but also offers numerous Lewis basic sites through the polar groups of carbonyl and ether groups (i.e., electron donors). The presence of the Lewis basic sites facilitates the dissociation of sodium salt and transportation of Na+ within the PVDF matrix. This results in the generation of additional Na+ transport pathways, which can enhance the performance of the battery. Among PPEs, the optimized PPE-50 exhibits a high ionic conductivity of 3.42 × 10–4 S cm−1 and a mechanical strength of 14.0 MPa. A Na||Na symmetric cell with PPE-50 displays high stability at 0.2 mA cm−2 for 800 h. PPE-50 further displays high capacity, e.g., a Na 3 V 2 (PO 4) 3 |PPE-50|Na battery delivers a decent discharge capacity of 101.5 mAh g−1 at 1.0C after 650 cycles. Our work demonstrates the development of high-performance quasi-solid polymer electrolytes with multiple transport pathways suitable for room-temperature SMBs. [ABSTRACT FROM AUTHOR]

[Display omitted] Solid polymer electrolytes (SPEs) have shown great promise in the development of lithium-metal batteries (LMBs), but SPEs' interfacial instability and limited ionic conductivity still prevent their widespread applications. Herein, high-concentration hybrid dual-salt "polymer-in-salt" electrolytes (HDPEs) through formulation optimization were facilely prepared to simultaneously boost ionic conductivity, improve interfacial compatibility, and ensure a wide-temperature-range operation with high safety. An optimized electrolyte (HDPE-0.6) shows negligible corrosion to the aluminum current collector after manipulating the salt ratio of lithium bis(trifluoromethane)sulfonimide and lithium bis(oxalato)borate. In addition, HDPE-0.6 has excellent ionic conductivity (i.e., ∼0.536, ∼0.898, and ∼1.28 mS cm−1 at 0, 30, and 60 °C), approaching 1 mS cm−1 at room temperature. Furthermore, HDPE-0.6 exhibits a high lithium transference number of 0.6 and a high electrochemical oxidation stability potential of > 4.8 V vs. Li/Li+. Additionally, due to the formulation of high-concentration thermally stable lithium salts and the employment of flame-retardant trimethyl phosphate as the solvent, HDPE-0.6 has no safety issues. The resultant LiFePO 4 |HDPE-0.6|Li cell exhibits high discharge capacity, good rate capability, and excellent cycle stability at extended temperatures of 0, 30, and 60 °C. By coupling theoretical calculations and in-depth X-ray photoelectron spectroscopy, we attribute the excellent cycle stability to the formation of a stable interphase. Moreover, our formulation strategy is suitable for the Na 3 V 2 (PO 4) 3 //Na battery when replacing the lithium salts with sodium salts (i.e., sodium bis(trifluoromethane)sulfonimide and sodium bis(oxalato)borate) to yield HDPE-0.6-Na, as demonstrated by excellent cycle stability (e.g., 98.6 % of capacity retention after 300 cycles). Our work demonstrates that the as-developed quasi-solid HDPEs are suitable for LMBs and sodium-metal batteries, and HDPEs can function normally in a wide temperature range. [ABSTRACT FROM AUTHOR]

Solid-state electrolytes (SSEs) play a crucial role in solid-state lithium metal batteries, with covalent organic frameworks (COFs) emerging as a promising materials class for SSE applications. In this study, a series of Tp-COFs materials were successfully synthesized through a solvothermal approach. Subsequently, these COFs underwent a coating process involving lithium salt and polyvinylidene fluoride film to yield TpMa, TpDa, and TpDa-Li SSEs. The materials subjected to characterization for their ionic conductivity, Li+ transfer number, electrochemical window, and charge-discharge cycle performance. Particularly noteworthy was the exceptional performance of TpDa-Li, exhibiting an ionic conductivity of 9.25 × 10−4 S cm−1, a Li+ transfer number of 0.89, an electrochemical window spanning 1.0–4.4 V, and a capacity retention rate of 77% after 300 cycles at 1 C rate and 83% after 300 cycles at 0.2 C rate. • TpMa, TpDa, and TpDa-Li COFs compounds were successfully synthesized through a solvothermal method. • TpPa-Li was applied to all-solid-state lithium metal batteries. • TpDa-Li solid electrolyte shows a high ionic conductivity of 9.25 × 10−4 S cm−1, a Li+ transfer number of 0.89. [ABSTRACT FROM AUTHOR]

Inorganic solid‐state electrolytes (SSEs) play a vital role in high‐energy all‐solid‐state batteries (ASSBs). However, the current method of SSE preparation usually involves high‐energy mechanical ball milling and/or a high‐temperature annealing process, which is not suitable for practical application. Here, a facile strategy is developed to realize the scalable synthesis of cost‐effective aluminum‐based oxyhalide SSEs, which involves a self‐propagating method by the exothermic reaction of the raw materials. This strategy enables the synthesis of various aluminum‐based oxyhalide SSEs with tunable components and high ionic conductivities (over 10−3 S cm−1 at 25 °C) for different cations (Li+, Na+, Ag+). It is elucidated that the amorphous matrix, which mainly consists of various oxidized chloroaluminate species that provide numerous sites for smooth ion migration, is actually the key factor for the achieved high conductivities. Benefit from their easy synthesis, low cost, and low weight, the aluminum‐based oxyhalide SSEs synthesized by our approach could further promote practical application of high‐energy‐density ASSBs. [ABSTRACT FROM AUTHOR]

The commercial potential of composite polymer electrolytes (CPEs) is significant due to their ability to combine the advantages of both inorganic and polymer solid electrolytes. However, the unstable interface and insufficient ionic conductivity remain important challenges in practical applications of CPEs for achieving high-performance solid-state lithium batteries (SLBs). Herein, we construct a double-layer composite polymer electrolyte (D-CPE) by incorporating nanosized TiO 2 fillers with adjustable concentrations of oxygen vacancies into poly (ethylene oxide) (PEO)-based electrolyte composites. In the D-CPE structure, one CPE layer containing TiO 2 fillers with oxygen vacancies exclusively interfaces with the LiFePO 4 cathode, while the other CPE layer consisting of pristine TiO 2 fillers (with negatively charged surfaces) solely contacts the lithium anode. This design of D-CPE achieves high ionic conductivity, a broad electrochemical window, and interfacial stability without additional resistance at the electrolyte-electrolyte interface simultaneously. The LiFePO 4 /D-CPEs/Li battery exhibits excellent cycling stability at 0.1 C, maintaining a capacity of 157.2 mAh g−1 with a capacity retention rate of 99.1% after 100 cycles. Furthermore, even at 0 °C, it delivers an impressive discharge capacity of 133.1 mAh g−1 at 0.1 C. This work presents a simple and effective approach to achieving superior polymer-based electrolytes for high-performance solid-state lithium batteries. [ABSTRACT FROM AUTHOR]

Li+ ion conduction in two aligned liquid crystalline electrolytes consisting of 10 mol% Li+ salt of a pro-mesogenic anion derived from [closo-1-CB11H12]− in non-ionic hosts was investigated. Using electrochemical impedance spectroscopy (EIS), the ionic conductivity in the parallel (σ‖) and perpendicular (σ⊥) directions of the electrolyte samples was determined using two types of cells: an interdigitated gold electrode and a nylon 6-coated ITO cell. The ratio of ionic conductivities σ⊥/σ‖ in the electrolyte with a nona(ethylene oxide) spacer was about 3 in the entire SmA phase, while in the shorter homologue, the ratio monotonically increases from about 0.4 to 2.9. The liquid crystalline behavior of the hosts and the electrolytes was investigated by optical, thermal, and powder XRD methods. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DES) exhibit comparable thermal and chemical stability to ionic liquids, coupled with excellent ionic conductivity. Moreover, they boast a higher degree of safety owing to lower toxicity and increased accessibility. Hence, the utilization of DES in gel preparation emerges as an effective solution to address the challenges associated with the inadequate stability of traditional hydrogels and the heightened toxicity of gels composed of ionic liquids. In this paper, eutectogels with excellent low-temperature sensing properties were prepared by using methacrylic acid (MAA) and pyrrole (Py) as monomers and DES as solvent. The eutectogel exhibits excellent sensing capability, with a gauge factor reaching 5.21. Additionally, DES prepared using choline chloride and urea endows the eutectogel with good freeze resistance, enabling sensing at −20 °C while maintaining stability. Moreover, the eutectogel accurately monitors changes in environmental temperature, providing a promising material for temperature-measuring flexible wearable sensor applications. [ABSTRACT FROM AUTHOR]

Physical hydrogels crosslinked by noncovalent interactions are promising in flexible zinc–metal batteries for their component controllability and environmental friendliness. However, the compatibility of PVA‐based electrolyte and kosmotropic salt remains a challenge, which shows an unclear mechanism. Here, a "good‐to‐poor" solvent substitution strategy is adopted to develop a PVA hydrogel electrolyte with good compatibility with kosmotropic salt (ZnSO4). Stretching the polymer conformation by preshielding the strong intrachain hydrogen bonds with good solvents and activating the polymer interchain interaction in situ with poor solvents will induce the formation of a homogeneous polymer network and the release of hydrated hydroxyl groups for fast ion transport. This multiscale microstructure improves the ionic conductivity and liquid retention of PVA hydrogels with kosmotropic salt. Additionally, this strong hydrogen bonds preshielded hydrogel electrolyte offers great battery performance, with 1300 h of stable cycling at 1 mA cm−2 with low voltage hysteresis; and an extended cycle life of 220 h at 68.4% zinc utilization. Importantly, the Zn//MnO2 pouch cell maintains 98.4% capacity after 100 cycles at 0.2 A g−1 and features strong environmental reliability. These concepts address the inherent barriers of kosmotropic salt‐based hydrogel electrolytes and advance their development in soft electronics. [ABSTRACT FROM AUTHOR]

Recently, halide solid state electrolytes (SSEs) have received great attention owing to their fast ionic conductivity, high oxidation potential, and good chemical and electrochemical compatibility with high voltage cathode materials. However, most of reported halide SSEs contain rather rare and expensive elements, which hinders their sustainable utilizations in practical batteries. Here in this work, under the guidance of systematic modelling based on the density functional theory (DFT), a low‐cost alternative is developed through optimizing the lattice chemistry in a recently identified spinel‐like chloride Li2CrCl4 into Li5/3Cr1/3Zr1/3Cl4 for remarkably enhanced ionic conductivity and stable electrochemical window with respect to the Li‐anode. This new phase has then been synthesized successfully, delivering an ionic conductivity over 1200 times of that of the pristine phase Li2CrCl4, in addition to a high oxidation potential (up to 4.1 V vs Li/Li+) to enable outstanding interfacial compatibility with high voltage cathodes. Such a high‐voltage and fast Li‐ion conducting solid‐state electrolyte is expected to provide a highly desirable basis toward developing high energy‐density all solid‐state batteries (ASSBs) using economical and Earth‐rich elements. [ABSTRACT FROM AUTHOR]

Polyethylene oxide (PEO) solid electrolytes are regarded as a promising candidate for all‐solid‐state lithium batteries owing to their high safety and interfacial compatibility. However, PEO electrolyte is plagued by relatively weak structural strength and unsatisfactory Li+ conductivity. Herein, a mechanically strong and Li+ conductively favorable cellulosic scaffold of PEO is fabricated through amino (‐NH2) modification and g‐C3N4 (CN) incorporation of bacterial cellulose (BC) under a microbial circumstance. The biologically ‐NH2 modified BC (B‐NBC) is entangled with CN nanosheets (CN@B‐NBC) through an in situ secretion of nanocellulose followed by hydrogen bond‐induced self‐assembly. The ‐NH2 groups from B‐NBC weaken the complexation of Li+ with its counterpart, thus facilitating the release of more free Li+. CN with strong C‐N covalence and extra lone electrons of N further strengthens the BC skeleton and meanwhile offers sufficient anchors for Li+ migration. After infiltrating by LiTFSI/PEO (LP), the LP/CN@B‐NBC composite solid electrolyte (CSE) exhibits high lithium transference number and ionic conductivity. Upon coupling with LiFePO4 cathode, the full battery exhibits a remarkably high specific capacity, superior rate capability, and decent cycling stability. This work pioneers the attempts of chemical decoration and ingredient incorporation of BC architecture in CSE with the aid of a bottom‐up biosynthetic avenue. [ABSTRACT FROM AUTHOR]

[Display omitted] Traditional dual-ion lithium salts have been widely used in solid polymer lithium-metal batteries (LMBs). Nevertheless, concentration polarization caused by uncontrolled migration of free anions has severely caused the growth of lithium dendrites. Although single-ion conductor polymers (SICP) have been developed to reduce concentration polarization, the poor ionic conductivity caused by low carrier concentration limits their application. Herein, a dual-salt quasi-solid polymer electrolyte (QSPE), containing the SICP network as a salt and traditional dual-ion lithium salt, is designed for retarding the movement of free anions and simultaneously providing sufficient effective carriers to alleviate concentration polarization. The dual salt network of this designed QSPE is prepared through in-situ crosslinking copolymerization of SICP monomer, regular ionic conductor, crosslinker with the presence of the dual-ion lithium salt, delivering a high lithium-ion transference number (0.75) and satisfactory ionic conductivity (1.16 × 10−3 S cm−1 at 30 °C). Comprehensive characterizations combined with theoretical calculation demonstrate that polyanions from SICP exerts a potential repulsive effect on the transport of free anions to reduce concentration polarization inhibiting lithium dendrites. As a consequence, the Li||LiFePO 4 cell achieves a long-cycle stability for 2000 cycles and a 90% capacity retention at 30 °C. This work provides a new perspective for reducing concentration polarization and simultaneously enabling enough lithium-ions migration for high-performance polymer LMBs. [ABSTRACT FROM AUTHOR]

Quasi‐solid polymer electrolyte (QPE) lithium (Li)‐metal battery holds significant promise in the application of high‐energy‐density batteries, yet it suffers from low ionic conductivity and poor oxidation stability. Herein, a novel self‐built electric field (SBEF) strategy is proposed to enhance Li+ transportation and accelerate the degradation dynamics of carbon‐fluorine bond cleavage in LiTFSI by optimizing the termination of MXene. Among them, the SBEF induced by dielectric Nb4C3F2 MXene effectively constructs highly conductive LiF‐enriched SEI and CEI stable interfaces, moreover, enhances the electrochemical performance of the QPE. The related Li‐ion transfer mechanism and dual‐reinforced stable interface are thoroughly investigated using ab initio molecular dynamics, COMSOL, XPS depth profiling, and ToF‐SIMS. This comprehensive approach results in a high conductivity of 1.34 mS cm−1, leading to a small polarization of approximately 25 mV for Li//Li symmetric cell after 6000 h. Furthermore, it enables a prolonged cycle life at a high voltage of up to 4.6 V. Overall, this work not only broadens the application of MXene for QPE but also inspires the great potential of the self‐built electric field in QPE‐based high‐voltage batteries. [ABSTRACT FROM AUTHOR]

Quasi‐solid polymer electrolyte (QPE) lithium (Li)‐metal battery holds significant promise in the application of high‐energy‐density batteries, yet it suffers from low ionic conductivity and poor oxidation stability. Herein, a novel self‐built electric field (SBEF) strategy is proposed to enhance Li+ transportation and accelerate the degradation dynamics of carbon‐fluorine bond cleavage in LiTFSI by optimizing the termination of MXene. Among them, the SBEF induced by dielectric Nb4C3F2 MXene effectively constructs highly conductive LiF‐enriched SEI and CEI stable interfaces, moreover, enhances the electrochemical performance of the QPE. The related Li‐ion transfer mechanism and dual‐reinforced stable interface are thoroughly investigated using ab initio molecular dynamics, COMSOL, XPS depth profiling, and ToF‐SIMS. This comprehensive approach results in a high conductivity of 1.34 mS cm−1, leading to a small polarization of approximately 25 mV for Li//Li symmetric cell after 6000 h. Furthermore, it enables a prolonged cycle life at a high voltage of up to 4.6 V. Overall, this work not only broadens the application of MXene for QPE but also inspires the great potential of the self‐built electric field in QPE‐based high‐voltage batteries. [ABSTRACT FROM AUTHOR]

Inferior air stability is a primary barrier for large‐scale applications of garnet electrolytes in energy storage systems. Herein, a deeply hydrated hydrogarnet electrolyte generated by a simple ion‐exchange‐induced phase transition from conventional garnet, realizing a record‐long air stability of more than two years when exposed to ambient air is proposed. Benefited from the elimination of air‐sensitive lithium ions at 96 h/48e sites and unobstructed lithium conduction path along tetragonal sites (12a) and vacancies (12b), the hydrogarnet electrolyte exhibits intrinsic air stability and comparable ion conductivity to that of traditional garnet. Moreover, the unique properties of hydrogarnet pave the way for a brand‐new aqueous route to prepare lithium metal stable composite electrolyte on a large‐scale, with high ionic conductivity (8.04 × 10−4 S cm−1), wide electrochemical windows (4.95 V), and a high lithium transference number (0.43). When applied in solid‐state lithium batteries (SSLBs), the batteries present impressive capacity and cycle life (164 mAh g−1 with capacity retention of 89.6% after 180 cycles at 1.0C under 50 °C). This work not only designs a new sort of hydrogarnet electrolyte, which is stable to both air and lithium metal but also provides an eco‐friendly and large‐scale fabrication route for SSLBs. [ABSTRACT FROM AUTHOR]

The development of highly producible and interfacial compatible in situ polymerized electrolytes for solid‐state lithium metal batteries (SSLMBs) have been plagued by insufficient transport kinetics and uncontrollable dendrite propagation. Herein, we seek to explore a rationally designed nanofiber architecture to balance all the criteria of SSLMBs, in which La0.6Sr0.4CoO3−δ (LSC) enriched with high valence‐state Co species and oxygen vacancies is developed as electronically conductive nanofillers embedded within ZnO/Zn3N2‐functionalized polyimide (Zn‐PI) nanofiber framework for the first time, to establish Li+ transport highways for poly vinylene carbonate (PVC) electrolyte and eliminate nonuniform Li deposits. Revealed by characterization and theoretical calculation under electric field, the positive‐negative electrical dipole layer in LSC derived from electron migration between Co and O atoms aids in accelerating Li+ diffusion kinetics through densified electric field around filler particle, featuring a remarkable ionic conductivity of 1.50 mS cm−1 at 25 °C and a high Li+ transference number of 0.91 without the risk of electron leakage. Integrating with the preferential sacrifice of ZnO/Zn3N2 on PI nanofiber upon immediate detection of dendritic Li, which takes part in reconfiguring hierarchical SEI chemistry dominated by LixNy/Li−Zn alloy inner layer and LiF outer layer, SSLMBs are further endowed with prolonged cycling lifespan and exceptional rate capability. [ABSTRACT FROM AUTHOR]

The development of highly producible and interfacial compatible in situ polymerized electrolytes for solid‐state lithium metal batteries (SSLMBs) have been plagued by insufficient transport kinetics and uncontrollable dendrite propagation. Herein, we seek to explore a rationally designed nanofiber architecture to balance all the criteria of SSLMBs, in which La0.6Sr0.4CoO3−δ (LSC) enriched with high valence‐state Co species and oxygen vacancies is developed as electronically conductive nanofillers embedded within ZnO/Zn3N2‐functionalized polyimide (Zn‐PI) nanofiber framework for the first time, to establish Li+ transport highways for poly vinylene carbonate (PVC) electrolyte and eliminate nonuniform Li deposits. Revealed by characterization and theoretical calculation under electric field, the positive‐negative electrical dipole layer in LSC derived from electron migration between Co and O atoms aids in accelerating Li+ diffusion kinetics through densified electric field around filler particle, featuring a remarkable ionic conductivity of 1.50 mS cm−1 at 25 °C and a high Li+ transference number of 0.91 without the risk of electron leakage. Integrating with the preferential sacrifice of ZnO/Zn3N2 on PI nanofiber upon immediate detection of dendritic Li, which takes part in reconfiguring hierarchical SEI chemistry dominated by LixNy/Li−Zn alloy inner layer and LiF outer layer, SSLMBs are further endowed with prolonged cycling lifespan and exceptional rate capability. [ABSTRACT FROM AUTHOR]

Aqueous zinc-ion batteries (ZIBs) offer numerous advantages, such as high energy density, enhanced safety, and low cost, making them an ideal choice for energy storage and conversion applications in the “postlithium” era. Hydrogel electrolytes, as the key component of flexible ZIBs, combine the ionic conductivity of traditional water electrolytes with the dimensional stability of solid polymer electrolytes. However, it remains a challenge to design comprehensive and appropriate hydrogel electrolytes to provide flexible ZIBs with good reversibility and versatility. This review discusses the engineering design of hydrogel electrolytes required for flexible ZIBs from the viewpoint of an electrolyte designer. The basic properties of the hydrogel electrolytes, zinc anodes, cathodes and electrolyte stabilization effects are described in detail. Furthermore, we explore the various challenges faced by hydrogel electrolytes and propose corresponding strategies. Finally, the review offers insights into the future development of hydrogel-stabilized ZIBs. [ABSTRACT FROM AUTHOR]

The practical application of polymer electrolytes is hindered due to the low ionic conductivity and the interfacial instability between the electrodes. Herein, a strategy for designing solid polymer electrolytes is developed that facilitates the rapid lithium‐ion migration through weak coordination with polymer chain segments, as well as the fast ion channel transport of oligomers. Moreover, the in situ‐produced solid polymer electrolyte (PFVS) can form stable LiF‐rich interfaces with both the lithium metal anode and different cathodes. When the PFVS is applied in Li‐metal batteries, excellent properties are achieved at room temperature. A Li||Li symmetric cell can be stably cycled for 4000 h at a current density of 0.1 mA cm−1, a Li||LiFePO4 full cell can maintain capacity retention as high as still 94.4% after 600 cycles at 1 C, and a Li||NCM811 full cell can retain 80% capacity after 180 cycles at 1 C. A 2.6 Ah Graphite|PFVS|NCM90 pouch cell is made for demonstrating the practical application potential, and it can be also stably cycled. The developed strategy provides a promising path for designing solid polymer electrolytes that can effectively extend the lifespan of Li metal batteries. [ABSTRACT FROM AUTHOR]

Ether‐based electrolyte is beneficial to obtaining good low‐temperature performance and high ionic conductivity in potassium ion batteries. However, the dilute ether‐based electrolytes usually result in ion‐solvent co‐intercalation of graphite, poor cycling stability, and hard to withstand high voltage cathodes above 4.0 V. To address the aforementioned issues, an electron‐withdrawing group (chloro‐substitution) was introduced to regulate the solid‐electrolyte interphase (SEI) and enhance the oxidative stability of ether‐based electrolytes. The dilute (~0.91 M) chloro‐functionalized ether‐based electrolyte not only facilitates the formation of homogeneous dual halides‐based SEI, but also effectively suppress aluminum corrosion at high voltage. Using this functionalized electrolyte, the K||graphite cell exhibits a stability of 700 cycles, the K||Prussian blue (PB) cell (4.3 V) delivers a stability of 500 cycles, and the PB||graphite full‐cell reveals a long stability of 6000 cycles with a high average Coulombic efficiency of 99.98 %. Additionally, the PB||graphite full‐cell can operate under a wide temperature range from −5 °C to 45 °C. This work highlights the positive impact of electrolyte functionalization on the electrochemical performance, providing a bright future of ether‐based electrolytes application for long‐lasting, wide‐temperature, and high Coulombic efficiency PIBs and beyond. [ABSTRACT FROM AUTHOR]

Here, we build a tunable multipolar conjugated polymer framework platform via pore wall chemistry to probe the role of electronic structure engineering in improving the Li+ conduction by theoretical studies. Guided by theoretical prediction, we develop a new cyano‐vinylene‐linked multipolar polymer framework namely CNF‐COF, which can act as efficient ion sieves to modify solid polymer electrolytes to simultaneously tune Li+ migration and stable Li anodes for long‐lifespan all‐solid‐state (ASS) Li metal batteries at high rate. The dual‐decoration of cyano and fluorine groups in CNF‐COF favorably regulates electronic structure via multipolar donor‐acceptor electronic effects to afford proper energy band structure and abundant electron‐rich sites for enhanced oxidative stability, facilitated ion‐pair dissociation and suppressed anion movements. Thus, the CNF‐COF incorporation into poly (ethylene oxide) (PEO) electrolytes not only renders fast selective Li+ transport but also facilitates the Li dendrite suppression. Specifically, the constructed PEO composite electrolyte with an ultra‐low CNF‐COF content of only 0.5 wt % is endowed with a wide electrochemical window, a high ionic conductivity of 0.634 mS cm−1 at 60 °C and a large Li+ transference number of 0.81—remarkably outperforming CNF‐COF‐free counterparts (0.183 mS cm−1 and 0.22). As such, the Li symmetric cell delivers stable Li plating/stripping over 1400 h at 0.1 mA cm−2. Impressively, by coupling with LiFePO4 (LFP) cathodes, the assembled ASS Li battery under 60 °C allows for stable cycling over 2000 cycles at 1 C and over 1000 cycles even at 2 C with a large capacity retention of ~75 %, surpassing most reported ASS Li batteries using PEO‐based electrolytes. [ABSTRACT FROM AUTHOR]

To realize high-energy-density Li metal batteries at low temperatures, a new electrolyte is needed to solve the high-voltage compatibility and fast lithium-ion de-solvation process. A gel polymer electrolyte with a small-molecular-weight polymer is widely investigated by combining the merits of a solid polymer electrolyte (SPE) and liquid electrolyte (LE). Herein, we present a new gel polymer electrolyte (P-DOL) by the lithium difluoro(oxalate)borate (LiDFOB)-initiated polymerization process using 1,3-dioxolane (DOL) as a monomer solvent. The P-DOL presents excellent ionic conductivity (1.12 × 10−4 S cm−1) at −20 °C, with an oxidation potential of 4.8 V. The Li‖LiCoO2 cell stably cycled at 4.3 V under room temperature, with a discharge capacity of 130 mAh g−1 at 0.5 C and a capacity retention rate of 86.4% after 50 cycles. Moreover, a high-Ni-content LiNi0.8Co0.1Mn0.1O2 (NCM811) cell can steadily run for 120 cycles at −20 °C, with a capacity retention of 88.4%. The underlying mechanism of high-voltage compatibility originates from the dense and robust B- and F-rich cathode interface layer (CEI) formed at the cathode interface. Our report will shed light on the real application of Li metal batteries under all-climate conditions in the future. [ABSTRACT FROM AUTHOR]

In this report, a facile wet chemical method using acetonitrile combined with thermal annealing was used to prepare Li2S‐P2S5 (LPS) based glass‐ceramic electrolytes with (1 wt%, 3 wt%, and 5 wt% Ce2S3) and without Ce2S3 doping. The crystal structure, ionic conductivity, and chemical stability of Li7P3S11 glass‐ceramic electrolytes were examined at varying temperatures (250–350°C). The results indicated that the highest ionic conductivity of 3.15 × 10−4 S cm−1 for pure Li7P3S11 was observed at a temperature of 325°C. By incorporating 1 wt% Ce2S3 and subjecting it to a heat treatment at 250°C, the glass ceramic electrolyte attained a remarkable ionic conductivity of 7.7 × 10−4 (S cm−1) at 25°C. Furthermore, it exhibited a stable and extensive electrochemical potential range, reaching up to 5 volts when compared to the Li/Li+ reference electrode. By tuning the glass transition and crystallization temperature, cerium doping seems to make Li7P3S11 more chemically stable, compared to its original 70Li2S‐30P2S5 counterpart. According to Raman and X‐ray photoelectron spectroscopy analyses, cerium doping inhibits the decomposition of highly conductive P2S74‐ (pyro‐thiophosphate) to PS43− and P2S64−. Doped LPS has a greater crystallinity and more uniform microstructure than pure LPS, according to XRD, Raman spectroscopy, and scanning electron microscopy analysis. Consequently, Li7P2.9Ce0.1S11 electrolyte shows great potential as a solid‐state electrolyte for constructing high‐performance sulfide‐based all‐solid‐state batteries. [ABSTRACT FROM AUTHOR]

Solid polymer electrolytes (SPEs) are the key components of lithium metal batteries to overcome the obstacle of insecurity in conventional liquid electrolytes; however, the trade-off between their ionic conductivity and mechanical properties remains a significant challenge. In this work, two-dimensional ZSM-5 nanosheets as fillers are incorporated into a poly(ethylene oxide) (PEO) matrix and lithium salts to obtain composite polymer electrolytes (CPEs). The improved physicochemical and electrochemical properties of the CPE membranes are characterized in full detail. Stripping/plating measurements in symmetric Li/Li cells and cyclic charge/discharge tests are performed to investigate the cyclability and stability of the CPEs. All-solid-state LiFePO4/Li batteries deliver excellent cycling performance with an initial discharge capacity of 152.3 mAh g−1 and 91.4% capacity retention after 200 cycles at 0.2 C, with a discharge specific capacity of 118.8 mAh g−1 remaining after 350 cycles at 0.5 C. Therefore, CPEs containing ZSM-5 nanosheets are a promising option for all-solid-state lithium-ion batteries. [ABSTRACT FROM AUTHOR]

The rechargeable aqueous Zn||MnO2 chemistry has been extensively explored, but its electrochemical reaction mechanisms, especially in the context of MnO2/Mn2+ conversion and Zn2+/H+ intercalation chemistry, remain not fully understood. Here, we designed an amphiphilic hydrogel electrolyte, which distinguished the MnO2/Mn2+ conversion, Zn2+ intercalation, and H+ intercalation and conversion processes at three distinct discharge plateaus of an aqueous Zn||MnO2 battery. The amphiphilic hydrogel electrolyte is featured with an extended electrochemical stability window up to 3.0 V, high ionic conductivity, Zn2+‐selective ion tunnels, and hydrophobic associations with cathode materials. This specifically designed electrolyte allows the MnO2/Mn2+ conversion reaction at a discharge plateau of 1.75 V. More interesting, the discharge plateaus of ~1.33 V, previously assigned as the co‐intercalation of Zn2+ and H+ ions in the MnO2 cathode, are specified as the exclusive intercalation of Zn2+ ions, leading to an ultra‐flat voltage plateau. Furthermore, with a distinct three‐step electrochemical energy storage process, a high areal capacity of 1.8 mAh cm−2 and high specific energy of 0.858 Wh cm−2, even at a low MnO2 loading mass of 0.5 mg cm−2 are achieved. To our knowledge, this is the first report to fully distinguish different mechanisms at different potentials in aqueous Zn||MnO2 batteries. [ABSTRACT FROM AUTHOR]

To date, the exploration of zwitterionic application is confined to the function of electrolyte's additives to improve the properties of the electrolytes. However, reports on the unique properties of zwitterions, namely the anti‐polyelectrolyte effect (APE), as the regulators of the electrochemical stability windows (ESWs) of the zwitterionic electrolytes are scarce. Herein, a zwitterionic electrolyte system is designed and study the relationship between the APE and the ESWs of the zwitterionic electrolytes. The hydrogen/oxygen evolution in the zwitterionic electrolytes is significantly inhibited under the action of the APE. On this basis, the ESWs of zwitterionic electrolytes can be expanded, ultimately achieving an effective improvement in the energy density of zinc‐ion hybrid capacitors (ZHCs). The sulfonic‐based zwitterionic hydrogel electrolytes prepared based on this strategy achieve a wide ESW of 2.58 V and high ionic conductivity of 29.3 mS cm−1. Meanwhile, the corresponding ZHCs possess a high working voltage of 2.1 V (1.6 V for the traditional ZHCs), a high capacity of 188.9 mAh g−1 and a high energy density of 110 Wh kg−1. The way utilizing the APE of zwitterions to expand the ESWs opens up a new avenue to improve the energy density of energy storage devices. [ABSTRACT FROM AUTHOR]

The current study focuses on the development of an antibacterial, conducting and biocompatible nanocomposite for wound healing applications comprising of polyvinyl alcohol (PVA), chitosan (CS), graphene oxide (GO), and zinc oxide–silver oxide composite (ZnO–Ag2O) through the solution casting method. The XRD, FTIR, Raman as well as the FESEM–EDAX results confirmed the presence of the ternary nanocomposite at different concentrations (5–15 wt%) in the polymer system. Additionally, variations in the surface roughness of the polymer composites were documented through the AFM images. The highest ionic conductivity value of 0.345 × 10−4 S cm−1 was reported for PVA–CS–GO–ZnO–Ag2O (5 wt%). The nanoparticles as well as polymeric nanocomposites showcased superior antibacterial activity against both E. coli and S. aureus. Furthermore, the prepared polymeric composites exhibited excellent cytocompatibility towards RBCs as well as RAW 264.7 cells. Hence, the developed polymeric composite exhibiting outstanding antibacterial efficacy, improved ionic conductivity, and excellent biocompatibility holds promise as an innovative candidate for the formulation of advanced wound dressings. [ABSTRACT FROM AUTHOR]

All‐solid‐state batteries suffer from high interface resistance and lithium dendrite growth leading to low Li plating/stripping Coulombic efficiency (CE) of <90% and low critical current density at high capacity. Here, simultaneously addresses both challenges are simultaneously addressed and the Li plating/stripping CE is significantly increased to 99.6% at 0.2 mA cm−2/0.2 mAh cm−2, and critical current density (CCD) of > 3.0 mA cm−2/3.0 mAh cm−2 by inserting a mixed ionic‐electronic conductive (MIEC) and lithiophobic LiF‐C‐Li3N‐Bi nanocomposite interlayer between Li6PS5Cl electrolyte and Li anode. The highly lithiophobic LiF‐C‐Li3N‐Bi interlayer with high ionic conductivity (10−5 S cm−1) and low electronic conductivity (3.4×10−7 S cm−1) enables Li to plate on the current collector (CC) surface rather than on Li6PS5Cl surface avoiding Li6PS5Cl electrolyte reduction. During initial Li plating on CC, Li penetrates into porous LiF‐C‐Li3N‐Bi interlayer and lithiates Bi nanoparticles into Li3Bi. The lithiophilic Li3Bi and Li3N nanoparticles in LiF‐C‐Li3N‐Li3Bi sub‐interlayer will move to CC along with plated Li, forming LiF‐C/Li3N‐Li3Bi lithiophobic/lithiophilic sublayer during the following Li stripping. This interlayer enables Co0.1Fe0.9S2/Li6PS5Cl/Li cell with an areal capacity of 1.4 mAh cm−2 to achieve a cycle life of >850 cycles at 150 mA g−1. The lithiophobic/lithiophilic interlayer enables solid‐state metal batteries to simultaneously achieve high energy and long cycle life. [ABSTRACT FROM AUTHOR]

Ionic thermoelectrics (TEs), in which voltage generation is based on ion migration, are suitable for applications based on their low cost, high flexibility, high ionic conductivity, and wide range of Seebeck coefficients. This work reports on the development of ionic TE materials based on the poly(vinylidene fluoride‐trifluoroethylene), Poly(VDF‐co‐TrFE), as host polymer blended with different contents of the ionic liquid, IL, 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI]. The morphology, physico‐chemical, thermal, mechanical, and electrical properties of the samples are evaluated together with the TE response. It is demonstrated that the IL acts as a nucleating agent for polymer crystallization. The mechanical properties and ionic conductivity values are dependent on the IL content. A high room temperature ionic conductivity of 0.008 S cm−1 is obtained for the sample with 60 wt% of [EMIM][TFSI] IL. The TE properties depend on both IL content and device topology‐vertical or planar‐the largest generated voltage range being obtained for the planar topology and the sample with 10 wt% of IL content, characterized by a Seebeck coefficient of 1.2 mV K−1. Based on the obtained maximum power density of 4.9 µW m−2, these materials are suitable for a new generation of TE devices. [ABSTRACT FROM AUTHOR]

Solid polymer electrolytes (SPEs) have garnered extensive attention as potential alternatives to traditional liquid electrolytes, primarily due to their prowess in curbing lithium dendrite formation and preventing electrolyte leaks. The quest for SPEs that are both mechanically robust and exhibit superior ionic conductivity has been vigorous. However, achieving a harmonious balance between these two attributes remains a significant challenge. In this study, we introduce a novel quasi‐solid electrolyte, ingeniously crafted from a poly(urethane‐urea) network, enriched with lithium salts and plasticizers. This innovative composition not only boasts remarkable toughness but also ensures commendable ionic conductivity. Our post‐gelation method yields gel polymer electrolytes that undergo rigorous evaluation, leading to an optimized version that stands out with its exceptional room‐temperature ionic conductivity (2.94×10−4 S cm−1) and outstanding toughness (11.9 MJ m−3). Moreover, it demonstrates a broad electrochemical window (4.73 V), remarkable stability across a 600‐hour cycle test, a high capacity retention exceeding 80 % after 100 cycles at 0.2 C, and a noteworthy self‐healing capability. This quasi‐solid polymer electrolyte emerges as a promising contender to replace current liquid electrolyte solutions. [ABSTRACT FROM AUTHOR]

Ionic liquids are an extraordinary group of compounds, fully ionic in structure like inorganic salts but with low melting points, that resemble organic molecular solvents. Their chemical, electrochemical, and thermal stability is what draws the attention and enables their use in many applications, including electrochemical power sources. Even though they are no longer considered eco‐friendly because of nonnegligible toxicity and long bioaccumulation, they can still be efficiently recovered, purified, and reused. These attributes can be harvested to enhance the properties of gel polymer electrolytes for the emerging sodium‐ion batteries. The variety of anions and cations for ILs and their influence on the final properties of the compound opens the road to tuning the properties of gel polymer electrolytes. Ionic liquids as plasticizers constitute a major part of gel polymer electrolytes (average of 70 wt%) and hence, they affect the fundamental properties of gel electrolytes like ionic conductivity and electrochemical window. They also improve the safety features of sodium‐ion batteries, which is relevant for their anticipated applications in stationary energy storage and electric vehicles. The presented review paper aims to explain the relationship between the cation and anion in ionic liquid and the properties of gel electrolytes for sodium‐ion batteries. [ABSTRACT FROM AUTHOR]

Sulfide solid electrolytes (SSEs) have become an ideal candidate material for all‐solid‐state Li metal batteries (ASSLMBs) because of their high ionic conductivity. However, the vile Li incompatibility and poor air stability of SSEs barriers their commercial application. Herein, novel Li6+2xP1−xInxS5−1.5xO1.5xCl (0 ≤ x ≤ 0.1) SSEs are synthesized via In and O co‐doped Li6PS5Cl. By regulating the substitution concentration, the prepared Li6.12P0.92In0.08S4.88O0.12Cl exhibits considerable ionic conductivity (2.67 × 10−3 S cm−1) and enhanced air stability. Based on the first‐principles density functional theory (DFT) calculation, it is predicted that In3+ replaces P5+ to form InS45− tetrahedron and O2− replaces S2− to form PS3O4− group. The mechanism of enhancing air stability by In, O co‐substituting Li6PS5Cl is clarified. More remarkably, the formation of Li‐In alloys induced by Li6.16P0.92In0.08S4.88O0.12Cl electrolyte at the anode interface is beneficial to reducing the migration barrier of Li‐ions, promoting their remote migration, and enhancing the stability of the Li/SSEs interface. The optimized electrolyte shows superior critical current density (1.4 mA cm−2) and satisfactory Li dendrite inhibition (stable cycle at 0.1 mA cm−2 over 3000 h). The ASSLMBs with Li6.16P0.92In0.08S4.88O0.12Cl electrolyte reveal considerable cycle stability. This work emphasizes In, O co‐doping to address redox issues of sulfide electrolytes. [ABSTRACT FROM AUTHOR]

The slow Li+ transport rate in the thick sulfur cathode of the Li--S battery affects its capacity and cycling performance. Herein, Fe-doped highly ordered mesoporous silica material (Fe--HSBA-15) as a sulfur carrier of the Li--S battery shows high ion conductivity (1.10 mS cm-1) and Li+ transference number (0.77). The Fe--HSBA-15/S cell has an initial capacity of up to 1216.7 mA h g-1 at 0.2C and good stability. Impressively, at a high sulfur load of 4.34 mg cm-2, the Fe--HSBA-15/S cell still maintains an area specific capacity of 4.47 mA h cm-2 after 100 cycles. This is because Fe--HSBA-15 improves the Li+ diffusion behavior through the ordered mesoporous structure. Theoretical calculations also confirmed that the doping of iron enhances the adsorption of polysulfides, reduces the band gap and makes the catalytic activity stronger. [ABSTRACT FROM AUTHOR]

Solid‐state lithium (Li) metal batteries (LMBs) have been developed as a promising replacement for conventional Li‐ion batteries due to their potential for higher energy. However, the current solid‐state electrolytes used in LMBs have limitations regarding mechanical and electrochemical properties and interfacial stability. Here, a fluorine (F)‐containing solid polymer electrolyte (SPE) having a bi‐continuous structure of F‐containing elastomers and plastic crystals is reported. The trifluoroethyl acrylate‐based SPE (T‐SPE) exhibits high ionic conductivity over 10−3 S cm−1, superior mechanical elasticity, and robust LiF‐rich interphases at both the Li metal anode and the LiNi0.83Mn0.06Co0.11O2 cathode. Full cells with thin T‐SPEs and low negative/positive capacity ratios below 0.5 at the high‐operating voltage of 4.5 V demonstrate a high specific energy of 538 Wh kganode+cathode+electrolyte−1 and maintain 393 Wh kg−1 at a high specific power of 804 W kganode+cathode+electrolyte−1. The F‐containing phase‐separated SPE system provides a powerful strategy for achieving high‐energy and ‐power solid‐state LMBs. [ABSTRACT FROM AUTHOR]

With the widespread use of batteries, their increased performance is of growing in importance. One avenue for this is the enhancement of ion diffusion, particularly for solid‐state electrolytes, for different ions such as lithium (Li+) and magnesium (Mg2+). Unraveling the origin of better cation diffusion in confined ionic liquids (ILs) in a polymer matrix (ionogels) is compared to that of the IL itself. Ionic conductivity measured by electrochemical impedance spectroscopy for ionogels (7.0 mS cm−1 at 30 °C) is very close to the conductivity of the non‐confined IL (8.9 mS cm−1 at 30 °C), that is, 1‐ethyl‐3‐methyimidazolium bis(trifluorosulfonyl)imide (EMIM TFSI). An even better ionic conductivity is observed for confined EMIM TFSI with high concentrations (1 m) of lithium or magnesium salt added. The improved macroscopic transport properties can be explained by the higher self‐diffusion of each ion at the liquid‐to‐solid interface induced by the confinement in a poly‐vinylidenedifluoride (PVDF) polymer matrix. Upon confinement, the strong breaking down of ion aggregates enables a better diffusion, especially for TFSI anion and strongly polarizing cations (e.g., Li+, Mg2+.). The coordination number of these cations in the liquid phase confirmed that Li+ and Mg2+ interact with the polymer matrix. Moreover, it is a major result that the activation energy for diffusion is lowered. [ABSTRACT FROM AUTHOR]

In solid‐state lithium metal batteries (SSLMBs), the inhomogeneous electrolyte‐electrode interphase layer aggravates the interfacial stability, leading to discontinuous interfacial ion/charge transport and continuous degradation of the electrolyte. Herein, we constructed an anion‐modulated ionic conductor (AMIC) that enables in situ construction of electrolyte/electrode interphases for high‐voltage SSLMBs by exploiting conformational transitions under multiple interactions between polymer and lithium salt anions. Anions modulate the decomposition behavior of supramolecular poly (vinylene carbonate) (PVC) at the electrode interface by changing the spatial conformation of the polymer chains, which further enhances ion transport and stabilizes the interfacial morphology. In addition, the AMIC weakens the "Li+‐solvation" and increases Li+ vehicle sites, thereby enhancing the lithium‐ion transport number (tLi+=~0.67). Consequently, Li || LiNi0.8Co0.1Mn0.1O2 cell maintains about 85 % capacity retention and Coulombic efficiency >99.8 % in 200 cycles at a charge cut‐off voltage of 4.5 V. This study provides a new understanding of lithium salt anions regulating polymer chain segment behavior in the solid‐state polymer electrolyte (SPE) and highlights the importance of the ion environment in the construction of interfacial phases and ionic conduction. [ABSTRACT FROM AUTHOR]

In solid‐state lithium metal batteries (SSLMBs), the inhomogeneous electrolyte‐electrode interphase layer aggravates the interfacial stability, leading to discontinuous interfacial ion/charge transport and continuous degradation of the electrolyte. Herein, we constructed an anion‐modulated ionic conductor (AMIC) that enables in situ construction of electrolyte/electrode interphases for high‐voltage SSLMBs by exploiting conformational transitions under multiple interactions between polymer and lithium salt anions. Anions modulate the decomposition behavior of supramolecular poly (vinylene carbonate) (PVC) at the electrode interface by changing the spatial conformation of the polymer chains, which further enhances ion transport and stabilizes the interfacial morphology. In addition, the AMIC weakens the "Li+‐solvation" and increases Li+ vehicle sites, thereby enhancing the lithium‐ion transport number (tLi+=~0.67). Consequently, Li || LiNi0.8Co0.1Mn0.1O2 cell maintains about 85 % capacity retention and Coulombic efficiency >99.8 % in 200 cycles at a charge cut‐off voltage of 4.5 V. This study provides a new understanding of lithium salt anions regulating polymer chain segment behavior in the solid‐state polymer electrolyte (SPE) and highlights the importance of the ion environment in the construction of interfacial phases and ionic conduction. [ABSTRACT FROM AUTHOR]

A tetra(ethylene glycol)‐based 1,3,4,5‐tetrasubstituted poly(1,2,3‐triazolium) is synthesized in two steps including: i) the catalyst‐free polyaddition of a diazide and an activated internal dialkyne and ii) the N‐alkylation of the resulting 1,2,3‐triazole groups. In order to provide detailed structure/properties correlations different analogs are also synthesized. First, parent poly(1,2,3‐triazole)s are obtained via AA+BB polyaddition using copper(I)‐catalyzed alkyne‐azide cycloaddition or metal‐free thermal alkyne‐azide cycloaddition (TAAC). Poly(1,2,3‐triazole)s with higher molar masses are obtained in higher yields by TAAC polyaddition. A 1,3,4‐trisubstituted poly(1,2,3‐triazolium) structural analog obtained by TAAC polyaddition using a terminal activated dialkyne and subsequent N‐alkylation of the 1,2,3‐triazole groups enables discussing the influence of the methyl group in the C‐4 or C‐5 position on thermal and ion conducting properties. Obtained polymers are characterized by 1H, 13C, and 19F NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and broadband dielectric spectroscopy. The targeted 1,3,4,5‐tetrasubstituted poly(1,2,3‐triazolium) exhibits a glass transition temperature of −23 °C and a direct current ionic conductivity of 2.0 × 10−6 S cm−1 at 30 °C under anhydrous conditions. The developed strategy offers opportunities to further tune the electron delocalization of the 1,2,3‐triazolium cation and the properties of poly(1,2,3‐triazolium)s using this additional substituent as structural handle. [ABSTRACT FROM AUTHOR]

Fully solid-state lithium-ion cells have the benefits of excellent safety, remarkable electrochemical stability, and extended cycle life. They are categorized as prospective candidates for new-generation energy storage devices capable of safe and stable operation for relatively long periods. In whole solid-state Li-ion cells, polymer-based solid electrolyte membranes (SEMs) are expected to serve as both the solid electrolyte and the partition material. Remarkably high ionic conductivity and efficient ion diffusion can be achieved in SEMs by incorporating inorganic filler materials. In the present work, solid electrolyte membranes are developed by a simple solution cast method. The addition of Al2O3 nanoparticles is found to enhance the ionic conductivity of SE membranes to 1.25 × 10−4 S cm−1 for optimum concentrations of lithium salt and filler material. These SE membranes show relatively high electrochemical stability window up to 4.75 V. Transparent and freestanding SE membranes developed using PEO-PVDF-LiNO3-Al2O3 have excellent thermal stability, ideal ion transport number, and good electrochemical properties, suitable for applications in solid-state lithium-ion cells. Assembled LiFePO4-MWCNT//SEM//Li metal half-cells are found to deliver an initial discharge capacity of 128 mAh g−1 at 0.1 C and an initial Coulombic efficiency of 98%. [ABSTRACT FROM AUTHOR]

This study reports five types of metal-doped (Co, Cu, Sn, V, and Zr) NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP)/polymer composite solid electrolytes (CSEs) enabling Li4Ti5O12 (LTO) anodes to have high rate capability and excellent cycling performance. The high Li+-conductivity LATP samples are successfully synthesized through a modified sol–gel method followed by thermal calcination. We find that the cation dopants clearly influence the substitution of Al for Ti, with the type of dopant serving as a crucial factor in determining the ionic conductivity and interfacial resistance of the solid electrolyte. The CSE containing poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and Sn-LATP shows an ionic conductivity of 1.88 × 10−4 S cm−1 at ambient temperature. The optimum conductivity can be attributed to alterations in the lattice parameters and Li+ transport pathways owing to Sn doping. The solid-state cell equipped with the LTO-supported CSE containing Sn-LATP fillers demonstrates both excellent high rate capability at 5 C (with a capacity retention of 86% compared to the value measured at 0.2 C) and superior cycling stability, maintaining high Coulombic efficiency (>99.0%) over 510 cycles. These findings indicate that the proposed CSE is highly promising for use in solid-state lithium batteries with desirable charge–discharge properties and high durability. [ABSTRACT FROM AUTHOR]

In this work, effect of varying lithium perchlorate (LiClO4) salt concentration in polymer gel electrolytes (PGE) containing heat resistant polymethyl methacrylate (PMMA), and succinonitrile (SN) is investigated via electrochemical and physical properties. The electrolyte specimen with high LiClO4 salt concentration of 1.5 M supports maximum ionic conductivity of 4.9 × 10–5 S cm−1 and electrochemical stability window of ~ 4 V. The ion-transport parameters evaluated from the tangent loss studies confirms that the optimized electrolyte possesses diffusivity (D) of 4.52 × 10–2, mobility (μ) of 1.746 cm2 V−1 s−1, number of charge carriers (N) of 1.78 × 1014 cm−3 and Nµ of 3.106 × 1014 cm−1 V−1 s−1. The dielectric constant studies show that the optimized electrolyte possesses maximum dielectric constant and lower value of modulus towards the high frequency region. The thermogravimetric and differential scanning calorimetry studies confirms that the prepared electrolytes offer weight loss of < 9% up to 373 K and maintains the gel phase up to 570 K, respectively. X-ray diffraction suggest that the PGE system becomes more amorphous with progressive addition of LiClO4 up to 1.5 M, while the Fourier transform Infra-red (FTIR) spectroscopy study reveal the salt-polymer interactions. [ABSTRACT FROM AUTHOR]

[Display omitted] Poor mechanical strength at working temperature and low ionic conductivity seriously hinder the application of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) in high performance all-solid-state lithium metal batteries (LMBs). Here, we design and prepare a series of rigid-flexible coupling network SPEs (RFN-SPEs) with soft poly(ethylene glycol) (PEG) chains and rigid crosslinkers containing the benzene structure. Compared with soft crosslinkers, rigid crosslinkers provide the same amount of active crosslinking points with smaller molecular weight, and meanwhile enhance the mechanical strength of the network. Therefore, based on the rigid crosslinkers, RFN-SPEs exhibit synchronously improved ionic conductivity and mechanical strength. With these RFN-SPEs, symmetrical cells can be cycled for over 2100 h at 0.5 mA cm−2. Meanwhile, stable cycling and high-rate capability could be achieved for LMBs, revealing that SPEs with the rigid-flexible coupling network are promising electrolyte systems for all-solid-state LMBs. [ABSTRACT FROM AUTHOR]

For the lithium (Li) metal anode, constructing a strong and durable protective layer with lithium‐ion permeability is crucial, especially in high donor number (DN) solvent system. High DN solvent‐based electrolytes can support both higher capacity and lower charge overpotential in the rechargeable lithium–oxygen batteries (LOBs). However, Li anodes in high DN solvent system suffer from severe corrosion and uncontrolled dendrite growth due to the unstable solid‐electrolyte interphase (SEI). Typically, this interface is formed in situ through electrochemical processes with complicated component and spatial distribution. Here, a functional molecule is introduced to construct an ion‐wall (IW) on Li surface by prechemical sequential reactions (p‐CSRs), through which the crystalline nanoparticles as bricks and amorphous hybrid compounds as the mortar can be produced to build such a "wall." Different from the conventional SEI, this wall is not only compact and uniform, but also possess high strength, excellent passivation properties and high ionic conductivity. With these properties, the IW could suppress Li dendrites and inhabit the side reaction, supporting highly reversible Li plating/stripping behavior in high DN solvent system. As a result, the cycle stability of LOBs based on the IW protected Li anode is significantly improved. [ABSTRACT FROM AUTHOR]