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Lithium-ion batteries increasingly play significant roles in modern technologies; however, increased energy density also raises concerns about electrolyte safety. Traditional electrolytes that use volatile organic solvents face risks of thermal runaways and fires from electrode shorting. In response, polymer-based solid electrolytes have been developed for replacement. Polyacrylonitrile (PAN) is a promising fire-resistant component for electrolyte fabrication, but its limited solubility necessitates using low-volatility solvents, which are notoriously difficult to remove in subsequent drying processes. Here, we use femtosecond two-dimensional infrared spectroscopy to provide an in-depth understanding of how residual solvent from processing affects the molecular structures and dynamics within a polymer electrolyte. To this end, linear and nonlinear infrared spectroscopies are employed to interrogate the molecular interactions in PAN-based electrolytes containing various contents of N,N-dimethylformamide (DMF). We show that the amount of DMF within the PAN electrolyte affects the Li+ structure. The coordination can proceed through the carbonyl group and/or the amide nitrogen to form antiparallel structures with the nitrile groups of PAN through dipole–dipole interactions. The free motion of DMF is drastically inhibited upon interaction with Li+ and PAN, which decreases the ionic conductivity and potentially affects the stability (resistance toward removal and chemical decomposition). These findings have implications for the design and processing of solid polymer electrolytes. [ABSTRACT FROM AUTHOR]

Molecular rotations influence numerous condensed matter phenomena but are often difficult to isolate in molecular dynamics (MD) simulations. This work presents a rotational/roto-translational constraint algorithm designed for condensed matter simulations. The method is based on the velocity Verlet scheme, ensuring a direct constraint on velocity and simplifying implementation within material simulation software packages. We implemented the algorithm in a customized version of a CP2K package and validated its effectiveness through MD simulations of molecule and crystal. The results demonstrate successful selective constraint of rotational and roto-translational motions, enabling stable long-term simulations. This capability opens avenues for studying rotation-related phenomena (e.g., paddle-wheel mechanism in solid-state electrolytes) and constrained sampling. [ABSTRACT FROM AUTHOR]

The glassy state of zeolitic imidazolate frameworks (ZIFs) has shown great potential for energy-related applications, including solid electrolytes. However, their thermal conductivity (κ), an essential parameter influencing thermal dissipation, remains largely unexplored. In this work, using a combination of experiments, atomistic simulations, and lattice dynamics calculations, we investigate κ and the underlying heat conduction mechanism in ZIF glasses with varying ratios of imidazolate (Im) to benzimidazolate (bIm) linkers. The substitution of bIm for Im tunes the node–linker couplings but exhibits only a minor impact on the average diffusivity of low-frequency lattice modes. On the other hand, the linker substitution induces significant volume expansion, which, in turn, suppresses the contributions from lattice vibrations to κ, leading to decreased total heat conduction. Furthermore, spatial localization of internal high-frequency linker vibrations is promoted upon substitution, reducing their mode diffusivities. This is ascribed to structural deformations of the bIm units in the glasses. Our work unveils the detailed influences of linker substitution on the dual heat conduction characteristics of ZIF glasses and guides the κ regulation of related hybrid materials in practical applications. [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]

BaSnF4 is a prospective solid state electrolyte for fluoride ion batteries. However, the diffusion mechanism of the fluoride ions remains difficult to study, both in experiments and in simulations. In principle, ab initio molecular dynamics could allow to fill this gap, but this method remains very costly from the computational point of view. Using machine learning potentials is a promising method that can potentially address the accuracy issues of classical empirical potentials while maintaining high efficiency. In this work, we fitted a dipole polarizable ion model and trained machine learning potential for BaSnF4 and made comprehensive comparisons on the ease of training, accuracy and efficiency. We also compared the results with the case of a simpler ionic system (NaF). We show that contrarily to the latter, for BaSnF4 the machine learning potential offers much higher versatility. The current work lays foundations for the investigation of fluoride ion mobility in BaSnF4 and provides insight on the choice of methods for atomistic simulations. [ABSTRACT FROM AUTHOR]

As a key component for the future high‐safety lithium batteries, solid polymer electrolyte (SPE) is gaining an attractive momentum toward large‐scale production due to their remarkable compatibility and processability with electrodes. Further, their excellent performance can be improved using the potential use of plasticizers. A deep eutectic solvent (DES) synthesized from choline chloride (ChCl) and citric acid monohydrate (CAM) demonstrates a promising plasticizer to design good SPE membranes along with poly (vinyl alcohol) (PVA). The changes in the surface chemistry of PVA‐based membranes, as determined by Fourier transform infrared (FTIR) spectroscopy, confirm the success of DES‐plasticizing effect, where detected by wavenumber shifting around main functional groups such as OH, CO, and COC. Following this, EIS characterization on electrical properties reveals the role of 30 wt% DES in improving the ionic conductivity, with the highest ionic conductivity equivalent to 4.66 × 10−4 S cm−1 and the crystallinity index as high as 41.09%. The presence of LiClO4 and DES significantly reduces mechanical performance, and glass transition of PVA‐based membranes, as characterized by tensile testing and differential thermal analysis/thermogravimetric analysis. Thus, the presence of DES in PVA and LiClO4 matrices could open another window for designing SPE with novel physicochemical properties. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: With the rapid development of solid‐state batteries, solid‐state polymer electrolytes (SPEs) have attracted widespread attention due to their excellent environmental friendliness, designability, and forming film ability. However, due to the limited conductive path of polymers, lithium‐ion diffusion kinetics are limited, and low ion conductivity is a huge challenge for SPEs in practical applications. This work provides a polyethylene oxide (PEO) based polymer electrolyte, which has multiple paths of ion diffusion caused by organic polymer framework of poly(hexaazatrinaphthalene) (PHATN). The unique porous channel, the specific surface characteristics, the coordination of ‐C=N‐ groups in PHATN with Li+, combined with the mobility of PEO segments, make the SPEs have a good ability to conduct Li+. Interestingly, the PHATN‐PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) composite electrolytes exhibit excellent electrochemical properties. At room temperature, the conductivity of PHATN‐PEO electrolyte can reach 1.03 × 10–4 S·cm–1, which is greatly improved compared with 3.9 × 10–6 S·cm–1 of PEO. Delightedly, the lithium‐ion transference number of PHATN‐PEO electrolyte achieves 0.61, and the electrochemical window increases to 4.82 V. The LFP/1%PH‐PEO/Li solid‐state batteries show good electrochemical cycles. This work reveals an efficient stratagem for the design of polymer solid‐state electrolytes. [ABSTRACT FROM AUTHOR]

Solid state lithium-ion batteries (SSLIBs) with high safety and high energy density are promising novel energy storage devices. However, the performance of SSLIBs would descend under a wide work temperature range. A flexible ceramic-polymer composite solid electrolyte membrane was created by solution casting to obtain good stability of SSLIBs at different temperatures. The PVDF-HFP-PES-LiClO 4 -Li 6.4 La 3 Zr 1·4 Ta 0·6 O 12 (LLZTO) composite solid electrolyte shows excellent electrochemical performances in the temperature range of 20–60 °C. The ionic conductivity of PVDF-HFP-PES-LiClO 4 -LLZTO (PPLL) is 4.26 × 10−4, 4.97 × 10−4, 5.26 × 10−4, 5.59 × 10−4 and 5.97 × 10−4 S cm−1 at 20, 30, 40, 50 and 60 °C, respectively. The PPLL was employed in LiFePO 4 (LFP)/PPLL/Li batteries, and their properties were tested at 0.2 C. The test results show that the LFP/PPLL/Li battery has a good charge-discharge, rate, and cyclic performance at 20–60 °C. After 150 cycles with 0.2C at 30 °C and 60 °C, the capacity retention rates of 75.6 % and 86.4 %, respectively. This work provides an effective strategy for designing and preparing SSLIBs. [ABSTRACT FROM AUTHOR]

Concurrent construction of robust SEI and CEI enriched with pyrrole/Ppy-analogues to achieve dendrite-free Zn anodes and enhance cathode capacity and stability towards advanced aqueous zinc-ion batteries. [Display omitted] • The pyrrole-based solid electrolyte interphase (SEI) guides uniform Zn2+ deposition and suppresses HER and side reactions. • A dendrite-free zinc anode is achieved with a prolonged cycle life of over 6000 h in Zn//Zn cell at 0.5 mA/cm2. • The cathode electrolyte interphase (CEI) comprising polypyrrole analogues achieves enhanced cathode capacity and stability for both PANI and MnO 2. The advancement of aqueous zinc-ion batteries (AZIBs) is impeded by challenges encompassing cathodic and anodic aspects, such as limited capacity and dendrite formation, constraining their broader utilization. Herein, pyrrole, an economically viable and readily accessible compound, is proposed as a versatile electrolyte additive to address these challenges. Experiments and DFT calculations reveal that pyrrole and its derivatives preferentially adsorb onto zinc foil, facilitating the formation of a pyrrole-based solid electrolyte interphase (SEI), which effectively guides uniform Zn2+ deposition through strong attraction force and suppresses hydrogen evolution reactions and parasitic reactions. On the cathode side, the additive promotes the formation of a durable cathode electrolyte interphase (CEI) enriched with poly-pyrrole (Ppy) analogues. Such layer significantly contributes to extra capacity of both polyaniline (PANI) and MnO 2 cathodes by leveraging the electrochemical reactivity of Ppy towards Zn2+ and improves their cyclic stability. Consequently, a dendrite-free Zn anode is realized with an extended cyclic lifespan surpassing 6000 h in Zn//Zn cell, coupled with an average Coulombic efficiency of 99.7 % in Cu//Zn cell. Moreover, the PANI//Zn and MnO 2 //Zn full cells demonstrate enhanced capacities along with improved cycling stability. This work provides a new additive strategy towards concurrent stabilization of cathode and Zn anode in AZIBs. [ABSTRACT FROM AUTHOR]

A uniform LiF-dominated SEI is in-situ fabricated by the spontaneous reactions between CaF 2 nanoparticles and Li anode, which enables dendrite-free Li deposition and restrains interfacial deterioration, thus performing ultra-stable cells operation and superior electrochemical performance. [Display omitted] • CaF 2 coating layer on Li surface in-situ forms LiF-dominated SEI layer. • The LiF-dominated SEI facilitates homogeneous Li deposition and restrains interfacial deterioration. • Li@CaF 2 anode performs excellent electrochemical stability of operation over 6000 h. The uncontrollable growth of Li dendrites and severe interfacial parasitic reactions on the Li anode are the primary obstacles to the practical application of lithium (Li) metal batteries. Effective artificial solid electrolyte interphase is capable of regulating uniform Li deposition and isolateing Li from electrolyte, thereby eliminating parasitic reactions. Herein, we rationally design a uniform LiF-dominated solid electrolyte interphase through an in-situ reaction between CaF 2 nanoparticles and the Li anode, which allows dendrite-free Li deposition and restrains interfacial deterioration. Accordingly, the protective Li electrode demonstrated exceptional stability, sustaining over 6000 h at a current density of 2 mA cm−2 in symmetric cells and attaining over 1000 cycles with a low capacity decay rate of 0.015 % per cycle in coupling with LiFePO 4 cathodes. [ABSTRACT FROM AUTHOR]

[Display omitted] Lithium metal is highly favored as an ideal anode material in future high-capacity lithium batteries due to its appealing properties. Nevertheless, the implementation of lithium metal batteries (LMBs) is severely plagued by challenges such as instable solid electrolyte interface (SEI), uncontrolled growth of dendrite, and severe volume expansion. Herein, to address the aforementioned issues, an artificial SEI layer is fabricated, which is comprised of LixSi alloy and Li 3 N. The in-situ generated LixSi/Li 3 N interface is formed on the carbon fiber (denoted as CF/LixSi/Li 3 N) through a spontaneous reaction between molten Li and Si 3 N 4. Density functional theory (DFT) calculations reveal that LixSi alloy has low ion diffusion energy barrier, which facilitates the low nucleation overpotential of Li+ and enables homogeneous lithium deposition. Li 3 N can further promote the rapid Li+ transport due to the excellent Li+ conductivity. In addition, the reserved 3D space effectively mitigates the volume change along cycling procedure. Owing to the synergistic effect of the LixSi/Li 3 N protective layer and the 3D structure, the composite anode shows higher cycling stability with a lifetime of more than 3000 cycles at 1 mA cm−2. Furthermore, matched with commercial LiFePO 4 (LFP) and LiNi 5 Co 2 Mn 3 O 2 (NCM523) cathodes, the full cells also exhibit impressive electrochemical properties. This work introduces an ingenious approach for constructing stable lithium metal anodes and effective lithium metal batteries. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: With the rapid development of solid‐state batteries, solid‐state polymer electrolytes (SPEs) have attracted widespread attention due to their excellent environmental friendliness, designability, and forming film ability. However, due to the limited conductive path of polymers, lithium‐ion diffusion kinetics are limited, and low ion conductivity is a huge challenge for SPEs in practical applications. This work provides a polyethylene oxide (PEO) based polymer electrolyte, which has multiple paths of ion diffusion caused by organic polymer framework of poly(hexaazatrinaphthalene) (PHATN). The unique porous channel, the specific surface characteristics, the coordination of ‐C=N‐ groups in PHATN with Li+, combined with the mobility of PEO segments, make the SPEs have a good ability to conduct Li+. Interestingly, the PHATN‐PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) composite electrolytes exhibit excellent electrochemical properties. At room temperature, the conductivity of PHATN‐PEO electrolyte can reach 1.03 × 10–4 S·cm–1, which is greatly improved compared with 3.9 × 10–6 S·cm–1 of PEO. Delightedly, the lithium‐ion transference number of PHATN‐PEO electrolyte achieves 0.61, and the electrochemical window increases to 4.82 V. The LFP/1%PH‐PEO/Li solid‐state batteries show good electrochemical cycles. This work reveals an efficient stratagem for the design of polymer solid‐state electrolytes. [ABSTRACT FROM AUTHOR]

Sulfide‐based superionic conductors present great promise to achieve high energy density and safety for all‐solid‐state sodium batteries (ASSSBs). However, the poor electrolyte/electrode interface compatibility and humid air stability seriously hinder their deployment in ASSSBs. Herein, a series of high‐performance Na3‐□Sb1‐4x(SnWCaTi)xS4 sulfide‐based solid electrolytes (SSEs) are reported by coupling the vacancy effect with configurational entropy, which displays an excellent interface stability against sodium metal and an extraordinary tolerance toward the moist atmosphere, even for water. The optimized electrolyte effectively inhibits the detrimental mixed ion‐electron conducting interphase formation, achieving the ultra‐stable operation of Na–Na symmetric cell up to 1000 h. Furthermore, the Na+ diffusion kinetics is obviously enhanced by increasing the Na sites local anisotropy and Na vacancies. Eventually, the assembled TiS2//Na5Sn ASSSBs deliver a remarkable reversible capacity of 211.6 mAh g−1 at 0.5C with a long‐term cycling performance of 450 cycles at room temperature. More importantly, it achieves a steady running up to 100 cycles at 1C even if this electrolyte is placed in the air with a dew temperature of 13.8 °C for 30 min, the highest values in the state‐of‐the‐art sulfide‐based ASSSBs. The well‐designed SSEs open a new avenue for realizing the advanced and powerful ASSSBs. [ABSTRACT FROM AUTHOR]

To facilitate the use of solid polymer electrolytes (SPEs) with high‐nickel (Ni) cathodes in high‐voltage lithium (Li) metal batteries (LMBs), it is crucial to address the challenges of low oxidative stability and the formation of vulnerable interphases. In this study, isocyanate groups (−N═C═O) are incorporated to develop an SPE with a bi‐continuous structure, consisting of elastomeric and plastic crystal phases. This rationally designed SPE exhibits high ionic conductivity (0.9 × 10−3 S cm−1 at 25 °C), excellent elasticity (elongation at break of 330%), and enhanced oxidative stability (over 4.8 V vs. Li/Li⁺). A full cell, incorporating this SPE with a thin Li foil of 40 µm, and a high‐Ni LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode operating at 4.7 V vs. Li/Li⁺, demonstrates excellent cyclability, retaining 70% of its initial capacity after 200 cycles under a high C‐rate of 1C at 25 °C. The extended cycling of isocyanate‐containing SPE at 4.7 V vs. Li/Li⁺ is attributed to robust and compact inorganic‐rich interphases enabled by antioxidative −N−C═O components, as well as uniform Li deposition attributed to the bi‐continuous structured SPE. This study suggests that the isocyanate‐containing SPE system is a promising candidate for high‐voltage solid‐state LMBs by constructing stable interphases. [ABSTRACT FROM AUTHOR]

A suitable solid electrolyte can turn the long‐standing dream of a safe commercial all‐solid‐statebattery into reality in the same way as appropriate liquid electrolytes kickstarted the first commercial lithium‐ion battery. Presently, halide‐based electrolytes despite their reactivity with lithium metal are extensively studied as they offer better processability, malleability, oxidative stability, and safety over sulfide‐based electrolytes. Particularly, LiMCl6 (M = Ta/Nb) chloride‐based amorphous electrolytes are generating widespread interest with their high conductivities, comparable to liquid electrolytes. In this context, with synchrotron X‐ray and neutron powder diffraction techniques, well‐crystallized triclinic layered LiMCl6 (M = Ta/Nb) chlorides with an hcp AB‐type stacking of chloride ions is reported. The hexagonally ordered NbCl6 octahedra share edges with LiCl6 octahedra forming a honeycomb pattern, whereas Li+ is intermixed with M5+ for M = Ta. Furthermore, it is found that crystalline LiTaCl6 has an ionic conductivity of ≈10−5 mS cm−1, six orders of magnitude lower than that reported for superionic amorphous LiTaCl6. Nevertheless, crystalline LiTaCl6 is utilized as an intercalation compound in an all‐solid‐state‐battery, uncovering a solid‐solution/two‐phase/conversion pathway for lithium‐insertion during the three distinct redox plateaus below 3 V versus Li+/Li°. Broadly, the findings give insights into the structure, ionic conduction, and intercalation in a new family of layered halides. [ABSTRACT FROM AUTHOR]

The advancement of aqueous zinc‐ion batteries (AZIBs) faces significant obstacles due to the typically loose and unstable solid electrolyte interphase (SEI), which fosters dendrite formation and undermines cycling performance, especially in cold environments. Here, a quasi‐high‐entropy solid electrolyte interphase (QHE‐SEI) formulated is introduced with diverse and functional inorganic compounds, achieved through the incorporation of dual salts and a blend of solvents. Shielded by the QHE‐SEI, AZIBs exhibit uniform zinc deposition and attain remarkable cycling stability, enduring for 1300 h in Zn||Zn symmetric cells under conditions of 3 mA cm−2 and 3 mAh cm−2 at room temperature. Furthermore, the full cell maintains over 4300 cycles at −20 °C with nearly full capacity retention. Notably, the pouch cell maintains a high capacity of ≈25 mAh across 50 cycles, even at −20 °C. This study offers a novel approach to designing a stable SEI and elevates the performance of AZIBs. [ABSTRACT FROM AUTHOR]

The hard carbon (HC) anodes with desirable electrochemical performances including high initial Coulombic efficiency, superior rate performance and long‐term cycling play an indispensable role in the practical application of sodium ion batteries (SIBs), which are closely related to the electrolytes them matched. Fully analyzing the mechanism of electrolyte engineering for HC anodes is crucial for promoting the commercialization of SIBs, but is still lacking. In this review, the correlation between physicochemical properties of the electrolyte and the electrochemical performance of HC is first summarized. And point out the crucial role of electrolyte properties, including ion conductivity, de‐solvation energy, and interface passivation ability for the Na+ storage in HC. Then, the formation process, composition, as well as structure of solid electrolyte interphase (SEI) on HC surface are mainly discussed, and the structure‐activity relationship of SEI is analyzed in depth. Moreover, based on the mechanism analysis, relevant electrolyte design strategies have been summarized. Finally, the challenges and future development directions of the electrolyte engineering of HC are proposed. This review is expected to provide professional theoretical guidance for the development of electrolyte and contribute to the rational design of high‐performance HC anodes, promoting the industrialization of SIBs. [ABSTRACT FROM AUTHOR]

Solid‐state batteries are compelling candidates for next‐generation energy storage devices, promising both high energy density and improved safety, by utilizing metallic Li as the negative electrode. However, they suffer from poor cyclability and rate capability, which limits their wide application. Degradation in these devices occurs through complex mechanical, chemical and electrochemical pathways, all of which produce heterogeneous deformation fields. Therefore, isolating solid‐state degradation mechanisms, and explicitly linking them to the associated deformation fields requires a multimodal characterization strategy. Here, a novel 3‐D, in situ methodology for linking degradation to deformation in solid‐state cells is presented. X‐ray imaging is used to measure the morphological degradation, and combined with X‐ray diffraction to quantify (electro)chemical aspects. Finally, the heterogeneous stress fields from these various pathways are mapped in situ. This heterogeneity is shown globally, from the interface to the bulk electrolyte, as well as locally, around features such as cracks and voids. Through these analyses, it is possible to delineate the effects of solid electrolyte processing, cell assembly, and cycling on the end‐of‐life state of the cell. Moreover, the importance of stress mitigation in these cells is highlighted, with mean stresses around the interface and some cracks comfortably exceeding the elastic limit of Li. [ABSTRACT FROM AUTHOR]

The combination of high‐voltage Ni‐rich cathodes and high‐capacity Si‐based anodes can result in high energy density for next‐generation batteries. However, the practical capacities accesses are severely hindered by unstable electrode/electrolyte interphases (EEI) and irreversible structural degradation, which necessitates efficient additives in electrolyte for generating stable EEI. Herein, a multifunctional additive, 3‐Fluoro‐5‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)picolinonitrile (FTDP) is proposed to construct robust interfaces at both cathodic and anodic surface, so as to enhance electrochemical performance. FTDP is preferentially decomposed to form B‐contained and cyano (CN) group‐rich cathode electrolyte interphase (CEI), as well as LiF‐, Li3N‐rich solid electrolyte interphase (SEI), simultaneously, resulting in the integrity and stability of electrodes. Moreover, the FTDP‐derived CEI can suppress transition metal ions dissolution, further facilitating battery cyclability. The multifunctionality of FTDP, including quenching free radicals, alleviating the hydrolysis of LiPF6 and inhibiting HF generation, thus greatly improving interfacial stability. With trace addition of 0.2 wt.%, NCM811/Li cell can be performed at an extreme condition, i.e., ultra‐high voltage (4.8 V), high temperature (60 °C) and high rate (10C). 1.6 Ah NCM811/SiOx pouch cell delivers a high capacity retention of 84.0% after 300 cycles. [ABSTRACT FROM AUTHOR]

All‐solid‐state Li‐metal batteries (ASSLBs) are the most attractive next‐generation batteries due to intrinsic safety and high energy density. Particularly, composite solid electrolyte (CSE)‐based ASSLBs, highly compatible with conventional Li‐ion batteries, are nearing commercialization. However, the understanding of ASSLBs’ failure remains deficient, thereby considerably hindering their advancement. Herein, the unrecognized failing mode of ASSLBs, voltage noise failure (VNF), characterized by irregular charging voltage configuration, is identified using comprehensive techniques, including laser‐induced breakdown spectroscopy. The VNF originates from micro‐penetration of Li dendrites, which is demonstrated through direct observation of 3D Li concentration map in CSE. In this phenomenon, the transition metals, dissolved from the cathode, hop to the anode and serve as seeds for dendritic growth in VNF. Inspired by this mechanism and with the aid of DFT calculations, a transition metal scavenging layer is proposed using Prussian blue analogue at the cathode‐CSE interface. Consequently, ASSLBs with transition metal scavenging layer exhibit superior capacity (189 mAh g−1 at 0.5 C, NCM811) and stable cyclability (1200 cycles without failure). [ABSTRACT FROM AUTHOR]

Advancing energy density, enabling lithium metal anodes, and ensuring unparalleled safety and operational reliability in lithium batteries hinge on advancing inorganic solid-state electrolytes. To overcome current impediments, we present an innovative approach that integrates glass-ceramics with a pioneering new Nasicon strategy involving molybdenum doping. In the conducted study, a series of 14Li 2 O-9Al 2 O 3 -38TiO 2 -(39-x)P 2 O 5 -xMoO 3 glasses, denoted as LATPMo x , along with their corresponding glass-ceramics (LATPMo x -GC), have exhibited a promising characteristic as solid electrolytes. X-ray diffraction (XRD) analysis confirms the formation of the novel Mo-doped Nasicon phases in the glass-ceramics, as validated by Rietveld refinement. Examination of the crystallization kinetic behavior of the glasses reveals a three-dimensional nucleation process with spherical particle growth, featuring an activation energy of 165 kJ mol−1. Transmission Electron Microscopy TEM characterization aligns crystallization behavior with crystallite and distribution within the glass matrix, resulting in a compact and dense microstructure. The structural properties of the resultant phases are examined through FT-IR, Raman spectroscopy, and TEM-SEAD analysis. Vickers indentation tests were employed to assess the microscopic fracture toughness, and both the glass and glass-ceramics materials demonstrated favorable mechanical performance. Optical characterization using UV–visible absorption highlights the reduction of Mo6+ to Mo5+, likely occupying tetrahedral sites within the crystalline lattice. Impedance spectroscopy measurement showcases the effective promotion of ionic conductivity following Mo doping, reaching a total conductivity value of 5.50 × 10−5 Ω−1 cm−1 along with a high lithium transference number of 0.99 at room temperature for LATPMo 2.6 -GC glass-ceramic. This value is larger than that of many other glass-ceramics as well as that of the well-known lithium phosphorous oxy-nitride LiPON solid electrolyte whose ionic conductivity at RT is around 2 × 10−6 Ω−1 cm−1. [ABSTRACT FROM AUTHOR]

Electric double layer effect in solid electrochemical systems is a key topic in energy storage applications. In this review, we outline recent investigations on the electric double layer effect of solid electrolyte interfaces by utilizing a semiconducting diamond surface as a probe of electrical charges at the solid/solid interfaces. Hall measurements with various solid electrolyte-based transistors evidenced that the electric double-layer effect strongly depends on the properties of the electrolyte and the very thin region from the interface. The unveiled features of the electric double layer at solid electrolyte interfaces are quantitatively discussed from the viewpoint of charge density and charging-discharging rate. Furthermore, applications of the unique switching response of the electric double layer transistors to neuromorphic computing are also demonstrated. [ABSTRACT FROM AUTHOR]

Li2S–P2S5–LiI-type solid electrolytes, such as Li4PS4I, Li7P2S8I, and Li10P3S12I, are promising candidates for anode layers in all-solid-state batteries because of their high ionic conductivity and stability toward Li anodes. However, few studies have been conducted on their detailed local structure and particle surface state. In this study, Li7P2S8I (Li2S: P2S5:LiI = 3:1:1) solid electrolytes as the chemical composition were synthesized by mechanical milling and liquid-phase shaking, and their local structures were analyzed by transmission electron microscopy. The particle surface states were analyzed by X-ray photoelectron spectroscopy, high-energy X-ray scattering measurements, and neutron total scattering experiments. The results showed that Li7P2S8I solid electrolytes are composed of nanocrystals, such as Li4PS4I, LiI, Li10P3S12I and an amorphous area as the main region, indicating that the crystalline components alone do not form ionic conductive pathways, with both the amorphous and crystalline regions contributing to the high ionic conductivity. Moreover, the ionic conductivity of the crystalline/amorphous interface of the glass-ceramic was higher than that of the Li2S–P2S5–LiI glass. Finally, an organic-solvent-derived stable surface layer, which was detected in the liquid-phase shaking sample, served as one of the factors that contributed to its high stability (which surpassed that of the mechanically milled sample) toward lithium anodes. We expect these findings to enable the effective harnessing of particle surface states to develop enhanced sulfide solid electrolytes. [ABSTRACT FROM AUTHOR]

Understanding the ionic conduction mechanisms in solid electrolyte glasses and glass-ceramics is an important task for improving the performance of next-generation all-solid-state batteries. Although many ionic conduction mechanisms have been proposed, the mechanism of increased ionic conductivity in partially crystallized glass is not fully understood. In this study, molecular dynamics was used to analyze the strain and local ion mobility in the glass around the crystal nano-particles of Li 3 PS 4 , which is a promising material for solid electrolytes. From the analysis of the results, we find that a local strain field is generated around the crystal particles and that the tensile strain field decreases the activation energy of ion migration and increases the ionic conductivity. This study opens the possibility of improving the ionic conductivity of glass-ceramics by controlling crystallization and dispersing the tensile strain field, even though the crystalline phase is not a high ionic conducting phase. [ABSTRACT FROM AUTHOR]

All-solid-state batteries are typically manufactured under high pressure to decrease the resistance of the solid interface. However, until now, there has been a lack of research concerning changes in the structure of solid electrolytes owing to pressurization. Our study addresses this gap by exploring the structural modifications of the sulfide solid electrolyte Li3PS4 under high-pressure conditions. We observed a tendency for PS4 molecules to converge upon each other in both β-Li3PS4 and g-Li3PS4 crystals when subjected to a pressure of 100 MPa. In g-Li3PS4, X-ray scattering and pair distribution function analyses following pressure application and subsequent return to ambient conditions remained consistent with pre-compression measurements. Conversely, in β-Li3PS4 crystals, post-pressure X-ray scattering differed from pre-compression measurements, suggesting pressure-induced atomic rearrangement within the crystal lattice. This underscores the importance of accounting for pressure-induced structural changes, especially in computational simulation studies where crystal structures are often assumed to remain static pre- and post-pressurization. Our findings demonstrate that under high pressure, the crystal structure of Li3PS4 slightly changes by approximately 1~2%, rendering it a viable candidate for utilization as a solid electrolyte in all-solid-state batteries. [ABSTRACT FROM AUTHOR]

All-solid-state lithium-ion batteries are a promising next-generation technology because they have higher energy densities than their liquid-electrolyte counterparts. Halogen-rich argyrodite, specifically Li5.4(PS4)(S0.4Cl1.0Br0.6), was recently shown to have higher ionic conductivities compared with those of other argyrodite-like sulfides. Although the Li5.4(PS4)(S0.4Cl1.0Br0.6) in Li | Li5.4(PS4)(S0.4Cl1.0Br0.6) | Li(Ni0.8Co0.1Mn0.1)O2–Li5.4(PS4)(S0.4Cl1.0Br0.6) batteries have shown good electrochemical stability, the low discharge capacity limits the application of the battery. In continuation, this study examined the potential of a carbon additive for altering the electronic conductivity of the cathode and enhancing the capacity of Li | Li5.4(PS4)(S0.4Cl1.0Br0.6) | Li(Ni0.8Co0.1Mn0.1)O2–Li5.4(PS4)(S0.4Cl1.0Br0.6) batteries. After a 50-cycle charge/discharge, the carbon additive (0.1 C) enhanced the discharge capacity from 3.1 to 167 mAh/g, resulted in a capacity retention rate and coulombic efficiency of 95.4% and 99.9% when using 0.1 C and 0.5 C, respectively, and increased the resistance of the battery from 53 to 56 Ω. Therefore, the all-solid-state battery employing high-ion-conductive Li5.4(PS4)(S0.4Cl1.0Br0.6) and a carbon-modified cathode showed improved capacity. This study provides a proven framework for developing all-solid-state batteries employing halogen-rich argyrodite (Li7-α(PS4)(S2-αXα); α > 1) with enhanced ionic conductivities. [ABSTRACT FROM AUTHOR]

Sulfide-based solid electrolytes are increasingly recognized as crucial materials for the practical application of all-solid-state batteries. In particular, halogen-rich argyrodites, featuring hybrid doping with chlorine and bromine, demonstrate that the Li-ion conductivity is influenced by the degree of elemental disorder among chlorine, bromine, and sulfur at the anion sites (4a, 4d). This study employed in situ XRD/PDF during the annealing process of sample synthesis to investigate the formation of disorder at these anion sites. Initially, a sulfur-rich argyrodite phase formed at lower annealing temperatures (200–320 °C). Subsequently, in the higher temperature range (320–460 °C), lithium halide amorphization and thermal diffusion led to the formation of a halogen-rich argyrodite phase. This phase is characterized by the substitution of sulfur with halogen at the 4a/4d sites in argyrodites. [ABSTRACT FROM AUTHOR]

Much attention has been paid on research and development on solid electrolytes for all-solid-state Li batteries. Although halide solid electrolytes such as Li3YCl6 and Li3InCl6 are promising due to fast Li ion conductivity and oxidation-resistant against positive electrode, a better understanding of their reactivity with atmospheric H2O is required for commercialization. In this study, the gas evolution tolerances of Li3YCl6 and Li3InCl6 were investigated. Temperature-programmed desorption mass spectrometry (TPD-MS) experiments at dew points below − 60 °C and gas detector tube experiments at dew points of − 30 °C both revealed significant differences in the H2O and HCl evolution behavior of Li3YCl6 and Li3InCl6. In TPD-MS, the onset temperature of HCl evolution for Li3YCl6 (~ 100 °C) was significantly lower than that for Li3InCl6 (~ 220 °C), indicating that Li3InCl6 solid electrolytes have superior gas evolution tolerance. This difference may be attributable to differences in the retention of H2O derived from the material synthesis stage and from contact with the atmosphere during the measurements. In particular, based on first-principles calculations, the low-temperature HCl evolution observed in Li3YCl6 was ascribed to the partial replacement of Cl− ions by OH− ions upon contamination with trace H2O. Because the heating and drying of solid electrolytes (including slurries) are inevitable processes during battery manufacturing, these findings can aid in the rational design of halide solid electrolytes for all-solid-state batteries. [ABSTRACT FROM AUTHOR]

This paper reports the fabrication of thin-film batteries which are composed of three stacking layers: LiCoO2, Li3PO4, and Li. First, a LiCoO2 layer is constructed on an electron-conductive substrate by pulsed laser deposition as a cathode. The crystallinity of the LiCoO2 layer is mainly controlled by the cationic ratio of Li and Co. Subsequently, an amorphous Li3PO4 layer with a high ionic conductivity is further deposited on the cathode LiCoO2 layer by radio frequency magnetron sputtering as a solid electrolyte. To avoid any possible damage which causes the formation of resistive species between LiCoO2 and Li3PO4, bias control of the substrate during Li3PO4 deposition is essential. Finally, a Li metal layer is deposited as an anode/current collector on the Li3PO4/LiCoO2 bilayer by resistive heating evaporation in a vacuum at an elevated temperature for the formation of a low resistive interface. The fabricated three-layer thin-film battery shows a high-rate capability when the LiCoO2 layer is a (104)-oriented epitaxial film. [ABSTRACT FROM AUTHOR]

Evaluating ion-conductive solid electrolytes (SEs) accurately is crucial for advancing solid-state battery technology. Scanning/transmission electron microscopy (S/TEM) is a valuable technique for examining the local characteristics of battery materials. However, the tolerance of SEs to high-energy electron beams is notably lower than that of electrode active materials, because SEs generally have low electron conductivity. Here, we propose a specialized coating technique for TEM samples, termed "nano-shield," which enables stable and accurate observation of their micro-/nano-structures. Nano-shield consists of a dual-layer coating combining an amorphous insulating layer of aluminum oxide (AlOx) with a conductive carbon (C) film. The AlOx layer blocks ion diffusion in the TEM samples, and the C layer minimizes electron charging during electron-beam irradiation. By applying a nano-shield, we successfully visualized the atomic structures of a lithium-ion-conductive SE, Li1.3Al0.3T1.7(PO4)3 (LATP), by using STEM at room temperature. Additionally, we performed a precise elemental analysis of a sodium-ion-conductive SE, Na3Zr2Si2PO12 (NZSP), via STEM equipped with energy-dispersive X-ray spectroscopy (STEM-EDS). Our findings demonstrate that nano-shield enhances the reliability of S/TEM observations of SEs and sheds light on its underlying protective mechanisms. [ABSTRACT FROM AUTHOR]

Lithium metal is a promising anode material for the development of advanced all-solid-state batteries (ASSBs) with high energy density. Among the various solid electrolytes, lithium phosphorus oxynitride glass electrolyte (LiPON) is notable for facilitating stable Li plating-stripping reactions in ASSBs employing Li metal. The aim of this study is to examine the Li/LiPON interface, with a specific emphasis on the reductive decomposition of LiPON near this interface. We employed time-of-flight elastic recoil detection analysis (TOF-ERDA) to assess changes in Li concentration around the Cu/LiPON interface immediately prior to the Li plating reaction. Our electrochemical measurements indicate that critical decomposition of LiPON occurs when the voltage at the Cu electrode is reduced to 0.1 V vs. Li/Li+ at 25 °C, resulting in the in situ formation of Li3P operating at 0.7 V vs. Li/Li+ as an anode material. The TOF-ERDA findings reveal that this decomposition reaction results in a layer with partial decomposition (ranging from 5 to 25% on average) extending up to approximately 30 nm from the Cu/LiPON interface. This insight is vital for enhancing the design and performance of ASSBs. [ABSTRACT FROM AUTHOR]

Low Mg diffusivity in solid-state oxides is an obstacle for the development of materials for Mg ion batteries, which are expected to have high capacity. In this study, we focused on NASICON-type and β-iron sulfate-type Mg2xHf1-xNb(PO4)3 that exhibit relatively high Mg ionic conductivity and investigated the Hf/Nb configuration and composition dependence of phase stability and ion conductivity by atomistic simulation using neural network potentials. The calculations show that the NASICON-type structure is slightly more stable and has higher Mg ionic conductivity than that of the β-iron sulfate-type. The effect of the Hf/Nb configuration was investigated and showed that the ordered stable structure had much lower ionic conductivity than the disordered structure. Furthermore, as the Mg ion concentration increased, the ionic conductivity increased monotonically at low concentrations but tended to converge to a constant value above a certain concentration. The saturation of the ionic conductivity despite increasing the Mg concentration may be due to the trapping effect of the Mg ions caused by the Hf vacancies as well as the Hf/Nb arrangement. [ABSTRACT FROM AUTHOR]

Li3xLa2/3−xTiO3 (LLT) single crystals with different Li compositions (x = 0.042–0.120) were grown by the traveling solvent floating zone (TSFZ) method. Because this material exhibits incongruent melting behavior, solvent of La2Ti2O7-poor composition rather than Li-rich LLT composition for a LLT feed was used. Crack- and inclusion-free single crystals were obtained for all the compositions. The Li composition in the grown crystals was lower than the nominal composition due to vaporization in the melt during growth. In addition, the anisotropic ionic conductivity of the annealed crystal was maximum at a Li composition of x = 0.059. The ionic conductivity along [100], σ[100] = 1.75 × 10–3 S·cm−1, is higher than that of [001], σ[001] = 7 × 10–4 S·cm−1, and the anisotropy σ[100]/σ[001] was determined to be 2.5. [ABSTRACT FROM AUTHOR]

Electron tomography is an observation technique for nanometer-scale three-dimensional structures, using transmission electron microscopy (TEM). TEM tomography has been used to examine the 3D structures of various materials, such as biological samples and catalysts. In this study, we applied TEM tomography to battery materials. All-solid-state lithium-ion batteries have recently received much attention owing to their thermal safety. In all-solid-state cells, the electrode layer is composed of nonflammable solid electrolytes and electrode active materials. In order to improve the charge–discharge cycle performance, it is necessary that the electrolyte–electrode interface has no void spaces or defects. We used TEM tomography to investigate the solid interfaces of Sn–Li3PS4 (LPS) negative electrode composites of all-solid-state cells. We observed that Sn, Li-Sn alloy nanoparticles, and LPS glass electrolytes formed a solid interfacial contact with no void spaces during initial charge–discharge cycles. We suggest that as a new cycle deterioration analysis method, TEM tomography is useful in evaluating solid interfaces in all-solid-state cells. [ABSTRACT FROM AUTHOR]

Polyvinyl butyral (PVB) integrated with varying compositions of potassium chloride (KCl) was prepared through a solution-cast method in methanol, forming a PVB-based electrolyte film for solid-state potassium batteries. The incorporation of KCl into PVB matrix significantly altered the composite electrolyte film's structural intricacies, bandgap modulation, thermal stability and facilitated functional group identification. Furthermore, the ionic conductivity of the PVB polymer electrolyte exhibited an initial enhancement followed by a subsequent reduction with the escalating ratio of KCl. Specifically, at 80 wt% PVB and 20 wt% KCl, its ionic conductivity reached a value of 1.87 × 10−5 S cm−1 at room temperature and 9.61 × 10−5 S cm−1 at 303 K temperature. The ion transference number, which denotes the relative ease with which potassium ions migrate within the PVB polymer-complexed electrolyte, was determined to be 0.98. Discharge tests on the cell, under 1.2 µA current and 2.1 V at room temperature, displayed an initial 9.16 µA h−1 discharge capacity. [ABSTRACT FROM AUTHOR]

Glasses formed from transition metal oxides have shown tailorable electrical and optical properties depending on the valence state and individual element. Vanadate glasses have received specific attention for their high conductivities as compared to most glass families. In this study, the frequency‐dependent capacitance and direct current (dc) conductivity properties of alkaline earth vanadate glasses were investigated. Glasses in the xSrO–(100 − x)V2O5 and xBaO–(100 − x)V2O5 systems, where x = 30, 40, and 50 in mol%, were prepared via melt‐quench synthesis. Capacitance measurements were used to calculate dielectric constants, dielectric loss, and alternating current (ac) conductivity for each sample. Dielectric constants varied between 10–13 and 14–16 for SrO–V2O5 and BaO–V2O5 glasses, respectively, at 1 MHz. Current measurements were made as a function of temperature and voltage for each glass sample. A strong dependence on vanadate content was noted where temperature had a less strong effect. Activation energies were calculated to describe electrical transport mechanisms. All samples showed activation energies governed by electron hopping mechanisms. Such vanadate glasses have properties suitable for applications as cathode materials for batteries, solid state electrolytes, and conductive glass paste with potential for electro‐optic effects involving nonlinear processes. [ABSTRACT FROM AUTHOR]

This study examines and compares the impact of various interfacial modification strategies in optimizing the contact resistance between the rigid ceramic electrolyte and cathode active material (AM) in solid‐state sodium‐ion batteries (SSBs). All the cells are fabricated using Na3.1V2P2.9Si0.1O12, Na3.456Mg0.128Zr1.872Si2.2P0.8O12, and Na as a cathode AM, solid electrolyte (SE) and anode, respectively. The AM/SE interface is modified by (1) wetting the interface with organic liquid electrolyte (LE), (2) slurry casting and sintering a thin layer of composite cathode, and (3) infiltrating AM precursors inside the porous SE structure followed by drying and sintering. Despite exhibiting a stable cyclability performance, the SSBs prepared using the LE modification and composite cathode approach possess a low AM loading of < 1 mg·cm−2. On the other hand, the SSBs with infiltrated‐cathode exhibit a superior discharge capacity of ∼ 102 mAh·g−1 at 0.2C and less than 5% capacity fading after 50 cycles at room temperature. Notably, these cells contain a high AM loading of 2.12 mg·cm−2. The microstructural analysis reveals the presence of AM particles inside the pores of the porous SE, allowing for the efficient insertion/removal of sodium ions. The porous scaffold of SE not only provides continuous sodium‐ion conduction pathways inside the cathode structure but also renders stability by accommodating stress induced by volume change during repeated cycling. The outcomes of this work demonstrate the effectiveness of the wet‐chemical infiltration technique in improving the AM loading and storage capacity performance of SSBs working at 25°C. [ABSTRACT FROM AUTHOR]

[Display omitted] The construction of solid-state electrolytes for flexible zinc-air batteries is extremely challenging. A flexible and highly conductive solid electrolyte designed with a "seaweed structure" is reported in this work. Sodium alginate serves as the backbone to form a robust network structure, and the grafted quaternary ammonium groups provide channels for rapid ion transport, achieving excellent flexibility and hydroxide conductivity. The conductivity of the modified electrolyte membrane (QASA) is 5.23 × 10−2 S cm−1 at room temperature and reaches up to 8.51 × 10−2 S cm−1 at 75 °C. In the QASA based battery, bending at any angle is realized, and the power density is up to 57.28 mW cm−2. This work provides a new way to prepare high conductivity, green solid-state zinc-air batteries, and opens up a research line of thought for flexible energy storage materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • An electronic-ionic bi-functional conduction β-LPS/SG/Li 4.4 Sn was prepared for lithium anode skeleton. • Internally loaded Li 4.4 Sn has high Li binding energy and low nucleation overpotential. • Externally coated β-L 3 PS 4 has high ion conductivity and low Li+ activation energy. • The bi-functional framework guides Li deposition in the hollow SG, inhibits the dendrite growth and side reactions. • The anode has a long life of up to 2800 h, low overpotential (∼13 mV) and high coulomb efficiency of 99.8 % after 470 cycles. Although Li metal is considered the most potential anode for Li based batteries, the repeatedly large volume variation and low Coulombic efficiency (CE) are still serious challenges for commercial application. Herein, the interconnect closed hollow graphene spheres with electronic-ionic bi-functional conduction network containing Li 4.4 Sn nanoparticles loaded internally and β-Li 3 PS 4 solid electrolyte layer coated externally (β-LPS/SG/Li 4.4 Sn) is proposed to achieve uniform and dense Li deposition. Density functional theory (DFT) calculation and experimental results show that Li 4.4 Sn owns larger Li binding energy and lower nucleation overpotential than spherical graphene (SG), thus being able to guide Li traversing and depositing inside the hollow spheres. The Tafel curves, Li+ diffusion activation energy and experimental results reveal that the β-Li 3 PS 4 coating layer significantly improves the ionic conductivity of the negative skeleton, covers the defect sites on the SG surface, provides continuous ion transmission channels and accelerates Li+ migration rate. The synergy of both can inhibit the formation of dendritic Li and reduce side reaction between freshly deposited lithium and the organic electrolyte. It's found that Li is preferentially deposited within the SG, evenly deposited on the spherical shell surface until it's completely filled to obtain a dense lithium layer without tip effect. As a result, the β-LPS/SG/Li 4.4 Sn anode exhibits a long life of up to 2800 h, an extremely low overpotential (∼13 mV) and a high CE of 99.8 % after 470 cycles. The LiFePO 4 -based full cell runs stably with a high capacity retention of 86.93 % after 800 cycles at 1C. It is considered that the novel structure design of Li anode skeleton with electron-ionic bi-functional conduction is a promising direction to construct long-term stable lithium metal anodes. [ABSTRACT FROM AUTHOR]

A CsSnCl3‐based solid electrolyte in which 5% of Sn sites are occupied by Y ions, CsSn0.95Y0.05Cl3.05 (CSYC), is developed using a one‐step mechanical ball‐milling method. CSYC exhibits a stable cubic perovskite crystal structure and a high chloride ion conductivity of 4.9 mS cm−1. The relative density of a CSYC pellet following cold pressing without heat treatment is 97.5%. The high relative density and ionic conductivity are considered to originate from the high mechanical plasticity of the pellets, as evidenced by a low Young's modulus of 8.2 GPa. An all‐solid‐state chloride ion battery cell using CSYC as the electrolyte, BiCl3 as the active cathode material, and Sn as the anode is confirmed to operate at room temperature. The cell shows a large initial discharge capacity of 178 mAh g−1, ≈70% utilization, and good capacity retention with a reversible capacity of 100 mAh g−1 after 40 cycles. The mechanical plasticity of CSYC is considered to be a major contributor to its high ionic conductivity and good battery cycling performance. [ABSTRACT FROM AUTHOR]

Given the vast compositional possibilities NanMmMm′′Si3−p−aPpAsaO12$\left(\text{Na}\right)_{n} \left(\text{M}\right)_{\text{m}} \text{M}_{m^{&amp;amp;amp;amp;amp;aposx;}}^{&amp;amp;amp;amp;amp;aposx;} \left(\text{Si}\right)_{3 - \text{p} - \text{a}} \left(\text{P}\right)_{\text{p}} \left(\text{As}\right)_{\text{a}} \left(\text{O}\right)_{12}$, Na‐ion superionic conductors are attractive but complicated for designing materials with enhanced room‐temperature Na‐ion conductivity σNa,300 K$\left(\sigma\right)_{\text{Na} , 300 \text{K}}$. An explicit regression model for σNa,300 K$\left(\sigma\right)_{\text{Na} , 300 \text{K}}$ with easily‐accessible descriptors is proposed by exploiting density functional theory molecular dynamics (DFT‐MD). Initially, it is demonstrated that two primary descriptors, the bottleneck width along Na‐ion diffusion paths d1$d_{1}$ and the average Na–Na distance ⟨dNa−Na⟩$$ &amp;amp;amp;amp;lt;{d}_{\text{Na}-\text{Na}}&amp;amp;amp;amp;gt;$$, modulate room‐temperature Na‐ion self‐diffusion coefficient DNa,300 K$D_{\text{Na} , 300 \text{K}}$. Then, two secondary easily‐accessible descriptors are introduced: Na‐ion content n, which influences d1$d_{1}$, ⟨dNa−Na⟩$$ &amp;amp;amp;amp;lt;{d}_{\text{Na}-\text{Na}}&amp;amp;amp;amp;gt;$$, and Na‐ion density ρNa$\left(\rho\right)_{\text{Na}}$; and the average ionic radius ⟨rM⟩$$ &amp;amp;amp;amp;lt;{r}_{\text{M}}&amp;amp;amp;amp;gt;$$ of metal ions, which impacts d1$d_{1}$ and ⟨dNa−Na⟩$$ &amp;amp;amp;amp;lt;{d}_{\text{Na}-\text{Na}}&amp;amp;amp;amp;gt;$$. These secondary descriptors enable the development of a regression model for σNa,300 K$\left(\sigma\right)_{\text{Na} , 300 \text{K}}$ with n and ⟨rM⟩$$ &amp;amp;amp;amp;lt;{r}_{\text{M}}&amp;amp;amp;amp;gt;$$ only. Subsequently, this model identifies a promising yet unexplored stable composition, Na2.75Zr1.75Nb0.25Si2PO12$\left(\text{Na}\right)_{2.75} \left(\text{Zr}\right)_{1.75} \left(\text{Nb}\right)_{0.25} \left(\text{Si}\right)_{2} \left(\text{PO}\right)_{12}$, which, upon DFT‐MD calculations, indeed exhibits σNa,300 K>10−3$\left(\sigma\right)_{\text{Na} , 300 \text{K}}&amp;amp;amp;amp;gt; \left(10\right)^{- 3}$ S cm−1. Furthermore, the adjusted version effectively fits 140$140$ experimental values with R2=0.718$R^{2} = 0.718$. [ABSTRACT FROM AUTHOR]

In all-solid lithium metal batteries, sulfide electrolytes offer superior ion conductivity. Nevertheless, they also confront significant challenges, such as the formation of internal dendrites and instability in lithium and humid air. In order to overcome these issues, a sulfide composite electrolyte has been prepared by mixing polyethylene oxide polymers with air-stable inorganic sulfide, Li4SnS4, which can achieve good chemical and electrochemical stability. Meanwhile, the introduced Li4SnS4 can facilitate the movement of Li+ ions in the composite electrolyte, which exhibits an elevated ion conductivity up to 2.55 × 10−5 S cm−1. [ABSTRACT FROM AUTHOR]

Aqueous zinc-ion batteries are an attractive type of energy storage device but face issues of dendrite growth and side reactions on the Zn anode interface. Here, a high-electronegativity C,N,F-solid electrolyte interphase (SEI) is built using a 2-fluoropyridine electrolyte additive to stabilize the Zn anode. Relying on the high electronegativity of element F, the interaction between the SEI and Zn anode is enhanced, and a robust SEI is produced. This robust high-electronegativity SEI induces Zn2+ to form homogeneous deposition without dendrites and repels anions away from Zn anode to impede side reactions over long-term cycling. Meanwhile, a poor-H2O solvation structure established by 2-fluoropyridine reduces the H2O content on the Zn anode interface to slow hydrogen evolution. Benefiting from the robust SEI and poor-H2O solvation structure, a long-term stable Zn anode is achieved. Therefore, the Zn-ion battery exhibits higher plating/stripping reversibility and longer cycling performance. [ABSTRACT FROM AUTHOR]

This study focused on achieving high ionic conductivity in Li-La-TiO (LLTO) solid electrolyte. To enhance ionic conductivity, the synthesis reaction was optimized by controlling the composite crystal structure of TiO2 at the B-site of the perovskite (ABO3) structured LLTO, incorporating rutile, brookite, and anatase phases. The solid-phase LLTO, synthesized utilizing the core – shell structured composite-phase TiO2 developed in this study for the first time, successfully transformed its crystal structure to β-LLTO (tetragonal to cubic). This resulted in a significant improvement in ionic conductivity (i.e. 1.11 × 10−4 Scm−1). The study findings confirmed that the composite crystal structure TiO2 used in the solid-phase synthesis of LLTO induced an increase in oxygen vacancies during the synthesis process, thereby reducing the step-free energy required for the final synthesis. [ABSTRACT FROM AUTHOR]

An artificial solid electrolyte interphase (SEI) with lithiophilic sites and chemical bonds anchoring lithium polysulfides (LiPSs) has been developed as a potential solution to protect the lithium (Li) metal anode of Lithium--sulfur (Li--S) batteries. This strategy aims to guide consistent Li deposition and relieve lithium corrosion. Herein, the evolution process of lithiophilic sites based on aluminum fluoride (AlF3) in an artificial SEI is disclosed in Li--S batteries with metal--based lithiophilic sites. The polyester polymer (PMMA and PPC)/AlF3 artificial SEI (MPAF--SEI) was homogeneously anchored on Li anode by in--situ polymerization. The conversion of AlF3 into Li--Al and LiF lithiophilic sites effectively reduce the Li nucleation overpotential and prevents the formation of Li dendrites. At the same time, the polymer can anchor LiPSs by chemical bonds and prevents Li corrosion. The optimized MPAF--SEI protected Li demonstrates excellent stability for over 3000 h at a capacity of 1 mAh cm-2 in Li jj Li symmetric cells. The Li--S battery with low N/P (4) exhibits a capacity of 532.6 mAh g-1 over 300 cycles lifespan at 0.5 C. [ABSTRACT FROM AUTHOR]

To surpass the energy density limit of current Li–S batteries, attaining a long lifespan under lean‐electrolyte conditions is imperative. The persistent challenge involves suppressing electrolyte decomposition while facilitating sulfur electrode reaction. In this study, the solvating power of 1dimethoxy ethane is fine‐tuned, the main solvent, using fluorinated ether cosolvents via H–F interactions. As the fluorination degree of the cosolvent increases, the coordination of anions around the Li‐ion increases, and the solubilities of Li polysulfides decrease. By systematically varying the solvating power, moderately solvating electrolytes are prepared that can effectively suppress the dissolution of Li polysulfides without hindering the redox kinetics. The moderately solvating electrolytes induce uniform Li deposition and reduce electrolyte decomposition owing to the formation of anion‐derived solid electrolyte interphase. An assembled pouch‐type Li–S battery containing an electrolyte with an optimized solvation power delivers 405 Wh kg−1 at an E/S ratio of 2.0 µL mgs−1 with a lifespan of over 80 cycles. This study suggests a strategy to finely tune the Li+ solvation structure for achieving well‐balanced performances of sulfur cathodes and Li‐metal anodes under lean‐electrolyte conditions. [ABSTRACT FROM AUTHOR]

Rechargeable batteries paired with lithium (Li) metal anodes are considered to be promising high‐energy storage systems. However, the use of highly reactive Li metal and the formation of Li dendrites during battery operation would cause safety concerns, especially with the employment of highly flammable liquid electrolytes. Herein, a general strategy by engineering coordination‐driven crosslinking networks is proposed to achieve high‐performance solid polymer electrolytes. Through the coordination of metal‐organic polyhedra (MOPs) with cellulose‐based copolymers, the Li+‐conducted hypercrosslinked MOP (CHMOP‐Li) polymer network is capable of enabling the rapid transport of Li+. In addition to the high Li+ conductivity (1.02×10−3 S cm−1 at 25 °C), CHMOP‐Li electrolyte also exhibits a high Li+ transference number (0.75) and a wide electrochemical stability window. Benefiting from the thermally stable and mechanically strong CHMOP‐Li electrolyte film, the short‐circuiting of the symmetric batteries is prevented even after 3200 h of cycling and a high specific energy of 300 Wh kg−1 is achieved for the Li‐metal battery. The solid‐state Li−O2 batteries fabricated with CHMOP‐Li electrolyte also show good cycling performance (500 cycles) and high discharge capacity (15740 mAh g−1). The proposed coordination‐driven crosslinking strategies offer an alternative route to design high‐performance next‐generation sustainable battery chemistries. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries (AZIBs) attract attention due to their safety and high specific capacity. However, their practical applications are constrained by Zn anode corrosion, dendritic growth, and poor high‐temperature adaptability induced by a strong hydrogen‐bond network in aqueous electrolytes. In this work, a dual network polyanionic gel electrolyte (denoted as PAM‐PAMPS‐10PD) is developed capable of withstanding high temperatures (100 °C) by in situ polymerization. The abundant anionic groups in the gel electrolyte greatly improve Zn2+ transport and inducing uniform deposition of Zn2+. Then the addition of the high‐boiling molecular crowding agent 1,5‐pentanediol (PD) can inhibit the water activity by enhancing hydrogen bonding with H2O and changing the solvation structure of Zn2+ to inhibit Zn anode corrosion. As a result, the symmetric battery using the PAM‐PAMPS‐10PD gel electrolyte can be stably cycled for at least 500 h at 100 °C and 0.5 mA cm−2/0.5 mAh cm−2, realizing dendrite‐free zinc anodes at high temperatures. Moreover, the Zn–AC full battery has a capacity retention of 47.8% after 3000 cycles at 100 °C and 4 mA cm−2. This study provides a beneficial reference for the design of high‐performance high‐temperature gel electrolytes and establishes a solid foundation for the practical application of AZIBs. [ABSTRACT FROM AUTHOR]

A MoO2-doped Li5.5PS4.5Cl1.5 solid electrolyte with ionic conductivity of 12 mS cm−1 and an electrochemical window of 4.3 V vs. Li/Li+ was prepared, which enables a LiNi0.8Co0.1Mn0.1O2-based full cell to deliver a specific capacity of 194 mA h g−1 at 0.1C and retain 80% capacity after 3500 cycles at 1C. [ABSTRACT FROM AUTHOR]