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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]

The global demand for high energy density batteries, mostly for application in electric vehicles, offering increased durability, safety, and sustainability is growing rapidly. In the past, this demand has been met primarily by the development and/or improvement of new/established battery materials and technologies. The high-entropy design concept—aiming at increasing chemical complexity/occupational disorder—has recently been introduced into the field of electrochemical energy storage. Various high-entropy battery materials that are seemingly capable of outperforming low-entropy counterparts by offering desirable properties have been reported. However, future studies are required to explore if the concept is broadly applicable and can be extended to all types of battery materials, especially those that are of industrial relevance. Herein, we provide a brief overview of the existing high-entropy anodes, cathodes, and solid/liquid electrolytes for use in rechargeable Li- or Na-ion batteries and discuss potential research directions and opportunities. [ABSTRACT FROM AUTHOR]

Glutaronitrile (GN) doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) at concentrations below and above the room-temperature conductivity optimum near 1M of Li salt is investigated using dielectric spectroscopy and shear rheology. The experiments are carried out from ambient down to the glass transition temperature Tg, which increases considerably as LiTFSI is admixed to GN. As the temperature is lowered, the conductivity optimum shifts to lower salt concentrations, while the power-law exponents connecting resistivity and molecular reorientation time remain smallest for the 1M composition. By contrast, the rheologically detected time constants, as well as those obtained using dielectric spectroscopy, increase monotonically with increasing Li salt concentration for all temperatures. It is demonstrated that the shear mechanical measurements are, nevertheless, sensitive to the 1M conductivity optimum, thus elucidating the interplay of the dinitrile matrix with the mobile species. The data for the Li doped GN and other nitrile solvents all follow about the same Walden line, in harmony with their highly conductive character. The composition dependent relation between the ionic and the reorientational dynamics is also elucidated. [ABSTRACT FROM AUTHOR]

Numerical simulations of the evolution of mobile and immobile dislocations in ceramics under applied pressure in dry pressing at a relatively low temperature are performed in order to study the possibility of production of all-dislocation-ceramics of solid electrolytes, which are expected to have extremely high ionic conductivity without dendrite formation because the diameter of a dislocation pipe is considerably larger than the distance between neighboring dislocations. The present numerical simulations are only for the densification process by plastic deformation of grains under high pressure under the assumption that the compaction of particles by their rearrangement is completed beforehand. By the plastic deformation, new dislocations are generated inside the grains. The required total dislocation density of about 1017 m−2 seems to be achievable under some conditions of dry pressing according to the present numerical simulations. Very short ultrasound irradiation at the beginning of the dry pressing sometimes considerably increases the dislocation density, while for other cases, it even considerably decreases the dislocation density due to enhanced annihilation of mobile dislocations by ultrasound. [ABSTRACT FROM AUTHOR]

Since the 1980s, the paddlewheel effect has been suggested as a mechanism to boost lithium-ion diffusion in inorganic materials via the rotation of rotor-like anion groups. However, it remains unclear whether the paddlewheel effect, defined as large-angle anion group rotations assisting Li hopping, indeed exists; furthermore, the physical mechanism by which the anion-group dynamics affect lithium-ion diffusion has not yet been established. In this work, we differentiate various types of rotational motions of anion groups and develop quaternion-based algorithms to detect, quantify, and relate them to lithium-ion motion in ab initio molecular dynamics simulations. Our analysis demonstrates that, in fact, the paddlewheel effect, where an anion group makes a large angle rotation to assist a lithium-ion hop, does not exist and thus is not responsible for the fast lithium-ion diffusion in superionic conductors, as historically claimed. Instead, we find that materials with topologically isolated anion groups can enhance lithium-ion diffusivity via a more classic nondynamic soft-cradle mechanism, where the anion groups tilt to provide optimal coordination to a lithium ion throughout the hopping process to lower the migration barrier. This anion-group disorder is static in nature, rather than dynamic and can explain most of the experimental observations. Our work substantiates the nonexistence of the long-debated paddlewheel effect and clarifies any correlation that may exist between anion-group rotations and fast ionic diffusion in inorganic materials.

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]

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]

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]

Polyanion rotations are often linked to cation diffusion, but the study of multiple polyanion systems is scarce due to the complexities in experimentally determining their dynamic interactions. This work focuses on BH4‐based argyrodites, synthesized to achieve a high conductivity of 11 mS cm−1. Advanced tools, including high‐resolution X‐ray diffraction, neutron pair distribution function analysis, and mutinuclear magic‐angle‐spinning nuclear magnetic resonance (NMR) spectroscopy and relaxometry, along with theoretical calculations, are employed to unravel the dynamic intricacies among the dual polyanion lattice and active charge carriers. The findings reveal that the anion sublattice of Li5.07PS4.07(BH4)1.93 affords an even temporal distribution of Li among PS43− and BH4−, suggesting minimal trapping of the charge carriers. Moreover, the NMR relaxometry unveils rapid BH4− rotation on the order of ∼GHz, affecting the slower rotation of neighboring PS43− at ∼100 MHz. The PS43− rotation synchronizes with Li+ motion and drives superionic transport. Thus, the PS43− and BH4− polyanions act as two‐staged dual motors, facilitating rapid Li+ diffusion. [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]

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]

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]

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]

Solvate ionic liquids (SILs) are promising electrolytes for Li metal batteries. In this study, Li plating-stripping reactions in SILs were investigated using electrochemical quartz crystal microbalance measurements and X-ray photoelectron spectroscopy (XPS). SILs were prepared by mixing Li salt and glyme (triglyme or tetraglyme) in a 1:1 molar ratio. During the Li plating-stripping reaction, a reversible mass change was observed in LiN(SO2F)2 (LiFSA) based SILs. In contrast, a considerably higher mass change than the theoretical value calculated from the Faraday current was observed in the LiN(SO2CF3)2 (LiTFSA) based SILs, owing to the accumulation of decomposition products of electrolytes on the electrode surface. XPS depth profiling for the deposited Li suggested the formation of thin solid-electrolyte interphase (SEI) in the LiFSA-based SILs while considerably thicker SEI was formed in the LiTFSA-based SILs. The SEI formed in LiFSA-based SILs effectively suppressed the decomposition of electrolytes. Thus, LiFSA-based SILs are favorable for achieving highly reversible charge–discharge of Li electrodes in Li metal batteries. [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]

Compared to Li+ and Na+ ion‐conducting sulfides with conductivities of ≈10⁻2 S cm⁻1 at room temperature, oxide ceramics typically exhibit conductivities an order of magnitude lower, rendering them less attractive as electrolytes for all‐solid‐state batteries (ASSBs). This study presents NASICON‐based electrolyte, achieving a remarkable conductivity of 6.0 × 10⁻3 S cm⁻1 at room temperature, rivaling that of sulfide‐based electrolytes. This is accomplished by optimizing the composition in the range Na3+x+yZr2−yAlySi2+xP1−xO12 (0.10 ≤ x ≤ 0.50, 0 ≤ y ≤ 0.1). Despite the issue of reduced sinterability with increasing Si/P ratio due to the formation of a viscous SiO2‐rich grain boundary interphase, the addition of Al2O3 effectively reduces the viscosity and improves the sinterability. In other words, a strategy of engineering the liquid phase that is in situ generated from the host phase is viable. The enhanced conductivity is attributed not only to the lowered grain boundary resistivity but also to lattice expansion from modified Na occupations in the crystal structure. Furthermore, this material demonstrates a wide electrochemical window, suppressed partial electronic conductivity, low polarization voltage in direct contact with a Na anode, and charge‐discharge cycles with minimal polarization when directly interfaced with a NASICON‐type cathode, repositioning it as a promising electrolyte for ceramic ASSBs. [ABSTRACT FROM AUTHOR]

Solid state lithium metal batteries using garnet solid electrolytes such as LLZTO (Li6.4La3Zr1.5Ta0.5O12) promise substantial improvements in energy density and safety. However, practical implementation is hindered by lithium dendrite penetration at high current densities. Recent work shows that internal electrochemically induced mechanical stresses are large enough to propagate lithium dendrites and subsequently fracture solid electrolytes. This study builds on this understanding and demonstrates that stress‐driven dendrite propagation can be controlled via deflection at weakly bonded internal interfaces. This approach, based on a fracture‐mechanics analysis of multilayered composites, is investigated with a variety of interlayer materials that are embedded into LLZTO. The viability and effectiveness of dendrite deflection are most clearly evident with reduced graphene oxide where the critical current density increased from 0.6 to 3.8 mA cm−2. In this material, both the weak interface with LLZTO and the mixed ionic–electronic conducting nature of the interlayer appear to contribute to the improved performance. Additional insight into the mechanics of multilayered electrolytes is also obtained with finite element modeling. The overall results present a promising proof‐of‐concept demonstration along with important generalized design guidelines for creating multilayered solid electrolyte architectures that can enable high‐performance solid‐state batteries. [ABSTRACT FROM AUTHOR]

To realize efficient solid‐state batteries, many efforts are directed toward maximizing the bulk Li+ conductivity of sulfide superionic conductors, as demonstrated for the argyrodite‐type materials Li6PS5Cl and Li6PS5Br. Notably, in these archetype materials, the fast Li+ transport benefits from considerable anion disorder on the halide and sulfur sublattices. To further improve the Li+ conductivity, however, one must consider not only the bulk properties of the solid electrolyte (SE) but also microstructural aspects. It is, however, controversially discussed whether grain boundary (GB) transport is generally detrimental for the overall ion conductivity in agyrodite‐type SEs. Thus, by means of atomistic computer simulations, the Li+ ion transport is studied in twist and tilt GBs of Li6PS5Br, revealing that the Br/S site exchange determines whether the presence of GBs deteriorates the ionic conductivity: Whereas the material with 0% Br/S site exchange only shows locally limited bulk diffusion but enhanced GB conductivity, at higher degrees of site exchange, GBs deteriorate Li+ diffusion. These results show that the interplay of GB transport directly depends on the degree of site exchange in argyrodite‐type materials. [ABSTRACT FROM AUTHOR]

Halide solid electrolytes (SEs) are attracting strong attention as one of the compelling candidates for the next‐generation of inorganic SEs due to their high ionic conductivity. Nevertheless, unsatisfactory high‐voltage stability restricts the further applications of halide SEs. Herein, the anion‐engineering of F−/O2− is evolved to construct the high‐voltage stable zirconium‐based halide superionic conductors (Li2.5ZrCl5F0.5O0.5, LZCFO). Benefiting from the thermodynamic/kinetic high‐voltage stability of F‐containing SE and the disordered localized structure introduced by O2−, LZCFO displays a practical electrochemical limit of 4.87 V versus Li/Li+ and an ionic conductivity of 1.17 mS cm−1 at 30 °C. With LZCFO and NCM955, the all‐solid‐state lithium battery exhibits a high discharge capacity of 207.1 mAh g−1 at 0.1C and a capacity retention of 81.2% after 500 cycles at 0.5C. The interfacial characterization further demonstrates the formation of the F‐rich cathode–electrolyte interphase (CEI), which inhibits side reactions between the cathode and the SE and boosts excellent cycling stability. This work affords fresh insights on the engineering of SEs with high‐voltage stability, high ionic conductivity, and stable CEI in all‐solid‐state lithium batteries. [ABSTRACT FROM AUTHOR]

The practical use of solid‐state lithium metal batteries is hindered by the rapid growth of lithium dendrites through the solid electrolyte, leading to a short lifespan, and poor performance at high rates. The mass transport in anode bulk is proposed as a critical reason related to the chemo‐mechanical failure of the interface and growth of lithium dendrites. In this study, a lithium‐composite anode with a smartly integrated LiC6 phase is developed using a thermodynamic reaction between molten Li and thermally expanded graphite. The gravity segregation effect creates a gradient dispersion of LiC6 in Li, resulting in improved bulk Li diffusion kinetics (70 times higher than that of a pure Li anode). This composite electrode exhibits low interfacial resistance (≈2.3 Ω cm2) and an ultra‐high critical current density of 2.4 mA cm−2 in all‐solid‐state symmetric cells at room temperature. During repeated Li stripping/plating cycles, the enhanced bulk Li diffusion kinetics maintain the close interfacial contact, leading to excellent long‐term cycling stability for over 4000 h with a high cumulative areal capacity. These findings provide valuable insights that promoted mass transport in lithium metal anode is of great benefit to high‐performance solid‐state lithium metal batteries. [ABSTRACT FROM AUTHOR]

The rapid development of the electronics market necessitates energy storage devices characterized by high energy density and capacity, alongside the ability to maintain stable and safe operation under harsh conditions, particularly elevated temperatures. In this study, a semi‐solid‐state electrolyte (SSSE) for Li‐metal batteries (LMB) is synthesized by integrating metal–organic frameworks (MOFs) as host materials featuring a hierarchical pore structure. A trace amount of liquid electrolyte (LE) is entrapped within these pores through electrochemical activation. These findings demonstrate that this structure exhibits outstanding properties, including remarkably high thermal stability, an extended electrochemical window (5.25 V vs Li/Li+), and robust lithium‐ion conductivity (2.04 × 10−4 S cm−1), owing to the synergistic effect of the hierarchical MOF pores facilitating the storage and transport of Li ions. The Li//LiFePO4 cell incorporating prepared SSSE shows excellent capacity retention, retaining 97% (162.8 mAh g−1) of their initial capacity after 100 cycles at 1 C rate at an extremely high temperature of 95 °C. It is believed that this study not only advances the understanding of ion transport in MOF‐based SSSE but also significantly contributes to the development of LMB capable of stable and safe operation even under extremely high temperatures. [ABSTRACT FROM AUTHOR]

Among optimization strategies for solving the poor ion transport ability and electrolyte/electrode interface compatibility problems of lithium (Li)‐based batteries, halogen elements, such as fluorine (F) and iodine (I), have gradually occupied an important position because of their superb electronegativity, oxidizability, ionic radius, and other properties. The study commences by outlining the shared mechanism by which F and I enhance solid‐state lithium metal batteries' electrochemical performance. In particular, F and I can considerably improve ion transport capacity through chemical means such as intermolecular interactions and halogenation reactions. Furthermore, the utilization of F and I significantly enhances the stability of the electrolyte/electrode interface via physical strategies, encompassing doping techniques, the application of surface coatings, and the fabrication of synthetic intermediate layers. Subsequently, the characteristics of F and I used in Li‐based batteries are elaborated in detail, focusing on the fact that F can provide additional energy density as an anode material but by different mechanisms. Additionally, I can considerably activate dead lithium at the negative electrode, and F can act as a new carrier. Finally, a rational concept of the synergistic effect of F and I is proposed and the feasibility of F–I bihalide solid electrolytes is explored. [ABSTRACT FROM AUTHOR]

Solid‐state batteries with lithium‐metal anodes have emerged as a promising alternative to traditional lithium‐ion batteries thanks to their enhanced energy density and safety. However, the integration of solid‐state electrolytes is still hindered by mechanical instabilities caused by the rigid nature of the system. Stress and strain can be transferred at the interface between electrodes and solid electrolyte, inducing material damage during cycling. To address this issue, a comprehensive understanding of the interplay between electrochemical reactions and mechanical effects is crucial. In this article, a critical review of various approaches to model the multiphysics behavior of Li‐metal solid‐state batteries is provided by analyzing their advancements and limitations. The focus lies on workflows which simulate the effect of microstructural and material property changes on the degradation processes. Continuum modeling of three key chemo‐mechanical challenges is explored: dendritic growth from Li‐metal anodes, structural instability in composite cathodes, and solid electrolyte degradation caused by the formation of unstable interphases. The conclusion highlights the existing challenges and upcoming trends in multiphysics and microscale modeling of batteries. [ABSTRACT FROM AUTHOR]

The study explored the effect of incorporating niobia (Nb 2 O 5) at 1, 3, and 5 wt percent into 8 mol% yttria-stabilized zirconia (8YSZ), made through a mechanochemical process. Niobia-doped 8YSZ samples were synthesized by a mechanochemical process and analyzed with methods including XRD, XPS, UV–Visible spectroscopy, particle size analysis, BET surface area analysis, FESEM-EDX, and EIS. Sintering was achieved at a reduced temperature of 1373 K , and all niobia-doped samples predominantly exhibited a tetragonal phase. Electrochemical impedance spectroscopy indicated that niobia doping inversely affected oxide ion conductivity-higher dopant concentrations resulted in lower conductivity. Nb-doped 8YSZ also displayed lower activation energy for conductivity compared to high-temperature (1473 K) sintered undoped 8YSZ, demonstrating equivalent performance. The combined benefits of lower sintering temperatures and enhanced ionic conductivities highlight crucial progress in developing cost-effective and energy-efficient electrolytes for clean energy applications. • Niobium pentoxide stabilizes the 8YSZ matrix, enhances densification and grain growth. • Intragranular conductivity affected by niobia doping, not grain boundary conductivity. • Nb 2 O 3 -doped 8YSZ performs similar to undoped at higher sinter temperatures, suggesting efficient lower temperature sintering. • The role of Nb5+ suggested to involve lattice distortion and phase alterations. • Optimal balance between low sintering temperatures and high ionic conductivity hard to achieve, with less than 1 % niobia doping aiding in converting 8YSZ to a cubic phase. This study assesses how niobia (Nb 2 O 5) affects the ionic conductivity of 8 mol% yttria-stabilized zirconia (8YSZ) when added at 1, 3, and 5 wt%. Despite niobia's ability to lower the sintering temperature to 1373 K , it inversely impacts ionic conductivity, with greater doping resulting in reduced conductivity. However, niobia-doped 8YSZ shows lower activation energy for conductivity compared to undoped 8YSZ sintered at temperatures of 1473 K. This suggests that lower sintering temperatures can be used without undermining performance. Yet, the challenge remains to balance the improved sinterability with achieving optimal ionic conductivity, a critical factor for solid electrolytes in clean energy technologies. [ABSTRACT FROM AUTHOR]

The numerous grainboundaries solid electrolyte interface, whether naturally occurring or artificially designed, leads to non-uniform Li metal deposition and consequently results in poor full-battery performance. Herein, a lithium-ion selective transport layer is reported to achieve a highly efficient and dendrite-free lithium metal anode. The layer-by-layer assembled protonated carbon nitride nanosheets present uniform macroscopical structure without grainboundaries. The carbon nitride with ordered pores in basal plane provides high-speed lithium-ion transport channels with low tortuosity. Consequently, the assembled 324 Wh kg−1 pouch cell exhibits 300 stable cycles with a capacity retention of 90.0% and an average Coulombic efficiency up to 99.7%. The ultra-dense Li metal anode makes current collector-free anode possible, achieving high energy density and long cycle life of a 7 Ah cell (506 Wh kg−1, 160 cycles). Thus, it is proved that a macroscopically uniform interface layer with lithium-ion conductive channels could achieve Li metal battery with promising application potential. Here, authors report a macroscopical grain boundary-free interface layer with microscopic Li + -selective conductive channels enables the ultra-dense Li metal deposition, resulting in a high energy density (506 Wh kg−1) and long cycle life (160 cycles) pouch cell performance. [ABSTRACT FROM AUTHOR]

Oxide ceramic electrolytes (OCEs) have great potential for solid-state lithium metal (Li0) battery applications because, in theory, their high elastic modulus provides better resistance to Li0 dendrite growth. However, in practice, OCEs can hardly survive critical current densities higher than 1 mA/cm2. Key issues that contribute to the breakdown of OCEs include Li0 penetration promoted by grain boundaries (GBs), uncontrolled side reactions at electrode-OCE interfaces, and, equally importantly, defects evolution (e.g., void growth and crack propagation) that leads to local current concentration and mechanical failure inside and on OCEs. Here, taking advantage of a dynamically crosslinked aprotic polymer with non-covalent –CH3⋯CF3 bonds, we developed a plastic ceramic electrolyte (PCE) by hybridizing the polymer framework with ionically conductive ceramics. Using in-situ synchrotron X-ray technique and Cryogenic transmission electron microscopy (Cryo-TEM), we uncover that the PCE exhibits self-healing/repairing capability through a two-step dynamic defects removal mechanism. This significantly suppresses the generation of hotspots for Li0 penetration and chemomechanical degradations, resulting in durability beyond 2000 hours in Li0-Li0 cells at 1 mA/cm2. Furthermore, by introducing a polyacrylate buffer layer between PCE and Li0-anode, long cycle life >3600 cycles was achieved when paired with a 4.2 V zero-strain cathode, all under near-zero stack pressure. Self-healing is an appealing property for solid-state battery electrolytes to combat Li metal dendrites that pierce through the solid electrolyte. Here, authors report a self-healing electrolyte and observe its self-repairing kinetics in real-time using advanced microscopy. [ABSTRACT FROM AUTHOR]

Polyethylene oxide (PEO)‐based solid polymer electrolytes are regarded as promising electrolyte materials because of their safety and flexibility. However, low ionic conductivity at ambient temperature and poor mechanical properties have been a hindrance to its development. In this work, we thermally compressed the PEO‐based electrolytes and explored the ionic conductivity, mechanical performance, free volume, and thermal properties of the electrolyte under different thermal pre‐compressing strains (TPC‐strains). The results show that TPC‐strain can significantly improve the ionic conductivity, in‐plane strength, stiffness, and cell specific capacity as well as the mechanical integrity of solid polymer electrolytes within the battery environment. However, it also results in a reduction in the modulus and stiffness of the SPEs in the through‐plane. In particular, applying a TPC‐strain of 10%–20% to the SPEs by thermal compressing may be a suitable option, which can increase the ionic conductivity of the through‐plane to a factor of 3.4 compared with the uncompressed electrolyte, and increase the in‐plane strength by up to 141%, resulting in better mechanical integrity during charging/discharging processes. At the same time, the compression modulus can be maintained at 80% or higher. [ABSTRACT FROM AUTHOR]

Solid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga62.5In21.5Sn16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self‐healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li‐ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li‐LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid‐state Li/LiFePO4 battery achieves promising full‐cell functionality with notable rate performance and stable cycle life. This active filler‐mediated self‐healing approach could bring new insights into the battery design in versatile solid‐state systems. [ABSTRACT FROM AUTHOR]

All‐solid‐state Li batteries are desired for better safety and energy density than Li‐ion batteries. However, the lack of a penetrating liquid electrolyte requires a much different approach to the design of cathodes. The solid catholyte must enable good Li+ conduction, form good interfaces with active material particles, and have the strength to bind the cathode together during repeated volume changes. Catholyte formulation is often simply adapted from Li‐ion design principles, adding a Li salt to the PVDF binder. Here we show that such a PVDF binder at 10 wt % loading is a starved catholyte condition that compromises cell performance. By substituting a 70 : 30 blend of PVDF:PEO, performance is improved while maintaining nearly the same areal loading of LFP active material. Increasing the catholyte fraction to 16 % can also improve performance, but in this case the benefit of including PEO is lessened, with PVDF alone being an adequate catholyte. EIS analysis shows that PEO helps to form charge transfer interfaces at 10 % catholyte, but that its inclusion can degrade interfaces when there is ample catholyte at 16 %. It is also shown that catholyte agglomeration can impede bulk Li conduction, indicating that microstructural factors are of critical importance. [ABSTRACT FROM AUTHOR]

Exploiting the synergy between organic polymer electrolytes and inorganic electrolytes via the development of composite electrolytes can suggest solutions to the current challenges of next‐generation solid‐state lithium‐metal batteries (SSLMBs). Depending upon a mass fraction of inorganic fillers and organic polymers, composite electrolytes are broadly classified into "ceramic‐in‐polymer" (CIP) and "polymer‐in‐ceramic" (PIC) categories, inheriting distinct structure and electrochemical properties. Since the stability and electrochemical characteristics of the inorganic phase are superior to those of the organic phase for lithium‐ion conduction, applying lithium‐enrich active filler in PIC seems more promising. The inorganic phase preserves the primary migratory channels in the PIC electrolyte, while the viscoelastic properties attempt to be introduced from the organic binder or host. The present work overviews the studies on state‐of‐the‐art PIC electrolytes, the fundamental mechanism of ionic conduction, preparation methods, and current progress in materials development for SSLMBs. In addition, the modification strategies for improving the electrode–electrolyte interface are also emphasized. Moreover, it further prospects the current challenges and effective strategies for the future development of PICs‐based CPEs to accelerate the practical application of SSLMBs. This review examines the progress and outlook of PIC‐based electrolytes for next‐generation lithium batteries. [ABSTRACT FROM AUTHOR]

Lithium–sulfur batteries with liquid electrolytes are discussed as the most promising post‐lithium‐ion‐battery technology in literature due to their high theoretical specific energy and first prototype cells delivering >470 Wh kg−1. Although several electrolyte and material concepts are developed that partially solve the issue of the so‐called shuttle mechanism, the most promising concept to genuinely confine sulfur species in the cathode is all‐solid‐state argyrodite–sulfur cathodes leading to almost theoretical active material utilization by maintaining reasonable sulfur loadings and electrolyte to sulfur ratios. However, this battery concept has so far not achieved reversible cycling against metallic lithium anodes as it requires high pressures for manufacturing, and ductile lithium metal creeps along the grain boundaries of the solid electrolyte particles leading to short cuts of the cells. Recent findings show that metallic lithium, however, can be stably cycled with dimethoxyethane/lithium‐bis(fluorosulfonyl)imide (DME/LiFSI)‐based electrolytes. Herein, for the first time, a semisolid concept is presented combining the benefits of an argyrodite‐based solid‐state cathode and a DME/LiFSI/hydrofluoroether‐based anolyte concept – in coin cells and first pouch cells. This disruptive approach enables projected specific energies higher than 600 Wh kg−1 at cell stack level. [ABSTRACT FROM AUTHOR]

This investigation employs first‐principles calculations to explore the interaction between imidazolium ionic liquids (ILs) and fluoride additives on lithium metal surface. Our focus lies in the comprehensive analysis of three distinct categories of fluorinated additives, each differing in their degree of fluorination. The computations reveal that fluorination plays a significant role in determining both the ionic conductivity and the formation of the solid–electrolyte interphase (SEI) film. Specifically, heightened fluorination enhances the oxidative stability of the system but diminishes the strength of solvent binding, resulting in the formation of larger salt/anion clusters and a decrease in ionic conductivity. Conversely, increased fluorination facilitates the interaction between fluorinated additives and the lithium metal surface, thereby aiding in the formation of a stable SEI film characterized by an abundance of inorganic LiF components. This is important as it serves to suppress dendrite growth and mitigate interface side reactions. Considering the combined influences of ionic conductivity and film formation, 1FP is suggested as the optimal candidate for pyridine‐based additive systems, with FEC preferred for cyclic ester‐based additive systems and BC for chain ester‐based additive systems. This study provides theoretical references for the design of ionic liquid‐fluorinated additive electrolyte systems that can protect the lithium metal anode. [ABSTRACT FROM AUTHOR]

Ionogels are emerging as high‐potential pseudosolid electrolytes for lithium‐metal batteries (LMBs), leveraging their intrinsic high ionic conductivity from entrapped ionic liquid (IL) electrolytes. However, their practical application is hindered by poor mechanical strength stemming from the confinement of ILs within a polymer matrix. To address this challenge, the formation of conformal polyion coatings with functional groups is reported to be relevant to LMBs’ application on ionogels, utilizing a layer‐by‐layer (LbL) assembly strategy. This approach significantly enhances the mechanical strength (Young's modulus and tensile strength) and electrochemical performance of ionogels, owing to the tailored interface modifications introduced by functional groups’ specific conformal polyion coatings. The core of this methodology leverages the inherent ionic structure of ionogels to enable facile interface modification through Coulombic interactions between polyanions and polycations. These conformally coated interface functionalized membranes show improved electrochemical performance when integrated with cathode materials such as LiFePO4 (LFP) and LiNi0.8Mn0.1Co0.1O2 (NMC811) in an LMB configuration, underscoring their potential for robust, high‐conductivity, pseudosolid membranes for LMB applications. These innovative pseudosolid membranes offer improved mechanical and electrochemical properties, leading to higher battery efficiency and safety, making them promising candidates for next‐generation LMB technology. [ABSTRACT FROM AUTHOR]

Garnet‐type solid‐state electrolytes with exceptional stability are believed to promote the commercialization of all solid‐state lithium metal batteries. However, the extensive application of garnet‐type solid‐state electrolytes is greatly impeded on account of their low ionic conductivity. Herein, a high‐entropy fast lithium‐ion conductor Li7(La,Nd,Sr)3(Zr,Ta)2O12 (LLNSZTO) with high lattice distortion is designed. It is found that the enhanced ionic conductivity of the high entropy garnet‐type solid‐state electrolyte LLNSZTO is achieved by introducing disorder in the lattice, which creates fast ion penetration paths with flattened energy landscapes within the pristine ordered lattice. Thus, the prepared high‐entropy garnet‐type solid electrolyte LLNSZTO exhibits low activation energy for Li+ migration (0.34 eV) and elevated ionic conductivity (6.26 × 10−4 S cm−1). Full cells assembled with LLNSZTO electrolyte, lithium metal anode, and LiFePO4 (LFP) cathode exhibit excellent capacity retention of 86.81% after 200 cycles at room temperature. Moreover, the superior ionic conductivity of LLNSZTO enables all solid‐state battery with high‐loading LFP cathode (>12 mg cm−2), achieving stable cycling exceeding 120 cycles. The large area pouch cell (5.5 cm × 8 cm) exhibits stable long‐term cycling performance, showing a capacity retention of 96.50% after 50 cycles. [ABSTRACT FROM AUTHOR]

Solid–state batteries based on Li7La3Zr2O12 (LLZO) garnet electrolyte are a robust and safe alternative to conventional lithium‐ion batteries. However, the large‐scale implementation of ceramic composite cathodes is still challenging due to a complex multistep manufacturing process. A new one‐step route for the direct synthesis of LLZO during the manufacturing of LLZO/LiCoO2 (LCO) composite cathodes based on cheap precursors and utilizing the industrially established tape casting process is presented. It is shown that Al, Ta:LLZO can be formed directly in the presence of LCO from metal oxide precursors (LiOH, La2O3, ZrO2, Al2O3, and Ta2O5) by heating to 1050 °C, eliminating the time‐ and energy‐consuming synthesis of preformed LLZO powders. In addition, performance‐optimized gradient microstructures can be produced by sequential casting of slurries with different compositions, resulting in dense and flat phase‐pure cathodes without unwanted ion interdiffusion or secondary phase formation. Freestanding cathodes with a thickness of 85 µm, a relative density of 95%, and an industrial relevant LCO loading of 15 mg show an initial capacity of 82 mAh g−1 (63% of the theoretical capacity of LCO) in a solid‐state cell with Li metal anodes, which is comparable to conventional LCO/LLZO cathodes and can be further improved in the future. [ABSTRACT FROM AUTHOR]

As a promising anode material for Na‐metal batteries, the practical application of Na metal is severely hindered due to the formation of the notorious dendrite and unstable solid‐electrolyte interface (SEI). To address these issues, a direct‐ink writing (DIW) 3D printing technology is proposed to construct an artificial 3D hierarchical porous sodiophilic Nb2CTx/reduced graphene‐oxide (Nb2CTx/rGO) aerogel monolith, which is employed as the matrix of Na metal anode. Benefiting from the homogeneous ion flux and exceptional sodiophilic features, the Nb2CTx nanoflakes embedded within the 3D scaffold regulate the uniform deposition of metallic Na with a stable SEI layer, achieving an ultralong cycle lifespan of 3000 h at 1 mA cm−2 with 1 mAh cm−2 and an impressive Coulombic efficiency of 99.68% over extended lifespan of 7064 h. Further, the in‐depth characterization analysis proves that the formed stable SEI layer consists of an inorganic NaF accumulated in the inner layer and loosely‐bound organic species in the outer layer. Remarkably, when integrated into a Na metal full cell, the reversible capacity reaches 90.22 mAh g−1 after 200 cycles at 100 mA g−1. The work provides a promising strategy to utilize Na metal anodes with long cycle lifespan for next‐generation sodium metal batteries. [ABSTRACT FROM AUTHOR]

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

Rigid‐flexible coupled composite polymer electrolytes (CPEs, e.g., polyethylene oxide/Li6.4La3Zr1.4Ta0.6O12, PEO/LLZTO) hold the promise of integrating the respective merits of organic polymer electrolyte and inorganic ceramic fillers to achieve better all‐solid‐state batteries (ASSBs), but commonly suffer from poor synergistic effect owing to the ionically/electronically resistive layer on the ceramic surface. Representatively, the Li2CO3 passivation layer‐isolated LLZTO not only contributes minimally to the Li+ conduction in PEO/LLZTO CPE, but also narrows the available electrochemical window. Herein, an interfacial reconstruction strategy is disclosed based on mild liquid‐phase chemical reaction and subsequent self‐assembly, allowing the detrimental Li2CO3 to fully react with succinic anhydride (SA), and simultaneously constructing a robust ultra‐thin lithium succinate (SALi) ionic conductor shell to eradicate its regeneration. Accordingly, the obtained PEO/LLZTO@SALi (PLS) CPE shows a high room‐temperature ionic conductivity (1.2 × 10−4 S cm−1), a wide electrochemical window (4.8 V), a notable Li+ transference number (0.37), as well as nonflammability and exceptional compatibility with Li metal in Li/Li symmetric cells (2000 h at 0.2 mA cm−2). More encouragingly, the Li/PLS CPE/LiFePO4 full ASSB maintains an ultrahigh capacity retention of 84.3% after 1400 cycles at room temperature. This work propels the design of high‐performance CPEs through the interfacial modulation of inorganic ceramic fillers. [ABSTRACT FROM AUTHOR]

The construction of poly‐dioxolane (PDOL) solid‐state electrolytes by in situ polymerization is an effective way to achieve high performance lithium‐metal batteries. However, the poor electrochemical stability and safety issues of linear PDOL limit their further application. In this work, a multifunctional crosslinker has been introduced to construct a flame retardant crosslinked quasi solid‐state electrolyte (FCDOL). Due to the synergistic effect of the crosslinked network, the prepared FCDOL achieves excellent room temperature ionic conductivity (0.72 mS cm−1), high Li+ transference number (0.655), wide electrochemical stabilization window (4.8 V vs Li/Li+), and impressive performance when matched with lithium metal anodes (>4000 h plating/stripping) and high‐voltage cathodes, and the corresponding pouch cells can withstand abusive tests such as bending and cutting, encouraging that in situ polymerization of SPEs provides new insights into high‐energy density and high‐safety solid‐state batteries. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) aerogels solve the restrictions on processability and application caused by the insolubility and non‐fusibility of powders while avoiding the inaccessibility of pore structures by dense stacking. At the current start‐up stage where COFs aerogels are scarce and difficult to synthesize, design of generalized synthetic methods play an indispensable role in guiding and developing COFs aerogels. Moreover, evolving the functionality of COF aerogels is equal vital, which achieves higher performance and broader practical applications. In this work, for the first time, processable BrCOFs aerogels have been synthesized without vacuum by seven kind polar solvents, which realizes general preparation of BrCOFs aerogels. It is extremely friendly to the inapplicability for some scenarios. Furthermore, by Suzuki‐Miyaura cross‐coupling reaction, BrCOFs aerogels are endows with cyano groups (‐CN), trifluoromethyl (‐CF3) and methyl sulfonyl (‐SO2‐CH3) efficiently. As a proof‐of‐concept, BrCOFs‐SO2‐CH3 aerogels served as a quasi‐solid electrolyte for lithium‐metal batteries (LMBs), which effectively enhance the performance of batteries. [ABSTRACT FROM AUTHOR]

All‐solid‐state lithium metal batteries (ASSLBs) have the potential to provide a significant increase in energy density and safety. However, most ASSLBs are still suffering from low cathode loading, poor rate capability, and low attainable energy/power densities, which seriously limit their practical application. Besides developing solid electrolytes with high conductivity, constructing a highly loaded cathode with rapid reaction kinetics is also essential for achieving high‐performance ASSLBs. Herein, the methylamine hydroiodide (CH6NI) is investigated as a functional electrode additive to enable rapid Li+ transport and charge transfer in LiFePO4 (LFP) cathode, whereby the CH6NI serves as a charge storage carrier that facilitates the reaction kinetics during the delithiation and lithiation process of LFP. As a result, the ASSLB assembled with LFP@CH6NI cathode shows excellent cycling stability over 700 cycles at 2 C with a high capacity retention of 87.6%, while the cell with bare LFP cathode shows no capacity at high current rates (≥0.5 C). Moreover, the ASSLB pared with a high active loading cathode (5.6 mg cm−2) still exhibits a high specific capacity of 144.9 mAh g−1 at 0.5 C. This work provides a facile strategy that opens new possibilities for designing high‐loading electrodes for high‐performance ASSLBs. [ABSTRACT FROM AUTHOR]

The solid‐state batteries (SSBs) with Li anode present one of the most promising energy storage systems due to their enhanced energy density and safety. However, interfacial problems between Li anode and solid‐state electrolyte hinder the advancement of SSBs. Among them, insufficient solid‐solid interfacial contact is the main issue, which causes large resistance and hinders Li+ diffusion, leading to current distribution unevenness and lithium dendrites growth. To meet these challenges, a silver/carbon interlayer composed of ultrafine Ag nanoparticles (≈5 nm) grown on COOH‐CNTs (nano‐Ag@COOH‐CNTs) is constructed. In which, nano‐Ag is designed to guide homogeneous Li deposition, while CNTs substrate bonds with Li6.5La3Zr1.5Ta0.5O12 (LLZTO) electrolyte by reactions between ─COOH groups and LLZTO alkaline surface, thus transforming loose physical solid‐solid contact to chemical bonding contact. In addition, nano‐Ag is immobilized by CNTs, avoiding the migration of Li+ implanted nano‐Ag during cycling. Therefore, nano‐Ag@COOH‐CNTs interlayer can boost Li+ transport at LLZTO/Li interface and inhibit Li dendrites, achieving an ultra‐low interfacial resistance of 0.25 Ω cm2, a high critical current density of 1.7 mA cm−2 and a long cycling over 2155 h at 0.5 mA cm−2. The modified SSBs with LiNi0.83Co0.12Mn0.05O2 cathode cycles stably over 500 cycles. Moreover, high‐loading SSBs operate stably for 85 cycles. [ABSTRACT FROM AUTHOR]

The composite solid electrolyte, which combines the advantages of inorganic conductors and organic polymer electrolytes, has become a crucial strategy for the construction of solid‐state batteries. However, the physical deposition and agglomeration of traditional composite fillers seriously affect their structural uniformity and ion transport performance, and the construction of uniform and stable composite electrolytes is still an insurmountable challenge. Herein, a strategy of in situ hybrid crosslinking polymerization of TiO2 nanoparticles is proposed for highly stable polymer composite electrolytes (NHCPE) with an ultrahigh ionic conductivity of 1.74 × 10−3 S cm−1 at 25 °C, and a high lithium‐ion transference number of 0.725. These properties enable the composed lithium symmetric battery to be stably deposited/plating off at 0.5 mA cm−2 for more than 1000 h. Moreover, the assembled LFP|PDOL@nanoTiO2|Li battery exhibits a superior specific discharge capacity of 142.6 mAh g−1 at 1 C and 25 °C, and an ultrahigh capacity retention rate of 90% after 1000 cycles. The proposed PDOL@nanoTiO2 NHCPE greatly inhibits the defects of easy agglomeration of composite electrolytes, solves the problems of easy decomposition, low thermal stability, and poor safety of polyether electrolytes, and opens up a new way for the design and industrial application of high‐stability composite polymer electrolytes. [ABSTRACT FROM AUTHOR]

Solid‐state lithium batteries (SSLBs) offer inherent safety and high energy density for next‐generation energy storage, but the large interfacial resistance and poor physical connection between electrode materials and the solid electrolyte (SE) severely impede their practical applications. This work reports a general strategy to introduce covalent bonds between electrode materials and SE, not only reducing interfacial resistance but also enhancing electrochemical stability and mechanical robustness of SSLBs. The covalent bonding is accomplished by functionalizing electrode surfaces with C═C groups, enabling in situ copolymerization with telechelic polymers in the SE. This approach is applicable to various cathode/anode materials and SEs. Particularly, the SSLBs comprising LiFePO4 cathode, Li6.75La3Zr1.75Ta0.25O12/(polyethylene oxide (PEO)/lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)/silk composite SE and metallic lithium anode exhibit a specific capacity of 158.4 mAh g−1 and can be cycled at 2 C for 2200 times with >80% retention. Additionally, the SSLBs containing the high nickel‐content LiNi0.96Co0.03Mn0.01O2 cathode can afford a high specific capacity of 201.8 mAh g−1. Comprehensive experimental examination and theoretical simulations confirm that the lowered interfacial resistance and intimately contacted electrode materials/electrolyte interfaces facilitate Li+ transport at different stages of charge. Furthermore, the covalently bonded electrode/electrolyte interfaces also endow SSLBs with outstanding mechanical stability, enabling flexible SSLB pouch cells to operate under various bending states without performance decay. [ABSTRACT FROM AUTHOR]

All‐solid‐state batteries relying on Li metal as negative electrode material and a ceramic electrolyte may severely suffer from unwanted interfacial processes. Here, Li1.3Al0.3Ti1.7(PO4)3 (LATP) serve as a model electrolyte which is known to form an ionic‐electronic, that is, mixed conducting interphase (MCI) when in contact with metallic Li or any other Li source. Li1.3+xAl0.3Ti1.7(PO4)3 with x = 0.2, 0.6 and 1.3 is prepared via ex situ chemical lithiation to mimic the formation of MCIs taking place otherwise operando. The preparation of large amounts of lithiated LATP with controlled Li contents allowed us to use nuclear and electric techniques to study local structures and ionic/electronic dynamics in detail. The results point to the formation of a core‐shell two‐phase morphology with the Li‐rich Li3Al0.3Ti1.7(PO4)3 phase covering the nonlithiated Li‐poor regions. The originally poor electronic conductivity σeon of 6.5 × 10−12 S cm−1 (293 K) increases by ≈3 orders of magnitude, hence reaching the order of 6.6 × 10−9 S cm−1 for x = 0.6. At even higher loadings (x = 1.3), a decrease in conductivity is seen, i.e., not exceeding alarming values for σeon. Quantifying electronic and ionic transport processes will help assessing the extent of damage through MCI formation and discussing whether any strategies to mitigate such formation is necessary at all. [ABSTRACT FROM AUTHOR]

Currently, the realization of controllable Li electrodeposits to further extend the cycling life of Li metal anode remains challenging. Herein, it is reported that carbon nanosheet array‐loaded ferromagnetic CoF2 nanoparticles on carbon cloth (CC@CoF2/C) as an internal micro‐magnetic field source to manipulate the dynamic trajectory of Li+ deposition via the magnetohydrodynamic effect. This approach ensures uniform lithium‐ion distribution and improves deep plating capacity, achieving a prolonged cycle life of the dendrite‐free Li anode. Finite element simulations, in situ characterizations, and electrochemical tests confirm that magnetic CoF2 not only guides Li+ migration through Lorentz force to prevent dendritic growth but also improves uniform Li deposition due to the in situ conversion of LiF‐rich solid electrolyte interphase during electroplating. Meanwhile, a CC@CoF2/C‐based half‐cell operates stably over 10 000 h at 1 mA cm−2 with a low 7.8 mV overpotential. When matched with a commercial LiFePO4 cathode, the full cell reveals a high capacity of 122.96 mAh g−1 at a 2 C rate after 1000 cycles, retaining 91.95% capacity. The proposed strategy can be effectively expanded and adapted to investigate the deposition behavior of a wide range of metal anodes, offering a versatile and robust analytical framework for addressing diverse metal‐based electrochemical systems. [ABSTRACT FROM AUTHOR]

Solid polymer electrolytes (SPEs) have been treated as a viable solution to build high‐performance solid‐state lithium metal batteries (SSLMBs) at the industrial level, bypassing the safety and energy density dilemmas experienced by today's lithium‐ion battery technology. To promote a wider application of SPEs‐based SSLMBs, the chemical and electrochemical characteristics of lithium metal (Li°) electrode in SPEs have to be clearly elucidated. In this work, the morphological evolution of Li° electrode in the SPEs‐based SSLMBs is comprehensively investigated, via a customized electrochemical cell allowing optical microscopic analyses. The results demonstrate that differing from inorganic solid electrolytes, the elastic feature of SPEs eliminates the “memory effect” of the dendrite formation, in which the previously formed dendrites can be dissolved and the resulting space can be simultaneously occupied by electrolyte components, instead of leaving for a second‐round growth of Li° dendrites. Furthermore, the largely increased electronic conductivities of the as‐formed interphases between Li° electrode and SPEs are found to be responsible for the notoriously soft short‐circuit behavior observed during cycling. These findings bring a fresh understanding of the formation and evolution of lithium dendrites in SPE‐based cells, which are vital for improving the long‐term stability of SSLMBs and other related high‐energy battery systems. [ABSTRACT FROM AUTHOR]

Recent studies have identified an imbalance between the electronic and ionic conductivities as the drivers of inhomogeneous reactions in composite cathodes, which cause the rapid degradation of all‐solid‐state battery (ASSB). To mitigate localized overcharge and utilize isolated active materials, the study proposes the coating of an argyrodite‐type Li6PS5Cl solid electrolyte (SE) with graphene‐like carbon (GLC@LPSCl), a 2D conductive material, to offer a continuous three‐dimensionally connected electron pathway within the composite cathode to facilitate ion mobility and promote homogeneous reactions. Despite reducing the content of the conducting agent, it is observed that the GLC@LPSCl cell exhibits high initial Coulombic efficiency and discharge capacity, reducing the inhomogeneous reactivity after 200 cycles compared with when ordinary conductive agents are deployed. Additionally, the presence of GLC@LPSCI surface suppresses the interfacial reaction between SE–cathode material, thus imparting the cell with excellent capacity retention (≈90%) after 200 cycles. Furthermore, the cell performance improves even after a fourfold increase in the cathode loading amount, demonstrating the criticality of a well‐developed continuous electron pathway to cell performance and highlighting the key role of ensuring a balance between the electron and ion conductivities in the development of high‐energy‐density and high‐power ASSBs. [ABSTRACT FROM AUTHOR]