Lithium metal serves as an outstanding anode material, providing a high theoretical capacity of 3860 mA h g-1 and a low reduction potential of-3.04 V vs. Li+ /Li relative to the typical hydrogen electrode. All-solid-state lithium-metal batteries demonstrate exceptionally high energy density within power battery technology. The existing inorganic solid-state electrolytes (SSEs), including oxides, sulfides, and halides, demonstrate particular interactions with lithium metal. This study categorizes nine inorganic solid-state electrolytes (SSEs) according to their electrochemical behavior with lithium metal electrodes during the deposition and stripping cycles of lithium-symmetric cells into three classifications: (1) unrestricted reaction and failure, (2) dendritic growth and short circuit, (3) self-limiting decomposition and passivation. Concentrating on the third category of solid-state electrolytes (SSEs), we investigate the complex Li|Li(3-5x-3y)TaxLayCl3|Li system, particularly examining the performance of the Li|Li0.233Ta0.217La0.559Cl3(LTLC)|Li cell, which demonstrates stable cycling for more than 7000 h at a current density of 0.2 mA cm-2/0.2 mA h cm-2 after a pre-fabrication resting period of 60 h. In situ X-ray photoelectron spectroscopy analysis semi-quantitatively elucidates the interfacial redox hierarchy in LTLC, indicating amore rapid reduction rate of Ta5+ with lithium metal compared to La3+. The byproducts at the interaction are identified as well. X-ray Computed Tomography research revealed that the interfacial layer created during the pre-fabrication process is homogeneous, unlike that produced during a 6-h fabrication time, underscoring the importance of pre-fabrication in interfacial layer development. This technology enables the discovery of halide solid-state electrolytes that demonstrate advantageous interactions with lithium metal and the selection of interfacial products that enhance the stabilization of the battery system. This study serves as a significant reference for examining the compatibility of solid-state electrolytes with lithium metal and offers insights to inform future research. (c) 2025 Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

A new class of quasi-one-dimensional quantum magnetic materials, BiAO2Cu2(SO4)2 (A = K, Rb, Cs), were successfully synthesized via a conventional hydrothermal method. Systematic characterization of their structural and magnetic properties reveals that the radius of alkali metal cation A + plays a critical role in structural tuning. Structurally, the K and Rb compounds are isostructural, crystallizing in the monoclinic system (P21/m). The Cu1O5 square pyramids and Cu2O4 square planes form a uniform chain via mu 2-O bridges. In contrast, substitution with the larger Cs+ ions at the A-site reduces the crystal symmetry to the triclinic system (P-1). Specifically, the pronounced steric effect induced by the Cs+ ions causes a relative rotation of the SO4 tetrahedra. This rotation consequently modifies the coordination geometry of the Cu2+ ions, resulting in a five-coordinate, distorted square-pyramidal configuration for each copper site and thereby transforming the copper chain into an alternating chain. Magnetic measurements indicate a nonmagnetic spin-singlet ground state for all compounds. The formation of this spin-singlet ground state may originate from the presence of significant antiferromagnetic next-nearest-neighbor interactions along the chain direction.

Conventional strategies for designing inorganic solid-state electrolytes, typically via doping superionic lattices, are constrained by dopant-lattice compatibility. Here we propose solid dissociation in which halide van der Waals materials act as solid solvents to dissolve salts, forming amorphous ion-conductive solids. Using this approach, we discover 73 materials, with 40 exhibiting ionic conductivities exceeding 10-3 S cm-1, conducting Li+, Na+, Ag+ and Cu+. We analyse atomic-scale interactions between solvents and salts, uncovering dynamic structural rearrangements that enable solid dissociation. Across diverse solvent-salt pairs, consistent ionic environments emerge, revealing universal mechanisms governing ion transport in this system. Analogous to the compositional tuning of liquid electrolytes, solid dissociation allows targeted engineering of solid-state electrolytes for specific application conditions. Prototype electrolytes have been developed for fast-charging cells, low-temperature cells and 4.8-V high-voltage cells, and demonstrate enhanced dry-room stability and cost advantages. Solid dissociation offers a versatile platform for advancing next generation solid-state electrolytes.

Residual lithium compounds (RLCs) in all-solid-state batteries (ASSBs) employing Ni-rich cathode materials (LiNixCoyMnzO2, NCM) are traditionally viewed either as ionically and electronically insulating layers hindering electrochemical performance or as protective buffer layers enhancing cycling stability. In this study, a beneficial role of Li2CO3 in ASSBs featuring an oxyhalide-based AlOCl-2LiCl (LAOC) solid-state electrolyte (SSE) is revealed. ASSBs containing NCM with residual Li2CO3 demonstrate superior electrochemical performance compared to those treated with a washing pretreatment to remove Li2CO3. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy shows that Li2CO3 facilitates spontaneous Li+ exchange at multiple sites within the LAOC SSE. This leads to faster ion mobility and shorter relaxation times at various lithium sites, indicating enhanced ion transport and improved interface dynamics. Moreover, the beneficial effects of Li2CO3 are confirmed in other halide-based ASSBs. This study uncovers an unexpected role for Li2CO3 in halide-based ASSBs, offering insights that may inspire further exploration of RLCs with functional properties for improving ASSBs performance.

Two new compounds Cu3Bi(SeO3)2O2X (X = F and NO3) were synthesized by means of hydrothermal reaction, both crystallizing in a orthorhombic system with space group Pmmn and exhibiting a layer structure, where the planar CuO4 squares connect to each other via corner-sharing to form a distorted kagome network, while nonmagnetic (SeO3)2-groups and Bi3+ ions are located between adjacent kagome layers. Magnetic results of magnetic and heat capacity measurements confirm that these two compounds both show an antiferromagnetic ordering and field-induced spin-flip transition at low temperature, which are similar to those observed in francisite-type compounds.

Solid‐solution‐based metal alloy phases are an important phase category and effective structural control method. Nevertheless, Hägg's rule retards the formation of metal−metal composite solid solution (CSS); consequently, there is a lack of understanding regarding its properties and potential applications. Herein, as a proof‐of‐concept study, a novel Cu–0.01 wt.% Ag CSS with a unique atomic structure containing both interstitial and substitutional Ag atoms in the Cu lattice is synthesized via a nonequilibrium method. When used as current collectors in Li||CSS metal cells, the CSS can significantly reduce the nucleation overpotential, improve the average Coulombic efficiency (CE) and cycle life, and mitigate uncontrolled Li dendrite deposition compared with Li||Cu cells. Noble metals are often used for interface modification of electrode materials, yet large‐scale applications require convenient and precise control of their content. Here, only a negligible Ag content is required, which, to the best of current knowledge, is almost the lowest noble metal content reported to date. The results provide new insights into the design and application of novel alloy phases such as lithium metal batteries.

The solution-based chemical prelithiation of electrode materials is an effective approach to elevate the initial coulombic efficiency (ICE) and energy-density of the Li-ion battery. Although various lithium-aromatic compound complex solutions (LACSs) have been reported as prelithiation reagents, fundamental understandings are still lacking regarding their drastic difference in prelithiation behavior. In this work, the rate-determining step and some key factors that affect the prelithiation capability were recognized via electrochemical evaluation, spectroscopic analysis, and density functional theory (DFT) calculations. Considering the inherent correlations between the potential of electrochemical Li + -extraction from LACS upon cyclic voltammetry (the oxidation potential of LACS, E O ), the calculated highest occupied molecular orbital (HOMO) energy level, the binding energy (BE) of the solvated Li-ions to the solution (BE solution ), and the prediction accuracy of prelithiation capability and calculations efficiency, we proposed BE-assisted E O as a descriptor for its prelithiation feasibility. This strategy will provide important guidance for the rapid selection and rational design of LACSs for efficient chemical prelithiation.

PbOCu3(SeO3)2(NO3)(OH) was synthesized by means of a replacement of (OH)- groups for F- ions of PbOCu3(SeO3)2(NO3)F, showing a transformation of kagomé and breathing kagomé lattices. Such a replacement did not change their intralayer ferromagnetic interactions and interlayer antiferromagnetic (AFM) interactions but slightly affected the Néel temperature and critical field, where PbOCu3(SeO3)2(NO3)(OH) possesses an AFM ordering at TN = 29.3 K, and a field-induced metamagnetic transition can occur at 2 K while a critical magnetic field of 1.45 T is applied.

Fast-charging lithium-ion batteries are highly required, especially in reducing the mileage anxiety of the widespread electric vehicles. One of the biggest bottlenecks lies in the sluggish kinetics of the Li+ intercalation into the graphite anode; slow intercalation will lead to lithium metal plating, severe side reactions, and safety concerns. The premise to solve these problems is to fully understand the reaction pathways and rate-determining steps of graphite during fast Li+ intercalation. Herein, we compare the Li+ diffusion through the graphite particle, interface, and electrode, uncover the structure of the lithiated graphite at high current densities, and correlate them with the reaction kinetics and electrochemical performances. It is found that the rate-determining steps are highly dependent on the particle size, interphase property, and electrode configuration. Insufficient Li+ diffusion leads to high polarization, incomplete intercalation, and the coexistence of several staging structures. Interfacial Li+ diffusion and electrode transportation are the main rate-determining steps if the particle size is less than 10 μm. The former is highly dependent on the electrolyte chemistry and can be enhanced by constructing a fluorinated interphase. Our findings enrich the understanding of the graphite structural evolution during rapid Li+ intercalation, decipher the bottleneck for the sluggish reaction kinetics, and provide strategic guidelines to boost the fast-charging performance of graphite anode.

High-performance Li-ion/metal batteries working at a low temperature (i.e., <−20 °C) are desired but hindered by the sluggish kinetics associated with Li + transport and charge transfer. Herein, the temperature-dependent Li + behavior during Li plating is profiled by various characterization techniques, suggesting that Li + diffusion through the solid electrolyte interface (SEI) layer is the key rate-determining step. Lowering the temperature not only slows down Li + transport, but also alters the thermodynamic reaction of electrolyte decomposition, resulting in different reaction pathways and forming an SEI layer consisting of intermediate products rich in organic species. Such an SEI layer is metastable and unsuitable for efficient Li + transport. By tuning the solvation structure of the electrolyte with a lower lowest unoccupied molecular orbital (LUMO) energy level and polar groups, such as fluorinated electrolytes like 1 mol L −1 lithium bis(fluorosulfonyl)imide (LiFSI) in methyl trifluoroacetate (MTFA): fluoroethylene carbonate (FEC) (8:2, weight ratio), an inorganic-rich SEI layer more readily forms, which exhibits enhanced tolerance to a change of working temperature (thermodynamics) and improved Li + transport (kinetics). Our findings uncover the kinetic bottleneck for Li + transport at low temperature and provide directions to enhance the reaction kinetics/thermodynamics and low-temperature performance by constructing inorganic-rich interphases.

Lithium iron phosphate (LiFePO 4 ) is widely applied as the cathode material for the energy storage Li‐ion batteries due to its low cost and high cycling stability. However, the low theoretical specific capacity of LiFePO 4 makes its initial capacity loss more concerning. Therefore, lithium compensation by way of prelithiation and applications of sacrificial Li‐rich additives in LiFePO 4 is imminent in elevating the energy density and/or prolonging the lifetime of the LiFePO 4 ‐based Li‐ion batteries (LIBs). Prelithiation in LiFePO 4 is herein carried out by electrochemical and chemical methods and its feasibility is proved on the basis of the electrochemical evaluations such as the initial charge capacity and the cycling stability. In addition, the site of the pre‐intercalated Li‐ions is found via comprehensive physical characterizations and the density functional theory (DFT) calculations. These findings open a new avenue for elevating the energy density and/or prolonging the lifetime of the high‐energy‐density batteries.

A novel transition metal tellurate single-crystal BaNi2TeO6 with layered honeycomb lattices has been successfully synthesized. The crystal structure of BaNi2TeO6 reveals that there are the Ni2+ honeycomb lattice layers and Te6+ triangle lattice layers in the ab plane. BaNi2TeO6 shows an antiferromagnetic (AFM) transition at ∼25 K, which is almost the same temperature as the Curie-Weiss temperature θ ∼ -27 K, indicating the presence of the AFM interactions without obvious magnetic frustration in the system. However, the field-induced successive magnetic transitions observed at Hc1 ∼ 16.2 T and Hc2 ∼ 42.2 T show the complicated spin structure in BaNi2TeO6. Compared with the isostructural Na2Ni2TeO6, the various magnetic properties indicate that the intercalated ions (Ba2+) can significantly affect the magnetic properties of the layered honeycomb lattices, which may be useful for exploring the spin-liquid state and valence bond liquid state in the layered honeycomb lattice compounds.

Lithium metal is a promising anode material for its low redox potential and high theoretical specific capacity. However, the commercial application of the lithium metal anode is hindered with safety concerns arising from the uncontrolled growth of the lithium dendrites and significant volume variation during the lithium plating and stripping processes. Modification to the current collector is effective in tailoring the morphology of the deposited lithium and improving the cycling performance of the lithium metal batteries This review summarizes at first the global research advances in the structural design and the selection of the current collectors and their textures. It then presents some of our efforts in realizing controlled lithium deposition by designing current collectors in three aspects, lithium deposition induced by the micro-to-nano structures, lithiophilic alloys and iron carbides. Finally, conclusions and prospects are made for the further research of the current collectors.

冷冻电镜(cryo-EM)是表征辐照敏感材料的有力工具,已经在生命科学领域得到了广泛的应用和认可,并在2017年获得了诺贝尔化学奖.同年,冷冻电镜首次被应用于观察金属锂的纳米结构,取得了一些前所未有的结果,从此也在电池领域备受关注和蓬勃发展.冷冻或低温不仅可以有效地缓解高能电子束对样品造成的辐照损伤,而且可以大幅降低样品的反应活性,提高样品的稳定性.冷冻电镜可以为辐照敏感材料提供纳米甚至是原子尺度的微观结构信息.本文重点介绍了冷冻电镜在表征锂电池中辐照敏感材料的相关应用和成果,包括冷冻聚焦离子束-扫描电子显微镜(cryo-FIB-SEM)和冷冻透射电子显微镜(cryo-TEM),以便读者了解冷冻电镜在解析电池工作机理和指导材料结构设计等方面发挥的优势和作用.随后,展示了冷冻电镜在金属锂的沉积/溶解行为、固体电解质界面(SEI)膜的纳米结构、亲锂材料的储锂机理、全固态电池中固-固界面以及正极材料表面的固体电解质界面(CEI)膜等方面的应用与研究成果.最后,展望了冷冻电镜在未来的技术发展及其在电池领域的潜在应用与机遇.冷冻电镜技术的发展将有助于解析电池材料与界面结构,了解电池运行和失效机制,从而促进高比能和高安全性电池的发展.

Poly(vinylidene fluoride) (PVDF) is the most popular electrode binder in the current lithium ion batteries (LIBs). Depending on solvent content, polymer electrolytes are classified into solid polymer electrolyte (SPE; solvent-free) and gel polymer electrolytes (GPE; solvent-rich). PVDF-based electrolytes with high contents of solvent undisputedly belong to GPE. However, the affiliation (SPE or GPE) of the PVDF-based electrolyte with low content of “solvent” is in argument as its “solvent” cannot be eliminated till 80°C in vacuum and its structure and ion transport mechanism remain unclear. By a series of studies, we demonstrate that this is actually a polymer electrolyte based on the interactions between the [solvent-Li+] complex and the polymer in structure and in Li-ion transport mechanism. The “residual solvent” (N,N-dimethylformamide, DMF, for example) plays critical roles in constructing the polymer electrolyte and in determining its ion transport and therefore such electrolyte cannot be assigned to any of the known polymer electrolytes. The Li+-associated DMF becomes difficult to be eliminated while the DMF-dehydrofluorinated PVDF has a larger dielectric constant, enhances the dissociation of the lithium salt and interacts with the [DMF-Li+] complex, the charge carrier of the electrolyte. These [solvent-Li+] complex-based polymer electrolytes have high ionic conductivity (10-4 S cm-1 at room temperature), Li-ion transference number (0.44) and Young’s modulus (45.87 MPa) and will find important applications in the solid lithium batteries and as an ion-conducting binder for the electrodes. These findings will enrich the gallery and deepen the fundamental understandings of the polymer electrolytes, spurring designing of novel electrolytes.

With the increasing demand for high energy-density batteries for portable electronics and large-scale energy storage systems, the lithium metal anode (LMA) has received tremendous attention because of its high theoretical capacity and low redox potential. However, the commercial application of LMAs is impeded by the uncontrolled growth of lithium dendrites. Such dendrite growth may result in internal short circuits, detrimental side reactions, and the formation of dead lithium. Therefore, the growth of lithium metal must be controlled. This article summarizes our recent efforts in inhibiting such dendrite growth, decreasing the detrimental side reactions, and elongating the LMA lifespan by optimizing the electrolyte structure and by designing appropriate current collectors. After identifying that the unstable solid electrolyte interface (SEI) film is responsible for the potential dropping in carbonate electrolytes, we developed LiPF6-LiNO3 dual-salt electrolyte and lithium bis(fluorosulfonyl)imide (LiFSI)-carbonate electrolyte to stabilize the SEI film of LMAs. In addition, we achieved controlled lithium deposition by designing the structure and material of the current collectors, including selective lithium deposition in porous current collectors, lithiophilic metal guided lithium deposition, and iron carbide induced underpotential lithium deposition in nano-cavities. The limitations of the current strategies and prospects for future research are also presented.

Two new potassium ytterbium sulfates KYb(SO4)(2)center dot H2O and KYb(SO4)F-2 have been obtained by a conventional hydrothermal method, which are found to crystallize in the monoclinic system with space group P2(1)/n and P2(1)/m, respectively. KYb(SO4)(2)center dot H2O features a three-dimensional open framework built by isolated Yb04 polyhedra and SO4 tetrahedra, while KYb(SO4)F-2 exhibits a zigzag-chain structure built by YbO4F4 polyhedra running along [010] direction. Magnetic measurements indicate that both of two compounds display a paramagnetic behavior down to 2 K with a dominant antiferromagnetic interactions between ytterbium ions. TGA and temperature-dependent PXRD measurements verify the excellent thermal stability of their frameworks. Solid-state UV-vis-NIR diffuse reflectance spectra show that they have wide optical band gaps of 4.95 eV and 5.36 eV, respectively.

The exploration of two-leg spin-ladder materials is a great challenge to the chemical community since it is one of the most ideal models for the study of low-dimensional magnetism and high-Tc superconductivity. Herein, we report on a successful synthesis of a new Cu2+-based two-leg ladder compound constructed by CuO4Cl2 octahedra along the [101] direction. The magnetic results exhibit a broad peak at Tmax ∼ 265 K, and suggest that CdCu2(SeO3)2Cl2 has a spin singlet ground state. The fitting of the isolated two-leg spin-ladder model shows J⊥/kB = 429 K and J‖/kB = 21 K, leading to a large spin gap of ∼409 K.