Thermoplastic polyurethane (TPU) consists of a hard segment and a soft segment, where the former affords mechanical strength and thermal stability, while the latter provides a possibility of good ionic conductivity by promoting dissociation of ions from the lithium salt. Thus, TPU attracts a wide interest recently as a promising polymer electrolyte for solid-state lithium batteries. However, the relatively low ionic conductivity of TPU still restricts its actual applications due to the aggregation of polymer chains, which greatly reduces the dissociation of lithium salts. Herein, a strategy to address this challenge was adopted by in situ polymerization poly(ethylene glycol diacrylate) (PEGDA) in fully dispersed TPU. Hence a stretchable solid-state electrolyte (denoted as TELL and the contrast sample was denoted as TLL) with high ionic conductivity of 7.18 x 10-4 S/cm was obtained at room temperature. The Li+ transference number is 0.85 in Li|TELL|Li cell and can stably undergo charge-discharge cycles for 1400 h at a current density of 0.1 mA/cm2 , while the contrast sample is short-circuited after 634 h of cycling. The LiFePO4 |TELL|Li cell achieves a capacity retention of 78.93 % after 200 cycles at 2 C. The LiFePO4 |TLL|Li cell only gains the capacity retention of 51.9 % after 50 cycles at the same current density. So, the method adopted here may provide a new approach to realize a flexible solid-state electrolyte with high ion-conductivity. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Strategic design of highly efficient electrocatalysts to achieve bidirectional optimization and dynamic equilibrium between polysulfide adsorption intensity and catalytic conversion activity is crucial for suppressing the ”shuttle effect” in Lithium–Sulfur (Li–S) batteries. Herein, we first synthesized a defect-rich CoFeP-capped N/B co-doped carbon nanotube (CoFeP@N/B–CNTs) catalyst via an in-situ catalytic pyrolysis coupled with a low-temperature phosphorization process to achieve chemical bonding-level interfacial contact between the metal active sites and the carbon scaffold. Experimental and theoretical investigations demonstrate the multi-dopant co-doping of N/B/P simultaneously increases the defect density and surface polarity of the carbon lattice while enhancing the chemical anchoring effect on polysulfides. Moreover, the electronic synergy precisely modulates the electronic structure of the CoFe active centers by moderately weakening their metallic characteristics and optimizing the central energy level of the d-band to achieve a bidirectional optimization and dynamic balance between polysulfide adsorption strength and catalytic conversion activity. Based on this, the Li–S battery utilizing CoFeP@N/B–CNTs delivers ultra-high sulfur utilization (1394.75 mAh·g–1), exceptional rate capability (745.52 mAh·g–1 at 3 C), and stable cycling performance (571.98 mAh·g–1 after 650 cycles at 2.0 C). Overall, this work demonstrates for the first time a multifunctional bimetallic catalyst strategy in Li–S batteries and offers new perspectives for the structural design and electronic state regulation of multifunctional catalytic materials for Li–S batteries.

Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising energy conversion and storage devices. Nevertheless, side reactions and dendrite growth on the zinc metal anode hinder their widespread application. In this study, hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions. Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode, thus blocking the interaction between the active zinc anode and electrolyte. Compared with zinc foil, the Hemin@Zn anode demonstrates enhanced corrosion resistance, a decrease in hydrogen evolution, and more orderly deposition of zinc. As expected, the symmetric cell with Hemin@Zn anode can sustain up to 40 0 0 h at 0.2 mA/cm2 , 0.2 mAh/cm2 . Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72 % during 500 cycles. Moreover, the full cell Hemin@Zn//NH4 V4 O10 delivers a superior capacity up to 367 mAh/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g. This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Lithium-metal batteries employing lithium-rich manganese-based oxide (LRMO) cathodes offer great potential for achieving gravimetric energy densities exceeding 750 Wh kg-1. However, their practical deployment is hindered by severe electrolyte decomposition and rapid capacity fade, particularly under high-voltage conditions. Herein, N-methyltrifluoroacetamide (NMTFA) as a novel electrolyte additive is introduced, in combination with lithium difluoro(oxalato)borate (LiDFOB), to modulate the electrolyte solvation structure and enhance interfacial stability. Endowed with lone pair electrons and an N-H bond, NMTFA acts as an electron donor capable of scavenging oxygen radicals released from the LRMO cathode, thereby mitigating electrolyte degradation and suppressing gas evolution. Additionally, hydrogen-bonding interactions between NMTFA and the primary solvent, along with the incorporation of DFOB- anions into the primary solvation sheath, weaken Li+-solvent interactions, promoting the formation of a nitrogen-/boron-rich interphase that facilitates faster Li+ desolvation and improves electrode stability. As a result, the Li||LRMO full cell delivers exceptional cycling stability, retaining over 70% of its initial capacity after 800 cycles at a cut-off voltage of 4.8 V and over 80% retention after 300 cycles at 5.0 V. This study provides critical insights into the rational design of advanced electrolytes for high-voltage lithium-metal batteries.

In the face of an escalating global energy crisis, the demand for sustainable and cost-effective energy storage solutions has significantly propelled sodium-ion batteries (SIBs) to the forefront of research, particularly due to the abundance and affordability of sodium. Among various SIB technologies, aqueous sodium-ion batteries (ASIBs) have garnered considerable attention for their superior safety, eco-friendliness, and potential for wide-temperature-range applications. However, the reliability under extreme conditions is limited by electrolyte instability and interfacial degradation. This review provides a comprehensive synthesis of the latest advancements in ASIBs over the past five years, focusing on breakthrough achievements in enhancing wide-temperature performance for key components, including electrolytes, electrodes, separators, binders, and current collectors. It also explores persistent challenges encountered during operation in extreme environments. A key innovation presented in this review is the integration of machine learning (ML) techniques into SIB research. This approach offers new perspectives and potential references for future ML-driven advancements, enabling accelerated material discovery and performance optimization. Furthermore, the review summarizes the current status and future trajectories of hydroxide-based sodium-ion batteries, providing researchers with valuable insights and directions for further exploration in this dynamic field. Overall, this review underscores the transformative potential of ASIBs in large-scale energy storage, while also identifying key areas for future research and development.

Lithium-ion batteries (LIBs) have become an integral part of electrical energy storage systems; however, the high price leads to a search for alternatives to LIBs. Sodium-ion batteries stand out because sodium is unlimited in the Earth’s crust and sea. Similar to LIBs, layered transition metal oxides are the optimal choice for practical application by virtue of good ion conductivity, high energy density, and facile synthesis. However, the air sensitivity will lead to the degradation of layered oxides, corresponding with poor electrochemical performance. For instance, capacity losses of 20%–50% after exposure to air with ∼50% relative humidity for 1 day to 30 days, accompanied by surface carbonate coverage exceeding 20% in many cases. It is also regrettable that the air sensitivity has plagued the commercialization of layered oxides for a long time, resulting in huge cost needs to be spent on storage and transportation. Hence, in this work, recent strategies on air stability are reviewed, and the comprehensive chemical evolution mechanisms of air-exposure are introduced that H2O and CO2 have the greatest impact on the structural degradation of layered oxides. In addition, the design principles of layered oxides that choose elements with higher electrochemical potential, increasing the cation competition coefficient, increasing the particle size, surface coating layer modification, and controlling exposed active facets for better air stability are given out. It is hoped that the attention of researchers to air stability can be aroused, and more studies about air stability will be done to address the problem of air sensitivity.

Solid-state sodium metal batteries (SSMBs) have attracted significant attention due to their high energy density and improved safety, but SSMBs are limited by low ionic conductivity and interfacial instability. Herein, we design a composite solid electrolyte (denoted as CSE-20) by embedding Na3Zr2Si2PO12 (NZSP) fillers into a 3D cross-linked copolymer matrix of pentaerythritol tetraacrylate (PETEA) and hexafluorobutyl acrylate (HFBA). This structure constructs continuous Na+ transport pathways, achieving a high ionic conductivity of 0.81 mS/cm at room temperature. The interaction between NZSP and HFBA weakens the C-F bond, and combined with the low LUMO energy of HFBA, this synergistically promotes the in-situ formation of a robust NaF-rich interphase at the Na metal anode by facilitating HFBA preferential reduction to release F-. Together with the mechanical reinforcement of NZSP on the CSE-20 electrolyte, these effects collectively inhibit sodium dendrite growth. Consequently, a Na||CSE-20||Na symmetric cell cycles stably for over 1300 h at 0.1 mA/cm2 and reaches a critical current density of 1.9 mA/cm2. A Na3V2(PO4)3 (NVP)||CSE-20||Na full cell also exhibits excellent cycling stability, retaining 93.5 % of its capacity after 1200 cycles at 1 C and 98.15 % at 2 C. This study provides an effective electrolyte solution for the development of high-performance and long-life solid sodium metal batteries through the design concept of NZSP-HFBA-PETEA multi-component collaboration.

Iron-based polyanionic cathode materials in potassium-ion batteries (KIBs) have appealed to an increasing number of interest due to these advantages of low cost, environmental friendliness and excellent structural stability. However, these inherent drawbacks of inferior electronic conductivity and terrible nanostructural stability hinder its practical application. Here, we report a novel low-strain iron-based polyanion-type cathode material FeOHSO4@C for KIBs. In this work, the surface of FeOHSO4 nanoparticles is well carbon encapsulated, carbon coating layer with large surface area and excellent electrical conductivity is ≈2.5 nm in thick, which can not only inhibit the aggregation and growth between FeOHSO4@C nanoparticles during charging and discharging, but also provide a 3D electronic conductive framework that activates electrochemical reactivity. As a result, the FeOHSO4@C cathode exhibits outstanding potassium storage capacity (capacity retention of 80.95% over 200 cycles at 20 mA g-1) attributed to a low-strain mechanism for K+ uptake/removal, high pseudocapacitance, as well as 3D electronic conductive framework. Operando XRD and ex situ XPS analyses revealed a single-phase reaction route of orthorhombic FeOHSO4@C during cycling.

Vanadium-based aqueous zinc-ion batteries (V-AZIBs) face significant challenges in terms of capacity degradation, zinc dendrite growth, and electrode corrosion; they are affected by the pH fluctuations of the electrolyte during cycling. In this study, a balloon-like bent fiber-optic sensor (BBFOS) was embedded into the electrode/electrolyte interface of a pouch cell, and light signals were collected during charging/discharging and further converted to pH values. Finally, a smart and nondestructive operando device was designed for operando real-time monitoring of the pH evolution of the electrolytes in V-AZIBs. The operando testing results showed a strong correlation between pH evolution and capacity decay in pouch cells and clarified the relationship between pH evolution mechanisms and capacity degeneration in V-AZIBs. Furthermore, the pH stability and the reversible layered chemical mechanism during the charging/discharging process were revealed by using operando BBFOS and operando X-ray powder diffraction analysis, respectively. The highly accurate and nondestructive operando device can promote the progress of AZIBs and other battery systems.

Zinc-ion batteries (ZIBs) have emerged as promising energy storage devices due to their high energy density, low cost, and environmental friendliness. However, the practical applications of ZIBs are curbed for challenges of hydrogen evolution reactions (HER), dendrite formations, dissolution of cathodes, and other intractable issues during charge/discharge. The aqueous electrolytes' properties strongly influence the performance and stability of ZIBs. This review offers a concise sketch of the fundamental theoretical knowledge about electrolytes. Moreover, comprehensive strategies and approaches for addressing the abovementioned issues are highlighted and summarized, unlocking the full potential of ZIBs and expanding their applications in various fields. In addition, efficient evaluation techniques for the trait of solvation structure and electrochemical performance are also reviewed, including experiments and computational simulations, which provide guidelines for the accurate evaluation and analysis of ZIBs in the future.

Mn-rich layered oxides are appealing cathodes for potassium ion batteries （PIBs） in view of their comprehensive virtues such as low cost,high energy density and mature craftsmanship.However,the insufficient covalency between transition metal （TM） and O usually induces irreversible structural evolution and cation migration during repeated insertion and extraction of K + ,resulting in capacity loss,voltage fading and sluggish kinetics.Herein,an anion substitution strategy is proposed for a stable operation of layered oxide cathode by adjusting the valence electron layer structure between TM and O.The resultant strong TM-O skeleton can inhibit the occurrence of side effects derive from Ni 4+ during the deep depotassium process,so as to achieve a gentle structural transition.Consequently,stable cycling performance of K 0.39 Mn 0.77 Ni 0.23 O 1.9 F 0.1 （KMNOF） cathode is achieved with 77%capacity retention over 350 cycles at100 m A/g,yielding high discharge capacity 93.5 mAh/g at 20 mA/g and significantly improved rate capability of 50.1 mAh/g at 500 mA/g,whereas irreversible structural evolution and rapid capacity fade with KMNO cathode.Finally,in situ/ex situ characterizations and theoretical computations sheds light on the charge transfer and structure evolution mechanisms of KMNOF.

Composite polymer electrolytes (CPE) have received widespread attention for conferring high interface compatibility and stability in solid-state batteries. Here, we propose a simple configuration approach to design a TPU/PVEC/LAGP (TVLL) solid electrolyte to address low ion conductivity and limited bulk conductivity. The introduction of PVEC with high dielectric constant promotes the dissociation of lithium salt and reduces the crystallinity of the polymer matrix, which can enhance the uniform distribution of ceramic and polymer phases and enable high-throughput ion exchange pathways, thus achieving a high ion conductivity of 3.86 x 10(-4) S cm(-1). Additionally, the physical dynamic bonds of TPU chains and the formation of hydrogen-bond network between N atoms in TPU and O atoms in PVEC polymer chains can buffer the local potential difference caused by Li+ aggregation, effectively solving the problems of high interface resistance and interface compatibility. This provides excellent cycling performance at room temperature for the symmetric Li|TVLL|Li cells and the solidstate Li|TVLL|LiFePO4 cells, which maintains a low and stable polarization voltage of 800 h and delivers a remarkable capacity retention of 89 % after 200 cycles at 0.5C. Molecular dynamics simulations (MD) reveal the mechanism of inter-component interactions and the Li+ transport pathway, which provides a new idea for the design of highly stable solid-state electrolytes.

Solid-state rechargeable lithium-metal batteries with garnet-type (Li7La3Zr2O12) solid electrolytes (SEs) represent promising candidates of the next-generation high-energy batteries yet their practical use are hindered by a short cycle life usually due to dendrite nucleation and penetration through the garnet. In the previous works, the dendrite nucleation is ascribed to poor wettability of Li metal at the alkaline-residue-covered garnet surface, and high electronic conductivity of garnet that invites Li+-electron recombination at grain boundary. In this work, it is showed by constructing a mathematical model on a residue-free garnet particles, that grain size of the garnet has profound influence on Li+ transport kinetics, and therefore, the dendrite nucleation. Smaller garnet grains tend to show faster Li+ transport in the bulk yet they also involve higher Li+ flux diffusing across grain boundaries and Li-garnet interface, which are considered kinetically more sluggish. As a result, more Li-ions tend to accumulate at the grain boundary and the interface, which accounts for unstable local environment and a sharply reduced electron migration barrier, and together they invite dendrite nucleation. Based on the findings, a new asymmetric garnet SE is proposed that features high ionic conductivity and dendrite suppression ability.

Lithium metal batteries with composite solid‐state electrolytes are considered a promising approach to breaking through the energy limit of current lithium‐ion batteries. However, the low ionic conductivity of polymer electrolytes at room temperature and the stability of the electrode/electrolyte interface have become the major obstacles to the practical application of solid‐state lithium metal batteries. Here, thermoplastic polyurethane is crosslinked with poly(vinylidene fluoride) via hydrogen bonding interactions and combined with Li 1+x Al x Ge 2−x (PO 4 ) 3 (LAGP) to form a novel hybrid solid‐state electrolyte (denoted as TPLL). Experimental characterization and theoretical calculations have demonstrated that the rich 3D hydrogen bonding network in TPLL effectively increases the Li─O coordination number and promotes lithium salt dissociation, resulting in a high ionic conductivity of 0.182 mS cm −1 at 25 °C. Moreover, the abundant F groups effectively construct a stable electrode/electrolyte interface, enabling stable cycling of symmetric Li/Li cells for over 600 h at 0.1 mA cm −2 at room temperature. The Li/LiFePO 4 full cell assembled with TPLL‐CPE achieves excellent long‐term cycling stability with a decay rate of only 0.016% per cycle at room temperature. This strategy of hydrogen‐bonded crosslinking for salt dissociation opens up a new path for improving the solid‐state electrolytes.

NASICON type solid electrolyte Li1+xAlxGe2−x(PO4)3 (LAGP) is one of the most potential candidates in view of their high ionic conductivity, high oxidation resistance and excellent air stability. However, inevitable interface issues often cause severe performance degradation, seriously affecting its commercial application. Herein, a lithiophilic carbon buffer layer is constructed on the LAGP surface adjacent to the Li electrode side by a facile pyrolysis reaction, then the LiCx interlayer is generated in situ between the carbon buffer layer and lithium metal, which can guide uniform ion transport while improving interface contact. Thus, the LiCx-LAGP showed excellent ionic conductivity, high flexibility and lithiophilic interphase. Specially, the Li|LiCx-LAGP|Li battery has achieved a 1000 h stable cycles at 0.1 mA/cm2, remarkably, the Li|LiCx-LAGP|LFP battery retains 85% of their initial capacity after 200 cycles under 1 C, even for the NCM811 cathode, the battery still has a good cycle performance.

Lithium metal batteries (LMBs) have attracted more attention for their high energy densities. Their applications are limited for the poor low temperature (LT) cycle performance and the growth of dendrite due to the root problems of high Li+ desolvation energy barrier and poor electrode/electrolyte interface. Here, an electrolyte was prepared using low dielectric constant solvents of ethyl acetate (EA), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (D2), and the high voltage endurance lithium salt lithium difluoro(oxalato)borate (LiDFOB), which exhibits high ionic conductivity of 1 mS/cm even at -50 degrees C and superior high voltage tolerance. Moreover, fluoroethylene carbonate (FEC) is further introduced to realize the temperature-responsive solvation structure, which induces an enriched inorganic solid electrolyte interphase (SEI) film and homogeneous lithium deposition. Therefore, Li parallel to NCM87 batteries not only deliver outstanding ambient temperature performance (89% capacity retention after 290 cycles) but also can operate at LT of -40 degrees C for 40 cycles with a stable capacity of 120 mA h/g. This work can enlighten the development and design of an electrolyte operating under extreme conditions.

Layered transition-metal (TM) oxides are of high application value as a cathode for potassium (K)-ion batteries toward high energy density. However, the inadequate covalency of the TM-O bond inevitably induces TM migration and subsequent irreversible structural transformation upon operating, which results in poor rate and long cycle reliability. To address this issue, we employed boron coordination chemistry to manipulate the local electronic structure in a prototype P2-layered K0.5Mn0.8Ni0.15B0.05O2 (KMNBO). The B ions with high electronegativity reside in the TM slabs to boost TM-O covalency of the layered cathode by attracting an electronic tendency surrounding oxygen, which upgrades the tolerance of the layered structure during the repeated K-ion (de)intercalation process. The sluggish intrinsic K+ migration could be simultaneously alleviated by reducing the Coulomb force between K and O. This study breaks the stereotype for a layered crystal lattice and provides new insight into developing long-durability potassium layered cathodes.

Electrochemical energy storage and conversion techniques that exhibit the merits such as high energy density, rapid response kinetics, economical maintenance requirements and expedient installation procedures will hold a pivotal role in the forthcoming energy storage technologies revolution. In recent years, aqueous zinc−ion batteries (AZIBs) have garnered substantial attention as a compelling candidate for large−scale energy storage systems, primarily attributable to their advantageous features encompassing cost−effectiveness, environmental sustainability, and robust safety profiles. Currently, one of the primary factors hindering the further development of AZIBs originates from the challenge of cathode materials. Specifically, the three mainstream types of mainstream cathode materials, in terms of manganese−based compounds, vanadium−based compounds and Prussian blue analogues, surfer from the dissolution of Mn2+, in the low discharge voltage, and the low specific capacity, respectively. Several strategies have been developed to compensation the above intrinsic defects for these cathode materials, including the ionic doping, defect engineering, and materials match. Accordingly, this review first provides a systematic summarization of the zinc storage mechanism in AZIBs, following by the inherent merit and demerit of three kind of cathode materials during zinc storage analyzed from their structure characteristic, and then the recent development of critical strategies towards the intrinsic insufficiency of these cathode materials. In this review, the methodologies aimed at enhancing the efficacy of manganese−based and vanadium−based compounds are emphasis emphasized. Additionally, the article outlines the future prospective directions as well as strategic proposal for cathode materials in AZIBs.

Manganese/nickel-based layered transition metal oxides have caught the attention of studies as promising cathodes for sodium-ion batteries (SIBs). It is reported that utilizing both cationic and anionic redox reactions is a promising method for higher energy density cathodes. However, the anionic redox reaction comes at the expense of irreversible oxygen release. Hence, a Li-Mg cosubstituted P2-Na0.67Li0.07Mg0.07Ni0.28Mn0.58O2 material with a honeycomb-ordered superstructure was designed. The Ni3+/Ni4+ redox couple and the anionic redox reaction are proven to have a competitive relationship. Density functional theory calculations reveal the effect of O 2p nonbonding states from Li and prove that Mg-O bonds can stabilize the Ni-O e(g) states. In situ electrochemical impedance spectroscopy measurements and galvanostatic charging/discharging derived dV/dQ, representing resistance changes with time, are obtained to reveal the mechanism of the anionic redox reaction. This study presents the effect and mechanism of the O 2p nonbonding state and Mg-O bonds of manganese/nickel-based layered oxides.

Hard carbon (HC) has demonstrated a significant potential in anode for sodium-ion batteries (SIBs) due to its superior electrochemical properties. Coal is considered a promising hard carbon precursor due to its high carbon yield. However, the widespread adoption of coal-derived HC faces challenges such as limited storage capacity and decreased rate performance, primarily attributed to the dense structure of coal. In this study, a molten saltassisted approach was developed to adjust the microstructure of coal-derived HC. The dense coal is etched into a flaky structure by molten salt, which is conducive to the diffusion and transport of sodium ions. The optimized HC materials possess large interlayer spacing and abundant pseudo-graphitic domains, exhibiting a remarkable reversible capacity of 303.6 mA h g- 1 at 30 mA g- 1 and 82.1 mA h g- 1 at 500 mA g- 1. Besides, a full cell with the configuration of as-prepared coal derived HC versus Na3V2(PO4)2O2F (NVPOF) is presented with a high initial coulombic efficiency of 76.15 % and capacity of 100.7 mA h g- 1. The results indicate that our synthesis strategy is feasible for the application of coal derived carbon materials in SIBs.