Fine-tuning the solid-electrolyte interface (SEI) on the Li anode has been widely developed to break through the cyclability bottleneck of Li metal batteries (LMBs). Meanwhile, the cycling behavior of LMBs is also dependent on cathode stability, and hence, it is promising to develop strategies that simultaneously constrain Li dendrite growth and cathode particle distortion. Herein, through copolymerization of maleic anhydride (MA) and hexafluorobutyl acrylate (HFA) monomers, an artificial interface (noted as MAF) is constructed on the Li anode. Such an MAF layer establishes hybrid SEI components consisting of an inorganic-rich interior and a polymer exterior. Its bifunctional contributions on the Li anode and the LiFePO4 (LFP) or LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode are validated by virtue of its dynamic polymer evolution upon LMB cycling. Besides providing lithophilic sites for even Li+ plating, the fluorinated oligomers within the MAF exterior further evolve under an ethylene carbonate (EC)-based electrolyte, inducing dynamic maturation of the LiF-rich cathode-electrolyte interface (CEI). As a result, Li||Li symmetric cells perform for over 900 h of cycling at 1 mA cm-2, while Li||LFP and Li||NCM811 cells maintain capacity retentions of 90.2% after 1500 cycles and 80.6% after 350 cycles at their respective 1 C rate.

The phase composition of polyanion-type cathode materials determines their electrochemical behaviors in sodium-ion batteries (SIBs). A multi-phase transition process is generally observed in conventional preparation pathways, which induce phase heterogeneity and are the main reason for structure and performance deterioration. As a result, the production of polyanion-type cathodes with high phase purity, good electrochemical performance, and scalability remains challenging. Herein, a one-step maturation pathway is developed, and it allows direct transformation from amorphous precursors towards NASICON-typed Na3V2(PO4)3 (NVP) materials of high purity. The amorphization of the precursors through mechanical activation is isolated as the key to preventing the multi-phase transition. The resulting NVP enables stable SIBs cycling at 2 C for over 2000 cycles with a capacity retention of 85 %, and it also exhibits superior rate capability up to 40 C. Such performance is mostly maintained even at low temperature down to -25 degrees C, outperforming the counterparts obtained via the multi-phase transition pathway. Moreover, the developed one-step maturation pathway is also feasible and straightforward for kilogram-scale production, and the NVP structure features, as well as the superior SIBs behaviors, are well reproduced. As a demonstration of practical potential, the one-step maturated NVP cathode and hard carbon anode are assembled into pouch cells of design capacity of 800 mAh, and their cyclability reaches over 1500 cycles at 0.8 C. This work provides an optimization strategy for enhancing consistency in the largescale production of polyanion cathode materials for SIBs.

The pursuit of high-energy solid-state lithium metal batteries (ssLMBs) is challenging, due to the sluggish ion transport in solid electrolytes and unstable electrode-electrolyte interfaces. Herein, we showcase regulating Li+ solid-state coordination as a feasible strategy. By constructing Li+ coordination with poly-1,3-dioxolane chains and anions, an in situ polymerized solid electrolyte (PDTE) is obtained with an ionic conductivity of 1.45 mS cm-1, Li+ transference number of 0.67, and high interfacial compatibility. As the bifunctional promoter, it alleviates Li+ hopping barriers via the ligand-field effects and establishes the conformal solid/cathode-electrolyte interfaces. Its derived Li|PDTE|LiFePO4 ssLMBs maintains cycling for over 1000 cycles at 2 C with 92.5% retention in capacity, and at the fast-charging rate up to 20 C. When coupled with a LiNi0.8Co0.1Mn0.1O2 cathode, PDTE further showcases promises in stable operation under a wide voltage window from 2.8 to 4.5 V and a low-temperature range down to -20 °C. Toward practical promises, 5.7 Ah solid-state pouch cells are further assembled with an energy density of 513 Wh kg-1 and the elevated safety for thermal runaway.

The practical application of zinc (Zn)–air batteries is largely restricted by their inferior cyclability, especially under fast‐charging conditions. Uneven Zn plating and dendrite formation result in their short circuits. In this work, an artificial solid‐electrolyte interphase (SEI) is constructed using indium–organic frameworks (IOF) on the Zn anode. It contains a hybrid architecture that integrates chemical and morphological contributions to regulate Zn plating behaviors and constrain dendrite growth. The atomically dispersed In 3+ provides zincophilic sites to tune Zn nucleation kinetics and promote preferential growth along (002) crystal facet. Meanwhile, IOF exhibits nanosheets‐assembled microspheres with a well‐ordered porous architecture, which promotes mass transfer and affords space for Zn electrodeposition. The influence of SEI microstructure on Zn plating/stripping behavior is further investigated and validated by the post‐cycling characterizations. With IOF based SEI, Zn symmetric cells perform stable cycling for over 1750 h at 10 mA cm −2 . When powering Zn–air batteries, their cycling life is extended to 800 h, which is approximately four times longer than that of pristine Zn foil.

Aqueous zinc-ion batteries represent a highly promising next-generation electrochemical energy storage system because of their safety, environmental friendliness, resource abundance, and simple assembly conditions. However, the formation and growth of zinc dendrites on zinc anode seriously hinder the practical application of zinc-ion batteries. Zincophilic design, which enables the uniform zinc nucleation/deposition, offers an effective solution to achieve dendrite-free zinc anodes. Despite significant progress in the field of zincophilic design, the research in this field currently lacks clear analysis and guidance. This paper provides a comprehensive overview of the current research status of zincophilic design and the mechanism for dendrite-free zinc anode from three aspects: construction of zinc anode zincophilic layers, addition of zincophilic additives in electrolyte, and construction of 3D zincophilic host. Moreover, the challenges facing the industrialization and commercialization of zinc-ion batteries in the further are briefly discussed.

Metal-organic frameworks (MOFs) hold promise as efficient electrode materials for supercapacitors, but their practical application is hindered by the intrinsic low electrical conductivity. Here, we employ CO2-derived carbon nanotubes based on molten salt electrolysis (MSE-CNTs) as the framework to guide the growth of nickel-based MOF (Ni-MOF). The resulting MSE-CNTs/Ni-MOF composite exhibits an impressive specific capacitance of 1714.2 F g(-1) at 1 A g(-1), 1.45 and 1.26 times greater than bare Ni-MOF (1185.7 F g(-1)) and CVD-CNTs/Ni-MOF (1364.3 F g(-1), the composite of Ni-MOF and commercial CNTs produced by chemical-vapor-deposition), respectively. Moreover, the assembled hybrid supercapacitor (MSE-CNTs/Ni-MOF//active carbon) achieves a remarkable specific capacitance of 136.5 F g(-1) at 1 A g(-1) and an energy density of 54.8 Wh kg(-1) at 850 W kg(-1), standing among the best of the state-of-the-art. The superior capacitive performance of MSE-CNTs/Ni-MOF than CVD-CNTs/Ni-MOF can be attributed to the better electrical conductivity of MSE-CNTs, the thinner nanosheet architecture of MSE-CNTs/Ni-MOF, and the effective electrically conductive network within the composite. This work marks a paradigm shift from greenhouse gas CO2 to excellent energy storage materials, paving the way for addressing both the energy and climate issues simultaneously.

The ionic conductivity of solid electrolytes is still insufficient to approach performance promises of solid-state Li metal batteries, suffering from their charged interfaces among phase components and movable Li+ concentration. Herein, an anion-capturing interface based on FeF3 is established on Li6.5La3Zr1.5Ta0.5O12 surface through a sol-gel method. It promotes Li-salt dissociation and formation of anion aggregated layer before blending with polymer. Coulombic interaction of anion on grains boundary showcases multiple merits, including their weakened built-in electric field, restrained charge gradient layer, spontaneous Li+ cross-phase migration, and homogenized interfacial charge distribution. As such, the resulting composite solid electrolytes exhibits an ion conductivity of 1.1×10-4 S/cm2 and Li+ migration number of 0.75 at 25°C. Its resulting Li symmetrical batteries maintain Li plating/stripping behaviors for over 1300 h and low polarization at 0.1 mA/cm2 current density. When being assembled with LiFePO4 positive electrode in solid-state batteries, it performs a specific capacity of 152.8 mAh/g at 1.0 C (170 mA/g) with 96% retention after 600 cycles. This work prioritizes the promises of interface engineering for solid electrolytes in solid-state Li metal batteries.

Regulating the electron-spin state of metal active sites is a rarely cultivated topic for oxygen electrocatalysis. Here, a dual-ligand metal-organic framework (DM) is developed to endow Co sites with D4h crystal symmetry, reconfiguring their orbital degeneracy and electron spin state. The discretized spin-orbital configuration offers the accelerated transformation of the O-related intermediate by accepting electrons via partial d-orbital occupation and mediation of the hydroxyl adsorption strength through electron donation to O p-orbitals. With this orbital flexibility, Co sites serve as "Lewis acid-base" pairs that hasten O redox of oxygen during Zn-air battery cycling, which is validated by operando X-ray absorption spectroscopy and theoretical modeling. Compared to counterparts with different crystal symmetries, Zn-air batteries using the DM electrocatalyst showcase reduced charge-discharge voltage gap and high round-trip energy efficiency at high areal capacity.

AbstractSurface and interfacial chemistry play a vital role in shaping the properties of two‐dimensional transition metal carbides and nitrides (MXenes). This study focuses on utilizing Lewis‐basic halides (LiCl/KCl) for thermal treatment of multilayered Ti3C2Tx, leading to the simultaneous modulation of interlayer spacing and surface functional groups. Compared to the pristine Ti3C2Tx, the LiCl/KCl treated sample (heating temperature: 450°C, denoted as LK‐Ti3C2Tx‐450) showcases a remarkable increase in the interlayer spacing and synergistic optimization of the functional groups. These modifications endow LK‐Ti3C2Tx‐450 with enhanced electrochemical properties, rendering it as a promising anode candidate for lithium‐ion batteries. The increased interlayer spacing is particularly advantageous, as it facilitates efficient and rapid Li+ diffusion, a vital factor in enhancing the performance of energy storage devices.

Introducing organic cosolvent is a common and cost-effective electrolyte engineering for aqueous Zn-battery, reshaping the solvation environment of electrolyte and modulating the interfacial electrochemistry on Zn-metal electrode. Clarifying the mechanisms governing interfacial dynamic evolution and electrochemical performance is essential for guiding cosolvent selection. However, the absence of direct visualization for dynamic interfacial evolution during Zn plating/stripping has impeded mechanistic understanding of cosolvent-mediated effects in electrolyte engineering. Here, we combine advanced in-situ spectroscopy with theoretical calculation to decouple the interfacial evolution at the molecular level. We find that cosolvents not only weaken the connectivity of the interfacial hydrogen-bond network between water molecules, thereby hindering the H+ transfer, but also accelerate the interfacial dynamic transition of Zn2+-(de)solvation from transient to steady state. Additionally, we observe a dynamic adsorption substitution between cosolvent and water, which weakens the electric field intensity exerted on interfacial water. Furthermore, we demonstrate that cosolvents can modify the components content and distribution of the passivation-layer via indirect regulation pathway, rather than a typical self-decomposition mechanism. These multidimensional insights bridge the knowledge gap in cosolvent functionality, offering rational principles for tailoring solvation structures and interfacial dynamics in next-generation aqueous batteries.

Despite the increasing effort in advancing oxygen electrocatalysts for zinc-air batteries (ZABs), the performance development gradually reaches a plateau via only ameliorating the electrocatalyst materials. Herein, a new class of external field-responsive electrocatalyst comprising Ni0.5Mn0.5Fe2O4 stably dispersed on N-doped Ketjenblack (Ni0.5Mn0.5Fe2O4/N-KB) is developed via polymer-assisted strategy for practical ZABs. Briefly, the activity indicator ΔE is significantly decreased to 0.618 V upon photothermal assistance, far exceeding most reported electrocatalysts (generally >0.680 V). As a result, the photothermal electrocatalyst possesses comprehensive merits of excellent power density (319 mW cm-2), ultralong lifespan (5163 cycles at 25 mA cm-2), and outstanding rate performance (100 mA cm-2) for liquid ZABs, and superb temperature and deformation adaptability for flexible ZABs. Such improvement is attributed to the photothermal-heating-enabled synergy of promoted electrical conductivity, reactant-molecule motion, active area, and surface reconstruction, as revealed by operando Raman and simulation. The findings open vast possibilities toward more-energy-efficient energy applications.

The escalating concentration of atmospheric CO2, now exceeding 423.68 ppm and representing a 50% increase since pre-industrial times, underscores an urgent imperative to curb emissions.

Hollow multishelled structures (HoMSs) are attracting great interest in lithium-ion batteries as the conversion anodes, owing to their superior buffering effect and mechanical stability. Given the synthetic challenges, especially elemental diffusion barrier in the multimetal combinations, this complex structure design has been realized in low- and medium-entropy compounds so far. It means that poor reaction reversibility and low intrinsic conductivity remain largely unresolved. Here, a hollow multishelled (LiFeZnNiCoMn)3O4 high entropy oxide (HEO) is developed through integrating molecule and microstructure engineering. As expected, the HoMS design exhibits significant targeting functionality, yielding satisfactory structure and cycling stability. Meanwhile, the abundant oxygen defects and optimized electronic structure of HEO accelerate the lithiation kinetics, while the retention of the parent lattice matrix enables reversible lithium storage, which is validated by rigorous in situ tests and theoretical simulations. Benefiting from these combined properties, such hollow multishelled HEO anode can deliver a specific capacity of 967 mAh g-1 (89% capacity retention) after 500 cycles at 0.5 A g-1. The synergistic lattice and volume stability showcased in this work holds great promise in guiding the material innovations for the next-generation energy storage devices.

The bottleneck of Li metal batteries toward practical applications lies at inferior cyclability as well as Li dendrite issues. As a promising solution, an interface engineering strategy is proposed herein for the Li anode through constructing a hybrid artificial interface. It is assembled onto the Li anode using photocontrolled free radical polymerization (photo-CRP) of polyethylene glycol diacrylate-hexafluorobutyl methacrylate and hexafluorobutyl methacrylate-trifluoroethyl carbonate (PEGDA-HFMBA@HFMBA-FEMC or PH@HF layer). Among such hybrid interfaces, the interior layer of PEGDA-HFMBA exists as a protective shield with flexibility and fracture resistance, while the exterior layer of HFMBA-FEMC plays a role as a LiF reservoir to promote Li mass transfer and its even electrodeposition. In the meantime, some excess HFMBA and FEMC monomers further dissolve into the electrolyte as molecular additives, followed by in situ generation of a thin and robust LiF-rich cathode electrolyte interface (CEI). With the resulting Li anode, Li/NCM811 full cells showcase multifold cyclability amplification in comparison to cells using Bare-Li, covering durable cyclability with a capacity retention of 81.8% after 400 cycles. When the cutoff voltage is elevated to 4.5 V or the working temperature is elevated to 45 °C, the cells still maintain a stable operation for extending 300 cycles.

High-entropy alloys (HEAs) have emerged as promising candidates to replace traditional precious metal catalysts, owing to their unique chemical and physical properties. This review commences by revisiting the fundamental concepts of HEAs, including their synthesis methods and structural control strategies in electrocatalysis. It underscores the critical role of meticulously manipulating both macroscopic and microscopic structures of the HEAs to optimize their catalytic performance. A deep understanding of the structure-activity relationship in HEAs across various configurations is pivotal in developing more effective electrocatalysts. This review methodically encapsulates the research progress of structural control strategies for HEAs in achieving efficient energy conversion, with the aim of gaining a better understanding of the relationship between structure and activity. The review concludes by summarizing the current achievements and challenges, and suggestions for potential future directions of HEAs in the fields of energy conversion and environmental purification.

The doping strategy effectively enhances the capacity and cycling stability of cobalt‐free nickel‐rich cathodes. Understanding the intrinsic contributions of dopants is of great importance to optimize the performances of cathodes. This study investigates the correlation between the structure modification and their performances of Mo‐doped LiNi0.8Mn0.2O2 (NM82) cathode. The role of doped Mo's valence state has been proved functional in both lattice structural modification and electronic state adjustment. Although the high‐valence of Mo at the cathode surface inevitably reduces Ni valence for electronic neutrality and thus causes ion mixing, the original Mo valence will influence its diffusion depth. Structural analyses reveal Mo doping leads to a mixed layer on the surface, where high‐valence Mo forms a slender cation mixing layer, enhancing structural stability and Li‐ion transport. In addition, it is found that the high‐valence dopant of Mo6+ ions partially occupies the unfilled 4d orbitals, which may strengthen the Mo─O bond through increased covalency and therefore reduce the oxygen mobility. This results in an impressive capacity retention (90.0% after 200 cycles) for Mo‐NM82 cathodes with a high Mo valence state. These findings underscore the valence effect of doping on layered oxide cathode performance, offering guidance for next‐generation cathode development.

Zinc-air batteries (ZABs) are promising energy storage systems because of high theoretical energy density, safety, low cost, and abundance of zinc. However, the slow multi-step reaction of oxygen and heavy reliance on noble-metal catalysts hinder the practical applications of ZABs. Therefore, feasible and advanced non-noble-metal electrocatalysts for air cathodes need to be identified to promote the oxygen catalytic reaction. In this review, we initially introduced the advancement of ZABs in the past two decades and provided an overview of key developments in this field. Then, we discussed the working mechanism and the design of bifunctional electrocatalysts from the perspective of morphology design, crystal structure tuning, interface strategy, and atomic engineering. We also included theoretical studies, machine learning, and advanced characterization technologies to provide a comprehensive understanding of the structure-performance relationship of electrocatalysts and the reaction pathways of the oxygen redox reactions. Finally, we discussed the challenges and prospects related to designing advanced non-noble-metal bifunctional electrocatalysts for ZABs.

Highly efficient transition-metal electrocatalysts hold great promise for overcoming the sluggish kinetics of the oxygen reduction reaction (ORR), while the dense stacking of active sites within bulk materials constrains electrocatalytic behaviors. Therefore, nano-structure engineering to obtain hierarchal morphology is crucial to enrich the active sites and facilitate the corresponding mass transfer. Here, the three-dimensional interconnected and ordered mesoporous (3DOM) Fe2Nx decorated on TiOy (Fe2Nx @TiOy) is constructed. By introducing nitrogen vacancies, the increased surface area, and active sites boost ORR kinetics, including a high half-wave potential (0.88 V vs reversible hydrogen electrode) and high current density (71 mA cm-2 at 0.8 V) have been reached. The zinc-air battery assembled with Fe2Nx @TiOy catalysts presents a high specific capacity of 809 mAh g-1. Density functional theory analysis and X-ray absorption spectroscopy further confirm the promoter effects of nitrogen vacancies on modulating electronic structure of Fe, through regulating intermediates adsorption/desorption. The shift of its d-band center is also found toward the Fermi energy level, strengthening the adsorbate-substrate interaction. This allows oxygen species to be favorably stabilized onto active sites of Fe2Nx @TiOy.

Sulfide‐based all‐solid‐state lithium‐ion batteries (ASSLIBs) are the widely recognized approach toward high safety owing to excellent ionic conductivity and nonflammable nature of solid‐state electrolytes (SSEs). However, narrow potential window of SSEs brings about serious interfacial parasitic reactions, resulting in fast degradation of the battery. Herein, a glassy/ceramic analogous solid electrolyte interface (SEI) is constructed on LiCoO 2 (LCO) to enhance interfacial stability between LCO and the Li 10 GeP 2 S 12 (LGPS) SSEs. In which, ceramic Li 2 TiO 3 guarantees good mechanical toughness of analogous SEI, while glassy LixByOz reinforces the coverage to avoid parasitic reactions. Analogous SEI endows ASSLIBs with excellent cycling and rate performance under an upper charge voltage of 4.3 V with 82.3% capacity retention after 300 cycles at 0.2 C. When pushing charge voltage to 4.5 V, analogous SEI also enables desirable performance with an initial capacity of 172.7 mAh g −1 and long lifespan of 200 cycles at 0.2 C. Both experiments and theoretical computation reveal excellent stability between analogous SEI and LGPS, which endows ASSLIBs with small polarization and improved performance. This work provides an insight on glassy/ceramic analogous SEI strategy to boost the interfacial stability of ASSLIBs.

Structure engineering on cathode materials is of great significance for sodium-ion batteries (SIBs) for large-scale practical applications. To achieve a long life-span, it is the major challenge to stabilize their internal bulk and surface structure. Herein, a layer-tunnel composite structure is employed by virtue of calcination chemistry. It is achieved via regulating competitive kinetics and thermodynamic differences between Na+ and Ti4+ when forming gradient layer-tunnel architecture with P2-type Mn-rich bulk and tunnel-type Ti-rich shell. This composite structure integrates superiorities of tunnel shell in stability and layered bulk in capacity. Meanwhile, the synergetic behavior in gradient layer-tunnel composite structure is also reflected by suppressing Mn2+ formation on tunnel-structure surface and P2-O2 layer-phase transformation of internal domain. The mechanical strength of holistic secondary particle is also improved during continuous Na+ (de)intercalation. The resulting Na0.6Mn0.95Ti0.05O2 enables sodium-ion batteries performing a cycle ability for capacity retention of 83.9% after 1000 cycles. More importantly, a high-loading electrode of 24.5 mg cm-2 with practical-target measurement shows a gravimetric energy density of 296.1 Wh kg-1, areal capacity of 2.6 mAh cm-2, and capacity retention 89.6% after 100 cycles. This study provides new perspective for bulk-structure design and construction of ultracyclicality cathode materials to reach the practical standard for SIBs.