Regulation of the d-band center of metal-organic frameworks for energy-saving hydrogen generation coupled with selective glycerol oxidation.

The hybrid electrolyzer coupled glycerol oxidation (GOR) with hydrogen evolution reaction (HER) is fascinating to simultaneously generate H2 and high value-added chemicals with low energy input, yet facing a challenge. Herein, Cu-based metal-organic frameworks (Cu-MOFs) are reported as model catalysts for both HER and GOR through doping of atomically dispersed precious and nonprecious metals. Remarkably, the HER activity of Ru-doped Cu-MOF outperformed a Pt/C catalyst, with its Faradaic efficiency for formate formation at 90% at a low potential of 1.40 V. Furthermore, the hybrid electrolyzer only needed 1.36 V to achieve 10 mA cm-2, 340 mV lower than that for splitting pure water. Theoretical calculations demonstrated that electronic interactions between the host and guest (doped) metals shifted downward the d-band centers (εd) of MOFs. This consequently lowered water adsorption and dissociation energy barriers and optimized hydrogen adsorption energy, leading to significantly enhanced HER activities. Meanwhile, the downshift of εd centers reduced energy barriers for rate-limiting step and the formation energy of OH*, synergistically enhancing the activity of MOFs for GOR. These findings offered an effective means for simultaneous productions of hydrogen fuel and high value-added chemicals using one hybrid electrolyzer with low energy input.

Regulation of anion-Na+ coordination chemistry in electrolyte solvates for low-temperature sodium-ion batteries.

High-performance sodium storage at low temperature is urgent with the increasingly stringent demand for energy storage systems. However, the aggravated capacity loss is induced by the sluggish interfacial kinetics, which originates from the interfacial Na+ desolvation. Herein, all-fluorinated anions with ultrahigh electron donicity, trifluoroacetate (TFA-), are introduced into the diglyme (G2)-based electrolyte for the anion-reinforced solvates in a wide temperature range. The unique solvation structure with TFA- anions and decreased G2 molecules occupying the inner sheath accelerates desolvation of Na+ to exhibit decreased desolvation energy from 4.16 to 3.49 kJ mol-1 and 24.74 to 16.55 kJ mol-1 beyond and below -20 °C, respectively, compared with that in 1.0 M NaPF6-G2. These enable the cell of Na||Na3V2(PO4)3 to deliver 60.2% of its room-temperature capacity and high capacity retention of 99.2% after 100 cycles at -40 °C. This work highlights regulation of solvation chemistry for highly stable sodium-ion batteries at low temperature.

Routes to high-performance layered oxide cathodes for sodium-ion batteries.

Sodium-ion batteries (SIBs) are experiencing a large-scale renaissance to supplement or replace expensive lithium-ion batteries (LIBs) and low energy density lead-acid batteries in electrical energy storage systems and other applications. In this case, layered oxide materials have become one of the most popular cathode candidates for SIBs because of their low cost and comparatively facile synthesis method. However, the intrinsic shortcomings of layered oxide cathodes, which severely limit their commercialization process, urgently need to be addressed. In this review, inherent challenges associated with layered oxide cathodes for SIBs, such as their irreversible multiphase transition, poor air stability, and low energy density, are systematically summarized and discussed, together with strategies to overcome these dilemmas through bulk phase modulation, surface/interface modification, functional structure manipulation, and cationic and anionic redox optimization. Emphasis is placed on investigating variations in the chemical composition and structural configuration of layered oxide cathodes and how they affect the electrochemical behavior of the cathodes to illustrate how these issues can be addressed. The summary of failure mechanisms and corresponding modification strategies of layered oxide cathodes presented herein provides a valuable reference for scientific and practical issues related to the development of SIBs.

Electrolyte-Induced Morphology Evolution to Boost Potassium Storage Performance of Perylene-3,4,9,10-tetracarboxylic Dianhydride.

Organic materials have attracted extensive attention for potassium-ion batteries due to their flexible structure designability and environmental friendliness. However, organic materials generally suffer from unavoidable dissolution in aprotic electrolytes, causing an unsatisfactory electrochemical performance. Herein, we designed a weakly solvating electrolyte to boost the potassium storage performance of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). The electrolyte induces an in situ morphology evolution and achieves a nanowire structure. The weakly dissolving capability of ethylene glycol diethyl ether-based electrolyte and unique nanowire structure effectively avoid the dissolution of PTCDA. As a result, PTCDA shows excellent cycling stability (a capacity retention of 89.1% after 2000 cycles) and good rate performance (70.3 mAh g-1 at 50C). In addition, experimental detail discloses that the sulfonyl group plays a key role in inducing morphology evolution during the charge/discharge process. This work opens up new opportunities in electrolyte design for organic electrodes and illuminates further developments of potassium-ion batteries.

Pre-Oxidation Strategy Transforming Waste Foam to Hard Carbon Anodes for Boosting Sodium Storage Performance.

Large reserves, high capacity, and low cost are the core competitiveness of disordered carbon materials as excellent anode materials for sodium-ion batteries (SIBs). And the existence and improper treatment of a large number of organic solid wastes will aggravate the burden on the environment, therefore, it is significant to transform wastes into carbon-based materials for sustainable energy utilization. Herein, a kind of hard carbon materials are reported with waste biomass-foam as the precursor, which can improve the sodium storage performance through pre-oxidation strategy. The introduction of oxygen-containing groups can promote structural cross-linking, and inhibit the melting and rearrangement of carbon structure during high-temperature carbonization that produces a disordered structure with a suitable degree of graphitization. Moreover, the micropore structure are also regulated during the high-temperature carbonization process, which is conducive to the storage of sodium ions in the low-voltage plateau region. The optimized sample as an electrode material exhibits excellent reversible specific capacity (308.0 mAh g-1) and initial Coulombic efficiency (ICE, 90.1%). In addition, a full cell with the waste foam-derived hard carbon anode and a Na3V2(PO4)3 cathode is constructed with high ICE and energy density. This work provides an effective strategy to conversion the waste to high-value hard carbon anode for sodium-ion batteries.

AIBI Modified Mesoporous Copper Sulfide Nanocomposites for Efficient Non-Oxygen Dependent Free Radicals-Assisted Photothermal Therapy in Uveal Melanoma.

Uveal melanoma (UM) is an ocular cancer predominantly affecting adults, characterized by challenging diagnostic outcomes. This research endeavors to develop an innovative multifunctional nanocomposite system sensitive to near-infrared (NIR) radiation, serving as both a non-oxygen free-radical generator and a photothermal agent. The designed system combines azobis isobutyl imidazoline hydrochloride (AIBI) with mesoporous copper sulfide (MCuS) nanoparticles. MCuS harnesses NIR laser energy to induce photothermal therapy, converting light energy into heat to destroy cancer cells. Simultaneously, AIBI is activated by the NIR laser to produce alkyl radicals, which induce DNA damage in remaining cancer cells. This distinctive feature equips the designed system to selectively eliminate cancers in the hypoxic tumor microenvironment. MCuS is also beneficial to scavenge the overexpressed glutathione (GSH) in the tumor microenvironment. GSH generally consumes free radicals and hiders the PDT effect. To enhance control over AIBI release in cancer cells, 1-tetradecyl alcohol (TD), a phase-changing material, is introduced onto the surface of MCuS nanoparticles to create the final AMPT nanoparticle system. In vitro and in vivo experiments confirm the remarkable anti-tumor efficacy of AMPT. Notably, the study introduces an orthotopic tumor model for UM, demonstrating the feasibility of precise and effective targeted treatment within the ocular system.

An Intrinsic Stable Layered Oxide Cathode for Practical Sodium-Ion Battery: Solid Solution Reaction, Near-Zero-Strain and Marvelous Water Stability.

Non-aqueous solvents, in particular N,N-dimethylaniline (NMP), are widely applied for electrode fabrication since most sodium layered oxide cathode materials are readily damaged by water molecules. However, the expensive price and poisonousness of NMP unquestionably increase the cost of preparation and post-processing. Therefore, developing an intrinsically stable cathode material that can implement the water-soluble binder to fabricate an electrode is urgent. Herein, a stable nanosheet-like Mn-based cathode material is synthesized as a prototype to verify its practical applicability in sodium-ion batteries (SIBs). The as-prepared material displays excellent electrochemical performance and remarkable water stability, and it still maintains a satisfactory performance of 79.6% capacity retention after 500 cycles even after water treatment. The in situ X-ray diffraction (XRD) demonstrates that the synthesized material shows an absolute solid-solution reaction mechanism and near-zero-strain. Moreover, the electrochemical performance of the electrode fabricated with a water-soluble binder shows excellent long-cycling stability (67.9% capacity retention after 500 cycles). This work may offer new insights into the rational design of marvelous water stability cathode materials for practical SIBs.

Carbon superstructure-supported half-metallic V2O3 nanospheres for high-efficiency photorechargeable zinc ion batteries.

Photorechargeable zinc ion batteries (PZIBs), which can directly harvest and store solar energy, are promising technologies for the development of a renewable energy society. However, the incompatibility requirement between narrow band gap and wide coverage has raised severe challenges for high-efficiency dual-functional photocathodes. Herein, half-metallic vanadium (III) oxide (V2O3) was first reported as a dual-functional photocathode for PZIBs. Theoretical and experimental results revealed its unique photoelectrical and zinc ion storage properties for capturing and storing solar energy. To this end, a synergistic protective etching strategy was developed to construct carbon superstructure-supported V2O3 nanospheres (V2O3@CSs). The half-metallic characteristics of V2O3, combined with the three-dimensional superstructure assembled by ultrathin carbon nanosheets, established rapid charge transfer networks and robust framework for efficient and stable solar-energy storage. Consequently, the V2O3@CSs photocathode delivered record zinc ion storage properties, including a photo-assisted discharge capacities of 463 mAh∙g-1 at 2.0 A∙g-1 and long-term cycling stability over 3000 cycles. Notably, the PZIBs assembled using V2O3@CSs photocathodes could be photorecharged without an external circuit, exhibiting a high photo conversion efficiency (0.354%) and photorecharge voltage (1.0 V). This study offered a promising direction for the direct capture and storage of solar energy.

Interfacial Engineering for Oriented Crystal Growth toward Dendrite-Free Zn Anode for Aqueous Zinc Metal Battery.

Zn deposition with a surface-preferred (002) crystal plane has attracted extensive attention due to its inhibited dendrite growth and side reactions. However, the nucleation and growth of the Zn(002) crystal plane are closely related to the interfacial properties. Herein, oriented growth of Zn(002) crystal plane is realized on Ag-modified surface that is directly visualized by in situ atomic force microscopy. A solid solution HCP-Zn (~1.10 at. % solubility of Ag, 30 °C) is formed on the Ag coated Zn foil (Zn@Ag) and possesses the same crystal structure as Zn to reduce its nucleation barrier caused by their lattice mismatch. It merits oriented Zn deposition and corrosion-resistant surface, and presents long cycling stability in symmetric cells and full cells coupled with V2O5 cathode. This work provides insights into interfacial regulation of Zn anodes for high-performance aqueous zinc metal batteries.

Stress Dissipation Driven by Multi-Interface Built-In Electric Fields and Desert-Rose-Like Structure for Ultrafast and Superior Long-Term Sodium Ion Storage.

The kinetics and durability of conversion-based anodes greatly depend on the intrinsic stress regulating ability of the electrode materials, which has been significantly neglected. Herein, a stress dissipation strategy driven by multi-interface built-in electric fields (BEFs) and architected structure, is innovatively proposed to design ultrafast and long-term sodium ion storage anodes. Binary Mo/Fe sulfide heterostructured nanorods with multi-interface BEFs and staggered cantilever configuration are fabricated to prove our concept. Multi-physics simulations and experimental results confirm that the inner stress in multiple directions can be dissipated by the multi-interface BEFs at the micro-scale, and by the staggered cantilever structure at the macro-scale, respectively. As a result, our designed heterostructured nanorods anode exhibits superb rate capability (332.8 mAh g-1 at 10.0 A g-1 ) and durable cyclic stability over 900 cycles at 5.0 A g-1 , outperforming other metal chalcogenides. This proposed stress dissipation strategy offers a new insight for developing stable structures for conversion-based anodes.

Insight into the Role of Fluoroethylene Carbonate on the Stability of Sb||Graphite Dual-Ion Batteries in Propylene Carbonate-Based Electrolyte.

Sodium dual-ion batteries (Na-DIBs) have attracted increasing attention due to their high operative voltages and low-cost raw materials. However, the practical applications of Na-DIBs are still hindered by the issues, such as low capacity and poor Coulombic efficiency, which is highly correlated with the compatibility between electrode and electrolyte but rarely investigated. Herein, fluoroethylene carbonate (FEC) is introduced into the electrolyte to regulate cation/anion solvation structure and the stability of cathode/anode-electrolyte interphase of Na-DIBs. The FEC modulates the environment of PF6 - solvation sheath and facilitates the interaction of PF6 - on graphite. In addition, the NaF-rich interphase caused by the preferential decomposition of FEC effectively inhibits side reactions and pulverization of anodes with the electrolyte. Consequently, Sb||graphite full cells in FEC-containing electrolyte achieve an improved capacity, cycling stability and Coulombic efficiency. This work elucidates the underlying mechanism of bifunctional FEC and provides an alternative strategy of building high-performance dual ion batteries.

Industrial-Scale Hard Carbon Designed to Regulate Electrochemical Polarization for Fast Sodium Storage.

Given the merits of abundant resource, low cost and high electrochemical activity, hard carbons have been regarded as one of the most commercializable anode material for sodium-ion batteries (SIBs). However, poor rate capability is one of the main obstacles that severely hinder its further development. In addition, the relationships between preparation method, material structure and electrochemical performance have not been clearly elaborated. Herein, a simple but effective strategy is proposed to accurately construct the multiple structural features in hard carbon via adjusting the components of precursors. Through detailed physical characterization of the hard carbons derived from different regulation steps, and further combined with in-situ Raman and galvanostatic intermittent titration technique (GITT) analysis, the network of multiple relationships between preparation method, microstructure, sodium storage behavior and electrochemical performance have been successfully established. Simultaneously, exceptional rate capability about 108.8 mAh g-1 at 8 A g-1 have been achieved from RHC sample with high reversible capacity and desirable initial Coulombic efficiency (ICE). Additionally, the practical applications can be extended to cylindrical battery with excellent cycle behaviors. Such facile approach can provide guidance for large-scale production of high-performance hard carbons and provides the possibility of building practical SIBs with high energy density and durability.

Enabling Efficient Anchoring-Conversion Interface by Fabricating Double-Layer Functionalized Separator for Suppressing Shuttle Effect.

Lithium-sulfur batteries (LiSBs) with high energy density still face challenges on sluggish conversion kinetics, severe shuttle effects of lithium polysulfides (LiPSs), and low blocking feature of ordinary separators to LiPSs. To tackle these, a novel double-layer strategy to functionalize separators is proposed, which consists of Co with atomically dispersed CoN4 decorated on Ketjen black (Co/CoN4@KB) layer and an ultrathin 2D Ti3C2Tx MXene layer. The theoretical calculations and experimental results jointly demonstrate metallic Co sites provide efficient adsorption and catalytic capability for long-chain LiPSs, while CoN4 active sites facilitate the absorption of short-chain LiPSs and promote the conversion to Li2S. The stacking MXene layer serves as a microscopic barrier to further physically block and chemically anchor leaked LiPSs from the pores and gaps of the Co/CoN4@KB layer, thus preserving LiPSs within efficient anchoring-conversion reaction interfaces to balance the accumulation of "dead S" and Li2S. Consequently, with an ultralight loading of Co/CoN4@KB-MXene, the LiSBs exhibit amazing electrochemical performance even under high sulfur loading and lean electrolyte, and the outperforming performance for lithium-selenium batteries (LiSeBs) can also be achieved. This work exploits a universal and effective strategy of a double-layer functionalized separator to regulate the equilibrium adsorption-catalytic interface, enabling high-energy and long-cycle LiSBs/LiSeBs.

Hollow Core-Shelled Na4Fe2.4Ni0.6(PO4)2P2O7 with Tiny-Void Space Capable Fast-Charge and Low-Temperature Sodium Storage.

Iron-based mixed polyanion phosphate Na4Fe3(PO4)2P2O7 (NFPP) is recognized as a promising cathode for Sodium-ion Batteries (SIBs) due to its low cost and environmental friendliness. However, its inherent low conductivity and sluggish Na+ diffusion limit fast charge and low-temperature sodium storage. This study pioneers a scalable synthesis of hollow core-shelled Na4Fe2.4Ni0.6(PO4)2P2O7 with tiny-void space (THoCS-0.6Ni) via a one-step spray-drying combined with calcination process due to the different viscosity, coordination ability, molar ratios, and shrinkage rates between citric acid and polyvinylpyrrolidone. This unique structure with interconnected carbon networks ensures rapid electron transport and fast Na+ diffusion, as well as efficient space utilization for relieve volume expansion. Incorporating regulation of lattice structure by doping Ni heteroatom to effectively improve intrinsic electron and Na+ diffusion path and energy barrier, which achieves fast charge and low-temperature sodium storage. As a result, THoCS-0.6Ni exhibits superior rate capability (86.4 mAh g-1 at 25 C). Notably, THoCS-0.6Ni demonstrates exceptional cycling stability at -20 °C with a capacity of 43.6 mAh g-1 after 2500 cycles at 5 C. This work provides a universal strategy to design the hollow core-shelled structure with tiny-void space cathode materials for reversible batteries with fast-charge and low-temperature storage features.

Entropy-Assisted Anion-Reinforced Solvation Structure for Fast-Charging Sodium-Ion Full Batteries.

Anion-reinforced solvation structure favors the formation of inorganic-rich robust electrode-electrolyte interface, which endows fast ion transport and high strength modulus to enable improved electrochemical performance. However, such a unique solvation structure inevitably injures the ionic conductivity of electrolytes and limits the fast-charging performance. Herein, a trade-off in tuning anion-reinforced solvation structure and high ionic conductivity is realized by the entropy-assisted hybrid ester-ether electrolyte. Anion-reinforced solvation sheath with more anions occupying the inner Na+ shell is constructed by introducing the weakly coordinated ether tetrahydrofuran into the commonly used ester-based electrolyte, which merits the accelerated desolvation energy and gradient inorganic-rich electrode-electrolyte interface. The improved ionic conductivity is attributed to the weakly diverse solvation structures induced by entropy effect. These enable the enhanced rate performance and cycling stability of Prussian blue||hard carbon full cells with high electrode mass loading. More importantly, the practical application of the designed electrolyte was further demonstrated by industry-level 18650 cylindrical cells.

Confining Polymer Electrolyte in MOF for Safe and High-Performance All-Solid-State Sodium Metal Batteries.

Nanoconfined polymer molecules exhibit profound transformations in their properties and behaviors. Here, we present the synthesis of a polymer-in-MOF single ion conducting solid polymer electrolyte, where polymer segments are partially confined within nanopores ZIF-8 particles through Lewis acid-base interactions for solid-state sodium-metal batteries (SSMBs). The unique nanoconfinement effectively weakens Na ion coordination with the anions, facilitating the Na ion dissociation from salt. Simultaneously, the well-defined nanopores within ZIF-8 particles provide oriented and ordered migration channels for Na migration. As a result, this pioneering design allows the solid polymer electrolyte to achieve a Na ion transference number of 0.87, Na ion conductivity of 4.01×10-4 S cm-1, and an extended electrochemical voltage window up to 4.89 V vs. Na/Na+. The assembled SSMBs (with Na3V2(PO4)3 as the cathode) exhibit dendrite-free Na-metal deposition, promising rate capability, and stable cycling performance with 96 % capacity retention over 300 cycles. This innovative polymer-in-MOF design offers a compelling strategy for advancing high-performance and safe solid-state metal battery technologies.

Weakly Coordinating Diluent Modulated Solvation Chemistry for High-Performance Sodium Metal Batteries.

Diluents have been extensively employed to overcome the disadvantages of high viscosity and sluggish kinetics of high-concentration electrolytes, but generally do not change the pristine solvation structure. Herein, a weakly coordinating diluent, hexafluoroisopropyl methyl ether (HFME), is applied to regulate the coordination of Na+ with diglyme and anion and form a diluent-participated solvate. This unique solvation structure promotes the accelerated decomposition of anions and diluents, with the construction of robust inorganic-rich electrode-electrolyte interphases. In addition, the introduction of HFME reduces the desolvation energy of Na+, improves ionic conductivity, strengthens the antioxidant, and enhances the safety of the electrolyte. As a result, the assembled Na||Na symmetric cell achieves a stable cycle of over 1800 h. The cell of Na||P'2-Na0.67MnO2 delivers a high capacity retention of 87.3 % with a high average Coulombic efficiency of 99.7 % after 350 cycles. This work provides valuable insights into solvation chemistry for advanced electrolyte engineering.

Anion-Reinforced Solvation Structure Enables Stable Operation of Ether-Based Electrolyte in High-Voltage Potassium Metal Batteries.

Electrolytes with anion-dominated solvation are promising candidates to achieve dendrite-free and high-voltage potassium metal batteries. However, it's challenging to form anion-reinforced solvates at low salt concentrations. Herein, we construct an anion-reinforced solvation structure at a moderate concentration of 1.5 M with weakly coordinated cosolvent ethylene glycol dibutyl ether. The unique solvation structure accelerates the desolvation of K+, strengthens the oxidative stability to 4.94 V and facilitates the formation of inorganic-rich and stable electrode-electrolyte interface. These enable stable plating/stripping of K metal anode over 2200 h, high capacity retention of 83.0 % after 150 cycles with a high cut-off voltage of 4.5 V in K0.67MnO2//K cells, and even 91.5 % after 30 cycles under 4.7 V. This work provides insight into weakly coordinated cosolvent and opens new avenues for designing ether-based high-voltage electrolytes.

Resolving the Origins of Superior Cycling Performance of Antimony Anode in Sodium-ion Batteries: A Comparison with Lithium-ion Batteries.

Alloying-type antimony (Sb) with high theoretical capacity is a promising anode candidate for both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). Given the larger radius of Na+ (1.02 Å) than Li+ (0.76 Å), it was generally believed that the Sb anode would experience even worse capacity degradation in SIBs due to more substantial volumetric variations during cycling when compared to LIBs. However, the Sb anode in SIBs unexpectedly exhibited both better electrochemical and structural stability than in LIBs, and the mechanistic reasons that underlie this performance discrepancy remain undiscovered. Here, using substantial in situ transmission electron microscopy, X-ray diffraction, and Raman techniques complemented by theoretical simulations, we explicitly reveal that compared to the lithiation/delithiation process, sodiation/desodiation process of Sb anode displays a previously unexplored two-stage alloying/dealloying mechanism with polycrystalline and amorphous phases as the intermediates featuring improved resilience to mechanical damage, contributing to superior cycling stability in SIBs. Additionally, the better mechanical properties and weaker atomic interaction of Na-Sb alloys than Li-Sb alloys favor enabling mitigated mechanical stress, accounting for enhanced structural stability as unveiled by theoretical simulations. Our finding delineates the mechanistic origins of enhanced cycling stability of Sb anode in SIBs with potential implications for other large-volume-change electrode materials.

Isostructural Synthesis of Iron-Based Prussian Blue Analogs for Sodium-Ion Batteries.

Rechargeable sodium ion batteries (SIBs) have promising applications in large-scale energy storage systems. Iron-based Prussian blue analogs (PBAs) are considered as potential cathodes owing to their rigid open framework, low-cost, and simple synthesis. However, it is still a challenge to increase the sodium content in the structure of PBAs and thus suppress the generation of defects in the structure. Herein, a series of isostructural PBAs samples are synthesized and the isostructural evolution of PBAs from cubic to monoclinic after modifying the conditions is witnessed. Accompanied by, the increased sodium content and crystallinity are discovered in PBAs structure. The as-obtained sodium iron hexacyanoferrate (Na1.75 Fe[Fe(CN)6 ]0.9743 ·2.76H2 O) exhibits high charge capacity of 150 mAh g-1 at 0.1 C (17 mA g-1 ) and excellent rate performance (74 mAh g-1 at 50 C (8500 mA g-1 )). Moreover, their highly reversible Na+ ions intercalation/de-intercalation mechanism is verified by in situ Raman and Powder X-ray diffraction (PXRD) techniques. More importantly, the Na1.75 Fe[Fe(CN)6 ]0.9743 ·2.76H2 O sample can be directly assembled in a full cell with hard carbon (HC) anode and shows excellent electrochemical performances. Finally, the relationship between PBAs structure and electrochemical performance is summarized and prospected.