Simultaneous Tailoring of Chemical Composition and Morphology Configuration in Metal Hexacyanoferrate for Ultrafast and Durable Sodium-ion Storage.

Metal hexacyanoferrates (MHCFs) with adjustable composition and open framework structures have been considered as intriguing cathode materials for sodium-ion batteries (SIBs). Exploiting MHCFs with ultrafast and durable sodium storage capability as well as comparable capacity is always a goal that many investigators pursue, but remains challenging. Herein, simultaneous tailoring of chemical composition and morphology configuration is carried out to design a hollow monoclinic high-entropy MHCF (HMHE-HCF) assembled by nanocubes for the first time to realize the objective. The "cocktail effect" of high-entropy construction, rich sodium content of monoclinic phase, and unique hollow structure endow HMHE-HCF cathode with fast reaction kinetics and energetically stable performance during continuous charging/discharging processes. As a result, the HMHE-HCF cathode demonstrates superior rate performance up to an ultra-high rate of 100 C (71.1% retention to 0.1 C), and remarkable cycling stability with a capacity retention of 77.8% over 25,000 cycles at 100 C, outperforming most reported sodium-ion cathodes. Further, the HMHE-HCF//hard carbon full-cell delivers capacities of 99.0 and 82.3 mAh g-1 at 0.1 C and 10 C, respectively, and retains 98.1% of the initial capacity after 1,600 cycles at 5C, demonstrating its potential application for sodium-ion storage.

Regulation of Interfacial Chemistry Enabling High-Power Dual-Ion Batteries at Low Temperatures.

Interfacial chemistry plays a crucial role in determining the electrochemical properties of low-temperature rechargeable batteries. Although existing interface engineering has significantly improved the capacity of rechargeable batteries operating at low temperatures, challenges such as sharp voltage drops and poor high-rate discharge capabilities continue to limit their applications in extreme environments. In this study, an energy-level-adaptive design strategy for electrolytes to regulate interfacial chemistry in low-temperature Li||graphite dual-ion batteries (DIBs) is proposed. This strategy enables the construction of robust interphases with superior ion-transfer kinetics. On the graphite cathode, the design endues the cathode interface with solvent/anion-coupled interfacial chemistry, which yields an nitrogen/phosphor/sulfur/fluorin (N/P/S/F)-containing organic-rich interphase to boost anion-transfer kinetics and maintains excellent interfacial stability. On the Li metal anode, the anion-derived interfacial chemistry promotes the formation of an inorganic-dominant LiF-rich interphase, which effectively suppresses Li dendrite growth and improves the Li plating/stripping kinetics at low temperatures. Consequently, the DIBs can operate within a wide temperature range, spanning from -40 to 45 °C. At -40 °C, the DIB exhibits exceptional performance, delivering 97.4% of its room-temperature capacity at 1 C and displaying an extraordinarily high-rate discharge capability with 62.3% capacity retention at 10 C. This study demonstrates a feasible strategy for the development of high-power and low-temperature rechargeable batteries.

Variant-Localized High-Concentration Electrolyte without Phase Separation for Low-Temperature Batteries.

Dual-ion batteries (DIBs) present great application potential in low-temperature energy storage scenarios due to their unique dual-ion working mechanism. However, at low temperatures, the insufficient electrochemical oxidation stability of electrolytes and depressed interfacial compatibility impair the DIB performance. Here, we design a variant-localized high-concentration solvation structure for universal low-temperature electrolytes (ν-LHCE) without the phase separation via introducing an extremely weak-solvating solvent with low energy levels. The unique solvation structure gives the ν-LHCE enhanced electrochemical oxidation stability. Meanwhile, the extremely weak-solvating solvent can competitively participate in the Li+-solvated coordination, which improves the Li+ transfer kinetics and boosts the formation of robust interphases. Thus, the ν-LHCE electrolyte not only has a good high-voltage stability of >5.5 V and proper Li+ transference number of 0.51 but also shows high ionic conductivities of 1 mS/cm at low temperatures. Consequently, the ν-LHCE electrolyte enables different types of batteries to achieve excellent long-term cycling stability and good rate capability at both room and low temperatures. Especially, the capacity retentions of the DIB are 77.7 % and 51.6 %, at -40 °C and -60 °C, respectively, indicating great potential for low-temperature energy storage applications, such as polar exploration, emergency communication equipment, and energy storage station in cold regions.

Chlorination Design for Highly Stable Electrolyte toward High Mass Loading and Long Cycle Life Sodium-Based Dual-Ion Battery.

Sodium-based dual ion batteries (SDIBs) have garnered significant attention as novel energy storage devices offering the advantages of high-voltage and low-cost. Nonetheless, conventional electrolytes exhibit low resistance to oxidation and poor compatibility with electrode materials, resulting in rapid battery failure. In this study, for the first time, a chlorination design of electrolytes for SDIB, is proposed. Using ethyl methyl carbonate (EMC) as a representative, chlorine (Cl)-substituted EMC not only demonstrates increased oxidative stability ascribed to the electron-withdrawing characteristics of chlorine atom, electrolyte compatibility with both the cathode and anode is also greatly improved by forming Cl-containing interface layers. Consequently, a discharge capacity of 104.6 mAh g-1 within a voltage range of 3.0-5.0 V is achieved for Na||graphite SDIB that employs a high graphite cathode mass loading of 5.0 mg cm-2, along with almost no capacity decay after 900 cycles. Notably, the Na||graphite SDIB can be revived for an additional 900 cycles through the replacement of a fresh Na anode. As the mass loading of graphite cathode increased to 10 mg cm-2, Na||graphite SDIB is still capable of sustaining over 700 times with ≈100% capacity retention. These results mark the best outcome among reported SDIBs. This study corroborates the effectiveness of chlorination design in developing high-voltage electrolytes and attaining enduring cycle stability of Na-based energy storage devices.

Constructing π-π Superposition Effect of Tetralithium Naphthalenetetracarboxylate with Electron Delocalization for Robust Dual-Ion Batteries.

Organics are gaining significance as electrode materials due to their merits of multi-electron reaction sites, flexible rearrangeable structures and redox reversibility. However, organics encounter finite electronic conductivity and inferior durability especially in organic electrolytes. To circumvent above barriers, we propose a novel design strategy, constructing conductive network structures with extended π-π superposition effect by manipulating intermolecular interaction. Tetralithium 1,4,5,8-naphthalenetetracarboxylate (LNTC) interwoven by carbon nanotubes (CNTs) forms LNTC@CNTs composite firstly for Li-ion storage, where multiple conjugated carboxyls contribute sufficient Li-ion storage sites, the unique network feature enables electrolyte and charge mobility conveniently combining electron delocalization in π-conjugated system, and the enhanced π-π superposition effect between LNTC and CNTs endows laudable structural robustness. Accordingly, LNTC@CNTs maintain an excellent Li-ion storage capacity retention of 96.4 % after 400 cycles. Electrochemical experiments and theoretical simulations elucidate the fast reaction kinetics and reversible Li-ion storage stability owing to the electron delocalization and π-π superposition effect, while conjugated carboxyls are reversibly rearranged into enolates during charging/discharging. Consequently, a dual-ion battery combining this composite anode and expanded graphite cathode exhibits a peak specific capacity of 122 mAh g-1 and long cycling life with a capacity retention of 84.2 % after 900 cycles.

Secondary Amines Functionalized Organocatalytic Iodine Redox for High-Performance Aqueous Dual-Ion Batteries.

Aqueous dual-ion batteries (ADIBs) based on the cooperative redox of cations and iodine anions at the anode and cathode respectively, are attracting increasing interest because of high capacity and safety. However, the full-cell performance is limited by the sluggish iodine redox kinetics between iodide and polyiodide involving multiple electron transfer steps, and the undesirable shuttling effect of polyiodides. Here, this work reports a versatile conjugated microporous polymer functionalized with secondary amine groups as an organocatalytic cathode for ADIB, which can be positively charged and electrostatically adsorb iodide, and organocatalyze iodine redox reactions through the amine groups. Both theoretical calculations and controlled experiments confirm that the secondary amine groups confine (poly)iodide species via hydrogen bonding, which is essential for accelerating iodine redox kinetics and reducing the polyiodide shuttling effect. The ADIB achieves an ultrahigh capacity of 730 mAh g-1 with an ultrasmall overpotential of 47 mV at 1 A g-1, which also exhibits excellent rate performance and long cycling stability with a capacity retention of 74% after 5000 cycles at a high current density of 5 A g-1. This work demonstrates the promise of developing organocatalysts for accelerating electrochemical processes, which remains a virtually unexplored area in electrocatalyst design for clean energy applications.

On-demand engineerable visible spectrum by fine control of electrochemical reactions.

Tunability of optical performance is one of the key technologies for adaptive optoelectronic applications, such as camouflage clothing, displays, and infrared shielding. High-precision spectral tunability is of great importance for some special applications with on-demand adaptability but remains challenging. Here we demonstrate a galvanostatic control strategy to achieve this goal, relying on the finding of the quantitative correlation between optical properties and electrochemical reactions within materials. An electrochromic electro-optical efficiency index is established to optically fingerprint and precisely identify electrochemical redox reactions in the electrochromic device. Consequently, the charge-transfer process during galvanostatic electrochemical reaction can be quantitatively regulated, permitting precise control over the final optical performance and on-demand adaptability of electrochromic devices as evidenced by an ultralow deviation of <3.0%. These findings not only provide opportunities for future adaptive optoelectronic applications with strict demand on precise spectral tunability but also will promote in situ quantitative research in a wide range of spectroelectrochemistry, electrochemical energy storage, electrocatalysis, and material chemistry.

Direct Regenerating Cathode Materials from Spent Lithium-Ion Batteries.

Recycling cathode materials from spent lithium-ion batteries (LIBs) is critical to a sustainable society as it will relief valuable but scarce recourse crises and reduce environment burdens simultaneously. Different from conventional hydrometallurgical and pyrometallurgical recycling methods, direct regeneration relies on non-destructive cathode-to-cathode mode, and therefore, more time and energy-saving along with an increased economic return and reduced CO2 footprint. This review retrospects the history of direct regeneration and discusses state-of-the-art development. The reported methods, including high-temperature solid-state, hydrothermal/ionothermal, molten salt thermochemistry, and electrochemical method, are comparatively introduced, targeting at illustrating their underlying regeneration mechanism and applicability. Further, representative repairing and upcycling studies on wide-applied cathodes, including LiCoO2 (LCO), ternary oxides, LiFePO4 (LFP), and LiMn2 O4 (LMO), are presented, with an emphasis on milestone cases. Despite these achievements, there remain several critical issues that shall be addressed before the commercialization of the mentioned direct regeneration methods.

Rational Design of High-Loading Electrodes with Superior Performances Toward Practical Application for Energy Storage Devices.

High-loading electrodes play a crucial role in designing practical high-energy batteries as they reduce the proportion of non-active materials, such as current separators, collectors, and battery packaging components. This design approach not only enhances battery performance but also facilitates faster processing and assembly, ultimately leading to reduced production costs. Despite the existing strategies to improve rechargeable battery performance, which mainly focus on novel electrode materials and high-performance electrolyte, most reported high electrochemical performances are achieved with low loading of active materials (<2 mg cm-2). Such low loading, however, fails to meet application requirements. Moreover, when attempting to scale up the loading of active materials, significant challenges are identified, including sluggish ion diffusion and electron conduction kinetics, volume expansion, high reaction barriers, and limitations associated with conventional electrode preparation processes. Unfortunately, these issues are often overlooked. In this review, the mechanisms responsible for the decay in the electrochemical performance of high-loading electrodes are thoroughly discussed. Additionally, efficient solutions, such as doping and structural design, are summarized to address these challenges. Drawing from the current achievements, this review proposes future directions for development and identifies technological challenges that must be tackled to facilitate the commercialization of high-energy-density rechargeable batteries.

A multifunctional optoelectronic device based on 2D material with wide bandgap.

Low-dimensional materials exhibit unique quantum confinement effects and morphologies as a result of their nanoscale size in one or more dimensions, making them exhibit distinctive physical properties compared to bulk counterparts. Among all low-dimensional materials, due to their atomic level thickness, two-dimensional materials possess extremely large shape anisotropy and consequently are speculated to have large optically anisotropic absorption. In this work, we demonstrate an optoelectronic device based on the combination of two-dimensional material and carbon dot with wide bandgap. High-efficient luminescence of carbon dot and extremely large shape anisotropy (>1500) of two-dimensional material with the wide bandgap of >4 eV cooperatively endow the optoelectronic device with multi-functions of optically anisotropic blue-light emission, visible light modulation, wavelength-dependent ultraviolet-light detection as well as blue fluorescent film assemble. This research opens new avenues for constructing multi-function-integrated optoelectronic devices via the combination of nanomaterials with different dimensions.

Significant Strain Dissipation via Stiff-Tough Solid Electrolyte Interphase Design for Highly Stable Alloying Anodes.

The pulverization of alloying anodes significantly restricts their use in lithium-ion batteries (LIBs). This study presents a dual-phase solid electrolyte interphase (SEI) design that incorporates finely dispersed Al nanoparticles within the LiPON matrix. This distinctive dual-phase structure imparts high stiffness and toughness to the integrated SEI film. In comparison to single-phase LiPON film, the optimized Al/LiPON dual-phase SEI film demonstrates a remarkable increase in fracture toughness by 317.8 %, while maintaining stiffness, achieved through the substantial dissipation of strain energy. Application of the dual-phase SEI film on an Al anode leads to a 450 % enhancement in cycling stability for lithium storage in dual-ion batteries. A similar enhancement in cycling stability for silicon anodes, which face severe volume expansion issues, is also observed, demonstrating the broad applicability of the dual-phase SEI design. Specifically, homogeneous Li-Al alloying has been observed in conventional LIBs, even when paired with a high mass loading LiNi0.5 Co0.3 Mn0.2 O2 cathode (7 mg cm-2 ). The dual-phase SEI film design can also accelerate the diffusion kinetics of Li-ions through interface electronic structure regulation. This dual-phase design can integrate stiffness and toughness into a single SEI film, providing a pathway to enhance both the structural stability and rate capability of alloying anodes.

Bottom-up strategy of multi-level structured boron-doped diamond for the durable electrode in water purification.

Long-term exposition of electrodes to aqueous media inevitably results in biofouling and adhesion of bacteria, reducing the electrolysis efficiency of electrodes for water treatment. To ensure technically efficient antifouling of materials for durable electrodes, hierarchical micro-/nano structured boron-doped diamond (BDD) electrodes were designed and synthesized. Multi-level structured BDD was coated on titanium mesh by a bottom-up strategy, based on a combination of self-assembly seeding and hot filament chemical vapor deposition (HFCVD) growth. The morphology of the BDD coating can be controlled by manipulating the seeding density and boron doping concentration. The designed micro/nano hierarchical structure of the BDD electrode suppressed bacterial adhesion greatly and exhibited excellent anti-biofouling efficiency with an antibacterial rate of âˆ¼ 93 %, which entails simplified self-cleaning and durable BDD-coated electrodes. The BDD-coated electrodes were employed to electrochemically treat Escherichia coli-contaminated water, killing virtually all bacteria (≥99.9 %) in 1 min. Finally, real river water was electrochemically treated, reducing the chemical oxygen demand (COD) down to 5 mg/L in 4 h. The excellent performance shows the great potential of the structured BDD electrodes for long-term water purification.

Maximizing Electrostatic Polarity of Non-Sacrificial Electrolyte Additives Enables Stable Zinc-Metal Anodes for Aqueous Batteries.

Although additives are widely used in aqueous electrolytes to inhibit the formation of dendrites and hydrogen evolution reactions on Zn anodes, there is a lack of rational design principles and systematic mechanistic studies on how to select a suitable additive to regulate reversible Zn plating/stripping chemistry. Here, using saccharides as the representatives, we reveal that the electrostatic polarity of non-sacrificial additives is a critical descriptor for their ability to stabilize Zn anodes. Non-sacrificial additives are found to continuously modulate the solvation structure of Zn ions and form a molecular adsorption layer (MAL) for uniform Zn deposition, avoiding the thick solid electrolyte interphase layer due to the decomposition of sacrificial additives. A high electrostatic polarity renders sucrose the best hydrated Zn2+ desolvation ability and facilitates the MAL formation, resulting in the best cycling stability with a long-term reversible plating/stripping cycle life of thousands of hours. This study provides theoretical guidance for the screening of optimal additives for high-performance ZIBs.

Acidic enol electrooxidation-coupled hydrogen production with ampere-level current density.

Hydrogen production coupled with biomass upgrading is vital for future sustainable energy developments. However, most biomass electrooxidation reactions suffer from high working voltage and low current density, which substantially hinder large-scale industrial applications. Herein, we report an acidic hydrogen production system that combined anodic ascorbic acid electrooxidation with cathodic hydrogen evolution. Unlike C-H and O-H bonds cleavage with slow kinetics in conventional organic oxidation, the highly active enol structure in ascorbic acid allows for an ultralow overpotential of only 12 mV@10 mA/cm2 using Fe single-atom catalysts, and reaches 1 A/cm2 at only 0.75 V (versus reversible hydrogen electrode) with approximately 100% Faraday efficiency for hydrogen production. Furthermore, the fabricated two-electrode membrane-free electrolyser delivers an industrial current density of 2 A/cm2@1.1 V at 60 °C (2.63 kWh/Nm3 H2), which requires half of the electricity consumption in conventional water electrolysis (~5 kWh/Nm3 H2). This work provides a new avenue for achieving industrial-scale hydrogen production from biomass.

Fundamental Understanding and Optimization Strategies for Dual-Ion Batteries: A Review.

There has been increasing demand for high-energy density and long-cycle life rechargeable batteries to satisfy the ever-growing requirements for next-generation energy storage systems. Among all available candidates, dual-ion batteries (DIBs) have drawn tremendous attention in the past few years from both academic and industrial battery communities because of their fascinating advantages of high working voltage, excellent safety, and environmental friendliness. However, the dynamic imbalance between the electrodes and the mismatch of traditional electrolyte systems remain elusive. To fully employ the advantages of DIBs, the overall optimization of anode materials, cathode materials, and compatible electrolyte systems is urgently needed. Here, we review the development history and the reaction mechanisms involved in DIBs. Afterward, the optimization strategies toward DIB materials and electrolytes are highlighted. In addition, their energy-related applications are also provided. Lastly, the research challenges and possible development directions of DIBs are outlined.

An Ultrahigh-Mass-Loading Integrated Free-Standing Functional All-Carbon Positive Electrode Prepared using an Architecture Tailoring Strategy for High-Energy-Density Dual-Ion Batteries.

Dual-ion batteries (DIBs) have been attracting great attention for the storage of stationary energy due to their low cost, environmental friendliness, and high working voltage. However, most reports on DIBs involve low-mass-loading electrodes (<2.5 mg), while the use of high mass-loading electrodes (>10 mg cm-2 ), which are critical for practical application, is overlooked. Herein, an integrated free-standing functional carbon positive electrode (named MSCG) with a "point-line-plane" hierarchical architecture at the practical level of ultrahigh mass-loading (>50 mg cm-2 ) is developed for high-energy-density DIBs. The rationally designed microstructure and the advanced assembly method that is adopted produce a well-interconnected ion/electron transport channel in the MSCG electrode, which confers rapid ion/electron kinetic properties while maintaining good mechanical properties. Consequently, the DIBs with ultrahigh-mass-loading MSCG electrodes exhibits a high discharge capacity of 100.5 mAh g-1 at 0.5 C (loading mass of 50 mg cm-2 ) and a long-term cycling performance with a capacity retention of 87.7% at 1 C after 500 cycles (loading mass of 23 mg cm-2 ). Moreover, the DIB with the ultrahigh-mass-loading positive electrode achieves a high energy density of 379 Wh kg-1 based on the mass of electrode materials, the highest value recorded to date for any DIBs.

Solvation Structure Modulation of High-Voltage Electrolyte for High-Performance K-Based Dual-Graphite Battery.

Due to the advantages of dual-ion batteries (DIBs) and abundant resources, potassium-based dual-carbon batteries (K-DCBs) have wide application prospects. However, conventional carbonate ester-based electrolyte systems have obvious drawbacks such as poor oxidation resistance and difficulty in sustaining the anion intercalation process at high voltages, which seriously affect the capacity and cycle performance of K-DCBs. Therefore, a rational design of more efficient novel electrolyte systems is urgently required to realize high-performance K-DCBs. Herein, a solvation structure modulation strategy for the K-DCB electrolyte systems is reported. Consequently, substantial K+ ion storage improvement at the graphite anode and enhanced bis(fluorosulfonyl)imide anion (FSI- ) intercalation capacity at the graphite cathode are successfully realized simultaneously. As a proof-of-concept, the assembled K-DCB exhibited a discharge capacity of 103.4 mAh g-1 , and after 400 cycles, ≈90% capacity retention is observed. Moreover, the energy density of the K-DCB full cell reached 157.6 Wh kg-1 , which is the best performance in reported K-DCBs till date. This study demonstrates the effectiveness of solvation modulation in improving the performance of K-DCBs.

Asymmetric Coordination of Iridium Single-atom IrN3 O Boosting Formic Acid Oxidation Catalysis.

Rational design of the proximal coordination of an active site to achieve its optimum catalytic activity is the ultimate goal in single-atom catalysis, but still challenging. Here, we report theoretical prediction and experimental realization of an asymmetrically coordinated iridium single-atom catalyst (IrN3 O) for the formic acid oxidation reaction (FAOR). Theoretical calculations reveal that the substitution of one or two nitrogen with more electronegative oxygen in the symmetric IrN4 motif splits and downshifts the Ir 5d orbitals with respect to the Fermi level, moderating the binding strength of key intermediates on IrN4-x Ox (x=1, 2) sites, especially that the IrN3 O motif shows ideal activity for FAOR with a near-zero overpotential. The as-designed asymmetric Ir motifs were realized by pyrolyzing Ir precursor with oxygen-rich glucose and nitrogen-rich melamine, exhibiting a mass activity of 25 and 87 times greater than those of state-of-the-art Pd/C and Pt/C, respectively.

Coordination Chemistry of Large-Sized Yttrium Single-Atom Catalysts for Oxygen Reduction Reaction.

Although being transition metals, the Fenton-inactive group 3-4 elements (Sc, Y, La, Ti, Zr, and Hf) can easily lose all the outermost s and d electrons, leaving behind ionic sites with nearly empty outermost orbitals that are stable but inactive for oxygen involved catalysis. Here, it is demonstrated that the dynamic coordination network can turn these commonly inactive ionic sites into platinum-like catalytic centers for the oxygen reduction reaction (ORR). Using density functional theory calculations, a macrocyclic ligand coordinated yttrium single-atom (YN4 ) moiety is identified, which is originally ORR inactive because of the too strong binding of hydroxyl intermediate, while it can be activated by an axial ligand X through the covalency competition between YX and YOH bonds. Strikingly, it is also found that the binding force of the axially coordinated ligand is an effective descriptor, and the chlorine ligand is screened out with an optimal binding force that behaves self-adaptively to facilitate each ORR intermediate steps by dynamically changing its YCl covalency. These experiments validate that the as-designed YN4 -Cl moieties embedded within the carbon framework exhibit a high half-wave potential (E1/2 = 0.85 V) in alkaline media, the same as that of the commercial Pt/C catalyst .

Design and Synthesis of a π-Conjugated N-Heteroaromatic Material for Aqueous Zinc-Organic Batteries with Ultrahigh Rate and Extremely Long Life.

Electroactive organic materials with tailored functional groups are of great importance for aqueous Zn-organic batteries due to their green and renewable nature. Herein, a completely new N-heteroaromatic material, hexaazatrinaphthalene-phenazine (HATN-PNZ) is designed and synthesized, by an acid-catalyzed condensation reaction, and its use as an ultrahigh performance cathode for Zn-ion batteries demonstrated. Compared with phenazine monomer, it is revealed that the π-conjugated structure of N-heteroaromatics can effectively increase electron delocalization, thereby improving its electrical conductivity. Furthermore, the enlarged aromatic structure noticeably suppresses its dissolution in aqueous electrolytes, thus enabling high structural stability. As expected, the HATN-PNZ cathode delivers a large reversible capacity of 257 mAh g-1 at 5 A g-1 , ultrahigh rate capability of 144 mAh g-1 at 100 A g-1 , and an extremely long cycle life of 45 000 cycles at 50 A g-1 . Investigation of the charge-storage mechanism demonstrates the synergistic coordination of both Zn2+ and H+ cations with the phenanthroline groups, with Zn2+ first followed by H+ , accompanying the reversible formation of zinc hydroxide sulfate hydrate. This work provides a molecular-engineering strategy for superior organic materials and adds new insights to understand the charge-storage behavior of aqueous Zn-organic batteries.