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.

Scalable Precise Nanofilm Coating and Gradient Al Doping Enable Stable Battery Cycling of LiCoO2 at 4.7†V.

The quest for smart electronics with higher energy densities has intensified the development of high-voltage LiCoO2 (LCO). Despite their potential, LCO materials operating at 4.7 V faces critical challenges, including interface degradation and structural collapse. Herein, we propose a collective surface architecture through precise nanofilm coating and doping that combines an ultra-thin LiAlO2 coating layer and gradient doping of Al. This architecture not only mitigates side reactions, but also improves the Li+ migration kinetics on the LCO surface. Meanwhile, gradient doping of Al inhibited the severe lattice distortion caused by the irreversible phase transition of O3-H1-3-O1, thereby enhanced the electrochemical stability of LCO during 4.7 V cycling. DFT calculations further revealed that our approach significantly boosts the electronic conductivity. As a result, the modified LCO exhibited an outstanding reversible capacity of 230 mAh g-1 at 4.7 V, which is approximately 28 % higher than the conventional capacity at 4.5 V. To demonstrate their practical application, our cathode structure shows improved stability in full pouch cell configuration under high operating voltage. LCO exhibited an excellent cycling stability, retaining 82.33 % after 1000 cycles at 4.5 V. This multifunctional surface modification strategy offers a viable pathway for the practical application of LCO materials, setting a new standard for the development of high-energy-density and long-lasting electrode materials.

Defect-Healing Induced Monoclinic Iron-Based Prussian Blue Analogs as High-Performance Cathode Materials for Sodium-Ion Batteries.

Prussian blue analogs (PBAs) have attracted wide interest as a class of ideal cathodes for rechargeable sodium-ion batteries due to their low cost, high theoretical capacity, and facile synthesis. Herein, a series of highly crystalline Fe-based PBAs (FeHCF) cubes, where HCF stands for the hexacyanoferrate, is synthesized via a one-step pyrophosphate-assisted co-precipitation method. By applying this proposed facile crystallization-controlled method to slow down the crystallization process and suppress the defect content of the crystal framework of the PBAs, the as-prepared materials demonstrate high crystallization and a sodium-rich induced rhombohedral phase. As a result, the as prepared FeHCF can deliver a high specific capacity of up to 152.0 mA h g-1 (achieving ≈90% of its theoretical value) and an excellent rate capability with a high-capacity retention ratio of 88% at 10 C, which makes it one of the most competitive candidates among the cathodes reported regarding both capacity and rate performance. A highly reversible three-phase-transition sodium-ion storage mechanism has been revealed via multiple in situ techniques. Furthermore, the full cells fabricated with as-prepared cathode and commercial hard carbon anode exhibit excellent compatibility which shows great prospects for application in the large-scale energy storage systems.

Ice-Assisted Synthesis of Highly Crystallized Prussian Blue Analogues for All-Climate and Long-Calendar-Life Sodium Ion Batteries.

For practical sodium-ion batteries, both high electrochemical performance and cost efficiency of the electrode materials are considered as two key parameters. Prussian blue analogues (PBAs) are broadly recognized as promising cathode materials due to their low cost, high theoretical capacity, and cycling stability, although they suffer from low-crystallinity-induced performance deterioration. Herein, a facile "ice-assisted" strategy is presented to prepare highly crystallized PBAs without any additives. By suppressing structure defects, the cathode exhibits a high capacity of 123 mAh g-1 with initial Coulombic efficiency of 87.2%, a long cycling lifespan of 3000 cycles, and significantly enhanced high/low temperature performance and calendar life. Remarkably, the low structure distortion and high sodium diffusion coefficient have been identified via in situ synchrotron powder diffraction and first-principles calculations, while its thermal stability has been analyzed by in situ heated X-ray powder diffraction. We believe the results could pave the way to the low-cost and large-scale application of PBAs in all-climate sodium-ion batteries.

Prussian Blue Analogues with Optimized Crystal Plane Orientation and Low Crystal Defects toward 450†Wh kg-1 Alkali-Ion Batteries.

Prussian blue analogues (PBAs) have been regarded as promising cathode materials for alkali-ion batteries owing to their high theoretical energy density and low cost. However, the high water and vacancy content of PBAs lower their energy density and bring safety issues, impeding their large-scale application. Herein, a facile "potassium-ions assisted" strategy is proposed to synthesize highly crystallized PBAs. By manipulating the dominant crystal plane and suppressing vacancies, the as-prepared PBAs exhibit increased redox potential resulting in high energy density up to ≈450 Wh kg-1 , which is at the same level of the well-known LiFePO4 cathodes for lithium-ion batteries. Remarkably, unconventional highly-reversible phase evolution and redox-active pairs were identified by multiple in situ techniques for the first time. The preferred guest-ion storage sites and migration mechanism were systematically analysed through theoretical calculations. We believe these results could inspire the design of safe with high energy density.

Stabilizing Low-Valence Single Atoms by Constructing Metalloid Tungsten Carbide Supports for Efficient Hydrogen Oxidation and Evolution.

Designing novel single-atom catalysts (SACs) supports to modulate the electronic structure is crucial to optimize the catalytic activity, but rather challenging. Herein, a general strategy is proposed to utilize the metalloid properties of supports to trap and stabilize single-atoms with low-valence states. A series of single-atoms supported on the surface of tungsten carbide (M-WCx , M=Ru, Ir, Pd) are rationally developed through a facile pyrolysis method. Benefiting from the metalloid properties of WCx , the single-atoms exhibit weak coordination with surface W and C atoms, resulting in the formation of low-valence active centers similar to metals. The unique metal-metal interaction effectively stabilizes the low-valence single atoms on the WCx surface and improves the electronic orbital energy level distribution of the active sites. As expected, the representative Ru-WCx exhibits superior mass activities of 7.84 and 62.52 A mgRu -1 for the hydrogen oxidation and evolution reactions (HOR/HER), respectively. In-depth mechanistic analysis demonstrates that an ideal dual-sites cooperative mechanism achieves a suitable adsorption balance of Had and OHad , resulting in an energetically favorable Volmer step. This work offers new guidance for the precise construction of highly active SACs.

A Disordered Rubik's Cube-Inspired Framework for Sodium-Ion Batteries with Ultralong Cycle Lifespan.

Sodium-ion batteries (SIBs) with fast-charge capability and long lifespan could be applied in various sustainable energy storage systems, from personal devices to grid storage. Inspired by the disordered Rubik's cube, here, we report that the high-entropy (HE) concept can lead to a very substantial improvement in the sodium storage properties of hexacyanoferrate (HCF). An example of HE-HCF has been synthesized as a proof of concept, which has achieved impressive cycling stability over 50 000 cycles and an outstanding fast-charging capability up to 75 C. Remarkable air stability and all-climate performance are observed. Its quasi-zero-strain reaction mechanism and high sodium diffusion coefficient have been measured and analyzed by multiple in situ techniques and density functional theory calculations. This strategy provides new insights into the development of advanced electrodes and provides the opportunity to tune electrochemical performance by tailoring the atomic composition.

Lattice Distortion and H-passivation in Pure Carbon Electrocatalysts for Efficient and Stable Two-electron Oxygen Reduction to H2 O2.

The exploration of inexpensive and efficient catalysts for oxygen reduction reaction (ORR) is crucial for chemical and energy industries. Carbon materials have been proved promising with different catalysts enabling 2 and 4e- ORR. Nevertheless, their ORR activity and selectivity is still complex and under debate in many cases. Many structures of these active carbon materials are also chemically unstable for practical implementations. Unlike the well-discussed structures, this work presents a strategy to promote efficient and stable 2e- ORR of carbon materials through the synergistic effect of lattice distortion and H-passivation (on the distorted structure). We show how these structures can be formed on carbon cloth, and how the reproducible chemical adsorption can be realized on these structures for efficient and stable H2 O2 production. The work here gives not only new understandings on the 2e- ORR catalysis, but also the robust catalyst which can be directly used in industry.

Ball Milling Solid-State Synthesis of Highly Crystalline Prussian Blue Analogue Na2-x MnFe(CN)6 Cathodes for All-Climate Sodium-Ion Batteries.

With a series of merits, Prussian blue analogs (PBAs) have been considered as superior cathode materials for sodium-ion batteries (SIBs). Their commercialization, however, still suffers from inferior stability, considerable [Fe(CN)6 ] defects and interstitial water in the framework, which are related to the rapid crystal growth. Herein, a "water-in-salt" nanoreactor is proposed to synthesize highly crystallized PBAs with decreased defects and water, which show both superior specific capacity and rate capability in SIBs. The air-stability, all-climate, and full-cell properties of our PBA have also been evaluated, and it exhibits enhanced electrochemical performance and higher volume yield than its counterpart synthesized via the water-based co-precipitation method. Furthermore, their highly reversible sodium-ion storage behavior has been measured and identified via multiple in situ techniques. This work could pave the way for the PBA-based SIBs in grid-scale energy-storage systems.

Critical Advances in Ambient Air Operation of Nonaqueous Rechargeable Li-Air Batteries.

Over the past few years, great attention has been given to nonaqueous lithium-air batteries owing to their ultrahigh theoretical energy density when compared with other energy storage systems. Most of the research interest, however, is dedicated to batteries operating in pure or dry oxygen atmospheres, while Li-air batteries that operate in ambient air still face big challenges. The biggest challenges are H2 O and CO2 that exist in ambient air, which can not only form byproducts with discharge products (Li2 O2 ), but also react with the electrolyte and the Li anode. To this end, recent progress in understanding the chemical and electrochemical reactions of Li-air batteries in ambient air is critical for the development and application of true Li-air batteries. Oxygen-selective membranes, multifunctional catalysts, and electrolyte alternatives for ambient air operational Li-air batteries are presented and discussed comprehensively. In addition, separator modification and Li anode protection are covered. Furthermore, the challenges and directions for the future development of Li-air batteries are presented.

Li2 S-Based Li-Ion Sulfur Batteries: Progress and Prospects.

The great demand for high-energy-density batteries has driven intensive research on the Li-S battery due to its high theoretical energy density. Consequently, considerable progress in Li-S batteries is achieved, although the lithium anode material is still challenging in terms of lithium dendrites and its unstable interface with electrolyte, impeding the practical application of the Li-S battery. Li2 S-based Li-ion sulfur batteries (LISBs), which employ lithium-metal-free anodes, are a convenient and effective way to avoid the use of lithium metal for the realization of practical Li-S batteries. Over the past decade, studies on LISBs are carried out to optimize their performance. Herein, the research progress and challenges of LISBs are reviewed. Several important aspects of LISBs, including their working principle, the physicochemical properties of Li2 S, Li2 S cathode material composites, LISBs full batteries, and electrolyte for Li2 S cathode, are extensively discussed. In particular, the activation barrier in the initial charge process is fundamentally analyzed and the mechanism is discussed in detail, based on previous reports. Finally, perspectives on the future direction of the research of LISBs are proposed.

The Dual Functions of Defect-Rich Carbon Nanotubes as Both Conductive Matrix and Efficient Mediator for LiS Batteries.

LiS batteries are considered a promising energy storage system owing to the great abundance of sulfur and its high specific capacity. Polysulfide shuttling and sluggish reaction kinetics in sulfur cathodes significantly degrade the cycle life of LiS batteries. A modified method is employed to create defects in carbon nanotubes (CNTs), anchoring polysulfides, and accelerating electrochemical reactions. The defect-rich CNTs (D-CNT) enable dramatic improvement in both cycling and rate performance. A specific capacity of 600 mAh g-1 with a current density of 0.5 C is achieved after 400 cycles, and even at a very high current density (5.0 C), a specific capacity of 434 mAh g-1 is observed. Cycling stability up to 1000 cycles is also achieved under the conditions of high sulfur loading and lean electrolyte. Theoretical calculations revealed that the improvement is mainly attributable to the electronic structure of defect-rich carbon, which has higher binding energy with polysulfides because of the upshift of the p-band center. Furthermore, rotating disk electrode measurements demonstrate that the defect-rich carbon can accelerate the polysulfide conversion process. It is anticipated that this new design strategy can be the starting point for mediator-like carbon materials with good conductivity and high catalytic activity for LiS batteries.

General Synthesis of Single-Atom Catalysts for Hydrogen Evolution Reactions and Room-Temperature Na-S Batteries.

Herein, we report a comprehensive strategy to synthesize a full range of single-atom metals on carbon matrix, including V, Mn, Fe, Co, Ni, Cu, Ge, Mo, Ru, Rh, Pd, Ag, In, Sn, W, Ir, Pt, Pb, and Bi. The extensive applications of various SACs are manifested via their ability to electro-catalyze typical hydrogen evolution reactions (HER) and conversion reactions in novel room-temperature sodium sulfur batteries (RT-Na-S). The enhanced performances for these electrochemical reactions arisen from the ability of different single active atoms on local structures to tune their electronic configuration. Significantly, the electrocatalytic behaviors of diverse SACs, assisted by density functional theory calculations, are systematically revealed by in situ synchrotron X-ray diffraction and in situ transmission electronic microscopy, providing a strategic library for the general synthesis and extensive applications of SACs in energy conversion and storage.

Component-Interaction Reinforced Quasi-Solid Electrolyte with Multifunctionality for Flexible Li-O2 Battery with Superior Safety under Extreme Conditions.

High-performance flexible lithium-oxygen (Li-O2 ) batteries with excellent safety and stability are urgently required due to the rapid development of flexible and wearable devices. Herein, based on an integrated solid-state design by taking advantage of component-interaction between poly(vinylidene fluoride-co-hexafluoropropylene) and nanofumed silica in polymer matrix, a stable quasi-solid-state electrolyte (PS-QSE) for the Li-O2 battery is proposed. The as-assembled Li-O2 battery containing the PS-QSE exhibits effectively improved anodic reversibility (over 200 cycles, 850 h) and cycling stability of the battery (89 cycles, nearly 900 h). The improvement is attributed to the stability of the PS-QSE (including electrochemical, chemical, and mechanical stability), as well as the effective protection of lithium anode from aggressive soluble intermediates generated in cathode. Furthermore, it is demonstrated that the interaction among the components plays a pivotal role in modulating the Li-ion conducting mechanism in the as-prepared PS-QSE. Moreover, the pouch-type PS-QSE based Li-O2 battery also shows wonderful flexibility, tolerating various deformations thanks to its integrated solid-state design. Furthermore, holes can be punched through the Li-O2 battery, and it can even be cut into any desired shape, demonstrating exceptional safety. Thus, this type of battery has the potential to meet the demands of tailorability and comformability in flexible and wearable electronics.

2D Titania-Carbon Superlattices Vertically Encapsulated in 3D Hollow Carbon Nanospheres Embedded with 0D TiO2 Quantum Dots for Exceptional Sodium-Ion Storage.

Two-dimensional (2D) superlattices offer promising technological opportunities in tuning the intercalation chemistry of metal ions. Now, well-ordered 2D superlattices of monolayer titania and carbon with tunable interlayer-spacing are synthesized by a molecularly mediated thermally induced approach. The 2D superlattices are vertically encapsulated in hollow carbon nanospheres, which are embedded with TiO2 quantum dots, forming a 0D-2D-3D multi-dimensional architecture. The multi-dimensional architecture with the 2D superlattices encapsulated inside exhibits a near zero-strain characteristic and enriched electrochemical reactivity, achieving a highly efficient Na+ storage performance with exceptional rate capability and superior long-term cyclability.

General π-Electron-Assisted Strategy for Ir, Pt, Ru, Pd, Fe, Ni Single-Atom Electrocatalysts with Bifunctional Active Sites for Highly Efficient Water Splitting.

Both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are crucial to water splitting, but require alternative active sites. Now, a general π-electron-assisted strategy to anchor single-atom sites (M=Ir, Pt, Ru, Pd, Fe, Ni) on a heterogeneous support is reported. The M atoms can simultaneously anchor on two distinct domains of the hybrid support, four-fold N/C atoms (M@NC), and centers of Co octahedra (M@Co), which are expected to serve as bifunctional electrocatalysts towards the HER and the OER. The Ir catalyst exhibits the best water-splitting performance, showing a low applied potential of 1.603 V to achieve 10 mA cm-2 in 1.0 m KOH solution with cycling over 5 h. DFT calculations indicate that the Ir@Co (Ir) sites can accelerate the OER, while the Ir@NC3 sites are responsible for the enhanced HER, clarifying the unprecedented performance of this bifunctional catalyst towards full water splitting.

Capillary-Induced Ge Uniformly Distributed in N-Doped Carbon Nanotubes with Enhanced Li-Storage Performance.

Germanium (Ge) is a prospective anode material for lithium-ion batteries, as it possesses large theoretical capacity, outstanding lithium-ion diffusivity, and excellent electrical conductivity. Ge suffers from drastic capacity decay and poor rate performance, however, owing to its low electrical conductivity and huge volume expansion during cycling processes. Herein, a novel strategy has been developed to synthesize a Ge@N-doped carbon nanotubes (Ge@N-CNTs) composite with Ge nanoparticles uniformly distributed in the N-CNTs by using capillary action. This unique structure could effectively buffer large volume expansion. When evaluated as an anode material, the Ge@N-CNTs demonstrate enhanced cycling stability and excellent rate capabilities.

Self-Assembled 3D Foam-Like NiCo2O4 as Efficient Catalyst for Lithium Oxygen Batteries.

A self-assembled 3D foam-like NiCo2O4 catalyst has been synthesized via a simple and environmental friendly approach, wherein starch acts as the template to form the unique 3D architecture. Interestingly, when employed as a cathode for lithium oxygen batteries, it demonstrates superior bifunctional electrocatalytic activities toward both the oxygen reduction reaction and the oxygen evolution reaction, with a relatively high round-trip efficiency of 70% and high discharge capacity of 10 137 mAh g(-1) at a current density of 200 mA g(-1), which is much higher than those in previously reported results. Meanwhile, rotating disk electrode measurements in both aqueous and nonaqueous electrolyte are also employed to confirm the electrocatalytic activity for the first time. This excellent performance is attributed to the synergistic benefits of the unique 3D foam-like structure and the intrinsically high catalytic activity of NiCo2O4 .

Binder-Free and Carbon-Free 3D Porous Air Electrode for Li-O2 Batteries with High Efficiency, High Capacity, and Long Life.

Pt-Gd alloy polycrystalline thin film is deposited on 3D nickel foam by pulsed laser deposition method serving as a whole binder/carbon-free air electrode, showing great catalytic activity enhancement as an efficient bifunctional catalyst for the oxygen reduction and evolution reactions in lithium oxygen batteries. The porous structure can facilitate rapid O2 and electrolyte diffusion, as well as forming a continuous conductive network throughout the whole energy conversion process. It shows a favorable cycle performance in the full discharge/charge model, owing to the high catalytic activity of the Pt-Gd alloy composite and 3D porous nickel foam structure. Specially, excellent cycling performance under capacity limited mode is also demonstrated, in which the terminal discharge voltage is higher than 2.5 V and the terminal charge voltage is lower than 3.7 V after 100 cycles at a current density of 0.1 mA cm(-2) . Therefore, this electrocatalyst is a promising bifunctional electrocatalyst for lithium oxygen batteries and this depositing high-efficient electrocatalyst on porous substrate with polycrystalline thin film by pulsed laser deposition is also a promising technique in the future lithium oxygen batteries research.

Graphite-Nanoplate-Coated Bi2 S3 Composite with High-Volume Energy Density and Excellent Cycle Life for Room-Temperature Sodium-Sulfide Batteries.

Graphite-nanoplate-coated Bi2 S3 composite (Bi2 S3 @C) has been prepared by a simple, scalable, and energy-efficient precipitation method combined with ball milling. The Bi2 S3 @C composite was used as the cathode material for sodium-sulfide batteries. It delivered an initial capacity of 550 mAh g(-1) and high stable specific energy in the range of 275-300 Wh kg(-1) at 0.1 C, with an enhanced capacity retention of 69 % over 100 cycles. The unique structure demonstrates superior cycling stability, with a capacity drop of 0.3 % per cycle over 100 cycles, compared with that of bare Bi2 S3 . The sodium storage mechanism of Bi2 S3 was investigated based on ex situ X-ray diffraction and scanning transmission electron microscopy.