Interfacial Spinel Local Interlocking Strategy Toward Structural Integrity in P3 Oxide Cathodes.

P3-layered transition oxide cathodes have garnered considerable attention owing to their high initial capacity, rapid Na+ kinetics, and less energy consumption during the synthesis process. Despite these merits, their practical application is hindered by the substantial capacity degradation resulting from unfavorable structural transformations, Mn dissolution and migration. In this study, we systematically investigated the failure mechanisms of P3 cathodes, encompassing Mn dissolution, migration, and the irreversible P3-O3' phase transition, culminating in severe structural collapse. To address these challenges, we proposed an interfacial spinel local interlocking strategy utilizing P3/spinel intergrowth oxide as a proof-of-concept material. As a result, P3/spinel intergrowth oxide cathodes demonstrated enhanced cycling performance. The effectiveness of suppressing Mn migration and maintaining local structure of interfacial spinel local interlocking strategy was validated through depth-etching X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and in situ synchrotron-based X-ray diffraction. This interfacial spinel local interlocking engineering strategy presents a promising avenue for the development of advanced cathode materials for sodium-ion batteries.

Linearly Interlinked Fe-Nx -Fe Single Atoms Catalyze High-Rate Sodium-Sulfur Batteries.

Linearly interlinked single atoms offer unprecedented physiochemical properties, but their synthesis for practical applications still poses significant challenges. Herein, linearly interlinked iron single-atom catalysts that are loaded onto interconnected carbon channels as cathodic sulfur hosts for room-temperature sodium-sulfur batteries are presented. The interlinked iron single-atom exhibits unique metallic iron bonds that facilitate the transfer of electrons to the sulfur cathode, thereby accelerating the reaction kinetics. Additionally, the columnated and interlinked carbon channels ensure rapid Na+ diffusion kinetics to support high-rate battery reactions. By combining the iron atomic chains and the topological carbon channels, the resulting sulfur cathodes demonstrate effective high-rate conversion performance while maintaining excellent stability. Remarkably, even after 5000 cycles at a current density of 10 A g-1 , the Na-S battery retains a capacity of 325 mAh g-1 . This work can open a new avenue in the design of catalysts and carbon ionic channels, paving the way to achieve sustainable and high-performance energy devices.

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.

Sodium Layered/Tunnel Intergrowth Oxide Cathodes: Formation Process, Interlocking Chemistry, and Electrochemical Performance.

Manganese-based layered oxides are prospective cathode materials for sodium-ion batteries (SIBs) due to their low cost and high theoretical capacities. The biphasic intergrowth structure of layered cathode materials is essential for improving the sodium storage performance, which is attributed to the synergistic effect between the two phases. However, the in-depth formation mechanism of biphasic intergrowth materials remains unclear. Herein, the layered/tunnel intergrowth Na0.6MnO2 (LT-NaMO) as a model material was successfully prepared, and their formation processes and electrochemical performance were systematically investigated. In situ high-temperature X-ray diffraction displays the detailed evolution process and excellent thermal stability of the layered/tunnel intergrowth structure. Furthermore, severe structural strain and large lattice volume changes are significantly mitigated by the interlocking effect between the phase interfaces, which further enhances the structural stability of the cathode materials during the charging/discharging process. Consequently, the LT-NaMO cathode displays fast Na+ transport kinetics with a remarkable capacity retention of ∼70.5% over 300 cycles at 5C, and its assembled full cell with hard carbon also exhibits high energy density. These findings highlight the superior electrochemical performance of intergrowth materials due to interlocking effects between layered and tunnel structures and also provide unique insights into the construction of intergrowth cathode materials for SIBs.

A strategy for anode modification for future zinc-based battery application.

In the past several years, rechargeable zinc batteries, featuring the merits of low cost, environmental friendliness, easy manufacturing, and enhanced safety, have, attracted much attention. Zinc (Zn) anodes for zinc metal batteries play an important role. In this review, the fundamental understanding of these batteries and modification strategies to deal with the problematic issues for Zn anodes, including dendrite growth, corrosion, and the hydrogen evolution phenomenon will be summarized. The practical application of Zn anodes can still lead to Zn dendrites, various side reactions, and serious safety risks. Therefore, metal-free anodes for "rocking chair" zinc ion batteries to replace Zn anodes are systemically reviewed. The performance and the zinc storage mechanism of metal-free anodes will be discussed. Subsequently, a "rocking chair" zinc ion battery prototype selected as a recent example is assessed to explore the merits and demerits of Zn anodes and metal-free anodes. To conclude, a perspective on the future of zinc metal batteries and "rocking chair" zinc ion batteries is presented. It is hoped that this review may provide for further improvement of commercial rechargeable zinc batteries.

Na1.51 Fe[Fe(CN)6 ]0.87 ·1.83H2 O Hollow Nanospheres via Non-Aqueous Ball-Milling Route to Achieve High Initial Coulombic Efficiency and High Rate Capability in Sodium-Ion Batteries.

Prussian blue analogues (PBAs) have attracted extensive attention as cathode materials in sodium-ion batteries (SIBs) due to their low cost, high theoretical capacity, and facile synthesis process. However, it is of great challenge to control the crystal vacancies and interstitial water formed during the aqueous co-precipitation method, which are also the key factors in determining the electrochemical performance. Herein, an antioxidant and chelating agent co-assisted non-aqueous ball-milling method to generate highly-crystallized Na2- x Fe[Fe(CN)6 ]y with hollow structure is proposed by suppressing the speed and space of crystal growth. The as-prepared Na2- x Fe[Fe(CN)6 ]y hollow nanospheres show low vacancies and interstitial water content, leading to a high sodium content. As a result, the Na-rich Na1.51 Fe[Fe(CN)6 ]0.87 ·1.83H2 O hollow nanospheres exhibit a high initial Coulombic efficiency, excellent cycling stability, and rate performance via a highly reversible two-phase transition reaction confirmed by in situ X-ray diffraction. It delivers a specific capacity of 124.2 mAh g-1 at 17 mA g-1 , presenting ultra-high rate capability (84.1 mAh g-1 at 3400 mA g-1 ) and cycling stability (65.3% capacity retention after 1000 cycles at 170 mA g-1 ). Furthermore, the as-reported non-aqueous ball-milling method could be regarded as a promising method for the scalable production of PBAs as cathode materials for high-performance SIBs.

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.

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.

Self-assembling RuO2 nanogranulates with few carbon layers as an interconnected nanoporous structure for lithium-oxygen batteries.

Electrocatalysis for cathodic oxygen is of great significance for achieving high-performance lithium-oxygen batteries. Herein, we report a facile and green method to prepare an interconnected nanoporous three-dimensional (3D) architecture, which is composed of RuO2 nanogranulates coated with few layers of carbon. The as-prepared 3D nanoporous RuO2@C nanostructure can demonstrate a high initial specific discharge capacity of 4000 mA h g-1 with high round-trip efficiency of 95%. Meanwhile, the nanoporous RuO2@C could achieve stable cycling performance with a fixed capacity of 1500 mA h g-1 over 100 cycles. The terminal discharge and charge potentials of nanoporous RuO2@C are well maintained with minor potential variation of 0.14 and 0.13 V at the 100th cycle, respectively. In addition, the formation of discharge products is monitored by using in situ high-energy synchrotron X-ray diffraction (XRD).

Binder-Free 3D Integrated Ni@Ni3Pt Air Electrode for Zn-Air Batteries.

Developing an air electrode with high efficiency and stable performance is essential to improve the energy conversion efficiency and lifetime of zinc-air battery. Herein, Ni3Pt alloy is deposited on 3D nickel foam by a pulsed laser deposition method, working as a stable binder-free air electrode for rechargeable zinc-air batteries. The polycrystalline Ni3Pt alloy possesses high oxygen-conversion catalytic activity, which is highly desirable for the charge and discharge process in zinc-air battery. Meanwhile, this sample technique constructs an integrated and stable electrode structure, which not only has a 3D architecture of high conductivity and porosity but also produces a uniform Ni3Pt strongly adhering to the substrate, favoring rapid gas and electrolyte diffusion throughout the whole energy conversion process. Employed as an air electrode in zinc-air batteries, it exhibits a small charge and discharge gap of below 0.62 V at 10 mA cm-2, with long cycle life of 478 cycles under 10 min per cycle. Furthermore, benefitting from the structural advantages, a flexible device exhibits similar electrochemical performance even under the bending state. The high performance resulting from this type of integrated electrode in this work paves the way of a promising technique to fabricate air electrodes for zinc-air batteries.

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.

Morphology tuning of inorganic nanomaterials grown by precipitation through control of electrolytic dissociation and supersaturation.

The precise control of the morphology of inorganic materials during their synthesis is important yet challenging. Here we report that the morphology of a wide range of inorganic materials, grown by rapid precipitation from a metal cation solution, can be tuned during their crystallization from one- to three-dimensional (1D to 3D) structures without the need for capping agents or templates. This control is achieved by adjusting the balance between the electrolytic dissociation (α) of the reactants and the supersaturation (S) of the solutions. Low-α, weak electrolytes promoted the growth of anisotropic (1D and 2D) samples, with 1D materials favoured in particular at low S. In contrast, isotropic 3D polyhedral structures could only be prepared in the presence of strong electrolyte reactants (α ≈ 1) with low S. Using this strategy, a wide range of materials were prepared, including metal oxides, hydroxides, carbonates, molybdates, oxalates, phosphates, fluorides and iodate with a variety of morphologies.

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.

Carbon-Encapsulated Sn@N-Doped Carbon Nanotubes as Anode Materials for Application in SIBs.

Carbon-encapsulated Sn@N-doped carbon tubes with submicron diameters were obtained via the simple reduction of C@SnO2@N-doped carbon composites that were fabricated by a hydrothermal approach. Sn nanoparticles encapsulated in carbon layers were distributed uniformly on the surfaces of the N-doped carbon nanotubes. The electrochemical performances of the composites were systematically investigated as anode materials in sodium-ion batteries (SIBs). The composite electrode could attain a good reversible capacity of 398.4 mAh g-1 when discharging at 100 mA g-1, with capacity retention of 67.3% and very high Coulombic efficiency of 99.7% over 150 cycles. This good cycling performance, when compared to only 17.5 mAh g-1 delivered by bare Sn particles prepared via the same method without the presence of N-doped carbon, could be mainly ascribed to the uniform distribution of the precursor SnO2 on the substrate of N-doped carbon tubes with three-dimensional structure, which provides more reaction sites to reduce the diffusion distance of Na+, further facilitating Na+-ion diffusion and relieves the huge volume expansion during charging/discharging. These outcomes imply that such a Sn/C composite would provide more options as an anode candidate for SIBs.

Reverse Microemulsion Synthesis of Sulfur/Graphene Composite for Lithium/Sulfur Batteries.

Due to its high theoretical capacity, high energy density, and easy availability, the lithium-sulfur (Li-S) system is considered to be the most promising candidate for electric and hybrid electric vehicle applications. Sulfur/carbon cathode in Li-S batteries still suffers, however, from low Coulombic efficiency and poor cycle life when sulfur loading and the ratio of sulfur to carbon are high. Here, we address these challenges by fabricating a sulfur/carboxylated-graphene composite using a reverse (water-in-oil) microemulsion technique. The fabricated sulfur-graphene composite cathode, which contains only 6 wt % graphene, can dramatically improve the cycling stability as well as provide high capacity. The electrochemical performance of the sulfur-graphene composite is further enhanced after loading into a three-dimensional heteroatom-doped (boron and nitrogen) carbon-cloth current collector. Even at high sulfur loading (∼8 mg/cm2) on carbon cloth, this composite showed 1256 mAh/g discharge capacity with more than 99% capacity retention after 200 cycles.

Ultrafine Mn3O4 Nanowires/Three-Dimensional Graphene/Single-Walled Carbon Nanotube Composites: Superior Electrocatalysts for Oxygen Reduction and Enhanced Mg/Air Batteries.

The exploration of highly efficient catalysts for the oxygen reduction reaction to improve sluggish kinetics still remains a great challenge for advanced energy conversion and storage in metal/air batteries. In this work, ultrafine Mn3O4 nanowires/three-dimensional graphene/single-walled carbon nanotube catalysts with an electron transfer number of 3.95 (at 0.60 V vs Ag/AgCl) and kinetic current density of 21.7-28.8 mA cm-2 were developed via a microwave-irradiation-assisted hexadecyl trimethylammonium bromide (CTAB) surfactant procedure to greatly enhance the overall catalytic performance in Mg/air batteries. To match the electrochemical activity of the cathode catalysts, a large-scale Mg anode prepared with micropersimmon-like particles via a mechanical disintegrator and Mg(NO3)2-NaNO2-based electrolyte containing 1.0 wt % trihexyl(tetradecyl)phosphonium chloride ionic liquid were applied. Combining the ultrafine Mn3O4 nanowires/three-dimensional graphene/single-walled carbon nanotube as an efficient electrocatalyst for the oxygen reduction reaction and an Mg micro-/nanoscale anode in the novel electrolyte, the advanced Mg/air batteries demonstrated a high cell open circuit voltage (1.49 V), a high plateau voltage (1.34 V), and a long discharge time (4177 min) at 0.2 mA cm-1, showing a high energy density. Therefore, it is believed that this device configuration has great potential for application in new energy storage technologies.

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.

Highly Ordered Single Crystalline Nanowire Array Assembled Three-Dimensional Nb3O7(OH) and Nb2O5 Superstructures for Energy Storage and Conversion Applications.

Three-dimensional (3D) metal oxide superstructures have demonstrated great potentials for structure-dependent energy storage and conversion applications. Here, we reported a facile hydrothermal method for direct growth of highly ordered single crystalline nanowire array assembled 3D orthorhombic Nb3O7(OH) superstructures and their subsequent thermal transformation into monoclinic Nb2O5 with well preserved 3D nanowire superstructures. The performance of resultant 3D Nb3O7(OH) and Nb2O5 superstructures differed remarkably when used for energy conversion and storage applications. The thermally converted Nb2O5 superstructures as anode material of lithium-ion batteries (LiBs) showed higher capacity and excellent cycling stability compared to the Nb3O7(OH) superstructures, while directly hydrothermal grown Nb3O7(OH) nanowire superstructure film on FTO substrate as photoanode of dye-sensitized solar cells (DSSCs) without the need for further calcination exhibited an overall light conversion efficiency of 6.38%, higher than that (5.87%) of DSSCs made from the thermally converted Nb2O5 film. The high energy application performance of the niobium-based nanowire superstructures with different chemical compositions can be attributed to their large surface area, superior electron transport property, and high light utilization efficiency resulting from a 3D superstructure, high crystallinity, and large sizes. The formation process of 3D nanowire superstructures before and after thermal treatment was investigated and discussed based on our theoretical and experimental results.

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.

Porous AgPd-Pd Composite Nanotubes as Highly Efficient Electrocatalysts for Lithium-Oxygen Batteries.

Porous AgPd-Pd composite nanotubes (NTs) are used as an efficient bifunctional catalyst for the oxygen reduction and evolution reactions in lithium-oxygen batteries. The porous NT structure can facilitate rapid O2 and electrolyte diffusion through the NTs and provide abundant catalytic sites, forming a continuous conductive network throughout the entire energy conversion process, with excellent cycling performance.