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.

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.

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.

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.

A Metal-Free, Free-Standing, Macroporous Graphene@g-C3N4 Composite Air Electrode for High-Energy Lithium Oxygen Batteries.

The nonaqueous lithium oxygen battery is a promising candidate as a next-generation energy storage system because of its potentially high energy density (up to 2-3 kW kg(-1)), exceeding that of any other existing energy storage system for storing sustainable and clean energy to reduce greenhouse gas emissions and the consumption of nonrenewable fossil fuels. To achieve high energy density, long cycling stability, and low cost, the air electrode structure and the electrocatalysts play important roles. Here, a metal-free, free-standing macroporous graphene@graphitic carbon nitride (g-C3N4) composite air cathode is first reported, in which the g-C3N4 nanosheets can act as efficient electrocatalysts, and the macroporous graphene nanosheets can provide space for Li2O2 to deposit and also promote the electron transfer. The electrochemical results on the graphene@g-C3N4 composite air electrode show a 0.48 V lower charging plateau and a 0.13 V higher discharging plateau than those of pure graphene air electrode, with a discharge capacity of nearly 17300 mA h g(-1)(composite) . Excellent cycling performance, with terminal voltage higher than 2.4 V after 105 cycles at 1000 mA h g(-1)(composite) capacity, can also be achieved. Therefore, this hybrid material is a promising candidate for use as a high energy, long-cycle-life, and low-cost cathode material for lithium oxygen batteries.

A Facile Synthesis of High-Surface-Area Sulfur-Carbon Composites for Li/S Batteries.

Small-grained elemental sulfur is precipitated from sodium thiosulfate (Na2 S2 O3 ) in a carbon-containing oxalic acid (HOOC-COOH) solution through a novel spray precipitation method. Surface area analysis, elemental mapping, and transmission electron micrographs revealed that the spray-precipitated sulfur particles feature 11 times higher surface area compared to conventional precipitated sulfur, with homogeneous distribution in the carbon. Moreover, the scanning electron micrographs show that these high-surface-area sulfur particles are firmly adhered to and covered by carbon. This precipitated S-C composite exhibits high discharge capacity with about 75 % capacity retention. The initial discharge capacity was further improved to 1444 mA h g(-1) by inserting a free-standing single-walled carbon nanotube layer in between the cathode and the separator. Moreover, with the help of the fixed capacity charging technique, 91.6 % capacity retention was achieved.

The mechanism of the one-step synthesis of hollow-structured Li(3)VO(4) as an anode for lithium-ion batteries.

In recent years, the controlled synthesis of inorganic micro- and nanostructures with hollow interiors has attracted considerable attention because of their widespread potential applications. A feasible method for synthesizing Li3 VO4 by a template-free, solution synthesis of single-crystalline microboxes with well-defined non-spherical morphologies has been reported. This study provides the useful information to produce other hollow structure materials to the broad audience of readers. The formation of hollow structure and the influence of raw materials have been presented. The thus-synthesized Li3 VO4 exhibited significantly improved conductivity, rate capability, and cycling life compared to commercial graphite, synthesized Li4 Ti5 O12 , and previously reported Li3 VO4 .

Small things make a big difference: binder effects on the performance of Li and Na batteries.

Li and Na batteries are very important as energy storage devices for electric vehicles and smart grids. It is well known that, when an electrode is analysed in detail, each of the components (the active material, the conductive carbon, the current collector and the binder) makes a portion of contribution to the battery performance in terms of specific capacity, rate capability, cycle life, etc. However, there has not yet been a review on the binder, though there are already many review papers on the active materials. Binders make up only a small part of the electrode composition, but in some cases, they play an important role in affecting the cycling stability and rate capability for Li-ion and Na-ion batteries. Poly(vinylidene difluoride) (PVDF) has been the mainstream binder, but there have been discoveries that aqueous binders can sometimes make a battery perform better, not to mention they are cheaper, greener, and easier to use for electrode fabrication. In this review, we focus on several kinds of promising electrode materials, to show how their battery performance can be affected significantly by binder materials: anode materials such as Si, Sn and transitional metal oxides; cathode materials such as LiFePO4, LiNi1/3Co1/3Mn1/3O2, LiCoO2 and sulphur.

Simply mixed commercial red phosphorus and carbon nanotube composite with exceptionally reversible sodium-ion storage.

Recently, sodium ion batteries (SIBs) have been given intense attention because they are the most promising alternative to lithium ion batteries for application in renewable power stations and smart grid, owing to their low cost, their abundant natural resources, and the similar chemistry of sodium and lithium. Elemental phosphorus (P) is the most promising anode materials for SIBs with the highest theoretical capacity of 2596 mA h g(-1), but the commercially available red phosphorus cannot react with Na reversibly. Here, we report that simply hand-grinding commercial microsized red phosphorus and carbon nanotubes (CNTs) can deliver a reversible capacity of 1675 mA h g(-1) for sodium ion batteries (SIBs), with capacity retention of 76.6% over 10 cycles. Our results suggest that the simply mixed commercial red phosphorus and CNTs would be a promising anode candidate for SIBs with a high capacity and low cost.

Hollow structured Li3VO4 wrapped with graphene nanosheets in situ prepared by a one-pot template-free method as an anode for lithium-ion batteries.

To explore good anode materials of high safety, high reversible capacity, good cycling, and excellent rate capability, a Li3VO4 microbox with wall thickness of 40 nm was prepared by a one-pot and template-free in situ hydrothermal method. In addition, its composite with graphene nanosheets of about six layers of graphene was achieved. Both of them, especially the Li3VO4/graphene nanosheets composite, show superior electrochemical performance to the formerly reported vanadium-based anode materials. The composite shows a reversible capacity of 223 mAh g(-1) even at 20C (1C = 400 mAh g(-1)). After 500 cycles at 10C there is no evident capacity fading.

Structural Engineering of Prussian Blue Analogues Enabling All-Climate and Ultralong Cycling Sodium-Ion Batteries.

The development of cost-efficient, long-lifespan, and all-climate sodium-ion batteries is of great importance for advancing large-scale energy storage but is plagued by the lack of suitable cathode materials. Here, we report low-cost Na-rich Mn-based Prussian blue analogues with superior rate capability and ultralong cycling stability over 10,000 cycles via structural optimization with electrochemically inert Ni atoms. Their thermal stability, all-climate properties, and potential in full cells are investigated in detail. Multiple in situ characterizations reveal that the outstanding performances benefit from their highly reversible three-phase transformations and trimetal (Mn-Ni-Fe) synergistic effects. In addition, a high sodium diffusion coefficient and a low volume distortion of 2.3% are observed through in situ transmission electron microscopy and first-principles calculations. Our results provide insights into the structural engineering of Prussian blue analogues for advanced sodium-ion batteries in large-scale energy storage applications.

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.

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.

CuS nanoflakes, microspheres, microflowers, and nanowires: synthesis and lithium storage properties.

CuS nanostructured materials, including nanoflakes, microspheres composed of nanoflakes, microflowers, and nanowires have been selectively synthesized by a facile hydrothermal method using CuSO4 and thiourea as precursors under different conditions. The morphology of CuS particles were affected by the following synthetic parameters: temperature, time, surfactant, pH value, solvent, and concentration of the two precursors. The synthesized CuS nanomaterials were characterized by X-ray diffraction, Brunauer-Emmett-Teller N2 adsorption, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The electrochemical tests, including constant current charge-discharge and cyclic voltammetry, show the specific capacities of the different morphologies, as well as their rate capability. The nanowire electrode has near theoretical specific capacity and the best rate capability.

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.

Enhanced cycling performance of nanocrystalline Fe3O4/C as anode material for lithium-ion batteries.

Fe3O4-carbon composite was prepared by the sol-gel method. The crystal structure, morphology, and phases present in the product were investigated by X-ray diffraction and by scanning electron microscopy (SEM) combined with energy dispersive X-ray spectroscopy and field-emission SEM. Electrochemical characterization was performed using constant current charge-discharge testing and electrochemical impedance spectroscopy. The Fe3O4/C electrode has high initial columbic efficiency (87%) and outstanding cycling performance (775.3 mAh g(-1) after 90 cycles at a current density of 100 mA g(-1)).

One-step spray pyrolysis synthesized CuO-carbon composite combined with carboxymethyl cellulose binder as anode for lithium-ion batteries.

Copper oxide-carbon composite with hollow sphere structure has been synthesized by a one-step spray pyrolysis method and tested as anode material for lithium-ion batteries. Different analytical methods, including X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometry, thermogravimetric analysis, and systematic electrochemical tests were performed. The results demonstrate that the CuO-carbon composite in conjunction with carboxymethyl cellulose (CMC) binder has an excellent electrochemical performance, with a capacity of 577 mAh g(-1) up to 100 cycles. The usage of the water soluble binder, CMC, not only obviously improves the electrochemical performance, but also makes the electrode fabrication process much easier and more environmentally friendly.