Due to massively growing demand arising from energy storage systems, sodium ion batteries (SIBs) have been recognized as the most attractive alternative to the current commercialized lithium ion batteries (LIBs) owing to the wide availability and accessibility of sodium. Unfortunately, the low energy density, inferior power density and poor cycle life are still the main issues for SIBs in the current drive to push the entire technology forward to meet the benchmark requirements for commercialization. Over the past few years, tremendous efforts have been devoted to improving the performance of SIBs, in terms of higher energy density and longer cycling lifespans, by optimizing the electrode structure or the electrolyte composition. In particular, among the established anode systems, those materials, such as metals/alloys, phosphorus/phosphides, and metal oxides/sulfides/selenides, that typically deliver high theoretical sodium-storage capacities have received growing interest and achieved significant progress. Although some review articles on electrodes for SIBs have been published already, many new reports on these anode materials are constantly emerging, with more promising electrochemical performance achieved via novel structural design, surface modification, electrochemical performance testing techniques, etc. So, we herein summarize the most recent developments on these high-performance anode materials for SIBs in this review. Furthermore, the different reaction mechanisms, the challenges associated with these materials, and effective approaches to enhance performance are discussed. The prospects for future high-energy anodes in SIBs are also discussed.

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Recent progress on sodium ion batteries: potential high-performance anodes

The rational design of an efficient and inexpensive electrocatalyst based on earth-abundant 3d transition metals (TMs) for the hydrogen evolution reaction still remains a significant challenge in the renewable energy area. Herein, a novel and effective approach is developed for synthesizing ultrafine Co nanoparticles encapsulated in nitrogen-doped carbon nanotubes (N-CNTs) grafted onto both sides of reduced graphene oxide (rGO) (Co@N-CNTs@rGO) by direct annealing of GO-wrapped core-shell bimetallic zeolite imidazolate frameworks. Benefiting from the uniform distribution of Co nanoparticles, the in-situ-formed highly graphitic N-CNTs@rGO, the large surface area, and the abundant porosity, the as-fabricated Co@N-CNTs@rGO composites exhibit excellent electrocatalytic hydrogen evolution reaction (HER) activity. As demonstrated in electrochemical measurements, the composites can achieve 10 mA cm-2 at low overpotential with only 108 and 87 mV in 1 m KOH and 0.5 m H2 SO4 , respectively, much better than most of the reported Co-based electrocatalysts over a wide pH range. More importantly, the synthetic strategy is versatile and can be extended to prepare other binary or even ternary TMs@N-CNTs@rGO (e.g., Co-Fe@N-CNTs@rGO and Co-Ni-Cu@N-CNTs@rGO). The strategy developed here may open a new avenue toward the development of nonprecious high-performance HER catalysts.

Ultrafine Co Nanoparticles Encapsulated in Carbon-Nanotubes-Grafted Graphene Sheets as Advanced Electrocatalysts for the Hydrogen Evolution Reaction.

Exploration of high-efficiency, economical, and ultrastable electrocatalysts for the oxygen reduction reaction (ORR) to substitute precious Pt is of great significance in electrochemical energy conversion devices. Single-atom catalysts (SACs) have sparked tremendous interest for their maximum atom-utilization efficiency and fascinating properties. Therefore, the development of effective synthetic methodology toward SACs becomes highly imperative yet still remains greatly challenging. Herein, a reliable SiO2 -templated strategy is elaborately designed to synthesize atomically dispersed Fe atoms anchored on N-doped carbon nanospheres (denoted as Fe-N-C HNSs) using the cheap and sustainable biomaterial of histidine (His) as the N and C precursor. By virtue of the numerous atomically dispersed Fe-N4 moieties and unique spherical hollow architecture, the as-fabricated Fe-N-C HNSs exhibit excellent ORR performance in alkaline medium with outstanding activity, high long-term stability, and superior tolerance to methanol crossover, exceeding the commercial Pt/C catalyst and most previously reported non-precious-metal catalysts. This present synthetic strategy will provide new inspiration to the fabrication of various high-efficiency single-atom catalysts for diverse applications.

Atomic Fe Dispersed on N-Doped Carbon Hollow Nanospheres for High-Efficiency Electrocatalytic Oxygen Reduction

Metal-Organic Frameworks for Batteries

Carbon materials derived from metal-organic frameworks (MOFs) have attracted much attention in the field of scientific research in recent years because of their advantages of excellent electron conductivity, high porosity, and diverse applications. Tremendous efforts are devoted to improving their chemical and physical properties, including optimizing the morphology and structure of the carbon materials, compositing them with other materials, and so on. Here, many kinds of carbon materials derived from metal-organic frameworks are introduced with a particular focus on their promising applications in batteries (lithium-ion batteries, lithium-sulfur batteries, and sodium-ion batteries), supercapacitors (metal oxide/carbon and metal sulfide/carbon), electrocatalytic reactions (oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction), water treatment (MOF-derived carbon and other techniques), and other possible fields. To close, some existing problem and corresponding possible solutions are proposed based on academic knowledge from the reported literature, along with a great deal of experimental experience.

Applications of Metal-Organic-Framework-Derived Carbon Materials.

Sponge-like composites assembled by cobalt sulfides quantum dots (Co9S8 QD), mesoporous hollow carbon polyhedral (HCP) matrix, and a reduced graphene oxide (rGO) wrapping sheets are synthesized by a simultaneous thermal reduction, carbonization, and sulfidation of zeolitic imidazolate frameworks@GO precursors. Specifically, Co9S8 QD with size less than 4 nm are homogenously embedded within HCP matrix, which is encapsulated in macroporous rGO, thereby leading to the double carbon-confined hierarchical composites with strong coupling effect. Experimental data combined with density functional theory calculations reveal that the presence of coupled rGO not only prevents the aggregation and excessive growth of particles, but also expands the lattice parameters of Co9S8 crystals, enhancing the reactivity for sodium storage. Benefiting from the hierarchical porosity, conductive network, structural integrity, and a synergistic effect of the components, the sponge-like composites used as binder-free anodes manifest outstanding sodium-storage performance in terms of excellent stable capacity (628 mAh g−1 after 500 cycles at 300 mA g−1) and exceptional rate capability (529, 448, and 330 mAh g−1 at 1600, 3200, and 6400 mA g−1). More importantly, the synthetic method is very versatile and can be easily extended to fabricate other transition-metal-sulfides-based sponge-like composites with excellent electrochemical performances.

General Synthesis of Dual Carbon‐Confined Metal Sulfides Quantum Dots Toward High‐Performance Anodes for Sodium‐Ion Batteries

Construction of hybrid hollow architectures by in-situ rooting ultrafine ZnS nanorods within porous carbon polyhedra for enhanced lithium storage properties

Transition metal chalcogenides represent a class of the most promising alternative electrode materials for high-performance lithium-ion batteries (LIBs) owing to their high theoretical capacities. However, they suffer from large volume expansion, particle agglomeration, and low conductivity during charge/discharge processes, leading to unsatisfactory energy storage performance. In order to address these issues, we rationally designed three-dimensional (3D) hybrid composites consisting of ZnSe nanodots uniformly confined within a N-doped porous carbon network (ZnSe ND@N-PC) obtained via a convenient pyrolysis process. When used as anodes for LIBs, the composites exhibited outstanding electrochemical performance, with a high reversible capacity (1,134 mA·h·g−1 at a current density of 600 mA·g−1 after 500 cycles) and excellent rate capability (696 and 474 mA·h·g−1 at current densities of 6.4 and 12.8 A·g−1, respectively). The significantly improved lithium storage performance can be attributed to the 3D architecture of the hybrid composites, which not only mitigated the internal mechanical stress induced by the volume change and formed a 3D conductive network during cycling, but also provided a large reactive area and reduced the lithium diffusion distance. The strategy reported here may open a new avenue for the design of other multifunctional composites towards high-performance energy storage devices.

Embedding ZnSe nanodots in nitrogen-doped hollow carbon architectures for superior lithium storage

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General Synthesis of Dual Carbon‐Confined Metal Sulfides Quantum Dots Toward High‐Performance Anodes for Sodium‐Ion Batteries

Construction of hybrid hollow architectures by in-situ rooting ultrafine ZnS nanorods within porous carbon polyhedra for enhanced lithium storage properties

Embedding ZnSe nanodots in nitrogen-doped hollow carbon architectures for superior lithium storage