Ganggang Zhao

Metal-Organic Framework-Derived Materials for Sodium Energy Storage

Recently, sodium-ion batteries (SIBs) are extensively explored and are regarded as one of the most promising alternatives to lithium-ion batteries for electrochemical energy conversion and storage, owing to the abundant raw material resources, low cost, and similar electrochemical behavior of elemental sodium compared to lithium. Metal-organic frameworks (MOFs) have attracted enormous attention due to their high surface areas, tunable structures, and diverse applications in drug delivery, gas storage, and catalysis. Recently, there has been an escalating interest in exploiting MOF-derived materials as anodes for sodium energy storage due to their fast mass transport resulting from their highly porous structures and relatively simple preparation methods originating from in situ thermal treatment processes. In this Review, the recent progress of the sodium-ion storage performances of MOF-derived materials, including MOF-derived porous carbons, metal oxides, metal oxide/carbon nanocomposites, and other materials (e.g., metal phosphides, metal sulfides, and metal selenides), as SIB anodes is systematically and completely presented and discussed. Moreover, the current challenges and perspectives of MOF-derived materials in electrochemical energy storage are discussed.

Preparation of S/N-codoped carbon nanosheets with tunable interlayer distance for high-rate sodium-ion batteries

The conventional strategies for obtaining S/N-codoped carbon materials suffer from a series of problems caused by their complicated experimental procedures. Here, S,N-codoped carbon nanosheets were firstly prepared by a solvent-free one-pot method, displaying an ultra-thin sheet-like structure, a tunable interlayer distance ranging from 0.37 nm to 0.41 nm, and a large surface area up to 809 m2 g−1. When they were used as an anode for sodium-ion batteries (SIBs), an outstanding sodium-ion storage performance of 380 mA h g−1 was acquired at 100 mA g−1, which can be attributed to the expanded interlayer distance caused by the introduction of the large covalent radius-sulfur. The initial coulombic efficiency improved to 60.9%, which may benefit from N-doping. Most importantly, an excellent rate capability of ∼178 mA h g−1 was observed at a current density of 5 A g−1 after 5000 cycles, which is among best of the state-of-the-art carbon-based SIBs. Interestingly, the morphology of the obtained carbon materials can be tuned from bulk to flake by adjusting the sulfur content or temperature. Given this, this work provides a new method to construct co-doped carbon (especially tri-doped and multi-doped carbon) and shows that the strategy of co-doping of heteroatoms can effectively optimize the nano/microstructure and enhance the rate capability of the carbon materials.

N-rich carbon coated CoSnO3 derived from in situ construction of a Co–MOF with enhanced sodium storage performance

In this study, N-rich carbon coated interconnected CoSnO3 nanoboxes (CoSnO3–NCs) with controllable amounts of N-rich carbon ranging from 7.5% to 24.6% were firstly prepared by the carbonization of CoSnO3–MOFs. Impressively, the preparation of CoSnO3–MOFs has been realized for the first time by directly utilizing CoSnO3 as the precursor under solvent-free conditions, bridging between the cobalt(II) ion in the skeleton of CoSnO3 and the 2-methylimidazole. Interestingly, the growth of these CoSnO3–MOFs can be manipulated by changing the amount of 2-methylimidazole used, resulting in a tunable N-rich carbon content. Furthermore, the electrochemical storage behavior of these materials for SIBs was initially explored. Compared with the pure CoSnO3, the as-resulted CoSnO3–NC materials showed largely enhanced sodium storage performance with a reversible capacity of 493.9 mA h g−1 at a current density of 0.1 A g−1 after 100 cycles. Moreover, the as-prepared materials showed an excellent high rate storage performance with a remarkable capacity of 273.8 mA h g−1 at 1 A g−1 after 1000 cycles. This work provides a new approach for constructing Co–MOFs as well as providing an efficient N-rich carbon-coating route, which may be expanded to other Co-based oxides and can greatly expand the development of new species of Co-based MOFs.

Multidimensional Evolution of Carbon Structures Underpinned by Temperature‐Induced Intermediate of Chloride for Sodium‐Ion Batteries

Abstract Different dimensions of carbon materials with various features have captured numerous interests due to their applications on the tremendous fields. Restricted by the raw materials and devices, the controlling of their morphology is a major challenge. Utilizing the catalytic features of the intermediates from the low‐cost salts and polymerization of 0D carbon quantum dots (CQDs), 0D CQDs are expected to self‐assemble into 1/2/3D carbon structures with the assistance of temperature‐induced intermediates (e.g., ZnO, Ni, and Cu) from the salts (ZnCl2, NiCl2, and CuCl). The formation mechanisms are illustrated as follows: 1) the “orient induction” to evoke “vine style” growth mechanism of ZnO; 2) the “dissolution–precipitation” of Ni; and 3) the “surface adsorption self‐limited” of Cu. Subsequently, the degree of graphitization, interlayer distance, and special surface area are investigated in detail. 1D structure from 700 °C as anode displays a high Na‐storage capacity of 301.2 mAh g−1 at 0.1 A g−1 after 200 cycles and 107 mAh g−1 at 5.0 A g−1 after 5000 cycles. Quantitative kinetics analysis confirms the fundamentals of the enhanced rate capacity and the potential region of Na‐insertion/extraction. This elaborate work opens up an avenue toward the design of carbon with multidimensions and in‐depth understanding of their sodium‐storage features.

Sulfur-doped carbon employing biomass-activated carbon as a carrier with enhanced sodium storage behavior

Restricted by their high specific surface area and porous structures, activated carbon (AC) materials display poor performances, such as a low initial coulombic efficiency in sodium-ion batteries (SIBs). Nevertheless, it is an ideal choice for carriers, where the high specific surface area is indispensable. Herein, a novel strategy to design S-doped carbon employing durian shell-based AC (DSAC) as the template is proposed and the effect of the amount of DSAC additive was investigated in detail. Impressively, an optimized amount of DSAC additive would contribute to the good dispersion of poly-2-thiophenemethanol (sulfur source) as well as an increased number of active sites for Na storage, thus resulting in excellent electrochemical performance. A high reversible specific capacity of 345 mA h g−1 was attained and the specific capacity of 264 mA h g−1 was retained after 200 cycles. In particular, a high initial coulombic efficiency of 56.02% and remarkable rate capability of 100.02 mA h g−1 were achieved at 5 A g−1 even after 4500 cycles. Meaningfully, the proposed route used to prepare carbon materials for SIBs can effectively facilitate the further application of AC and the construction of high-performance electrode materials for SIBs.

Synergistic effect of cross-linked carbon nanosheet frameworks and Sb on the enhancement of sodium storage performances

As an anode material for sodium-ion batteries (SIBs), antimony (Sb) has attracted significant interest due to its high theoretical specific capacity. However, it suffers from a huge volume change during the sodiation–desodiation process that leads to poor cyclability. Herein, cross-linked carbon nanosheet frameworks (CCNFs) and Sb nanoparticles (NPs) were combined to construct a high-performance anode material for SIBs. In this composite, Sb nanoparticles were tightly anchored on the carbon frameworks; this provided enhanced structural stability to Sb and prevented the agglomeration during the charge–discharge process. Sb provides a high specific capacity, and the carbon frameworks ensure structural integrity and conductive networks. Moreover, due to this synergistic effect, the as-prepared Sb/CCNFs composite exhibits an excellent cycle stability and rate performances. Considering both the capacity and rate property, the overall performances of the obtained Sb/CCNFs reach the highest level in comparison with those of the reported Sb/C composites. The reversible (charge) capacity can remain 549.3 mA h g−1 after 100 cycles at a current density of 100 mA g−1. Moreover, a superior rate performance is observed as the reversible capacity still reaches 318 mA h g−1 at a high current density of 3200 mA g−1. Therefore, this study proposes an effective methodology to improve the key performances of the SIB anode.

3D hollow porous carbon microspheres derived from Mn-MOFs and their electrochemical behavior for sodium storage

Extensive efforts have been put into developing new materials with a 3D hollow porous spherical structure for increasing their applications in energy storage. In this work, 3D hollow porous carbon microspheres (3DHPCMs) are firstly prepared by the carbonization and post acid-treatment of 3D hollow microspherical Mn-MOFs (3DMn-MOFs), showing a high surface area of 788.2 m2 g−1 and a diameter of about 2 μm. Importantly, this is the first time that the conversion from 1D nanorods to 3D hollow spheres of Mn-MOFs through regulating the amount of poly(vinylpyrrolidone) (PVP) has been realized. Besides, the sodium storage behavior of 3D hollow porous carbon microspheres is also firstly studied. When utilized as anodes for sodium ion batteries (SIBs), the 3DHPCMs deliver excellent electrochemical storage performances with a high specific capacity of 313.8 mA h g−1 at a current density of 100 mA g−1. Impressively, a high discharge specific capacity of 112.5 mA h g−1 is obtained at 5 A g−1. The outstanding electrochemical performances can be attributed to the 3D hollow porous microsphere structure, which can enhance the mechanical stability, buffer the volume expansion, and accelerate the transport of Na+ and electrons. This work provides a new route for the development of materials with a 3D hollow spherical structure.

Evaluating the influences of the sulfur content in precursors on the structure and sodium storage performances of carbon materials

As an efficient method to promote the electrochemical performances of carbon materials for sodium-ion batteries (SIBs), heteroatom (S, N, etc.) doping has attracted significant interest from researchers, and great efforts have been devoted to explore the functional mechanism of SIBs. Heteroatom doping enlarges the layer distance of carbon, provides more active sites, and enhances the conductivity for the promotion of sodium storage; however, the influences of heteroatom-containing precursors on the structures, morphologies and electrochemical sodium storage performances of carbon materials have rarely been explored. In this study, a series of S/N co-doped carbon materials (SNC) has been designed, and the influences of the S contents in precursors on the structures and morphologies of the carbon materials have been evaluated. Furthermore, the electrochemical sodium storage performances of the obtained materials have been investigated. With the introduction of S, the insertion/extraction behaviors of Na+ in the microcrystals of carbon materials were obviously enhanced. Meaningfully, the integrated influence of the precursor S content on the materials and sodium storage performances obtained in this study can contribute to the design and preparation of similar materials.