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Layered sodium transition metal (TM) oxides exhibit great potential as high energy density cathode materials for sodium-ion batteries (SIBs). The large Na ions, nevertheless, adopts various coordination environments that are dependent of the sodium concentration, giving rise to cyclical gliding of TM layers and P-O phase transitions upon Na extraction/insertion process. The detrimental interlayer-gliding induced phase transformations lead to deteriorated round-trip energy efficiency, rate capability and cycling stability of electrodes. Herein, we demonstrate a shear-resistant interface via the supersaturation of lithium to overcome the interlayer-gliding behavior and inhibit the multiple P-O phase transitions in P2-type Na0.67Mn0.67Ni0.33O2. The results indicate that the nanoscale interface is composed of lithium-enriched O3 nanodomains in the P2 phase matrix, resulting in smooth charge/discharge profiles and superior cycling stability of P2-type Na0.67Mn0.67Ni0.33O2 cathode under a high cut-off voltage of 4.5V. This work highlights the concept of modulating the interfacial shear stress for improving the long-term cycling stability of high-voltage layered cathode materials that suffer from severe phase transformations.

With great superiorities in energy density, rate capability and structural stability, Na3V2(PO4)2F3 (NVPF) has attracted much attentions as cathode of sodium ion battery (SIB), but it also faces challenges on its poor intrinsic electronic conductivity and the controversial de/sodiation mechanism. Herein, a series of Zr-doped NVPF coated by N-doped carbon layer (~5 nm in thickness, homogenously) materials are fabricated by a sol–gel method, and the optimized heteroatom-doping amounts of Zr and N doping improve intrinsic properties on enlarging lattice distance and enhancing electronic conductivity, respectively. Specifically, among all samples of Na3V2−xZrx(PO4)2F3/NC (NVPF-Zr-x/NC, x = 0, 0.01, 0.02, 0.05, and 0.1), the optimized electrode of NVPF-Zr-0.02/NC delivers high reversible capacities (119.2 mAh g−1 at 0.5 C), superior rate capability (98.1 mA h g−1 at 20 C) and excellent cycling performance. The structural evolution of NVPF-Zr-0.02/NC electrode, in-situ monitored by X-ray diffractometer, follows a step-wise Na-extraction/intercalation mechanism with reversible multi-phase changes, not just a solid-solution-reaction one. Full cells of NVPF-Zr-0.02/NC//hard carbon demonstrate high capacity (99.8 mA h g−1 at 0.5 C), high out-put voltage (3.5 V) and good cycling stability. This work is favorable to accelerate the development of high-performance cathode materials and explore possible redox reaction mechanisms of SIBs.

The research of borate materials as sodium-ion batteries (SIBs) anode is still in the early stages, but the boron polyoxoanions are attracting intense interest due to their low atomic weight and high electronegative features. In this work, FeBO3 was prepared with low-cost raw materials and evaluated as SIBs anode. The FeBO3 shows a high reversible capacity of 328 mAh/g at the current density of 0.4 A/g. In addition, the electrochemical performance of FeBO3 can be improved by carbon coating. The prepared carbon-coated FeBO3 composite has a reversible capacity of 426 mAh/g (at 0.4 A/g) and an outstanding rate capability of 272 mAh/g (at 1.6 A/g). Furthermore, the sodium storage mechanism of FeBO3 was studied by in-situ XRD and ex-situ XPS.

Porous carbon materials with a synergistically large specific surface area (SBET) and an adjustable structure are urgently needed to meet the demands of high-performance supercapacitors (SCs) and o...

Iron oxides are regarded as promising anodes for both lithium-ion batteries (LIBs) and potassium-ion batteries (KIBs) due to their high theoretical capacity, abundant reserves, and low cost, but they are also facing great challenges due to the sluggish reaction kinetics, low electronic conductivity, huge volume change, and unstable electrode interphases. Moreover, iron oxides are normally prepared at high temperature, forming large particles because of Ostwald ripening, and exhibiting low electronic/ionic conductivity and unfavorable mechanical stability. To address those issues, herein, we have synthesized ultra-small Fe3O4 nanodots encapsulated in layered carbon nanosheets (Fe3O4@LCS), using the coordination interaction between catechol and Fe3+, demonstrating fast reaction kinetics, high capacity, and typical capacitive-controlled electrochemical behaviors. Such Fe3O4@LCS nanocomposites were derived from coordination compounds with layered structures via van der Waals's force. Fe3O4@LCS-500 (annealed at 500 °C) nanocomposites have displayed attractive features of ultra-small particle size (∼5 nm), high surface area, mesoporous and layered feature. When used as anodes, Fe3O4@LCS-500 nanocomposites delivered exceptional electrochemical performances of high reversible capacity, excellent cycle stability and rate performance for both LIBs and KIBs. Such exceptional performances are highly associated with features of Fe3O4@LCS-500 nanocomposites in shortening Li/K ion diffusion length, fast reaction kinetics, high electronic/ionic conductivity, and robust electrode interphase stability.

Lithium–sulfur batteries are attracting more attention due to their high theoretical capacity and energy density. However, they have the problems of short cycling performance, low sulfur loading and shuttle effect; in order to overcome these problems, more efforts have been devoted to the exploration of effective host materials for sulfur confinement. Herein, we report a facile approach for the synthesis of nitrogen-doped porous carbon (NPC) nanosheets, derived from imine-based covalent organic frameworks (COFs), as the host material. In situ nitrogen doping is very uniform due to the inherited nitrogen element distributed uniformly in the COF skeleton. Sulfur-loaded NPC composites can achieve a high sulfur loading amount of 71.8% and enhanced lithium–sulfur battery performance, in terms of a high initial discharge capacity (1398 mA h g−1 at 0.1C) and good cycling properties (reversible capacity of 833 mA h g−1 after 250 cycles). The existence of nitrogen doped carbon nanosheets with a high surface area and controlled porosity can lead to effective immobilization of the polysulfides and simultaneous improvement of the reaction kinetics of the sulfur species. This design strategy provides an extended method for fabricating high performance cathodes for lithium–sulfur batteries.

Compared to inorganic electrodes, organic materials are regarded as promising electrodes for lithium-ion batteries (LIBs) due to the attractive advantages of light elements, molecular-level structural design, fast electron/ion transferring, favorable environmental impacts, and flexible feature, etc. Not only specific capacities but also working potentials of organic electrodes are reasonably tuned by polymerization, electron-donating/withdrawing groups, and multifunctional groups as well as conductive additives, which have attracted intensive attention. However, organic LIBs (OLIBs) are also facing challenges on capacity loss, side reactions, electrode dissolution, low electronic conductivity, and short cycle life, etc. Many strategies have been applied to tackle those challenges, and many inspiring results have been achieved in the last few decades. In this review, we have introduced the basic concepts of LIBs and OLIBs, followed by the typical cathode and anode materials with various physicochemical properties, redox reaction mechanisms, and evolutions of functional groups. Typical charge-discharge behaviors and molecular structures of organic electrodes are displayed. Moreover, effective strategies on addressing problems of organic electrodes are summarized to give some guidance on the synthesis of optimized organic electrodes for practical applications of OLIBs.

Metal fluoride (MF) conversion cathodes theoretically show higher gravimetric and volumetric capacities than Ni- or Co-based intercalation oxide cathodes, which makes metal fluoride-lithium batteries promising candidates for next-generation high-energy-density batteries. However, their high-energy characteristics are clouded by low-capacity utilization, large voltage hysteresis, and poor cycling stability of transition MF cathodes. A variety of reasons is responsible for this: poor reaction kinetics, low conductivities, unstable MF/electrolyte interfaces and dissolution of active species upon cycling. Herein, we combine the synthesis of the metal-organic-framework (MOF) with the low-temperature fluorination to prepare MOF-shaped CoF2@C nanocomposites that exhibit confinement of the CoF2 nanoparticles and efficient mixed-conducting wiring in the produced architecture. The ultrasmall CoF2 nanoparticles (5-20 nm on average) are uniformly covered by graphitic carbon walls and embedded in the porous carbon framework. Within the CoF2@C nanocomposite, the cross-linked carbon wall and interconnected nanopores serve as electron- and ion-conducting pathways, respectively, enabling a highly reversible conversion reaction of CoF2. As a result, the produced CoF2@C composite cathodes successfully restrain the above-mentioned challenges and demonstrate high-capacity utilization of ∼500 mAh g-1 at 0.2C, good rate capability (up to 2C), and long-term cycle stability over 400 cycles. Overall, the presented study not only reports on a simple composite design to achieve high-energy characteristics in CoF2-Li batteries but also may provide a general solution for many other metal fluoride-lithium batteries.

Metal-organic frameworks (MOFs) with controllable shapes and sizes show a great potential in Li-S batteries. However, neither the relationship between shapes and specific capacity nor the influence of MOF particle size on cyclic stability have been fully established yet. Herein, MIL-96-Al with various shapes, forming hexagonal platelet crystals (HPC), hexagonal bipyramidal crystals (HBC), and hexagonal prismatic bipyramidal crystals (HPBC) were successfully prepared via co-solvent methods. Density functional theory (DFT) calculations demonstrate that the HBC shape with highly exposed (101) planes can effectively adsorb lithium polysulfides (LPS) during the charge/discharge process. By changing the relative proportion of the co-solvents, HBC samples with different particle sizes were prepared. When these MIL-96-Al crystals were used as sulfur host materials, it was found that those with the smaller size of HBC shape deliver the higher initial capacity. These investigations establish that different crystal planes have different adsorption abilities for LPS, and that the MOF particle size should be considered for a suitable sulfur host. More broadly, this work provides a strategy for designing sulfur hosts in Li-S batteries. This article is protected by copyright. All rights reserved.

Potassium ion batteries (PIBs) are expected to become the next large-scale energy storage candidates due to its low cost and abundant resources. And the covalent organic framework (COF), with designable periodic organic structure and ability to organize redox active groups predictably, has been considering as the promising organic electrode candidate for PIB. Herein, we report the facile synthesis of the cyano-COF with Co coordination via a facile microwave digestion reaction and its application in the high-energy potassium ion batteries for the first time. The obtained COF-Co material exhibits the enhanced π-π accumulation and abundant defects originated from the Co interaction with the two-dimensional layered sheet structure of COF, which are beneficial for its energy-storage application. Adopted as the inorganic-metal boosted organic electrode for PIBs, the COF-Co with Co coordination can promote the formation of the π-K+ interaction, which could lead to the activation of aromatic rings for potassium-ion storage. Besides, the porous two-dimensional layered structure of COF-Co with abundant defects can also promote the shortened diffusion distance of ion/electron with promoted K+ insertion/extraction ability. Enhanced cycling stability with large reversible capacity (371 mAh g-1 after 400 cycles at 100 mA g-1) and good rate properties (105 mAh g-1 at 2000 mA g-1) have been achieved for the COF-Co electrode.

Due to the adjustable structure and the broad application prospects in energy and other fields, the exploration of porous organic materials [metal-organic polymers (MOPs), covalent organic frameworks (COFs), etc.] has attracted extensive attention. In this work, an imine-induced metal-organic and covalent organic coexisting framework (Co-MOP@COF) hybrid was designed based on the combination between the amino units from the organic ligands of Co-MOP and the aldehyde groups from COF. The obtained Co-MOP@COF hybrid with layer-decorated microsphere morphology exhibited good electrochemical cycling performance (a large reversible capacity of 1020 mAh g-1 after 150 cycles at 100 mA g-1 and a reversible capacity of 396 mAh g-1 at 500 mA g-1 ) as the anode for Li-ion batteries. The coexisting framework structure endowed the Co-MOP@COF hybrid with more surface area exposed in the exfoliated COF structure, which provided rapid Li-ion diffusion, better electrolyte infiltration, and effective activation of functional groups. Therefore, the Co-MOP@COF hybrid material achieved an enhanced Li storage mechanism involving multi-electron redox reactions, related to the CoII center and organic groups (C=C groups of benzene rings and C=N groups), and furthermore improved electrochemical performance.

Sodium-based rechargeable batteries are very promising energy storage and conversion systems owing to their wide availability and the low cost of Na resources, which is beneficial to large-scale electric energy storage applications in future. In the context of attempting to achieve high-energy densities and low cost, multi-electron reaction materials for both cathodes and anodes are attracting significant attention due to high specific capacities involved. Here, we present a brief review on recently reported multi-electron reaction materials for sodium-based batteries. We mostly concentrate on true multi-electron reactions that involve individually valence changes greater than one per redox center, but in addition include materials in the discussion, which undergo multi-electron processes per formula unit. The theoretical gravimetric and volumetric (expanded state) capacities are studied for a broad range of examples. Then, the practically achievable volumetric energy density and specific energy of Na cells with hard carbon, sodium (Na), and phosphorus (P) anodes are compared. For this purpose, various data are recalculated and referred to the same basis cell. The results show the potential superiority of the cells using multi-electron reaction materials and provide an intuitive understanding of the practically achievable energy densities in future Na-based rechargeable batteries. However, these multi-electron reaction materials are facing several key challenges, which are preventing their high-performance in current cells. In order to overcome them, general strategies from particle design to electrolyte modification are reviewed and several examples in both cathode and anode materials using such strategies are studied. Finally, future trends and perspectives for achieving promising Na-based batteries with better performance are discussed.

Transition metal sulfides are regarded as a category of promising electrodes for alkaline ion batteries because of their high theoretical capacities, fast ionic conductivity and low cost, but they also face many challenges on large volume changes, sluggish kinetics and instability of solid electrolyte interphase (SEI). To tackle these issues, this work designs iron sulfide/molybdenum disulfide (FeS / MoS2) yolk-shell sphere electrodes coated by few-nanometer thick alumina film. Such alumina film is adopted to minimize side reactions, promote the formation of stable SEI, and enhance the mechanical stability of the electrode. Specifically, when used as anode materials at 100 mA g−1 in Li/Na/K-ion batteries, the coated electrode (ALD-40-E) can deliver reversible capacities of 1007, 570 and 367 mAh g−1 after 100 cycles, respectively, which are substantially larger than those of bare FeS / MoS2 electrode (ALD-0-E: 538, 311 and 213 mAh g−1) and FeS / MoS2 with direct alumina coating on powder surface (ALD-40-P: 429, 116 and 86 mAh g−1). Good electrochemical properties are mainly ascribed to the yolk-shell structure, and the alumina thin film on the electrode, which work synergistically to maintain the electrical contact, facilitate the ion/electron diffusion paths, accommodate volume change and preserve structural stability.

Magnesium aluminate spinel is of great importance for nuclear industry, and its structure, showing a great impact on properties, is sensitive to the composition. In order to explore the stoichiometric effect on structure and properties of spinels, several different spinel compositions with MgO· n Al 2 O 3 ( n = 0.5–2.4) were synthesized via solid state reaction. Synthetic samples were characterized by X-ray diffraction, scanning electron microscope and nanoindentation tests. The results of XRD and SEM indicate that the single-phase magnesia alumina spinels have been prepared successfully for the first time ranging from n = 0.667 to n = 1.5, which is beyond the previous reported ranges of n ≥ 0.91. The hardness and modulus decrease with increasing n, implying further that the nonstoichiometric spinel crystal structures are likely to exhibit superior mechanical properties.

Sodium-ion batteries (SIB) are regarded as the most promising competitors to lithium-ion batteries in spite of expected electrochemical disadvantages. Here a “cross-linking” strategy is proposed to mitigate the typical SIB problems. We present a SIB full battery that exhibits a working potential of 3.3 V and an energy density of 180 Wh kg–1 with good cycle life. The anode is composed of cross-linking hollow carbon sheet encapsulated CuP2 nanoparticles (CHCS-CuP2) and a cathode of carbon coated Na3V2(PO4)2F3 (C-NVPF). For the preparation of the CHCS-CuP2 nanocomposites, we develop an in situ phosphorization approach, which is superior to mechanical mixing. Such CHCS-CuP2 nanocomposites deliver a high reversible capacity of 451 mAh g–1 at 80 mA g–1, showing an excellent capacity retention ratio of 91% in 200 cycles together with good rate capability and stable cycling performance. Post mortem analysis reveals that the cross-linking hollow carbon sheet structure as well as the initially formed SEI layers are...

Nanoparticle-based electrode materials have sparked enormous excitement in the sodium-ion battery community because of potentially fast transport kinetics. However, they may suffer from many challenging static and dynamic problems, such as agglomeration of nanoparticles, high contact resistance, volume change, and instability of solid electrolyte interphase. Herein, we develop inter-connected 2D carbon nanosheets in which ultrasmall 0D Sb nanodots are embedded homogenously through a previously unexplored “top-down” strategy. Starting from the laminar structure K3Sb3P2O14, H3Sb3P2O14 nanosheets are exfoliated by ion exchange and then serve as templates for the synthesis of carbon sheets and Sb nanodots. Such combination of multi-dimensional and multi-scale nanostructures in the electrode materials lead to excellent electron/ion transport kinetics and pronounced integrity of the electrode structure on cycling, providing a promising pathway for developing advanced electrode materials in terms of reversibility, rate capability and cycle life.

© 2017, Tsinghua University Press and Springer-Verlag GmbH Germany. Activated graphene (AG) with various specific surface areas, pore volumes, and average pore sizes is fabricated and applied as a matrix for sulfur. The impacts of the AG pore structure parameters and sulfur loadings on the electrochemical performance of lithium-sulfur batteries are systematically investigated. The results show that specific capacity, cycling performance, and Coulombic efficiency of the batteries are closely linked to the pore structure and sulfur loading. An AG3/S composite electrode with a high sulfur loading of 72 wt.% exhibited an excellent long-term cycling stability (50% capacity retention over 1,000 cycles) and extra-low capacity fade rate (0.05% per cycle). In addition, when LiNO3 was used as an electrolyte additive, the AG3/S electrode exhibited a similar capacity retention and high Coulombic efficiency (∼98%) over 1,000 cycles. The excellent electrochemical performance of the series of AG3/S electrodes is attributed to the mixed micro/mesoporous structure, high surface area, and good electrical conductivity of the AG matrices and the well-distributed sulfur within the micro/mesopores, which is beneficial for electrical and ionic transfer during cycling. [Figure not available: see fulltext.].

Metal fluoride-lithium batteries with potentially high energy densities, even higher than lithium-sulfur batteries, are viewed as very promising candidates for next-generation lightweight and low-cost rechargeable batteries. However, so far, metal fluoride cathodes have suffered from poor electronic conductivity, sluggish reaction kinetics and side reactions causing high voltage hysteresis, poor rate capability, and rapid capacity degradation upon cycling. Herein, it is reported that an FeF3 @C composite having a 3D honeycomb architecture synthesized by a simple method may overcome these issues. The FeF3 nanoparticles (10-50 nm) are uniformly embedded in the 3D honeycomb carbon framework where the honeycomb walls and hexagonal-like channels provide sufficient pathways for the fast electron and Li-ion diffusion, respectively. As a result, the as-produced 3D honeycomb FeF3 @C composite cathodes even with high areal FeF3 loadings of 2.2 and 5.3 mg cm-2 offer unprecedented rate capability up to 100 C and remarkable cycle stability within 1000 cycles, displaying capacity retentions of 95%-100% within 200 cycles at various C rates, and ≈85% at 2C within 1000 cycles. The reported results demonstrate that the 3D honeycomb architecture is a powerful composite design for conversion-type metal fluorides to achieve excellent electrochemical performance in metal fluoride-lithium batteries.

With the porous feature, high aspect ratio and high electronic conductivity, nitrogen-doped one-dimensional carbon nanofibers can effectively shorten ionic transport pathways and enhance the intrinsic electronic conductivity of metal selenides electrodes, showing a great potential as anode material for the next-generation lithium-ion batteries (LIBs). In this work, we have synthesized nitrogen-doped carbon nanofibers encapsulated Cu2-xSe (N-CNFs@Cu2-xSe) with an average particle size of 20 nm, via electrospinning and in-situ selenization process, giving an excellent lithium storage capability. Specifically, such electrodes delivered a specific capacity of 1079.1 mA h g−1 at 0.1 A g−1 after 100 cycles, while 639.4 mA h g−1 at 2 A g−1 after 1000 cycles, exhibiting an ultralong cycle life. The gradually increased capacity was attributed to phase transformation of Cu2-xSe from crystalline to amorphous state, which leads to the capacity improvement from increased capacitive behavior. The in-situ X-ray diffraction harvest at the real time state of battery demonstrated the phase transition of Cu2-xSe with lithium and phase regeneration among cycles, verifying copper selenide has the features of the high reversibility of conversion reaction and superior thermostability. The high capacity and long cycling life of N CNFs@Cu2-xSe make it possible for great application potentials for high-performance lithium-ion batteries.

Sodium-ion batteries (SIBs) are recognized as an alternative to lithium ion batteries due to the abundance of sodium and potentially low cost of the whole battery system. One of the major challenges facing SIBs is to develop suitable anode materials with high capacity and long cycling life. Herein, we report the synthesis of porous carbon nanocage-Sn (PCNCs-Sn) nanocomposites as anodes of SIBs, demonstrating a high capacity of 828 mAh g −1 at 40 mA g −1 . The electrodes also exhibited good rate capabilities (up to 3C) and superior cycling performances (1000 cycles). Post-mortem analyses verified the efficient volume change restriction by carbon nanocages and the well-preserved porous structure. Theoretical calculations indicated that the pulverization of bare Sn electrodes could be ascribed to strong bonds formed between amorphous carbon and the discharge product (Na 15 Sn 4 ), which also deteriorated the conductivity. In contrast, the relatively weak interaction between Na 15 Sn 4 and graphitic carbon can maintain superior conductivity and structural stability for better cycling performance.

© 2016 The Royal Society of Chemistry. Lithium-ion batteries (LIBs) are widely implemented to power portable electronic devices and are increasingly in demand for large-scale applications. One of the major obstacles for this technology is still the low cost-efficiency of its electrochemical active materials and production processes. In this work, we present a novel impregnation-carbothermal reduction method to generate a LiFePO4-carbon paper hybrid electrode, which doesn't require a metallic current collector, polymeric binder or conducting additives to function as a cathode material in a LIB system. A shell of LiFePO4 crystals was grown in situ on carbon fibres during the carbonization of microcrystalline cellulose. The LiFePO4-carbon paper electrode achieved an initial reversible areal capacity of 197 μA h cm-2 increasing to 222 μA h cm-2 after 500 cycles at a current density of 0.1 mA cm-2. The hybrid electrode also demonstrated a superior cycling performance for up to 1000 cycles. The free-standing electrode could be potentially applied for flexible lithium-ion batteries.

This work introduces a simple microwave method for the preparation of α-Fe 2 O 3 nanoparticles with two different sizes. Both the materials were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller methods. The lithium storage properties were evaluated and compared in terms of their reversible capacity, rate capability and cycling performance. Interestingly, the electrode made of large particles (200–300 nm) show the reversible capacity of 1012 mA h g −1 , better rate capability and excellent cycling stability than those of the small particles (20–30 nm). The poor electrochemical performances of small particles can be ascribed to their agglomeration during repeated charging and discharge process. The agglomeration of small particles may substantially decrease the surface area, which results in the lack of sufficient electro active sites for electrochemical reaction.

Metal molybdates are regarding as promising electrode materials for next-generation lithium-ion batteries (LIBs). However, the poor electronic conductivity and sluggish ion diffusion are the two main obstacles that limit their electrochemical performances. In this work, self-assembled hierarchical Fe2(MoO4)3 microspheres with a thin amorphous shell (FMO-A) were prepared via a morphology-tunable and template-free hydrothermal method as an example of metal molybdates for LIBs. The morphologies were easily tunable by changing experimental parameters, such as the pH value, and reaction time. When applied as anode of LIBs, FMO-A delivered a high reversible capacity of 1138.2 mAh g−1 after 250 cycles at 100 mA g−1 and displayed remarkable rate performances. This is mainly ascribed to the unique hierarchical structure and high surface area of Fe2(MoO4)3 and the thin amorphous shell on providing low Gibbs free energy on redox reactions, reduced grain boundaries, isotropic nature, and buffering volume variations during cycles.

The lithium-sulfur battery is considered as one of the most promising energy storage systems and has received enormous attentions due to its high energy density and low cost. However, polysulfide dissolution and the resulting shuttle effects hinder its practical application unless very costly solutions are considered. Herein, a sulfur-rich polymer termed sulfur-limonene polysulfide is proposed as powerful electroactive material that uniquely combines decisive advantages and leads out of this dilemma. It is amenable to a large-scale synthesis by the abundant, inexpensive, and environmentally benign raw materials sulfur and limonene (from orange and lemon peels). Moreover, owing to self-protection and confinement of lithium sulfide and sulfur, detrimental dissolution and shuttle effects are successfully avoided. The sulfur-limonene-based electrodes (without elaborate synthesis or surface modification) exhibit excellent electrochemical performances characterized by high discharge capacities (≈1000 mA h g-1 at C/2) and remarkable cycle stability (average fading rate as low as 0.008% per cycle during 300 cycles).

Achieving rechargeable batteries with high-energy density, long cycle life and excellent rate capability is of significant importance for a vast energy-consuming society. Lithium sulfur (Li–S) batteries, attracting extensive attentions, are regarded as one of the most promising energy storage system. However, Li–S batteries are facing big challenges, owing to the fast capacity degradation, low Coulombic efficiency and poor rate capabilities. By adopting a dual confinement strategy, we successfully synthesized homogenous poly(3,4-ethylenedioxythiophene) (PEDOT) coated multi-chambered micro/mesoporous carbon nanocube encapsulated sulfur (P@CNC-S) composites. Sulfur is impregnated in individual interconnected multi-chambered micro/mesoporous carbon nanocubes, which act as the physical confinement and multilayered reservoirs for soluble lithium polysulfides. The PEDOT conductive polymer provides chemical bondings to soluble lithium polysulfides. When applied as cathodes in Li–S batteries, the P@CNC-S composites exhibited superior performances, including high specific capacities, long cycle life and outstanding high rate capabilities. Ex-situ TEM analysis confirmed the successful confinement of the dissolution of lithium polysulfides and volume expansion of the discharged product (Li2S), which could contribute to the high Coulombic efficiency and excellent cyclabilities.

© 2014 Elsevier B.V. Porous polymer membrane with a sandwich-like architecture has been prepared by coating poly(methyl methacrylate) (PMMA) on poly(vinylidene fluoride-co-hexafluoropylene) (PVDF-HFP) porous membranes. Field emission scanning electron microscopy analysis identified that the PMMA/PVDF-HFP porous polymer membrane consists of the stacking of several porous layers with one layer of large pores in the middle of the membrane. This unique sandwich-like structure provides large porosity and good affinity towards a liquid organic electrolyte, leading to a high electrolyte uptake of 342wt%, excellent electrolyte retention, and enhanced tolerance towards high temperature and fire. The gel polymer electrolyte membrane achieved a high ionic conductivity of 1.31mScm-1 with similar activation energy as the conventional Celgard 2400 separator in liquid electrolyte. The porous polymer electrolyte membrane also has an outstanding thermal and electrochemical stability. When applied in lithium ion batteries with LiFePO4 cathode and lithium metal anode, the PMMA/PVDF-HFP electrolyte membrane demonstrated high discharge capacity, enhanced high rate capability, and extended cycle life. The PMMA/PVDF-HFP porous polymer membrane could be employed as an integrated separator and electrolyte for lithium ion batteries with high safety.

Abandoned peanut shells, a common farm waste, have caused tremendous environmental pollution and huge waste deposits through burned and buried disposal approaches. In targeting to enhance the potential value of peanut shells and discover a new alternative candidate for lithium ion batteries, we adopted an easy to scale-up and highly repeated method to treat fresh and dry peanut shells via acid-treatment and pyrolysis, making porous structures on carbonized peanut shells. The pyrolysis process transformed the peanut shells to porous carbon (PC) materials in a quartz tube furnace at a series of temperatures from 500°C to 700°C in N2 under the condition of 40°C gradient temperatures with a heating rate of 2°C min−1. Scanning electron microscopy (SEM) images show that the irregular porous structures and hundreds of micropores are distributed on the PC materials. The cyclic voltammogram (CV) test and particle size analysis are employed to investigate their characteristics of voltammetry and particle size distribution. PC material obtained at 620°C (PC-620) exhibited good particle distribution, porous structure and less agglomerated particles. When applied as anode materials in lithium ion batteries, the PC-620 electrode displayed the high reversible capacity of 608 mAh g−1. Moreover, the cycling performance of PC-620 was the most stable, with a high Coulombic efficiency of 98.9% at the 20th cycle, demonstrating a reversible capacity of 418 mAh g−1, which is higher than the theoretical capacity of graphite. Most importantly, the PC materials harvested from the wastes of natural resources are turned into valuable electrode materials for the high demand energy storage devices, which can significantly reduce severe environmental pollution and alleviate an energy shortage. Open image in new window

Lithium–sulfur batteries are regarded as a promising energy storage system. However, they are plagued by rapid capacity decay, low coulombic efficiency, a severe shuttle effect and low sulfur loading in cathodes. To address these problems, effective carriers are highly demanded to encapsulate sulfur and extend the cycle life. Here, we report an aqueous emulsion approach and in situ sulfur impregnation to synthesize multi-shelled hollow carbon nanosphere-encapsulated sulfur composites with a high percentage of sulfur loading (86 wt%). When applied as cathodes in lithium–sulfur batteries, the composite materials delivered a high specific capacity of 1350 mA h g−1 and excellent capacity retention (92% for 200 cycles). Further measurements at high current densities also demonstrate significantly enhanced cyclability and high rate capability.

Urchin-like NiO nanospheres were synthesised by a microwave hydrothermal method. The as-synthesised NiO nanospheres were characterised by X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. It was found that NiO nanosphere consists of a nanoporous structure and nanosize crystals. When applied as anode materials in lithium-ion batteries, NiO nanospheres exhibited a high reversible specific capacity of 1027 mA h g-1, an excellent cycling performance and a good high rate capability. NiO nanospheres also showed a high specific capacitance as electrode materials for supercapacitors. © 2013 Elsevier B.V. All rights reserved.

Nickel hydroxide nanosheets were synthesized by a simple microwave assisted heating method and investigated as electrochemical pseudo-capacitive materials for supercapacitors. The crystalline structure and morphology of the as-obtained Ni(OH)2 nanosheets were characterized by X-ray diffraction, nitrogen adsorption–desorption isotherms, field emission scanning electron microscopy and transmission electron microscopy. The electrochemical properties of the Ni(OH)2 nanosheets were evaluated by cyclic voltammetry and chronopotentiometry technology in 2 M KOH solution. The nickel hydroxide nanosheet electrode shows a maximum specific capacitance of 2570 F g−1 at a current density of 5 A g−1 and exhibits superior cycling stability. These results suggest its potential application as an electrode material for supercapacitors.

We report a simple synthetic approach to coaxially grow transition metal oxide (TMO) nanostructures on carbon nanotubes (CNT) with ready control of phase and morphology. A thin (~4 nm) sulfonated-polystyrene (SPS) pre-coating is essential for the deposition of transition metal based materials. This layer has abundant sulfonic groups (−SO3−) that can effectively attract Ni2+, Co2+, Zn2+ ions through electrostatic interaction and induce them via hydrolysis, dehydration and recrystallization to form coaxial (NiO, Co3O4, NiCoO2 and ZnCo2O4) shells and a nanosheet-like morphology around CNT. These structures possess a large active surface and enhanced structural robustness when used as electrode materials for lithium-ion batteries (LIBs) and electrochemical capacitors (ECs). As electrodes for LIBs, the ZnCo2O4@CNT material shows extremely stable cycling performance with a discharge capacity of 1068 mAh g−1 after 100 cycles at a current density of 400 mAg−1. For EC applications, the NiCoO2@CNT exhibits a high capacitance of 1360 Fg−1 at current densities of 10 Ag−1 after 3000 cycles and an overall capacitance loss of only 1.4%. These results demonstrate the potential of such hybrid materials meeting the crucial requirements of cycling stability and high rate capability for energy conversion and storage devices.

Silicon has been recognized as the most promising anode material for high capacity lithium ion batteries. However, large volume variations during charge and discharge result in pulverization of Si electrodes and fast capacity loss on cycling. This drawback of Si electrodes can be overcome by combination with well-organized graphene foam. In this work, hierarchical three-dimensional carbon-coated mesoporous Si nanospheres@graphene foam (C@Si@GF) nanoarchitectures were successfully synthesized by a thermal bubble ejection assisted chemical-vapor-deposition and magnesiothermic reduction method. The morphology and structure of the as-prepared nanocomposites were characterized by field emission scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. When employed as anode materials in lithium ion batteries, C@Si@GF nanocomposites exhibited superior electrochemical performance including a high specific capacity of 1,200 mAh/g at the current density of 1 A/g, excellent high rate capabilities and an outstanding cyclability. Post-mortem analyses identified that the morphology of 3D C@Si@GF electrodes after 200 cycles was well maintained. The synergistic effects arising from the combination of mesoporous Si nanospheres and graphene foam nanoarchitectures may address the intractable pulverization problem of Si electrode. [Figure not available: see fulltext.] © 2014 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

Nickel oxide nanosheets have been successfully synthesized by a facile ethylene glycol mediated hydrothermal method. The morphology and crystal structure of the nickel oxide nanosheets were characterized by X-ray diffraction, field-emission SEM, and TEM. When applied as electrode materials for lithium-ion batteries and supercapacitors, nickel oxide nanosheets exhibited a high, reversible lithium storage capacity of 1193 mA h g-1 at a current density of 500 mA g-1, an enhanced rate capability, and good cycling stability. Nickel oxide nanosheets also demonstrated a superior specific capacitance of 999 F g-1 at a current density of 20 A g-1 in supercapacitors. Between the sheets: NiO nanosheets were synthesized by a facile ethylene glycol mediated hydrothermal method (see picture). The NiO nanosheets exhibited a high, reversible lithium storage capacity of 1193 mA h g-1 at a current density of 500 mA g-1 for lithium-ion batteries and a superior specific capacitance of 999 F g-1 at a current density of 20 A g-1 in supercapacitors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fe 2 O 3 –CNT–graphene nanosheet (Fe 2 O 3 –CNT–GNS) hybrid materials were synthesized using a chemical vapor deposition method. The as-prepared materials consist of Fe 2 O 3 nanorings, bamboo-like carbon nanotubes and graphene nanosheets, which form an open three-dimensional architecture . For the first time, we observed the growth of bamboo-like carbon nanotubes with open tips, which were catalyzed by iron nanorings. When applied as anode materials in lithium ion batteries, the Fe 2 O 3 –CNT–GNS hybrid materials exhibited a high specific capacity of 984 mAh g −1 with a superior cycling stability and high rate capability. This could be ascribed to short Li + diffusion path of bamboo-like CNTs, more active reaction sites provided by graphene layers inside CNTs, flexible and highly conductive graphene nanosheets, and an open three-dimensional structure.

Tinegraphene nanocomposites are prepared by a combination of microwave hydrothermal synthesis and a one-step hydrogen gas reduction. Altering the weight ratio between tin and graphene nanosheets has critical influences on their morphologies and electrochemical performances. Field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) analysis confirm the homogeneous distribution of tin nanoparticles on the surface of graphene nanosheets. When applied as an anode material in lithium ion batteries, tinegraphene nanocomposite exhibits a high lithium storage capacity of 1407 mAh g

Sodium-ion batteries are emerging as promising candidates for grid energy storage because of the abundant sodium resources and low cost. However, the identification and development of suitable anode materials is far from being satisfactory. Here, it is demonstrated that the Ti2 Nb2 O9 nanosheets with tunnel structure can be used as suitable anode materials for sodium-ion batteries. Ti2 Nb2 O9 nanosheets are synthesized by liquid exfoliation combined with topotactic dehydration, delivering a high reversible capacity of 250 mAh g-1 at 50 mA g-1 at a suitable average voltage of ≈0.7 V. It is found that a low energy diffusion barrier, enlarged interlayer spacing, and exceptional nanoporosity together give rise to high rate performance characterized by pseudocapacitive behavior. The observed high reversible capacity, excellent rate capability, and good cyclability of Ti2 Nb2 O9 nanosheets make this material competitive when compared to other sodium insertion anode materials.

This paper reports the preparation and Li-storage properties of graphene nanosheets(GNS), GNS supported Sn–Sb@carbon (50–150 nm) and Sn–Sb nanoparticles (5–10 nm). The best cycling performance and excellent high rate capabilities were observed for GNS-supported Sn–Sb@carbon core-shell particles, which exhibited initial capacities of 978, 850 and 668 mAh/g respectively at 0.1C, 2C and 5C (1C=800 mA/g) with good cyclability. Besides the GNS support, the carbon skin around Sn–Sb particles is believed to be a key factor to improve electrochemical properties of Sn–Sb. Keywords: Core-shell nanostructure, Graphene nanosheets, Lithium-ion battery, Sn-Sb

Mesoporous Co3O4 nanoflakes with an interconnected architecture were successfully synthesized using a microwave-assisted hydrothermal and low-temperature conversion method, which exhibited excellent electrochemical performances as anode materials in lithium ion batteries and as catalysts in the oxygen evolution reaction (OER). Field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) observations showed the unique interconnected and mesoporous structure. When employed as anode materials for lithium ion batteries, mesoporous Co3O4 nanoflakes delivered a high specific capacity of 883 mAh/g at 0.1C current rate and stable cycling performances even at higher current rates. Post-mortem analysis of ex situ FESEM images revealed that the mesoporous and interconnected structure had been well maintained after long-term cycling. The mesoporous Co3O4 nanoflakes also showed both OER active properties and good catalytic stability. This could be attributed to both the stability of unique mesoporous structure and highly reactive facets.

Lithium ion capacitors are new energy storage devices combining the complementary features of both electric double-layer capacitors and lithium ion batteries. A key limitation to this technology is the kinetic imbalance between the Faradaic insertion electrode and capacitive electrode. Here, we demonstrate that the Li3 VO4 with low Li-ion insertion voltage and fast kinetics can be favorably used for lithium ion capacitors. N-doped carbon-encapsulated Li3 VO4 nanowires are synthesized through a morphology-inheritance route, displaying a low insertion voltage between 0.2 and 1.0 V, a high reversible capacity of ≈400 mAh g-1 at 0.1 A g-1 , excellent rate capability, and long-term cycling stability. Benefiting from the small nanoparticles, low energy diffusion barrier and highly localized charge-transfer, the Li3 VO4 /N-doped carbon nanowires exhibit a high-rate pseudocapacitive behavior. A lithium ion capacitor device based on these Li3 VO4 /N-doped carbon nanowires delivers a high energy density of 136.4 Wh kg-1 at a power density of 532 W kg-1 , revealing the potential for application in high-performance and long life energy storage devices.

To address the challenge of huge volume change and unstable solid electrolyte interface (SEI) of silicon in cycles, causing severe pulverization, this paper proposes a "double-shell" concept. This concept is designed to perform dual functions on encapsulating volume change of silicon and stabilizing SEI layer in cycles using double carbon shells. Double carbon shells coated Si nanoparticles (DCS-Si) are prepared. Inner carbon shell provides finite inner voids to allow large volume changes of Si nanoparticles inside of inner carbon shell, while static outer shell facilitates the formation of stable SEI. Most importantly, intershell spaces are preserved to buffer volume changes and alleviate mechanical stress from inner carbon shell. DCS-Si electrodes display a high rechargeable specific capacity of 1802 mAh g-1 at a current rate of 0.2 C, superior rate capability and good cycling performance up to 1000 cycles. A full cell of DCS-Si//LiNi0.45 Co0.1 Mn1.45 O4 exhibits an average discharge voltage of 4.2 V, a high energy density of 473.6 Wh kg-1 , and good cycling performance. Such double-shell concept can be applied to synthesize other electrode materials with large volume changes in cycles by simultaneously enhancing electronic conductivity and controlling SEI growth.

A mesoporous flake-like manganese-cobalt composite oxide (MnCo2O4) is synthesized successfully through the hydrothermal method. The crystalline phase and morphology of the materials are characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller methods. The flake-like MnCo2O4 is evaluated as the anode material for lithium-ion batteries. Owing to its mesoporous nature, it exhibits a high reversible capacity of 1066 mA h g(-1), good rate capability, and superior cycling stability. As an electrode material for supercapacitors, the flake-like MnCo2O4 also demonstrates a high supercapacitance of 1487 F g(-1) at a current density of 1 A g(-1), and an exceptional cycling performance over 2000 charge/discharge cycles.

A facile microwave method was employed to synthesize NiCo2 O4 nanosheets as electrode materials for lithium-ion batteries and supercapacitors. The structure and morphology of the materials were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller methods. Owing to the porous nanosheet structure, the NiCo2 O4 electrodes exhibited a high reversible capacity of 891 mA h g(-1) at a current density of 100 mA g(-1) , good rate capability and stable cycling performance. When used as electrode materials for supercapacitors, NiCo2 O4 nanosheets demonstrated a specific capacitance of 400 F g(-1) at a current density of 20 A g(-1) and superior cycling stability over 5000 cycles. The excellent electrochemical performance could be ascribed to the thin porous structure of the nanosheets, which provides a high specific surface area to increase the electrode-electrolyte contact area and facilitate rapid ion transport.

Lithium-sulfur batteries have been plagued for a long time by low Coulombic efficiency, fast capacity loss, and poor high rate performance. Here, the synthesis of 3D hyperbranched hollow carbon nanorod encapsulated sulfur nanocomposites as cathode materials for lithium-sulfur batteries is reported. The sulfur nanocomposite cathodes deliver a high specific capacity of 1378 mAh g-1 at a 0.1C current rate and exhibit stable cycling performance. The as-prepared sulfur nanocomposites also achieve excellent high rate capacities and cyclability, such as 990 mAh g-1 at 1C, 861 mAh g -1 at 5C, and 663 mAh g-1 at 10C, extending to more than 500 cycles. The superior electrochemical performance are ascribed to the unique 3D hyperbranched hollow carbon nanorod architectures and high length/radius aspect ratio of the carbon nanorods, which can effectively prevent the dissolution of polysulfides, decrease self-discharge, and confine the volume expansion on cycling. High capacity, excellent high-rate performance, and long cycle life render the as-developed sulfur/carbon nanorod nanocomposites a promising cathode material for lithium-sulfur batteries. 3D hyperbranched carbon nanorod-sulfur nanocomposites are synthesized and applied as cathode materials for lithium-sulfur batteries. The composite materials deliver high specific capacity, excellent high rate capability, and extended cycle life. The superior performance is attributed to the nanomaze architecture and high aspect ratio of carbon nanorods, which suppress the dissolution of polysulfides and confine volume expansion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.