Due to their small footprint and flexible siting, rechargeable batteries are attractive for energy storage systems. A super-valent battery based on aluminium ion intercalation and deintercalation is proposed in this work with VO2 as cathode and high-purity Al foil as anode. First-principles calculations are also employed to theoretically investigate the crystal structure change and the insertion-extraction mechanism of Al ions in the super-valent battery. Long cycle life, low cost and good capacity are achieved in this battery system. At the current density of 50 mAg−1, the discharge capacity remains 116 mAhg−1 after 100 cycles. Comparing to monovalent Li-ion battery, the super-valent battery has the potential to deliver more charges and gain higher specific capacity.
SnO2 nanoparticles were dispersed on graphene nanosheets through a solvothermal approach using ethylene glycol as the solvent. The uniform distribution of SnO2 nanoparticles on graphene nanosheets has been confirmed by scanning electron microscopy and transmission electron microscopy. The particle size of SnO2 was determined to be around 5 nm. The as-synthesized SnO2/graphene nanocomposite exhibited an enhanced electrochemical performance in lithium-ion batteries, compared with bare graphene nanosheets and bare SnO2 nanoparticles. The SnO2/graphene nanocomposite electrode delivered a reversible lithium storage capacity of 830 mAh g−1 and a stable cyclability up to 100 cycles. The excellent electrochemical properties of this graphene-supported nanocomposite could be attributed to the insertion of nanoparticles between graphene nanolayers and the optimized nanoparticles distribution on graphene nanosheets.
SnO2; Graphene nanosheets; Nanocomposite; Lithium-ion batteries
High-performance and cost-effective rechargeable batteries are key to the success of electric vehicles and large-scale energy storage systems. Extensive research has focused on the development of (i) new high-energy electrodes that can store more lithium or (ii) high-power nano-structured electrodes hybridized with carbonaceous materials. However, the current status of lithium batteries based on redox reactions of heavy transition metals still remains far below the demands required for the proposed applications. Herein, we present a novel approach using tunable functional groups on graphene nano-platelets as redox centers. The electrode can deliver high capacity of ~250 mAh g−1, power of ~20 kW kg−1 in an acceptable cathode voltage range, and provide excellent cyclability up to thousands of repeated charge/discharge cycles. The simple, mass-scalable synthetic route for the functionalized graphene nano-platelets proposed in this work suggests that the graphene cathode can be a promising new class of electrode.
One of the most exciting areas in lithium ion batteries is engineering structured silicon anodes. These new materials promise to lead the next generation of batteries with significantly higher reversible charge capacity than current technologies. One drawback of these materials is that their production involves costly processing steps, limiting their application in commercial lithium ion batteries. In this report we present an inexpensive method for synthesizing macroporous silicon particulates (MPSPs). After being mixed with polyacrylonitrile (PAN) and pyrolyzed, MPSPs can alloy with lithium, resulting in capacities of 1000 mAhg−1 for over 600+ cycles. These sponge-like MPSPs with pyrolyzed PAN (PPAN) can accommodate the large volume expansion associated with silicon lithiation. This performance combined with low cost processing yields a competitive anode material that will have an immediate and direct application in lithium ion batteries.
We have designed a novel hybrid nanostructure by coating Fe2O3 nanoparticles with multi-walled carbon nanotubes to enhance the lithium storage capability of Fe2O3. The strategy to prepare Fe2O3@MWCNTs involves the synthesis of Fe nanoparticles wrapped in MWCNTs, followed by the oxidation of Fe nanoparticles under carbon dioxide. When used as the anode in a Li-ion battery, this hybrid material (70.32 wt% carbon nanotubes, 29.68 wt% Fe2O3) showed a reversible discharge capacity of 515 mAhg−1 after 50 cycles at a density of 100 mAg−1 and the capacity based on Fe2O3 nanoparticles was calculated as 1147 mAhg−1, Three factors are responsibile for the superior performance: (1) The hollow interiors of MWCNTs provide enough spaces for the accommodation of large volume expansion of inner Fe2O3 nanoparticles, which can improving the stability of electrode; (2) The MWCNTs increase the overall conductivity of the anode; (3) A stable solid electrolyte interface film formed on the surface of MWCNTs may reduce capacity fading.
In this article, we investigate the storage of lithium ions between two parallel graphene sheets using the continuous approximation and the 6-12 Lennard-Jones potential. The continuous approximation assumes that the carbon atoms can be replaced by a uniform distribution across the surface of the graphene sheets so that the total interaction potential can be approximated by performing surface integrations. The number of ion layers determines the major storage characteristics of the battery, and our results show three distinct ionic configurations, namely single, double, and triple ion forming layers between graphenes. The number densities of lithium ions between the two graphenes are estimated from existing semi-empirical molecular orbital calculations, and the graphene sheets giving rise to the triple ion layers admit the largest storage capacity at all temperatures, followed by a marginal decrease of storage capacity for the case of double ion layers. These two configurations exceed the maximum theoretical storage capacity of graphite. Further, on taking into account the charge-discharge property, the double ion layers are the most preferable choice for enhanced lithium storage. Although the single ion layer provides the least charge storage, it turns out to be the most stable configuration at all temperatures. One application of the present study is for the design of future high energy density alkali batteries using graphene sheets as anodes for which an analytical formulation might greatly facilitate rapid computational results.
Chemical reduction of graphene oxide (GO) is the main route to produce the mass graphene-based materials with tailored surface chemistry and functions. However, the toxic reducing circumstances, multiple steps, and even incomplete removal of the oxygen-containing groups were involved, and the produced graphenes existed usually as the assembly-absent precipitates. Herein, a substrate-assisted reduction and assembly of GO (SARA-GO) method was developed for spontaneous formation of 3D graphene network on arbitrary conductive substrates including active and inert metals, semiconducting Si, nonmetallic carbon, and even indium-tin oxide glass without any additional reducing agents. The SARA-GO process offers a facile, efficient approach for constructing unique graphene assemblies such as microtubes, multi-channel networks, micropatterns, and allows the fabrication of high-performance binder-free rechargeable lithium-ion batteries. The versatile SARD-GO method significantly improves the processablity of graphenes, which could thus benefit many important applications in sensors and energy-related devices.
The high theoretical capacity and low discharge potential of silicon have attracted much attention on Si-based anodes. Herein, hollow porous SiO2 nanocubes have been prepared via a two-step hard-template process and evaluated as electrode materials for lithium-ion batteries. The hollow porous SiO2 nanocubes exhibited a reversible capacity of 919 mAhg−1 over 30 cycles. The reasonable property could be attributed to the unique hollow nanostructure with large volume interior and numerous crevices in the shell, which could accommodate the volume change and alleviate the structural strain during Li ions' insertion and extraction, as well as allow rapid access of Li ions during charge/discharge cycling. It is found that the formation of irreversible or reversible lithium silicates in the anodes determines the capacity of a deep-cycle battery, fast transportation of Li ions in hollow porous SiO2 nanocubes is beneficial to the formation of Li2O and Si, contributing to the high reversible capacity.
Nanoarchitectured electroactive materials can boost rates of Li insertion/extraction, showing genuine potential to increase power output of Li-ion batteries. However, electrodes assembled with low-dimensional nanostructured transition metal oxides by conventional approach suffer from dramatic reductions in energy capacities owing to sluggish ion and electron transport kinetics. Here we report that flexible bulk electrodes, made of three-dimensional bicontinuous nanoporous Cu/MnO2 hybrid and seamlessly integrated with Cu solid current collector, substantially optimizes Li storage behavior of the constituent MnO2. As a result of the unique integration of solid/nanoporous hybrid architecture that simultaneously enhances the electron transport of MnO2, facilitates fast ion diffusion and accommodates large volume changes on Li insertion/extraction of MnO2, the supported MnO2 exhibits a stable capacity of as high as ~1100 mA h g−1 for 1000 cycles, and ultrahigh charge/discharge rates. It makes the environmentally friendly and low-cost electrode as a promising anode for high-performance Li-ion battery applications.
In this paper, we report a facile low-cost synthesis of the graphene-ZnO hybrid nanocomposites for solid-state supercapacitors. Structural analysis revealed a homogeneous distribution of ZnO nanorods that are inserted in graphene nanosheets, forming a sandwiched architecture. The material exhibited a high specific capacitance of 156 F g−1 at a scan rate of 5 mV.s−1. The fabricated solid-state supercapacitor device using these graphene-ZnO hybrid nanocomposites exhibits good supercapacitive performance and long-term cycle stability. The improved supercapacitance property of these materials could be ascribed to the increased conductivity of ZnO and better utilization of graphene. These results demonstrate the potential of the graphene-ZnO hybrid nanocomposites as an electrode in high-performance supercapacitors.
Zinc oxide nanorods; Graphene nanosheets; Solid-state supercapacitor
Current battery systems have severe cost and resource restrictions, difficultly to meet the large scale electric storage applications. Herein, we report an all-organic Na-ion battery using p-dopable polytriphenylamine as cathode and n-type redox-active poly(anthraquinonyl sulphide) as anode, excluding the use of transition-metals as in conventional electrochemical batteries. Such a Na-ion battery can work well with a voltage output of 1.8 V and realize a considerable specific energy of 92 Wh kg−1. Due to the structural flexibility and stability of the redox-active polymers, this battery has a superior rate capability with 60% capacity released at a very high rate of 16 C (3200 mA g−1) and also exhibit an excellent cycling stability with 85% capacity retention after 500 cycles at 8 C rate. Most significantly, this type of all-organic batteries could be made from renewable and earth-abundant materials, thus offering a new possibility for widespread energy storage applications.
Current lithium batteries operate on inorganic insertion compounds to power a diverse range of applications, but recently there is a surging demand to develop environmentally friendly green electrode materials. To develop sustainable and eco-friendly lithium ion batteries, we report reversible lithium ion storage properties of a naturally occurring and abundant organic compound purpurin, which is non-toxic and derived from the plant madder. The carbonyl/hydroxyl groups present in purpurin molecules act as redox centers and reacts electrochemically with Li-ions during the charge/discharge process. The mechanism of lithiation of purpurin is fully elucidated using NMR, UV and FTIR spectral studies. The formation of the most favored six membered binding core of lithium ion with carbonyl groups of purpurin and hydroxyl groups at C-1 and C-4 positions respectively facilitated lithiation process, whereas hydroxyl group at C-2 position remains unaltered.
A well-designed nanostructure of transition metal oxides has been regarded as a key to solve their problems of large volume changes during lithium insertion-desertion processes which are associated with pulverization of the electrodes and rapid capacity decay. Here we report an effective approach for the fabrication of porous iron oxide ribbons by controlling the nucleation and growth of iron precursor onto the graphene surface and followed by an annealing treatment. The resultant iron oxide ribbons possess large aspect ratio, porous structure, thin feature and enhanced open-edges. These characteristics are favorable for the fast diffusion of lithium ions and electrons, and meanwhile can effectively accommodate the volume change of iron oxides during the cycling processes. As a consequence, the graphene-induced porous iron oxide ribbons exhibit a high reversible capacity and excellent cycle stability for lithium storage.
Aprotic rechargeable Li–O2 batteries are currently receiving considerable interest because they can possibly offer significantly higher energy densities than conventional Li-ion batteries. The electrochemical behavior of Li–O2 batteries containing bis(trifluoromethane)sulfonimide lithium salt (LiTFSI)/tetraglyme electrolyte were investigated by galvanostatic cycling and electrochemical impedance spectroscopy measurements. Ex-situ X-ray diffraction and scanning electron microscopy were used to evaluate the formation/dissolution of Li2O2 particles at the cathode side during the operation of Li–O2 cells.
aprotic electrolyte; impedance spectroscopy; Li–O2 batteries; scanning electron microscopy
Battery systems have been developed that provide years of service for implantable medical devices. The primary systems utilize lithium metal anodes with cathode systems including iodine, manganese oxide, carbon monofluoride, silver vanadium oxide and hybrid cathodes. Secondary lithium ion batteries have also been developed for medical applications where the batteries are charged while remaining implanted. While the specific performance requirements of the devices vary, some general requirements are common. These include high safety, reliability and volumetric energy density, long service life, and state of discharge indication. Successful development and implementation of these battery types has helped enable implanted biomedical devices and their treatment of human disease.
This study reports on a facile and economical method for the scalable continuous synthesis of graphene sheets by the thermocatalytic decomposition of methane using a unique and novel unsupported catalyst of iron particles. Single-layered and few-layered graphene sheets were continuously synthesized by the isothermal decomposition reaction of methane over a catalyst of iron particles under atmospheric pressure without the need for a cooling precipitation process. In contrast with the methods currently reported in the published literature, this method exhibits remarkably high capacity and efficiency in terms of graphene throughput and yield, respectively. A maximum graphene yield rate of 20 mg/min per g of catalyst and a graphene output of 6 g per g of catalyst were achieved in this study; this graphene output has far surpassed the best graphene yield of 50 mg per 500 mg of catalyst, thus reported so far, by 60 times.
The shortage of nitrogen active sites and relatively low nitrogen content result in unsatisfying eletrocatalytic activity and durability of nitrogen-doped graphene (NG) for oxygen reduction reaction (ORR). Here we report a novel approach to substantially enhance electrocatalytic oxygen reduction on NG electrode by the implantation of nitrogen active sites with mesoporous graphitic carbon nitride (mpg-C3N4). Electrochemical characterization revealed that in neutral electrolyte the resulting NG (I-NG) exhibited super electrocatalytic activity (completely 100% of four-electron ORR pathway) and durability (nearly no activity change after 100000 potential cyclings). When I-NG was used as cathode catalyst in microbial fuel cells (MFCs), power density and its drop percentage were also much better than the NG and Pt/C ones, demonstrating that the current I-NG was a perfect alternative to Pt/C and offered a new potential for constructing high-performance and less expensive cathode which is crucial for large-scale application of MFC technology.
Transition metal oxides have been suggested as innovative, high-energy electrode materials for lithium-ion batteries because their electrochemical conversion reactions can transfer two to six electrons. However, nano-sized transition metal oxides, especially Co3O4, exhibit drastic capacity decay during discharge/charge cycling, which hinders their practical use in lithium-ion batteries. Herein, we prepared nano-sized Co3O4with high crystallinity using a simple citrate-gel method and used electrochemical impedance spectroscopy method to examine the origin for the drastic capacity fading observed in the nano-sized Co3O4anode system. During cycling, AC impedance responses were collected at the first discharged state and at every subsequent tenth discharged state until the 100th cycle. By examining the separable relaxation time of each electrochemical reaction and the goodness-of-fit results, a direct relation between the charge transfer process and cycling performance was clearly observed.
Nano-sized Co3O4; Li-ion batteries; Capacity fading; Electrochemical impedance spectroscopy; Charge transfer reaction
Graphene has a unique atom-thick two-dimensional structure and excellent properties, making it attractive for a variety of electrochemical applications, including electrosynthesis, electrochemical sensors or electrocatalysis, and energy conversion and storage. However, the electrochemistry of single-layer graphene has not yet been well understood, possibly due to the technical difficulties in handling individual graphene sheet. Here, we report the electrochemical behavior at single-layer graphene-based electrodes, comparing the basal plane of graphene to its edge. The graphene edge showed 4 orders of magnitude higher specific capacitance, much faster electron transfer rate and stronger electrocatalytic activity than those of graphene basal plane. A convergent diffusion effect was observed at the sub-nanometer thick graphene edge-electrode to accelerate the electrochemical reactions. Coupling with the high conductivity of a high-quality graphene basal plane, graphene edge is an ideal electrode for electrocatalysis and for the storage of capacitive charges.
In this work, material-sensitive atomic force microscopy (AFM) techniques were used to analyse the cathodes of lithium–sulfur batteries. A comparison of their nanoscale electrical, electrochemical, and morphological properties was performed with samples prepared by either suspension-spraying or doctor-blade coating with different binders. Morphological studies of the cathodes before and after the electrochemical tests were performed by using AFM and scanning electron microscopy (SEM). The cathodes that contained polyvinylidene fluoride (PVDF) and were prepared by spray-coating exhibited a superior stability of the morphology and the electric network associated with the capacity and cycling stability of these batteries. A reduction of the conductive area determined by conductive AFM was found to correlate to the battery capacity loss for all cathodes. X-ray diffraction (XRD) measurements of Li2S exposed to ambient air showed that insulating Li2S hydrolyses to insulating LiOH. This validates the significance of electrical ex-situ AFM analysis after cycling. Conductive tapping mode AFM indicated the existence of large carbon-coated sulfur particles. Based on the analytical findings, the first results of an optimized cathode showed a much improved discharge capacity of 800 mA·g(sulfur)−1 after 43 cycles.
conductive AFM; high capacity; lithium-sulfur batteries; material-sensitive AFM; sulfur cathode
The intrinsic low conductivity of sulfur which leads to a low performance at a high current rate is one of the most limiting factors for the commercialization of lithium-sulfur battery. Here, we present an easy and convenient method to synthesize a mono-dispersed hollow carbon sphere with a thin graphitic wall which can be utilized as a support with a good electrical conductivity for the preparation of sulfur/carbon nano-composite cathode. The hollow carbon sphere was prepared from the pyrolysis of the homogenous mixture of the mono-dispersed spherical silica and Fe-phthalocyanine powder in elevated temperature. The composite cathode was manufactured by infiltrating sulfur melt into the inner side of the graphitic wall. The electrochemical cycling shows a capacity of 425 mAh g−1 at 3 C current rate which is more than five times larger than that for the sulfur/carbon black nano-composite prepared by simple ball milling.
Lithium-sulfur battery; Hollow carbon sphere; Graphitic carbon; Nano-composite; Cathode
Flexible asymmetric supercapacitors with excellent electrochemical performance and aesthetic property are realized by using ultrathin two-dimensional (2D) MnO2 and graphene nanosheets as cathode and anode materials, respectively. 2D MnO2 nanosheets (MSs) with a thickness of ca. 2 nm are synthesized with a soft template method for the first time, which achieve a high specific capacitance of 774 F g−1 even after 10000 cycles. Asymmetric supercapacitors based on ultrathin MSs and graphene exhibit a very high energy density up to 97.2 Wh kg−1 with no more than 3% capacitance loss after 10000 cycles in aqueous electrolyte. Most interestingly, we show that the energy storage device can have an aesthetic property. For instance, a “Chinese panda” supercapacitor is capable of lighting up a red light emitting diode. This work has another, quite different aspect that a supercapacitor is no longer a cold industry product, but could have the meaning of art.
Lithium-ion batteries, which have been widely used to power portable electronic devices, are on the verge of being applied to new automobile applications. To expand this emerging market, however, an electrode that combines fast charging capability, long-term cycle stability, and high energy density is needed. Herein, we report a novel layered lithium vanadium fluorophosphate, Li1.1Na0.4VPO4.8F0.7, as a promising positive electrode contender. This new material has two-dimensional lithium pathways and is capable of reversibly releasing and reinserting ~1.1 Li+ ions at an ideal 4 V (versus Li+/Li) to give a capacity of ~156 mAh g−1 (energy density of 624 Wh kg−1). Moreover, outstanding capacity retentions of 98% and 96% after 100 cycles were achieved at 60°C and room temperature, respectively. Unexpectedly high rate capability was delivered for both charge and discharge despite the large particle size (a few microns), which promises further enhancement of power density with proper nano-engineering.
Graphene has shown enormous potential for innovation in various research fields. The current chemical approaches based on exfoliation of graphite via graphite oxide (GO) are potential for large-scale synthesis of graphene but suffer from high cost, great operation difficulties, and serious waste discharge. We report a facile preparation of graphene by rapid reduction and expansion exfoliation of sulfuric acid intercalated graphite oxide (SIGO) at temperature just above 100°C in ambient atmosphere, noting that SIGO is easily available as the immediate oxidation descendent of graphite in sulfuric acid. The oxygenic and hydric groups in SIGO are mainly removed through dehydration as catalyzed by the intercalated sulfuric acid (ISA). The resultant consists of mostly single layer graphene sheets with a mean diameter of 1.07 μm after dispersion in DMF. This SIGO process is reductant free, easy operation, low-energy, environmental friendly and generates graphene with low oxygen content, less defect and high conductivity. The provided synthesis route from graphite to graphene via SIGO is compact and readily scalable.
The high transparency of graphene, together with its good electrical conductivity and mechanical robustness, enable its use as transparent electrodes in optoelectronic devices such as solar cells. While initial demonstrations of graphene-based organic photovoltaics (OPV) have been promising, realization of scalable technologies remains challenging due to their performance and, critically, poor device reproducibility and yield. In this work, we demonstrate by engineering the interface between graphene and organic layers, device performance and yield become close to devices using indium tin oxide. Our study confirms that the key issue leading to the poor performance or irreproducibility in graphene-based OPV originates from the graphene interface, and can be addressed by a simple interface modification method introduced in this work. We also show similar approach allows graphene to be used as cathode in inverted OPV geometry, thereby demonstrating the universal application of graphene as transparent conductors for both the anode and cathode.