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The effect of nickel doping on the structure of Li2FeSiO4 is examined by X-ray diffraction, Mössbauer spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectrometer, and magnetization measurements. Both, the pristine and nickel doped Li2FeSiO4, crystallize in a monoclinic structure with (P21/n) symmetry. Their lattice parameters are similar, which suggests that Ni2+ doesn’t destroy the lattice structure. Some small amounts of Fe3+ impurity phases and unreacted Li2SiO3 are detected. Samples doped with more than 10 mol% contain some magnetic impurity of Fe-Ni alloy. Magnetic measurements indicated that Li2FeSiO4 is paramagnetic and becomes antiferromagnetic below 23 K. Nickel dopant does not modify the paramagnetic nature of this material.
Previous reports have suggested that the ablation of the Period 2 gene (Per 2) leads to enhanced development of lymphoma and leukemia in mice. Employing immunoblot analyses, we have demonstrated that PER 2 is endogenously expressed in human breast epithelial cell lines but is not expressed or is expressed at significantly reduced level in human breast cancer cell lines. Expression of PER 2 in MCF-7 breast cancer cells significantly inhibited the growth of MCF-7 human breast cancer cells, and, when PER 2 was co-expressed with the Crytochrome 2 (Cry 2) gene, an even greater growth-inhibitory effect was observed. The inhibitory effect of PER 2 on breast cancer cells was also demonstrated by its suppression of the anchorage-independent growth of MCF-7 cells as evidenced by the reduced number and size of colonies. A corresponding blockade of MCF-7 cells in the G1 phase of the cell cycle was also observed in response to the expression of PER 2 alone or in combination with CRY 2. Expression of PER 2 also induced apoptosis of MCF-7 breast cancer cells as demonstrated by an increase in PARP [poly (ADP-ribose) polymerase] cleavage. Finally, our studies demonstrate that PER 2 expression in MCF-7 breast cancer cells is associated with a significant decrease in the expression of cyclin D1 and an up-regulation of p53 levels.
Among various solid electrolytes, the lithium–phosphorus oxynitride (Lipon) electrolyte synthesized by sputtering of Li3PO4 in pure N2 has a good ionic conductivity of 2(±1)×10−6 Scm−1 at 25°C. As the nitrogen concentration increases in the Lipon electrolyte, the ionic conductivity is reported to increase as a result of a higher degree of cross-links. When Lipon films are deposited by sputtering, however, it is reported that the maximum nitrogen concentration saturates approximately at 6at.%. By non-equilibrium processes, such as ion-implantation, nitrogen concentration can be controlled over 6at.%. This study investigates the effect of nitrogen concentration on the ionic conductivity in Lipon films by using ion-implantation. Impedance measurements at 25°C show that the nitrogen-implanted Lipon films enhance or retard the ionic conductivity over a wide range after nitrogen-implantation, when compared with as-deposited thin-films.
Significant capacity losses are generally seen for batteries containing high-capacity lithium alloy forming anode materials such as silicon, tin and aluminium. These losses are generally ascribed to a combination of volume expansion effects and irreversible electrolyte reduction reactions. Here, it is shown, based on e.g. elemental analyses of cycled electrodes, that the capacity losses for tin nanorod and silicon composite electrodes in fact involve diffusion controlled trapping of lithium in the electrodes. While an analogous effect is also demonstrated for copper, nickel and titanium current collectors, boron-doped diamond is shown to function as an effective lithium diffusion barrier. The present findings indicate that the durability of lithium based batteries can be improved significantly via proper electrode design or regeneration of the used electrodes.
LiMn2O4 thin films were deposited on Au substrates by pulsed laser deposition (PLD). The Li-ion chemical diffusion coefficients of the films, D ˜ Li , were measured by cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT), potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS). It was found that the D ˜ Li values by CV and PITT were in the order of 10−13 cm2 s−1, and those by EIS and GITT were in the range of 10−13 to 10−11 and 10−14 to 10−11 cm2 s−1, respectively. These data were compared with the previously reported values.
Hierarchical-structured SnO-SnO2 composite powders and SnO nanoplates with some SnO2 nanorods are prepared by one-pot spray pyrolysis. Dicyandiamide dissolved in the spray solution plays a key role in the preparation of the hierarchical-structured SnO-SnO2 composite powder and SnO nanoplates. The hierarchical-structured SnO-SnO2 composite powders, in which the SnO nanoplates are trapped in the porous SnO2 nanosphere, are prepared by spray pyrolysis at 800 °C. Sufficient conversion of the porous SnO2 nanospheres to SnO at 900 °C results in aggregation-free SnO2 nanoplates. SnO2 nanorods with a spherical nanodroplet at the tip are formed by Ostwald ripening. The hierarchical-structured SnO-SnO2 composite powder having high structural stability during repeated lithium alloying and dealloying reactions, shows superior discharge capacities and rate performances for lithium-ion storage compared to those of the dense-structured SnO2 powders. The discharge capacities of the hierarchical-structured SnO-SnO2 composite powders, SnO nanoplates with SnO2 nanorods, and dense-structured SnO2 powders at a current density of 1 A g−1 for the 300th cycle are 561, 504, and 416 mA h g−1, respectively. The SnO nanoplates with SnO2 nanorods and hierarchical-structured SnO-SnO2 powders deliver high reversible discharge capacities of 433 and 379 mA h g−1 at an extremely high current density of 10 A g−1, respectively.
In this study, carbon nanotube (CNT) film anodes are prepared for use in flexible lithium ion batteries, and the electrochemical performance of the CNT film anodes is evaluated. The CNT films are synthesized via chemical vapor deposition and direct spinning. The films are heat-treated under a nitrogen atmosphere at a high temperature to study the effects of heat treatment on the battery performance. The electrodes made with the CNT films are characterized via charge–discharge test, cyclic voltammetry, and impedance measurement. The results indicate that batteries with films heat-treated under a nitrogen atmosphere show a higher capacity, which can be a result of their high crystalline perfection. The impedance analysis shows that a lower resistance at the interface can be obtained by using heat-treated films. The charge–discharge tests are carried out by adjusting the rate from C/2 to 10C, and when the rate slows from 10C to 1C, the capacity of the samples largely recovers. The nitrogen/heat-treated CNT film electrodes present a capacity that is twice as high, such as 2C, 5C, and 10C, than untreated CNT film electrodes. These results indicate that the carbon nanotube film anodes have high potential for use in portable and wearable computers due to their flexibility.
The sulfur cathode has a gravimetric theoretical energy of 3500 W h kg−1 which is 3.5× higher than that of the most energy dense cathode material used in commercial lithium ion batteries (1000 W h kg−1 for LiNi0.8Co0.15Al0.05O2 (NCA)). The lithium–sulfur battery also promises a dramatic drop in the cost of high energy density batteries due to the wide availability of sulfur which may compensate costs associated with the operation of lithium metal sheets or powder anodes which are not stable in moist air and require dry rooms or an inert atmosphere. High sulfur loading cathodes have been typically assembled by infiltrating sulfur into porous conductive hosts or interlayers. However, a different approach is that of synthesizing sulfur particles in situ by the reaction of strong acids and sulfur precursors such as sodium thiosulfate. In this communication we propose (A) a novel, eco-safe method for the bottom-up synthesis of sulfur particles which is based on the reaction of weak acids such as vitamin C and commercial potassium polysulfides; (B) layer by layer assembly of hybrid inorganic/organic membrane encapsulating the sulfur particle impedes polysulfide dissolution or protecting the lithium metal anode; (C) a close relationship between the utilization of the lithium metal anode and the short cycle life of lithium–sulfur cells.
Spinel LiMn2O4 is a promising cathode candidate for lithium ion batteries whose electrochemical properties strongly depend on the surface orientation. In this work, we have successfully synthesized a high crystalline and well-defined truncated octahedral LiMn2O4 through the hydrothermal and heat treatment. The main {111} facets are aligned along the orientations mitigating Mn dissolution while the truncated {100} and {110} facets are along those facilitating Li+ diffusion. Benefiting from the unique structure, the octahedral LiMn2O4 delivers 143.4 mAh g−1 (close to the theoretical capacity of 148 mAh g−1) at 0.2 C and over 120 mAh g−1 at 30 C (discharged within 2 min) at 55 °C. Moreover, the fabricated LiMn2O4/Li4Ti5O12-TiO2 full cell demonstrates 121.6 mAh g−1 at 1 C and 56.0 mAh g−1 at 30 C with ∼81.2% capacity retention following 1000 cycles. The facilely synthesized truncated octahedral LiMn2O4 shows great potentials in practical applications for ultrafast and long-life lithium-ion batteries.
In a follow-up to the recent Consumer Electronics Show in Las Vegas, PolyFuel CEO Jim Balcom notes that the explosion of new mobile device applications – particularly those featuring downloaded or broadcast video – will speed the market's recognition of a looming ‘run-time gap’.
Layered LiCoO2 as a cathode material for rechargeable lithium battery is prepared using the acetate self-mixing method. Using this method, the preparation procedure consists of just two steps: spontaneous and homogeneous mixing of molten acetates at 80°C, as well as direct thermal reaction at high temperature without any pulverization, grinding, agglomeration, particle morphology controlling, particle size controlling, and even artificial stirring of reactants. When lithium and cobalt acetates are exposed to the temperature of 80°C, they can be fluidized substances by themselves without any solvents and spontaneously mixed together. In this way, layered LiCoO2 phase is prepared by just simple heat treatment. The heating at 350°C is interposed to accomplish steady intermediate phase translation without any intermittent cooling. The 7Li MAS NMR and Raman spectra upon the thermal exposure of the reactants demonstrate the feature of the spontaneous mixing process of the molten reactants. The LiCoO2 prepared by the acetate self-mixing method show quite prospective properties as a cathode material for lithium rechargeable battery, an initial discharge capacity of 149.5mAh/g and the discharge capacity retention of 98.9% and 97.5% after 10 and 20 cycles, respectively.
We develop a facile method for the synthesis of size-controlled nano-crystaline palladium incorporated into ordered mesoporous carbon (OMC) as oxygen reduction reaction (ORR) electrocatalyst, applied in the cathode of fuel cell and metal-air battery. The catalyst with 18wt.% Pd in ordered mesoporous carbon, pyrolyzed at 900°C shows excellent catalytic performance for ORR. The onset and half-wave potentials are 0.963V and 0.872V (vs. RHE) in 0.1M KOH, respectively, which are comparable to those of commercial 30wt.% Pt/C, 0.975V and 0.854V (vs. RHE). The catalyst with 12wt.% Pd in ordered mesoporous carbon shows largest limiting current density when the current is normalized by the mass of noble metal. The efficient utilization of active Pd in the mesoporous carbon framework endows the catalyst an almost direct four-electron reduction pathway. The transferred electron number of 12Pd-OMC-900 is calculated to be 4.14 at 0.4V (vs. RHE). Its excellent ORR activity should be ascribed to the optimized balance between active sites (Pd nanoparticles) density and capability for mass and charge transport. In addition, the protection for active moieties in the OMC frameworks contributes to its superior durability compared with Pt/C.
Although batteries and supercapacitors can store electrical energy, they cannot convert energy like solar cells. Here, we introduce a new asymmetric hybrid energy conversion and storage (HECS) cell consisting of thin photoactive cobalt oxide (Co3O4) film with a thickness of 1 μm coated on the fluorine-doped tin oxide (FTO) glass as the positive electrode and thin N-doped reduced graphene oxide aerogel (N-rGOAE) film with a thickness of 10 μm coated on the FTO glass as the negative electrode. The HECS cell can convert light to electricity, which is subsequently stored within its electrode materials. The as-fabricated asymmetric HECS cell of Co3O4//N-rGOAE thin films exhibits 140% higher specific capacitance under red LED light illumination than that under dark condition and provides a specific energy and a specific power of ca. 3.5 Wh kg−1 and ca. 7000 W kg−1, respectively. The Co3O4 can absorb all visible light spectrum and excite its valence electron to the conduction band via its indirect band gap (1.45 eV) so-called the photovoltaic effect. Whilst, the N-rGOAE can balance all charges generated at the Co3O4 positive electrode via the electrochemical double-layer capacitance. The asymmetric HECS of Co3O4//N-rGOAE may be an ideal solution for future renewable and sustainable energy.
Between February and May 1998, approximately 100 horses died of African horse sickness (AHS) in the cooler, mountainous, central region of South Africa. On 14 affected farms, 156875 Culicoides of 27 species were captured. C. imicola Kieffer, hitherto considered the only field vector for AHS virus (AHSV), constituted <1% of the total Culicoides captured, and was not found on 29% of the farms. In contrast, 65% of the Culicoides were C. bolitinos Meiswinkel, and was found on all farms. Five isolations of AHSV were made from C. bolitinos, and none from 18 other species of Culicoides (including C. imicola).
Emotional processing (EP) from the emotional approach coping measure has been shown to moderate the effect of writing interventions. This study targeted writing interventions to EP level, with low EP participants receiving a best possible self (BPS) script and high EP participants receiving an emotional expression (EMO) script, versus a control (CTL) writing script. A factorial experimental design was used to balance the potential factors gender, spacing of interventions, and whether participants were instructed to keep or give their writing samples to the administrator. Post-test measures were taken 1 month after completion of writing. Sixty-four undergraduates (66 % female) participated. Those with high EP (
Composite cathodes comprising the solid powders of LiCoO2, electrolyte and Super P carbon are prepared using three different mixing methods to apply to all-solid-state lithium batteries, and their morphological and electrochemical properties are compared. By applying the wet-mixing method, composite cathodes with greater homogenous distribution of solid particles are obtained when compared to those prepared by dry-mixing. As a result of this favorable feature, a higher discharge capacity of 84 mAh g−1 and a capacity retention of 73% are maintained at the 50th cycle in the all-solid-state cell using the composite cathode prepared by wet-mixing with a ball mixer, which resulted from the smaller interfacial resistance for the intercalation/deintercalation of the Li ions in this composite cathode. This is determined to be due to the homogenous distribution of the constituent particles leading to significantly reduced electrode polarization.
Rechargeable lithium–air (O2) batteries have received much attention due to their extremely high theoretical energy densities, which far exceeds that of current lithium-ion batteries. The considerable high energy densities come from (i) pure metal lithium as anode and (ii) the cathode oxidant, oxygen, which comes from the surrounding air. However, there are still many scientific and technical challenges especially nanomaterial challenges to overcome before it turns into reality. In this review, the fundamental principles and understanding of the electrochemical reaction in the aprotic lithium–air batteries are first presented. We emphasized on the discussion of the nanomaterial's issues which prevent their practical implementation, including the material status and challenges from cathode, electrolyte, anode and other components. These problems will be discussed in detail and possible solutions are also suggested. Finally, we explore future research directions in the field of aprotic rechargeable lithium–air batteries.
1,1,1,3,3,3-Hexafluoropropan-2-ol (HFIP) was tested for its applicability as solvent in electrolytes for energy storage devices. A comprehensive characterization with respect to solubility, conductivity, as well as chemical and electrochemical stability was carried out with different conducting salts. Furthermore, different HFIP solutions containing standard supporting electrolytes and alkali metal fluorides, respectively, were applied in electrochemical double layer capacitor cells. Their behavior was studied with impedance spectroscopy and cyclic voltammetry at low scan rates and compared to the current benchmark electrolytes based on propylene carbonate (PC) and acetonitrile (AN). The studied electrolytes exhibit a surprisingly high potential window at glassy carbon electrodes and provide good solubility for the common conducting salts. In double layer capacitors equipped with high surface area carbon derived electrodes and small pore sizes they can easily compete with PC-based electrolytes in terms of capacitance and rate capability. Due to the presence of electrochemically active surface functionalities on the electrode material, the potential window is narrower compared to the glassy carbon electrode.
In this paper, N,P co-doped carbon microsphere (CMS-NP) was investigated as electrocatalyst for VO2+/VO2 + redox reaction for vanadium redox flow batteries. CMS-NP was prepared by hydrothermal treatment followed by calcination with (NH4)2HPO4 as N and P sources. X-ray photoelectron spectroscopy confirms the incorporation of N and P atoms into carbon frameworks of carbon microsphere (CMS), and co-doping has no obvious influence on its morphology. The VO2+/VO2 + redox reaction on CMS-NP exhibits the best electrochemical kinetics compared with pristine CMS and N mono-doped CMS. The cell using CMS samples as electrocatalyst was assembled and its electrochemical performance was evaluated. The comprehensive energy storage performances of the cell are improved by using CMS samples, leading to higher discharge capacity and energy efficiency. The average energy efficiency of the cell increases by 5.1% at 50 mA cm−2 by using CMS-NP. The superior electrocatalytic properties of CMS-NP is mainly ascribed to the increased total number of heteroatoms as active sites and synergistic effect of N,P co-doping resulting from the unique structural features. Our study reveals that N,P co-doping is beneficial for the electrochemical kinetics of VO2+/VO2 + redox reaction on carbon frameworks, and CMS-NP can be employed as superior electrocatalyst in positive electrode.
The novel composites of sulfonated multi-walled carbon nanotubes (sMWCNTs) modified polyaniline (PANI) nanorods (PANI/sMWCNTs) were synthesized successfully by in situ oxidative polymerization method in the HClO4 solution. FTIR and Raman spectra revealed the presence of π–π interaction between the PANI and the sulfonated carbon nanotubes and the formation of charge transfer composites. It was found that the specific capacitance of the PANI/sMWCNT composites was markedly influenced by their morphological structure and the content of PANI which was coated onto the sMWCNT. The specific capacitance of the PANI/sMWCNT composite exhibited a maximum value of 515.2Fg−1 at the 76.4wt% PANI. The charge–discharge tests showed the PANI/sMWCNT composites possessed a good cycling stability (below 10% capacity loss after 1000 cycles) compared to PANI nanorods.
Lithium (Li) metal has received huge attention as a promising anode candidate due to its high theoretical capacity, the lowest negative potential, and its potential as next-generation energy storage devices (such as Li-S and Li-O2 batteries), where Li metal electrode is indispensable for the system. However, systemic issues, which are mainly associated with Li dendritic growth, result in poor electrochemical performances and safety problems (e.g. short-circuit). This article describes a unique design of multifunctional membrane, comprising of nanoporous inorganic (SiO2) nanosheet layer, in order to uniformly distribute metal-ion flux and delay the penetration of Li dendrites through the separator. When a designed membrane was employed, the propagation of Li dendrites against the separator was dramatically restrained and suppressed by structural and materialistic benefits of nanoporous inorganic (SiO2) nanosheets, thus leading to the significant enhancement of electrochemical performances of Li metal batteries. Similar to Li metal batteries, it showed analogous promising results and possibilities in achieving high electrochemical stabilities and cycle performances of Na metal batteries. Moreover, Li-S prototype cell coupled with a designed membrane delivered stable cycle retention (over 400 cycles) with high Coulombic efficiency by selectively allowing Li ions to pass through membrane but suppressing the migration of polysulfides.
Metal recovery is an essential part of the recycling of hybrid electric vehicle battery waste and the first step in a hydrometallurgical treatment is dissolution of the solid material. The properties of separated battery electrode materials were investigated. Focus was put on both the solid waste and then the dissolution behaviour. The cathode contains metallic nickel that remains undissolved when utilizing non-oxidizing conditions such as hydrochloric or sulphuric acid in combination with a low oxygen atmosphere. In these conditions the cathode active electrode material is fully dissolved. Not dissolving the nickel metal saves up to 37% of the acid consumption for the cathode electrode material. In the commonly used case of oxidizing conditions the nickel metal dissolves and a cobalt-rich phase remains undissolved from the cathode active material. For the anode material a complete and rapid dissolution can be achieved at mild conditions with hydrochloric, nitric or sulphuric acid. Optimal parameters for all cases of dissolution was pH 1 with a reaction time of approximately ⩾20,000s.
The demand of highly efficient energy storage system has significantly increased along with the rapid development of electric vehicles and hybrid electric vehicles. However, the energy and power density of standard energy storage devices, such as Li-ion batteries or supercapacitors still cannot meet the requirement of the state-of-the-art electric vehicles. Herein, free-standing Li4Ti5O12/graphene foam (LTO/GF) composite is synthesized via a hydrothermal method, and applied as anode material for Li-ion hybrid supercapacitor. The as-synthesized LTO/GF delivers specific capacities of 186, 179 and 175 mAh g−1 at 0.2, 0.5 and 1 C, respectively. Li-ion hybrid supercapacitors have been assembled with LTO/GF as anodes and activated carbon as cathodes, which have energy densities of 46 and 26 Wh kg−1 at power densities of 625 and 2500 W kg−1, respectively. Furthermore, the hybrid supercapacitor exhibits a superior cycle performance with capacity retention of 83% after 4000 cycles at 1 A g−1. GF sponge substrate can speed up ions and electrons transport with short diffusion lengths and large electrode/electrolyte contact area. Hierarchically structured LTO/GF electrode is lightweight, flexible, and is promising for energy storage applications.