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Maricite NaFePO4 (m-NaFePO4) was investigated as a positive electrode material for intermediate-temperature operation of sodium secondary batteries using ionic liquid electrolytes. Powdered m-NaFePO4 was prepared by a conventional solid-state method at 873 K and subsequently fabricated in two different conditions; one is ball-milled in acetone and the other is re-calcined at 873 K after the ball-milling. Electrochemical properties of the electrodes prepared with the as-synthesized m-NaFePO4, the ball-milled m-NaFePO4, and the re-calcined m-NaFePO4 were investigated in Na[FSA]-[C2C1im][FSA] (C2C1im+ = 1-ethyl-3-methylimidazolium, FSA− = bis(fluorosulfonyl)amide) ionic liquid electrolytes at 298 K and 363 K to assess the effects of temperature and particle size on their electrochemical properties. A reversible charge-discharge capacity of 107 mAh g−1 was achieved with a coulombic efficiency >98% from the 2nd cycle using the ball-milled m-NaFePO4 electrode at a C–rate of 0.1 C and 363 K. Electrochemical impedance spectroscopy using m-NaFePO4/m-NaFePO4 symmetric cells indicated that inactive m-NaFePO4 becomes an active material through ball-milling treatment and elevation of operating temperature. X-ray diffraction analysis of crystalline m-NaFePO4 confirmed the lattice contraction and expansion upon charging and discharging, respectively. These results indicate that the desodiation-sodiation process in m-NaFePO4 is reversible in the intermediate-temperature range.
Lithium ion battery electrode materials generally experience significant volume changes during charging and discharging caused by concentration changes within the host particles. Electrode failure, in the form of fracture or decrepitation, may occur as a result of a highly localized stress, strain energy, and stress cycles over time. In this paper, we develop analytic expressions for the evolution of stress and strain energy within a spherically shaped electrode element under either galvanostatic (constant current) or potentiostatic (constant potential) operation when irreversible phenomena are dominated by solute diffusion resistance within host particles. We show that stresses and strain energy can evolve quite differently under potentiostatic vs. galvanostatic control. The findings of this work suggest the possibility of developing new battery charging strategies that minimize stress and strain energy and thus prolong battery life.
Silicon is one of the most promising anode materials for the next-generation high energy density lithium-ion batteries as its superior specific capacity and ultralow lithiation/delithiation voltage. Whereas, silicon suffers massive volume change during cycling, resulting in drastic pulverization of active material and iterative growth of solid electrolyte interphase, largely limiting their widely applications. To address the challenge, water-soluble glycinamide modified PAA (PAA-GA) is synthesized through a facile and low-cost coupling method as a polymer binder to assemble silicon anode for alleviating its huge volume change. The carboxyl and double amide groups of the PAA-GA can form hydrogen bonds with the hydration layer of silicon, and meanwhile the double amide groups of PAA-GA can form double hydrogen bonds via interchain cohesion. These strong supramolecular interactions are reversible and can recover the dissociated bonds more efficiently upon the elimination of the mechanical stress. The PAA-GA-based silicon electrodes exhibit excellent cycling stability and high coulombic efficiency, demonstrating the PAA-GA binder being great potential in fabricating high energy density silicon anodes for next-generation lithium-ion batteries.
An attapulgite clay-supported cobalt-boride (Co-B) catalyst used in portable fuel cell fields is prepared in this paper by impregnation–chemical reduction method. The cost of attapulgite clay is much lower compared with some other inert carriers, such as activated carbon and carbon nanotube. Its microstructure and catalytic activity are analyzed in this paper. The effects of NaOH concentration, NaBH4 concentration, reacting temperature, catalyst loadings and recycle times on the performance of the catalysts in hydrogen production from alkaline NaBH4 solutions are investigated. Furthermore, characteristics of these catalysts are carried out in SEM, XRD and TEM analysis. The high catalytic activity of the catalyst indicates that it is a promising and practical catalyst. Activation energy of hydrogen generation using such catalysts is estimated to be 56.32kJmol−1. In the cycle test, from the 1st cycle to the 9th cycle, the average hydrogen generation rate decreases gradually from 1.27lmin−1 g−1 Co-B to 0.87lmin−1 g−1 Co-B.
Satellite tagging programs have provided detailed information about the migratory patterns of northeastern Pacific white sharks, revealing a seasonal migration between a vast offshore region and coastal aggregation sites. Although adult males undergo annual round-trip migrations, photo-identification programs have noted that sexually mature females may only visit coastal aggregation sites once every 2 years, a behavior that is presumably linked to an estimated 18-month gestation period. The whereabouts of females during their full 2-year migration were previously unknown, because of the limited battery capacity of satellite pop-up tags.
A composite electrode between three-dimensionally ordered macroporous (3DOM) Li0.35La0.55TiO3 (LLT) and LiMn2O4 was fabricated by colloidal crystal templating method and sol–gel process. A close-packed PS beads with the opal structure was prepared by filtration of a suspension containing PS beads. Li–La–Ti–O sol was injected by vacuum impregnation process into the voids between PS beads, and then was heated to form 3DOM-LLT. Three-dimensionally ordered composite material consisting of LiMn2O4 and LLT was prepared by sol–gel process. The prepared composite was characterized with SEM and XRD. All solid-state Li-ion battery was fabricated with the LLT–LiMn2O4 composite electrode as a cathode, dry polymer electrolyte and Li metal anode. The prepared all solid-state cathode exhibited a volumetric discharge capacity of 220mAhcm−3.
Vanadium pentoxide/polyaniline (V2O5/PANi) composite films were prepared by a two-step electrochemical method and evaluated for their application in lithium batteries. As a first step the PANi film was potentiodynamically grown in an acid solution containing aniline monomer, and secondly vanadium oxide was oxidatively deposited on the polyaniline film in a temperature controlled VOSO4 solution. The increased current efficiency obtained with the larger anodic current in the high temperature solutions results in high contents of V2O5 in the composites, even if the oxidative dissolution of PANi also occurs. The large value of the diffusion coefficient estimated from the cyclic voltammograms for the composite film provides evidence for the synergistic effect of the conducting polymer and the inorganic composite. The cell exhibited excellent cycle stability with a high charge storage capacity. The large increase in the specific capacity for the composite film prepared in this work demonstrates that the conducting polymer in the composite acts as a binding and conducting element by contributing its electroactivity. The V2O5/PANi composite film cathodes show a large specific capacity (ca. 270mAh/g) and improved cyclability with an extremely small amount of capacity fading (ca. 3.4%) during repeated charge/discharge cycles.
The cDNA sequences encoding manganese superoxide dismutase (Mn–SOD) and catalase (CAT) were isolated in the freshwater bivalve Unio tumidus by reverse-transcription polymerase chain reaction (RT-PCR) using degenerate primers. Quantitative real-time PCR approach was used to evaluate the mRNA expression patterns of SOD, CAT, selenium-dependent glutathione peroxidase (Se-GPx), pi class glutathione S-transferase (pi-GST) and metallothionein (MT), in the digestive gland of Unio tumidus transplanted from a control site to four stations in the Moselle River (M1–M4), for periods of 8 and 21 days. These sites were chosen upstream and downstream of populated areas. Chemical analysis performed on sediments from the Moselle river sites did not show high levels of pollutants. Decrease of SOD, CAT, Se-GPx and MT mRNA levels were observed at M3 site after a 21-day exposure compared to control site. These results suggest inefficiency of antioxidant systems affected by cytotoxic mechanisms and confirm an environmental perturbation. Organisms transplanted at M4 site showed a strong increase of biomarkers transcription levels after 21 days of exposure. These inductions could correspond to an adaptive response to an altered environment. Our results showed that biological approaches using multibiomarkers appear as essential tools complementary to measurement of contaminants, to detect environmental degradations.
A special issue of the journal Solar Energy Materials and Solar Cells has just been published, dedicated to Stanford R. Ovshinsky — one of the most illustrious photovoltaic pioneers.
The use of the high energy Li-ion battery technology for emerging markets like electromobility requires precise appraisal of their safety levels in abuse conditions. Combustion tests were performed on commercial pouch cells by means of the Fire Propagation Apparatus also called Tewarson calorimeter in the EU, so far used to study flammability parameters of polymers and chemicals. Well-controlled conditions for cell combustion are created in such an apparatus with the opportunity to analyse standard decomposition/combustion gases and therefore to quantify thermal and toxic threat parameters governing the fire risk namely the rate of heat release and the effective heat of combustion as well as the toxic product releases. Using the method of O2 consumption, total combustion heats and its kinetic of production were determined as a function of the cell state of charge unveiling an explosion risk in the case of a charged cell. The resulting combustion heat is revealed to be consistent with cumulated contribution values pertaining to each organic part of the cell (polymers and electrolytes) as calculated from thermodynamic data. The first order evaluation of the dangerousness of toxic gases resulting from fire induced combustion such as HF, CO, NO, SO2 and HCl was undertaken and stressed the fact that HF is the most critical gas originating from F-containing cell components in our test conditions.
The effect of carbon-coating on the elevated temperature performance of Li|graphite half-cells is investigated for 1M LiPF6 in PC|EC|DEC (3:2:5) and 1M LiBF4 in EC|DMC (2:1) electrolytes (PC = propylene carbonate; EC = ethylene carbonate; DEC = diethyl carbonate; DMC = dimethyl carbonate). Carbon-coated graphite is prepared by mixing synthetic graphite particles with polyvinylchloride powders, followed by heating to 1000°C under a flow of argon gas. For LiPF6-based cells, when pre-cycled cells are stored at 80°C and then cycled at 30°C, the loss of charge after storage at elevated temperature is much less with carbon-coated graphite than with untreated graphite electrode. When cycled at 80°C without pre-cycling, the carbon-coated graphite electrode shows stable cycling behaviour, but untreated graphite results in premature cell failure. It appears that the carbon-coating preserves the graphite electrode even after storage at 60°C in LiBF4-based electrolyte. From cycling and storage tests, it is concluded that surface modification through carbon-coating is very effective for the improvement of electrochemical performance and thermal stability of graphite electrodes at elevated temperatures.
Iron hydroxyl phosphate, with the formula Fe1.5(PO4)(OH), used as a cathode material in lithium ion batteries, is synthesised by a sample hydrothermal method. Scanning electron microscopy (SEM), X-ray diffraction and galvanostatical charge/discharge tests are employed to characterise the morphology, structure and electrochemical performance of the iron hydroxyl phosphate, respectively. FE-SEM shows that the morphologies are closely related to the hydrothermal temperatures at which they are synthesised. The morphologies, such as spherical, cubic, multi-armed and cross-like structures, could be easily regulated by adjusting the hydrothermal temperature. It is found that different morphologies of iron hydroxyl phosphate gave rise to different electrochemical performances. Compared to the others, iron hydroxyl phosphate spherical composites exhibit not only a high reversible capacity but also good cycling stability, with a reversible initial discharge specific capacity of around 176 mAh g−1 and a remaining 95% of the initial discharge specific capacity after 60 cycles at 0.1C. The improved electrochemical performance is attributed to the spherical morphology and smaller particle size, which increase the reaction interfaces and shorten the diffusion distance of the lithium ions.
Unknown ‘Note: Page numbers followed by “f” indicate figures, “t” indicate tables and “b” indicate boxes.’
Novel ternary Fe-Sn-P alloys prepared by simple single-step electrodeposition are investigated as promising anodes for Li-ion batteries. The Fe51Sn38P11 electrode, in particular, shows outstanding Li-storage properties, with initial specific discharge/charge capacities of 857.8 and 655mAhg−1, respectively. The reversible capacity remains stable at 427mAhg−1, even after 90 cycles, corresponding to a coulombic efficiency of 96% and a capacity retention of 65%. The cauliflower-like morphology of the above anode is well preserved after 90 cycles, suggesting that this alloy could significantly mitigate the electrode volume expansion by exerting a positive multiphase synergistic effect. The superior electrochemical performance of the ternary Fe-Sn-P alloys confirmed its potential as an alternative Li-ion storage anode; the large-scale suitability of the developed electroplating method provides an additional advantage.
Co3O4-doped TiO2 nanotube array electrodes were prepared by anodizing the Co–Ti alloys with different Co contents. Morphologies, elemental compositions, crystal structures, and electrochemical properties of the samples were characterized through scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and electrochemical workstation. The effects of Co content, annealing temperature and testing electrolyte on the electrochemical properties of the electrodes were studied. Results show that the areal capacitance values of TiO2 nanotube arrays were obviously improved by doping with Co3O4. The electrochemical properties of Co3O4-doped TiO2 nanotube array electrodes were best when the Co content in the alloys was 9%; the annealing temperature was 100 °C and the testing electrolyte was 0.5 M Na2SO4. The Co3O4-doped TiO2 nanotube array electrodes prepared under the optimal conditions had a high areal capacitance value of 937.9 µF cm−2 when the scan rate was 10 mV s−1 and the electrodes exhibited good rate and superior cycling performance.
Energy-dispersive x-ray diffraction (EDXRD) is one of the few techniques that can internally probe a sealed battery under operating conditions. In this paper, we use EDXRD with ultrahigh energy synchrotron radiation to track inhomogeneity in a cycled high-capacity lithium iron phosphate cell under in-situ and operando conditions. A sequence of depth-profile x-ray diffraction spectra are collected with 40 μm resolution as the cell is discharged. Additionally, nine different locations of the cell are tracked independently throughout a second discharge process. In each case, a two-peak reference intensity ratio analysis (RIR) was used on the LiFePO4 311 and the FePO4 020 reflections to estimate the relative phase abundance of the lithiated and non-lithiated phases. The data provide a first-time look at the dynamics of electrochemical inhomogeneity in a real-world battery. We observe a strong correlation between inhomogeneity and overpotential in the galvanic response of the cell. Additionally, the data closely follow the behavior that is predicted by the resistive-reactant model originally proposed by Thomas-Alyea. Despite a non-linear response in the independently measured locations, the behavior of the ensemble is strikingly linear. This suggests that effects of inhomogeneity can be elusive and highlights the power of the EDXRD technique.
LiNi0.5−x Co2x Mn1.5−x O4 (0≤2x ≤0.2) was prepared by a spray dry process and comparative studies were carried out between the as-prepared series and the series re-annealed in O2. The cobalt substitution resulted in significant structural and electrochemical variations, such as the transformation of the space group from P4332 to F d 3 ¯ m , the increase in the occupancy of cobalt in the tetrahedral sites, and the change in the shape of the charge and discharge profiles, which are related to the progressive oxygen loss. Moreover, an improved rate capability and cyclic performance at high rate was observed for the sample with 2x ≥0.1.
We report all carbon-based high energy Li-ion capacitor from environmentally threatening bio-source, prosopis juliflora. The pyrolyzed carbon exhibits a few layers of graphene-like structure and tubular morphology with multiple inherent heteroatoms like N, S, and Ca. Presence of such heteroatoms are certainly beneficial to the betterment of electrical conductivity, and pore generation which eventually results in an enhancement in capacity/capacitance of carbonaceous materials. The electrochemical pre-lithiation strategy is used to mitigate the irreversibility observed, and eventually employed as a negative electrode in a hybrid configuration. This LIC delivered a high energy density of ∼216 and 185 Wh kg−1 at ambient (25 °C) and elevated temperature (55 °C) conditions, respectively. Further, ∼94% initial capacity is retained after 5000 cycles with minimum fading of 0.0013% per cycle at ambient temperature. This results clearly demonstrate that the surface functionality and heteroatom doping with tubular structure synergistically facilitates the Li+ and electron transport properties to realize higher energy density for this fascinating all carbon-based Li-ion capacitor.
Carbon nanotube (CNT) has been widely applied to transition metal oxides anodes for lithium ion batteries, acting as a buffer, hollow backbone and conductive additive. Since the presence of N in carbon materials can enhance the reactivity and electrical conductivity, N-doped carbon nanotube (N-CNT) might be a better choice than pure CNT, which is exemplified by coaxial manganese dioxide@N-doped carbon nanotubes as a superior anode. The electrochemical properties of MnO2@N-CNT are investigated in terms of cycling stability and rate capability. The nanocomposite can deliver a specific capacity of 1415mAhg−1 after 100 cycles at the current density of 100mAg−1, which is better than that of MnO2@commercial CNT and MnO2. The excellent performance might be related to the integration of hollow structure, one-dimensional nanoscale size as well as combination with N-doped carbon materials.
Spherical Li[Ni0.8Co0.2−x Mn x ]O2 (x =0, 0.1) with phase-pure and well-ordered layered structure have been synthesized by heat-treatment of spherical [Ni0.8Co0.2−x Mn x ](OH)2 and LiOH·H2O precursors. The structure, morphology, electrochemical properties, and thermal stability of Li[Ni0.8Co0.2−x Mn x ]O2 (x =0, 0.1) were studied. The average particle size of the powders was about 10–15μm and the size distribution was narrow due to the homogeneity of the metal hydroxide [Ni0.8Co0.2−x Mn x ](OH)2 (x =0, 0.1). The Li[Ni0.8Co0.2−x Mn x ]O2 (x =0, 0.1) delivered a discharge capacity of 197–202mAhg−1 and showed excellent cycling performance. Compared to Li[Ni0.8Co0.2]O2, Li[Ni0.8Co0.1Mn0.1]O2 exhibited greater thermal stability resulting from improved structural stability due to Mn substitution.
The activities in the battery field currently in progress in Italian academic and industrial laboratories will be briefly reviewed. After reporting the key achievements obtained in lead-acid batteries, the presentation will be focused on systems of more recent development with particular attention to the lithium batteries. Interestingly, there is in Italy quite an intense research and development activity on these new-concept batteries which are now the power sources of choice for popular electronic devices, e.g. cellular phones, and in prospect valid systems for powering electric vehicles. Basic research is carried out in various university and government centers with the aim of characterizing new lithium ion electrode and electrolyte materials. This intense research is backed by substantial development activity since few Italian industries are presently engaged in the production of lithium batteries of different size and characteristics. Italy is then well established in battery R&D, confirming the country’s historical involvement in the field since Volta’s pile invention in 1800.
Solar home systems (SHSs) are the real hope for electrification of the off-grid areas in Bangladesh by utilizing the solar energy in renewable and sustainable basis. This paper demonstrates the solar energy prospect, the present status and dissemination schemes of SHSs in off-grid and coastal areas of Bangladesh by several government and Non-government organizations (NGOs). The country has an average daily solar radiation ranges between 4–6.5kWh/m2. Currently, more than 3.8 million SHSs of capacity range 10–135Wp (watt peak) with a total capacity of 150MW have been disseminated in rural and isolated areas in Bangladesh. In this paper, ten case studies of capacity 20Wp, 30Wp and 42Wp were investigated to evaluate economic viability at two randomly selected villages in Sirajgonj district and Jessore district, Bangladesh. The analysis showed that the SHSs for small business enterprise and household with small income generation are economically viable rather than only household lighting.
In this work the high capacity anode material Sn4P3 for sodium ion batteries is investigated by electrochemical cycling and synchrotron-based hard x-ray photoelectron spectroscopy (HAXPES) in order to elucidate the solid electrolyte interphase (SEI) properties during the first 1.5 cycles. The electrochemical properties of tin phosphide (Sn4P3) when used as an anode material are first established in half cells versus metallic sodium in a 1M NaFSI in EC:DEC electrolyte including 5 vol% FEC as SEI forming additive. The data from these experiments are then used to select the parameters for the samples to be analysed by HAXPES. A concise series of five cycled samples, as well as a soaked and pristine sample, were measured at different states of sodiation after the initial sodiation and after the following full cycle of sodiation and desodiation. Our results indicate that the SEI is not fully stable, as both significant thickness and composition changes are detected during cell cycling.