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Solar water splitting is an effective approach to hydrogen production and application of solar energy. However, the photo-generated hydrogen should be initially stored in high pressure cylinder and subsequently applied in hydrogen-oxygen fuel cells. Herein, a solar rechargeable battery is proposed based mainly on hydrogen storage mechanism in dual-phase electrolyte. Specifically, the hydrogen production, storage and utilization are integrated into a hybrid system of the dye-sensitized solar cell and electrochemical cell with the dye-sensitized TiO2 as photo-anode, LiI as the cathode active material in organic electrolyte, AB5-type hydrogen storage alloy as anode in alkaline solution, and PEDOT-modified Nafion membrane as separator. Here, the photo-generated electrons in organic electrolyte pass to the AB5-type hydrogen storage alloy to split water in alkaline aqueous electrolyte for generating hydrogen, which is in situ stored into AB5-type hydrogen storage alloy. Subsequently, the hydrogen stored in the AB5-type hydrogen storage alloy can be oxidized by electrochemical way to generate electricity, coupled with LiI cathode in organic electrolyte. The solar rechargeable battery demonstrates a new solution of the solar energy conversion, hydrogen production, storage, and utilization, achieving the new energy conversion and storage from solar energy to chemical energy, and further to electrical energy.
Lignin is often overlooked in the valorization of lignocellulosic biomass, but lignin-based materials and chemicals represent potential value-added products for biorefineries that could significantly improve the economics of a biorefinery. Fluctuating crude oil prices and changing fuel specifications are some of the driving factors to develop new technologies that could be used to convert polymeric lignin into low molecular weight lignin and or monomeric aromatic feedstocks to assist in the displacement of the current products associated with the conversion of a whole barrel of oil. We present an approach to produce these chemicals based on the selective breakdown of lignin during ionic liquid pretreatment.
In this paper, we report a detailed investigation of the effect of varying concentrations of sodium dodecyl sulfate (SDS) on the rate of polymerization of aniline. Quantitative analysis of the data is done in order to propose a probable mechanism for the growth of polyaniline (PANI) in presence of SDS (SDS–PANI). The SDS–PANI films were characterized by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM), in situ conductance, in situ UV–vis spectroscopy and scanning electron microscopy (SEM) and were contrasted with polyaniline prepared under identical conditions in the absence of SDS. The polymerization rate was found to decrease initially with increase in concentration of SDS; it passes through a minimum at 1.5 mM and then increases rapidly on further increasing the SDS concentration. EQCM studies showed that the polymerizing species is a charge transfer complex formed between SDS and aniline. Leaching out of SDS was observed during redox cycling of the SDS–PANI films, which results in the formation of a porous polymer film allowing more inclusion of ions. This was further confirmed by observing a higher transport rate of urea across SDS–PANI coated membrane. These porous polyaniline films were then used as transducer for sensing urea.
Electrode architectures with large capacity and good stability are exceedingly desired but remain an intriguing challenge for energy storage applications such as on-chip integrated microbatteries, where there is a grand need for high-energy and high-power three-dimensional (3D) electrodes to replace the conventional planar electrodes. Here we report a highly efficient and durable lithium electrode based on 3D self-supported nanoporous tantalum pentoxide (Ta2O5) film. The Ta2O5 film is prepared by electrochemically anodizing tantalum metal in ammonium fluoride electrolyte and subsequent thermal annealing at 450°C in argon atmosphere, which does not crystallize the film but gives rise to significant amount of oxygen deficiency. The Ta2O5 film exhibits a high lithium capacity of ~ 480mAhg−1 and remarkable cycling stability over 8000 cycles at a rate of 5C, which could be attributed to improved transport kinetics and structural integrity as a result of amorphous structure, oxygen deficiency, and nanoporous architecture.
Nickel iron (III) oxyphosphate NiFeOPO4 (NFP) was successfully synthesized using solid-state route and modified with carbon layer using sucrose as carbon source. The electrochemical performances of the composite anode material NiFeOPO4/C (NFP/C) vs. Li+/Li0 were investigated at C/5 current rate and in a wide voltage window 0.01–3.0 V. During the first lithiation at C/5, NFP/C was able to uptake more than six lithium ions into the structure delivering a capacity of 736.63 mAh g−1. In this study, NFP phosphate was characterized using XRD, SEM, EDS mapping, and Raman spectroscopy. The first cycle was investigated using high energy spectroscopies including: in-situ synchrotron X-Ray Diffraction and ex-situ X-ray Absorption Near Edge Spectroscopy (XANES). In-situ synchrotron XRD revealed that the crystal structure of NFP/C undergoes structural transformations leading to lower degrees of crystallinity during the first lithiation. Ex-situ XANES measurements disclosed that the redox reaction of iron and nickel during the first lithiation and delithiation is reversible.
Properties of a γ-butyrolactone-acetonitrile solution of triethylmethylammonium tetrafluoroborate were systematically measured for its potential to be used as an electrolyte in double-layer capacitors and for demonstrating the ways in which these properties can be optimized through choosing an appropriate solvent mixture and an appropriate salt and adjusting the electrolyte composition. These properties included the liquid range of the solvent and the solution at different compositions, the dielectric constant of the binary solvent as a function of solvent composition and temperature, the conductivity of the solution as a function of salt content, solvent composition, and temperature and the oxidative stability of the electrolytes at different solvent compositions. To correlate the properties of the electrolytes with the properties and performance of the double-layer capacitors utilizing the electrolytes, such capacitors were built and their equivalent series resistance, cyclic voltammogram, and operating voltage were measured for different solvent compositions of the capacitor electrolytes. The results revealed a clear correlation between the conductivity and the oxidative stability of the electrolytes and the equivalent series resistance and the operating voltage of the capacitors, respectively. Furthermore, it is clearly demonstrated that by using a binary solvent and adjusting its composition properly, the electrolyte it makes with an appropriate salt can be effectively optimized with regard to its liquid range, conductivity, and electrochemical stability window, which in turn imparts the double-layer capacitor utilizing such an electrolyte with a set of optimal properties such as a wide range of operating temperature, low equivalent series resistance, and high operating voltage.
Since NiMH and NiCd batteries are still used in the electronic devices market, a treatment and recycling plant has many advantages both from the environmental and the economic points of view. Unfortunately, there is no relationship between shape, size and chemical composition of spent batteries, consequently the characterization and the leaching method of the starting material becomes an important step of the overall treatment process in choosing the best conditions for the selective separation of the metals by hydrometallurgy. Leaching at 20°C with H2SO4 2M for about 2h seems to be a good solution in terms of cost and efficiency for both battery types. The hydroxide compounds can be readily leached while Ni present as metallic form requires more aggressive conditions due to kinetic constraints. In this paper, the characterization of NiMH and NiCd spent batteries and the results of leaching tests in different conditions are reported.
Lithium insertion in anatase is studied by considering simultaneously the effects of crystallinity and surface area on storage mechanism, namely intercalation vs. pseudocapacitive. 6 nm anatase crystallites with high surface area (222 m2 g−1), synthesized via a novel continuous aqueous process and annealed at different temperatures (200 °C, 300 °C, and 400 °C), were electrochemically tested. By annealing, crystallinity was increased, while surface area decreased allowing for the investigation of the contributions of each toward lithiation and delithiation behavior. The as-synthesized and best-annealed (at 300 °C) samples were compared at various rates. At low rate (1C and 2C) the annealed anatase had higher reversible capacity than the as-synthesized, due to increased diffusion-based storage. At high rate however, as-synthesized anatase had much higher capacity due to increased surface area and ability to store Li-ions pseudocapacitively. Increased crystallinity leads to increased diffusivity as determined by electrochemical impedance spectroscopy, explaining why the 300 °C anneal had higher capacity at low rate. Long-term cycling at high rate, however, showed that reliance on diffusion-based storage (intercalation) in the case of the 300 °C anneal causes increased polarization that leads to electrode performance decline. These results point to the importance of simultaneous nanoanatase property (crystallinity and surface area) optimization for achieving stable performance.
Left ventricular assist device (LVAD) is considered a standard care for patients with advanced heart failure. The aim of this work was to study in vitro the effects of direct exposure of the Jarvik 2000 LVAD to 10-MV photon beams.
The electrochemical extraction/insertion of Li from/into LiCoMnO4 in the potential range of 3.7–5.25V is studied by electron paramagnetic resonance (EPR) of Mn4+. Structural characterization of initial LiCoMnO4 has been performed by neutron diffraction. The EPR spectra are consistent with a single-phase mechanism of electrochemical extraction/insertion of Li from/into LiCoMnO4. During Li extraction, the intensity of the main EPR signal due to Mn4+ ions in Mn4+/Co3+ environment decreases drastically concomitantly with the appearance of resonance absorption from magnetically correlated Mn4+–Co4+ spins. From EPR, the complex [Co n+–Mn3+–Mn4+] clusters indicative of the oxygen non-stoichiometry of LiCoMnO4 also take part in the electrochemical reaction, especially up to 4.7V. During the Li reinsertion, the EPR signal from Mn4+ ions in Mn4+/Co3+ environment is recovered, but its intensity remains lower (30%) as compared to that of the initial composition, which is consistent with an unrecovered composition of LiCoMnO4 electrode after first charge/discharge. Contrary to the narrow main signal, there is a reverse reduction of the paramagnetic ions present in the clusters, but their oxidation state as compared to the initial composition is not recovered.
The evolution of charge capacity with cycle number into 50/50 TiFe intermetallic compound (IMC) has been investigated. It has been found that in lithiated KOH electrolyte the passivation of a TiFe pressed powder electrode is slowed but not eliminated. Mechanical mixing of the IMC with minor amounts of Ni powder results in better cycle life, probably due to the reduction of passivating oxides, electrocatalytically induced by finely divided Ni. However the best improvement of cycle life was obtained from TiFe+Fe composite electrodes. Although the main charge storage route is again hydrogen insertion into TiFe, the onset of passivation of the IMC is significantly delayed by the presence of Fe.
This paper takes a critical look at the materials aspects of thermal runaway of lithium-ion batteries and correlates contributions from individual cell components to thermal runaway trends. An accelerating rate calorimeter (ARC) was used to evaluate commercial lithium-ion cells based on LiCoO2 (LCO), LiFePO4 (LFP), and LiNixCoyAl1-x-yO2 (NCA) at various states of charge (SOC). Cells were disassembled and the component properties were evaluated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and temperature-resolved X-ray diffraction (TR-XRD). The whole cell thermal runaway onset temperature decreases and peak heating rate increases with SOC due to cathode destabilization. LCO and NCA cathodes are metastable, with NCA cells exhibiting the highest thermal runaway rates. By contrast, the LFP cathode is stable to >500 °C, even when charged. For anodes, the decomposition and whole cell self-heating onset temperature is generally independent of SOC. DSC exotherm onset temperatures of the anodes were generally within 10 °C of the onset of self-heating in whole cell ARC. However, onset temperatures of the cathodes were typically observed above the ARC onset of whole cell runaway. This systematic evaluation of component to whole cell degradation provides a scientific basis for future thermal modeling and design of safer cells.
Thin-film molybdenum oxysulfide films were deposited electrochemically on both nickel foils and nickel-coated silicon substrates, and used as cathodes in lithium battery cells that included a lithium anode and a hybride gel electrolyte (HPE) or solid polymer electrolyte (SPE). X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) characterizations indicated that the sub-micron thick MoO y S z films were amorphous, with the stoichiometry of the films varying with depth. A Li/HPE/MoO y S z on nickel and nickel-coated silicon ran at i d=i ch=100μA/cm2 and room temperature for 1000 charge/discharge cycles with 0.05% per cycle capacity loss and 100% Faradaic efficiency. Cells with SPE cycled at 125°C showed a higher per cycle capacity loss of 0.5%.
Marine sponges are a rich source of structurally and biologically active metabolites of biomedical importance. We screened polar and non-polar samples of crude extracts obtained from marine sponges collected in different locations of Argentinean south sea coast, as a novel approach for their characterization. The evaluation was performed using cytotoxic and genotoxic biomarkers such as mitotic index (MI), cell proliferation kinetics (CPK) and sister chromatid exchanges (SCE), monitored in vitro using peripheral blood lymphocytes. Statistical analysis was performed using two-way analysis of variance (ANOVA). The extracts evaluated belonged to: Callyspongia flabellata (BURTON, 1932) (Callyspongiidae); Plicatellopsis sp.(Suberitidae); Callyspongia fortis (RIDLEY, 1881) (Callyspongiidae); Clathria (Microciona) antarctica (TOPSENT, 1917) (Microcionidae); Spongia (Spongia) magellanica (THIELE, 1905) (Spongiidae); Halicnemia papillosa (THIELE, 1905) (Axinellidae); Cliona chilensis (THIELE, 1905) (Clionidae); Haliclona sp. 1; Haliclona sp. 2(Chalinidae). Genotoxicity studies revealed that the evaluated sponge extracts did not exhibit cytotoxic activity measured from mitotic index MI and cell proliferation kinetics(CPK). In contrast, sister chromatid exchanges (SCE) showed that the non-polar extract of Callyspongia fortis and the polar extract of Cliona chilensis presented significant differences in SCE frequency (p<0.001), when compared with control cultures. These results emphasize the need to set up a standard battery of “in vitro” genotoxicity testing for new chemicals, pharmaceutical and drugs.
Change in the content of lithium sulfide is quantitatively studied through the methods of precipitation and back iodometric titration in lithium-sulfur cells during charge-discharge cycling for 100 cycles. It is shown that in the initial cycles (25 cycles) of charge-discharge cycling, electrochemically inactive lithium sulfide accumulates. The predominantly inactive lithium sulfide accumulates in the sulfur electrode. It is likely that lithium sulfide is deposited in the pores of the carbon material, blocks the pores and loses the ability to participate in the electrochemical reactions. On the surface of the lithium electrode, a surface layer containing lithium sulfide is formed during the cycling of the lithium-sulfur cells and is in equilibrium with the electrolyte system. It is found that lithium sulfide does not accumulate on the lithium electrode for at least 100 charge-discharge cycles.
A new type of LiFePO4/C composite surrounded by a web containing both amorphous and crystalline carbon phases was synthesized by incorporating malonic acid as a carbon source using a high temperature solid-state method. SEM, TEM/SAED/EDS and HRTEM were used to analyze surface morphology and confirmed for the first time that crystalline carbon was present in LiFePO4/C composites. The composite was effective in enhancing the electrochemical properties such as capacity and rate capability, because its active component consists of nanometer-sized particles containing pores with a wide range of sizes. An EDS elemental map showed that carbon was uniformly distributed on the surface of the composite crystalline particles. TEM/EDS results clearly show a dark region that is LiFePO4 with a trace of carbon and a gray region that is carbon only. To evaluate the materials’ electrochemical properties, galvanostatic cycling and conductivity measurements were performed. The best cell performance was delivered by the material coated with 60wt.% malonic acid, which delivered first cycle discharge capacity of 149mAhg−1 at a C/5 rate and sustained 222 cycles at 80% of capacity retention. When carboxylic acid was used as a carbon source to produce LiFePO4, overall conductivity increased from 10−5 to 10−4 Scm−1, since particle growth was prevented during the final sintering process.
Radio links are used to provide backhaul connectivity for base stations of mobile networks, in cases in which cable-based alternatives are not available and cannot be deployed in an economic or timely manner. While such wireless backhauls have been predominantly used in redundant tree and ring topologies in the past, mobile network operators have become increasingly interested in meshed topologies for carrier-grade wireless backhauls. However, wireless mesh backhauls are potentially more susceptible to security vulnerabilities, given that radio links are more exposed to tampering and given their higher system complexity. This article extends prior security threat analyses of 3rd generation mobile network architectures for the case of wireless mesh backhauls. It presents a description of the security model for the considered architecture and provides a list of the basic assumptions, security objectives, assets to be protected and actors of the analysis. On this foundation, potential security threats are analyzed and discussed and then assessed for their corresponding risk. The result of this risk assessment is then used to define a set of security requirements. Finally, we give some recommendations for wireless mesh backhaul designs and implementations following these requirements.
CN(CH2)2Si(CH3)(OCH2CH2OCH3)2 (BNS) is used as electrolyte solvent to improve the safety for LiNi1/3Co1/3Mn1/3O2 (NCM)/graphite battery. BNS increases the thermal stability of the carbonate-based electrolyte with (de) lithiated cathode/anode and the electrochemical stability of coin cells. By using an optimal BNS-based electrolyte formula, 13 Ah NCM/graphite prismatic cell achieves 95.8% retain of capacity at 2 C/3 C (charge/discharge) rate after 600 cycles. Meanwhile, 13 Ah prismatic cell exhibits improved safety performance in the nail penetration test.
The authors regret that titles were incorrectly placed in the table of the appendix and that an error in the calculations plotted in Figs. 2 and 4 were also incorrect. Please find the corrected version of Figs. 2 and 4 below. Fig. 2Image 1 Fig. 4Image 2 The authors would like to apologise for any inconvenience caused.
This study reports on solid-state batteries operating at 120 °C prepared with metal hydride MH nanocomposites xMgH2+(1-x)TiH2 used as active materials for the positive electrode, metallic Li as the negative electrode and LiBH4 as the solid electrolyte. The molar content x of the MH nanocomposites ranged from 0.2 to 0.8. The electrochemical properties of the metal hydride electrodes are here scrutinized as a function of the chemical composition of the active materials. Mg-rich nanocomposites offer higher specific capacity (over 1700 mAh g−1 at C/50 regime for x = 0.7), whereas Ti-rich ones exhibit better cycle-life (ca. 100% capacity retention after 10 cycles for x = 0.2). In comparison to equivalent liquid electrolyte cells operated at RT, solid-state cells show improved properties such as a coulombic efficiency above 98% and a rate capability of ca. 50% of delivered capacity at 1C-rate. It is also evidenced that mass transport within the working electrode is a key factor limiting the reversibility of hydride conversion reactions. This work represents a deep insight on the hurdles of metal hydrides to be used as efficient anode materials for Li-ion batteries.
Clean technology company Pu Neng has attracted a major investment from High Power Exploration (HPX), a metals-focused exploration firm that also invests in minerals-dependent, high-growth emerging technologies – bringing the total invested capital to-date to over $90 million.
The present work offers a facile, cost-effective and green strategy to efficiently regulate the pore dimensions and surface morphology of Nickel based Metal organic frameworks (MOFs) using three carboxylic acids of different molecular lengths. The material characterization studies revealed that Ni MOF with longer organic linker i.e., 4, 4‘-Biphenyl dicarboxylic acid (Ni-BPDC) exhibits large surface area and large pore dimensions which enables swift movement of electrolyte ions through the framework. Also, the interconnected network of Ni-BPDC nanoplates results into continuous charge distribution, thus delivering better electrochemical performance amongst three Ni MOFs. Furthermore, to enhance the electrochemical performance of Ni-BPDC, it was combined with carbon nanofibers (CNF) and the electrochemical characterization studies of Ni-BPDC/CNF as a single electrode material shows its high specific capacity of 250.6 mA h g−1 at current density of 1 A g−1. To further explore real time application of Ni-BPDC/CNF composite, a symmetric supercapacitor device was fabricated in a Swagelok cell and it is found to deliver excellent energy density of 48.1 Wh kg−1 and power density of 1064.7 W kg−1 at an operating voltage of 1.2 V. Besides, it manifests a long cycle life with only 8% deterioration of initial specific capacity after 5000 cycles. We believe that these encouraging results not only suggests the possibility for tuning properties of existing MOFs using different organic linkers but also provides an efficient way to develop hybrid MOF composites for future energy storage applications.
The aims were to use different techniques to assess the degree of sensory changes and magnitude of perceived size changes in the facial region induced by nerve blocks of two different trigeminal nerve branches in healthy participants.