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In this work, we select four types of substitute cations, Ti4+, Al3+, Mg2+ and Zn2+, to compare their influence on LiNi0.8Co0.1Mn0.1O2. After modification, the average lengths of NiO bonds are elongated with the turn of the Ti, Al, Mg, pristine and Zn-substituted, namely the bond energies are diminished with this sequence, according to their roughly inverse square relation. This tendency is also obeyed by oxygen defects, which induces the NiLi exchanging and surface decomposition, and then exert the effect on electrochemical behavior of Ni-rich cathodes. Among the investigated samples, the Ti-modified sample, which possesses the highest NiO bond energy, presents the best cyclic stability and rate capability, retaining 93.8% in the 200th cycle and 155.1 mAh g−1 under 5C, which is ∼12% higher than the pristine sample. Our approaches illustrate the importance of NiO network and provide a novel thought to further improve these promising cathodes.
The manufacture of lithium ion batteries requires some processing steps to be carried out in a dry room, where the moisture content should remain below 100 parts per million. The design and operation of such a dry room adds to the cost of the battery. This paper studied the humidity management of the air to and from the dry room to understand the impact of design and operating parameters on the energy demand and the cost contribution towards the battery manufacturing cost. The study was conducted with the help of a process model for a dry room with a volume of 16,000 cubic meters. For a defined base case scenario it was found that the dry room operation has an energy demand of approximately 400 kW. The paper explores some tradeoffs in design and operating parameters by looking at the humidity reduction by quenching the make-up air vs. at the desiccant wheel, and the impact of the heat recovery from the desiccant regeneration cycle.
Composite WO3–Nb2O5 thin films were deposited on the glass and fluorine-doped tin oxide (FTO)-coated glass substrates using simple and inexpensive spray pyrolysis technique. The process parameters, like nozzle-to-substrate distance, spray rate, concentration of sprayed solution, etc., were optimized to good quality films. The films were characterized for the structural, morphological, optical, and electrochromic properties. Structural and morphological characterizations of the films were carried out using scanning electron microscopy and X-ray diffraction techniques. Electrochemical properties of the Composite WO3–Nb2O5 thin films were further studied using cyclic-voltammetry, chronoamperometry, chronocoulometry, and electrochemical Impedance spectroscopy.
Ictal asystole is a cardiac phenomenon associated with epileptic seizures, and may play a role in sudden unexplained death in epilepsy. We present a 17-year-old boy with chronic intractable epilepsy and a vagus nerve stimulator who developed ictal asystole many years after the onset of epilepsy. The asystole was not linked to the vagus nerve stimulator, and ultimately necessitated the placement of a cardiac pacemaker. A cardiac pacemaker and vagus nerve stimulator can be safely used simultaneously after careful testing during placement. The onset of asystolic events many years after the onset of epilepsy suggests that repeated seizures may exert long-term effects on cardiac function.
Summary Synovial sarcoma of the pleural cavity is exceptionally rare and may be confused, both clinically and histologically, with malignant mesothelioma, with subsequent inappropriate therapy. To address this dilemma, four biphasic synovial sarcomas (BSSs) and four biphasic malignant mesotheliomas (BMMs) were studied with a panel of mucin and immunohistochemical stains to determine if they would allow one to distinguish between the two. The BMMs were all pleural-based. The BSSs were extrapleural. The mucin and immunohistochemical stains were all performed on formalin-fixed, paraffin-embedded tissue using standard techniques, with appropriate positive and negative controls. Mucin present in BSS is, in general, mucicarmine-positive and resistant to both hyaluronidase and diastase. Of the immune markers evaluated, only calretinin, Ber-Ep4 and bcl-2 were of limited discriminatory value. Subsets of cytokeratins, CEA and CD 34 were not helpful. With the exception of bcl-2, the apoptotic markers p53, bax and cpp32 (caspase) also were not useful. However, when the apoptotic stains were viewed collectively, variations in expression between the two tumours raised the possibility that alterations in apoptotic activity might be responsible for their pathogenesis and behavior. The diagnosis of BSS or BMM of the pleural should be made only after total consideration of clinical, radiological, histochemical and immunohistochemical findings. Although mucin stains are useful in differential diagnosis, reliance solely on immunohistochemical markers, with the possible exception of calretinin, Ber-Ep4 and bcl-2, is not dependable. The role of apoptosis in the pathogenesis of these tumours needs to be explored with a much larger series.
We present a new design of a lithium-ion gel polymer battery which is fabricated using a semi-interpenetrating network (semi-IPN) type gel polymer and LiCoO2, covered by an ion conductive polyurethane. A 7wt.% solution of a semi-IPN gel polymer, composed of a fully cyanoethylated cellulose derivative and multifunctional poly(oxyethylene)methacrylate has an ionic conductivity of 2.7×10−3 Scm−1 at 25°C, and has a higher degree of control of liquid electrolyte evaporation when compared with conventional fluoride polymer gels. Another ion conductive polymer, a caprolactone segmented polyurethane, arranged on the surface of the cathode active material in order to increase the start temperature of the thermal runaway reaction worked as planned, raising the exothermic decomposition temperature by 50°C. A large (2500mAh) cell showed good discharge performance and improved safety characteristics as judged by a nail penetration test. Furthermore, this battery system exhibited a unique phenomenon, that of preventing overcharging. The new design of this lithium-ion gel polymer battery could be promising for large batteries that must be inherently safe, such as batteries for mobile applications.
Building and transportation sectors account for approximately 75% of CO2 emissions. A mitigation strategy that combines both renewable energy sources and adoption of all-electric vehicles (EVs) instead of conventional gasoline powered vehicles thus seems most promising. The desired outcome of this strategy cannot be achieved without taking into consideration human activities in building and transportation. This study compares the energy use in building and transportation, aiming to provide a proper approach for evaluating the effectiveness and possible CO2 emissions reductions of GHG mitigation strategies. The analysis of the collected data showed that on average each individual produced around 20lbs of CO2 per day, 62% of the total CO2 was emitted in transportation. The mitigation strategy including EVs powered by electricity generated from coal-fired power plants resulted in average CO2 emissions reductions of 3.7%. The mitigation strategy using the EVs powered by solar energy obtained from grid-tied solar panels have led to 12.2% CO2 emissions reductions per day (from 12.38lbs/day to 10.87lbs/day), and the strategy incorporating EVs with the off-grid source of power was the most successful strategy and resulted in an average CO2 emissions savings of 12.38lbs/day. This study also estimates the initial cost per pound of CO2 emissions reduction per day for each of the mitigation strategies.
Three-Dimensional graphene (3D-G) material is regarded as an excellent carbon material, which reveals cross-linked porous structure, high specific surface area, strong mechanical strength and high conductivity inheriting from the graphene. In this work, we fabricate the novel 3D-G based materials by decoration of sodium citrate (SC) for supercapacitor and lithium ion batteries (LIBs) applications. SC with abundant functional groups and short carbon chain can ensure the interface between graphene sheets or between graphene and other composite materials, lead to shorter diffusion path for ions transportation. Owing to the large surface area and pore volume, 3D-G (SC) shows outstanding specific capacitance (301 F g−1) when it is applied in supercapacitors. Besides that, 3D-G (SC) compounds with Fe3O4 particles and 3D-G@Fe3O4(SC) are applied in LIBs. The 3D-G@Fe3O4 (SC) has a higher discharge capacity (1310.6 mAh g−1) than 3D-G@Fe3O4 (1270 mAh g−1) at 0.1 C, and it even increase to an excellent capacity (1550 mAh g−1) after 100 cycles. Moreover, 3D-G@Fe3O4(SC) shows excellent cycling stability that specific capacity retains 1031 mAh g−1 after 1000 cycles. This work may extend a novel approach to prepare 3D-G electrode material for efficient storage devices.
Particle/polymer electrospinning was used to prepare fiber mat cathodes containing LiCoO2 nanoparticles, carbon powder, and poly(vinylidene fluoride) for Li-ion batteries. The fibers had a high LiCoO2 particle content (70wt%) which allowed for a high gravimetric capacity of 90mAhg−1 (corresponding to 128 m A h g L i C o O 2 − 1 ) at 0.1C (1C=274 m A h g L i C o O 2 − 1 ). Cathode performance was stable in a half cell with 78% capacity retention over 200 cycles at 0.5C. Unlike previous work on electrospun LiCoO2 nanofibers prepared using sol-gel chemistry and high temperature processing, the particle/polymer fiber mat cathodes reported here were made thick with a high fiber volume fraction for high areal and volumetric capacities at fast charge/discharge rates (e.g., 0.81mAhcm−2 and 62mAhcm−3 at 2C) which were much greater than that of a slurry cast cathode of the same composition (0.004mAhcm−2 and 0.30mAhcm−3 at 2C). Full cells containing a LiCoO2/C/PVDF fiber mat cathode and C/PVDF fiber mat anode were also prepared and characterized. These electrospun batteries exhibited a high energy density of 144Whkg−1 at 0.1C and an areal capacity of 1.03mAhcm−2 at 1C. The excellent performance of the electrospun particle/polymer cathodes and anodes is attributed to electrolyte penetration throughout the 3D fiber electrode mats, a large electrode/electrolyte interfacial area, and short Li+ transport pathways between the electrolyte and active material nanoparticles in the radial fiber direction.
High theoretical capacity of metal phosphides makes them promising candidates for anode application in sodium ion batteries. In this work, we report a ternary compound phosphide—copper tin phosphide (Cu4SnP10) nanowires for sodium ion battery anode applications. The introduction of Cu helps to stabilize a rather high P content in the compound (as compared to Sn4P3, for example), enabling a high capacity of 811mAhg−1 at a current density of 25mAg−1 for phase pure Cn4SnP10 nanowire anode. Cu incorporation is also found to effectively alleviate Sn aggregation in the anode during charge/discharge cycles, which is known as a major contributor to the faded cycle performance of Sn-P compound. On the other hand, we show that possible volume expansion and instability of the solid electrolyte interface in the Cn4SnP10 nanowire anode remain as problems causing cycle instability of the electrode. By forming composite with multiwall carbon nanotubes, we demonstrate significantly improved cycle performance of the composite anode, which delivers a stable capacity of 512mAhg−1 after 100th cycle at a current density of 100mAg−1. At higher current density of 1Ag−1, the capacity of the composite electrode retains at 412mAhg−1, showing its good rate performance.
Dealloying is an important industrial technique for generating nanoporous metallic structures by selectively leaching out the more reactive metal component from an alloy material. A constant voltage is often applied to facilitate the dealloying process. Here we report the first study on dealloying with the application of a voltage waveform—specifically, pulsed voltage waveforms are applied for dealloying Ni–Cu alloys. It is found that pulsed dealloying voltage waveforms can exert a strong impact on the dealloying process by 1) significantly lowering the compositional threshold of the more reactive metal component for the dealloying reaction to take place, 2) more thoroughly removing the more reactive metal component and thus producing a porous metal of higher purity and higher porosity (volume fraction of voids), and 3) greatly affecting the morphology of the generated porous metal structure (e.g., leading to significantly thinner ligaments). The nanoporous metallic materials obtained by the pulsed voltage waveform enable supercapacitor electrodes of significantly better performance than the counterpart dealloyed with a constant voltage.
In this study, two issues regarding the use of the Portrait Value Questionnaire (PVQ; Schwartz et al.: J. Cross. Cult. Psychol. 32:519–542, 2001) with older adults were addressed: (1) whether the quasi-circumplex structure of values, developed on younger adult samples, also emerges among older adults; and (2) whether the PVQ demonstrates measurement invariance across age groups and equivalence over time. The 40-item version of the PVQ was completed by 433 retired adults and 173 university students in Montreal, Canada. In both retired and student samples, the quasi-circumplex structure of values emerged using exploratory techniques, but was not supported by constrained confirmatory factor analyses. A modified 26-item model was necessary to achieve adequate fit indices in both samples, suggesting problems of multi-collinearity and internal discriminant validity. However, using the revised 26-item model of the values, support was found for most types of measurement invariance across age groups and time. The PVQ should, therefore, be considered appropriate for use across the adult lifespan and in longitudinal research. Results are discussed with regard to the Schwartz (In: Zanna M (ed) Advances in experimental social psychology. New York: Academic Press, pp. 1–65, 1992) value theory and the conceptualizing of values across the lifespan.
The structures and anode performances of graphitized pristine and boron-doped shot and sponge cokes have been comparatively studied by means of scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and galvanostatic measurement. The results show that high degree of graphitization can be obtained by the substituted boron atom in the carbon lattice, and boron in the resultant boron-doped graphites mainly exist in the form of boron carbide and boron substituted in the carbon lattice. Both of boron-doped graphites from shot and sponge cokes obtain discharge capacity of 350mAhg−1 and coulombic efficiency above 90%. Apart from commonly observed discharge plateau for graphite, boron-doped samples in this study also show a small plateau at ca. 0.06V. This phenomenon can be explained that Li ion stores in the site to be void-like spaces that are produced by “molecular bridging” between the edge sites of graphene layer stack with a release of boron atoms substituted at the edge of graphene layer. The effect of the amount of boron dopant and graphitization temperature on the anode performance of boron-doped graphite are also investigated in this paper.
The use of a nonflammable electrolyte in a lithium secondary battery will greatly improve battery safety. Therefore, we focused on the nonflammability of ionic liquids and investigated these liquids as possible electrolyte solvents. In this study, we synthesized 1,2-diethyl-3,4(5)-dimethyl imidazolium (DEDMI) cations with imido anions. DEDMI cations with bis(trifluoromethylsulfonyl)imido anions (DEDMI-TFSI) showed a lower solidification point of −35°C, and higher specific conductivity than DEDMI cations with BF4−. We prepared an electrolyte consisting of DEDMI-TFSI with LiTFSI, and applied it to a Li/LiCoO2 cell. The cell was capable of charge–discharge cycling with LiCoO2 cathode material showing a specific capacity of about 100mAhg−1.
Li3V2(PO4)3 and Li3V2(PO4)3/C powders are prepared by ultrasonic spray pyrolysis from spray solutions with and without sucrose. The precursor powders have a spherical shape and the crystal structure of V2O3 irrespective of the concentration of sucrose in the spray solution. The powders post-treated at 700°C have the pure crystal structure of the Li3V2(PO4)3 phase irrespective of the concentration of sucrose in the spray solution. The Li3V2(PO4)3 powders prepared from the spray solution without sucrose have a non-spherical shape and hard aggregation. However, the Li3V2(PO4)3/C powders prepared from the spray solution with sucrose have a spherical shape and non-aggregation characteristics. The Li3V2(PO4)3 powders prepared from the spray solution without sucrose have a low initial discharge capacity of 122mAhg−1. However, the Li3V2(PO4)3/C powders prepared from the spray solutions with 0.1, 0.3, and 0.5M sucrose have initial discharge capacities of 141, 130, and 138mAhg−1, respectively. After 25 cycles, the discharge capacities of the powders formed from the spray solutions with and without 0.1M sucrose are 70% and 71% of the initial discharge capacities, respectively.
The Li–air (or Li–O2) battery has attracted wide attention, since it has the highest theoretical specific gravimetric energy density. In spite of the rapid progress made on improving its cyclic performance and reducing its voltage polarization, many key issues on thermodynamics and kinetics in nonaqueous Li–O2 batteries are still unresolved. In this study, by using the galvanostatic intermittent titration technique, several novel phenomena have been observed, such as zero voltage gap for the open circuit voltage (OCV) between charging and discharging, asymmetrical polarization behaviours at different current densities and temperatures, a continuous increase of overpotential during charging, and a negative temperature coefficient of the cell's thermodynamic equilibrium voltage. These results could inspire other researchers to comprehensively investigate the complicated reaction mechanisms, thermodynamics, and kinetic properties of the Li–air battery, as well as other advanced batteries.
The LiCoO2/graphite full cells (CP523450A) are cycled at different rates (0.6C, 1.2C, 1.8C and 3.0C), and the degradation mechanisms are evaluated in this paper. The lithium metal is deposited on the anode when the cycling rate is higher than or equal to 1.8C, which is confirmed by the tests of the incremental capacity (IC) curves, XPS, DSC and SEM. The root cause of the lithium deposition is analyzed by the available capacities of the single electrodes as well as the actual capacity ratio of anode to cathode (actual A/C ratio). The rate capability of the anodes recovered from the fresh and the aged full cells is quite poor in comparison with the cathodes. Therefore, the capacity of full cell is limited by the anode when the test rate is relatively high. In such situation, the coulombic efficiency is less than 1, and its value is slightly larger than the actual A/C ratio which is the root cause of the deposition of lithium metal. Compared with the generation of SEI film, the lithium deposition leads to an accelerated loss rate of active lithium which results in the rapid capacity fade of full cell. The research about the actual A/C ratio provides a guidance for the design of the initial reversible capacity ratio of anode to cathode (initial A/C ratio) of lithium ion batteries.
Cathode materials LiMn0.5Fe0.5PO4/C and LiMnPO4/C were synthesized by a high-energy ball-milling assisted sol-gel method. The LiMn0.5Fe0.5PO4 consists of nanorods and nanoparticles homogeneously wrapped with highly ordering carbon. The increased Néel-temperature and decreased effective magnetic moment of LiMn0.5Fe0.5PO4/C revealed the microstructure differences from LiMnPO4/C. Meanwhile, tiny amount of ferromagnetic impurities is detected in LiMn0.5Fe0.5PO4/C by magnetic tests. The synergetic effects of Fe substitution and carbon coating remarkably improve rate capacity and cyclic stability of LiMn0.5Fe0.5PO4/C. This solid solution delivers initial discharge capacities of 128.6mAhg−1 and 116.3mAhg−1 and capacity retentions of 93.5% and 90.3% after 100 cycles at 1C and 2C respectively, significantly better than LiMnPO4/C.
Electrochemical synthesis, in situ spectroelectrochemistry of conducting polyindole (PIn), polyindole-TiO2 (PIn-TiO2) and polyindole-ZnO (PIn-ZnO) nanocomposites were investigated. The PIn and polymer nanocomposites were tested electrochemically for rechargeable batteries. The films were characterized by means of CVs, in situ UV-visible, FT-IR spectroscopies, in situ resistivity measurements, energy dispersive X-ray (EDX), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The charge-discharging behavior of a Zn/1M ZnSO4/PIn cell with a capacity of around 90AhKg−1 and on open circuit potential of around 1.45V was compared with Zn/1M ZnSO4/PIn-nanocomposite. The potential differences of redox couples (ΔE) for nanocomposites films show very good reversibility. A positive shift of potential was observed for polymer nanocomposites during redox scan. A significant variability was observed for in situ conductivity of the PIn and polymer nanocomposites. During in situ UV-visible and FT-IR measurements, intermediate spectroscopic behavior and positive shifts of wavelengths were observed for PIn and polymer nanocomposites. The SEM, TEM and EDX of nanocomposite films show the presence of nano particle in PIn.
In this study, two cadmium-tolerant endophytic bacteria (Microbacterium sp. D2-2 and Bacillus sp. C9-3) were employed as biosorbents to remove Cd(II) from aqueous solutions. The influence of initial pH, initial Cd(II) concentration, adsorbent biomass, temperature and contact time on Cd(II) removal were investigated. Results showed that the Langmuir isotherms were found to best fit the equilibrium data, and the maximum biosorption capacities were found to be 222.22 and 163.93 mg/g at a solution pH of 5.0 for Microbacterium sp. D2-2 and Bacillus sp. C9-3, respectively. The biosorption kinetics followed well pseudo-second-order kinetics. Fourier transform infrared spectroscopic analysis suggested that the hydroxyl, carboxyl, carbonyl and amino groups on Microbacterium sp. D2-2 and Bacillus sp. C9-3 biomass were the main binding sites for Cd(II). The results presented in this study showed that Microbacterium sp. D2-2 and Bacillus sp. C9-3 are potential and promising adsorbents for the effective removal of Cd(II) from aqueous solutions.
Owing to the exceptionally high energy potential of lithium–oxygen chemistry, lithium–air batteries have received much attention as appealing alternatives to current state-of-art lithium ion batteries. However, owing to the presence of non-O2 components in ambient air, the practical performance of Li–air batteries is limited to only a few cycles with low energy efficiency. In particular, when CO2 is incorporated into the battery system, Li2CO3 is formed during discharging, which results in serious climbing of the charge potential and subsequent decomposition of the cell components. Herein, by introducing an appropriate electrolyte into an aggregated contact ion pair (CIP) structure, we demonstrate a Li–O2/CO2 battery, via formation of stabilized peroxodicarbonate (C2O62−) rather than Li2CO3 in the electrolyte, that operates with a very low charge potential (3.5 V). We anticipate that this discovery will provide a rational design strategy for modifying the reaction pathway of Li–O2/CO2 battery and accelerating the evolution of Li–O2 batteries to Li–air batteries.