Preparation of silicon-metal nanocomposites based on electrophoretic deposition

Silicon has long been considered as one of the most promising anode material for lithium-ion batteries. However, the poor cycle life due to stress during charge/discharge cycling has been a major concern for its practical applications. In this report, novel Si-metal nanocomposites have been explored to accommodate the stress generated in the intercalation process. Several approaches have been studied with the aim of getting uniform mixing, good mechanical stability and high Si content. Among the three approaches being investigated, Si- Galinstan nanocomposite based on electrophoretic deposition showed the best promise by achieving at least 32.3% Si theoretical weight percentage, and our in current experiments we’ve already get 13% Silicon weight percentage, which gave us an anode material 46% more capacity than the current commercial product.

Advanced Nanostructured Electro-Catalysts for Electricity Generation and Biorenewable Alcohol Conversion

In my Ph.D research, a wet chemistry-based organic solution phase reduction method was developed, and was successfully applied in the preparation of a series of advanced electro-catalysts, including 0-dimensional (0-D) Pt, Pd, Au, and Pd-Ni nanoparticles (NPs), 1-D Pt-Fe nanowires (NWs) and 2-D Pd-Fe nanoleaves (NLs), with controlled size, shape, and morphology. These nanostructured catalysts have demonstrated unique electro-catalytic functions towards electricity production and biorenewable alcohol conversion. The molecular oxygen reduction reaction (ORR) is a long-standing scientific issue for fuel cells due to its sluggish kinetics and the poor catalyst durability. The activity and durability of an electro-catalyst is strongly related with its composition and structure. Based on this point, Pt-Fe NWs with a diameter of 2 - 3 nm were accurately prepared. They have demonstrated a high durability in sulfuric acid due to its 1-D structure, as well as a high ORR activity attributed to its tuned electronic structure. By substituting Pt with Pd using a similar synthesis route, Pd-Fe NLs were prepared and demonstrated a higher ORR activity than Pt and Pd NPs catalysts in the alkaline electrolyte. Recently, biomass-derived alcohols have attracted enormous attention as promising fuels (to replace H2) for low-temperature fuel cells. From this point of view, Pd-Ni NPs were prepared and demonstrated a high electro-catalytic activity towards ethanol oxidation. Comparing to ethanol, the biodiesel waste glycerol is more promising due to its low price and high reactivity. Glycerol (and crude glycerol) was successfully applied as the fuel in an Au-anode anion-exchange membrane fuel cell (AEMFC). By replacing Au with a more active Pt catalyst, simultaneous generation of both high power-density electricity and value-added chemicals (glycerate, tartronate, and mesoxalate) from glycerol was achieved in an AEMFC. To investigate the production of valuable chemicals from glycerol electro-oxidation, two anion-exchange membrane electro-catalytic reactors were designed. The research shows that the electro-oxidation product distribution is strongly dependent on the anode applied potential. Reaction pathways for the electro-oxidation of glycerol on Au/C catalyst have been elucidated: continuous oxidation of OH groups (to produce tartronate and mesoxalate) is predominant at lower potentials, while C-C cleavage (to produce glycolate) is the dominant reaction path at higher potentials.

EVALUATION OF MAGNESIUM AS A HALL THRUSTER PROPELLANT

In this study, the use of magnesium as a Hall thruster propellant was evaluated. A xenon Hall thruster was modified such that magnesium propellant could be loaded into the anode and use waste heat from the thruster discharge to drive the propellant vaporization. A control scheme was developed, which allowed for precise control of the mass flow rate while still using plasma heating as the main mechanism for evaporation. The thruster anode, which also served as the propellant reservoir, was designed such that the open area was too low for sufficient vapor flow at normal operating temperatures (i.e. plasma heating alone). The remaining heat needed to achieve enough vapor flow to sustain thruster discharge came from a counter-wound resistive heater located behind the anode. The control system has the ability to arrest thermal runaway in a direct evaporation feed system and stabilize the discharge current during voltage-limited operation. A proportional-integral-derivative control algorithm was implemented to enable automated operation of the mass flow control system using the discharge current as the measured variable and the anode heater current as the controlled parameter. Steady-state operation at constant voltage with discharge current excursions less than 0.35 A was demonstrated for 70 min. Using this long-duration method, stable operation was achieved with heater powers as low as 6% of the total discharge power. Using the thermal mass flow control system the thruster operated stably enough and long enough that performance measurements could be obtained and compared to the performance of the thruster using xenon propellant. It was found that when operated with magnesium, the thruster has thrust ranging from 34 mN at 200 V to 39 mN at 300 V with 1.7 mg/s of propellant. It was found to have 27 mN of thrust at 300 V using 1.0 mg/s of propellant. The thrust-to-power ratio ranged from 24 mN/kW at 200 V to 18 mN/kW at 300 volts. The specific impulse was 2000 s at 200 V and upwards of 2700 s at 300 V. The anode efficiency was found to be ~23% using magnesium, which is substantially lower than the 40% anode efficiency of xenon at approximately equivalent molar flow rates. Measurements in the plasma plume of the thruster—operated using magnesium and xenon propellants—were obtained using a Faraday probe to measure off-axis current distribution, a retarding potential analyzer to measure ion energy, and a double Langmuir probe to measure plasma density, electron temperature, and plasma potential. Additionally, the off axis current distributions and ion energy distributions were compared to measurements made in krypton and bismuth plasmas obtained in previous studies of the same thruster. Comparisons showed that magnesium had the largest beam divergence of the four propellants while the others had similar divergence. The comparisons also showed that magnesium and krypton both had very low voltage utilization compared to xenon and bismuth. It is likely that the differences in plume structure are due to the atomic differences between the propellants; the ionization mean free path goes down with increasing atomic mass. Magnesium and krypton have long ionization mean free paths and therefore require physically larger thruster dimensions for efficient thruster operation and would benefit from magnetic shielding.

NANOSCALE ELECTROCHEMISTRY BY IN-SITU TRANSMISSION ELECTRON MICROSCOPY

Nanoscale research in energy storage has recently focused on investigating the properties of nanostructures in order to increase energy density, power rate, and capacity. To better understand the intrinsic properties of nanomaterials, a new and advanced in situ system was designed that allows atomic scale observation of materials under external fields. A special holder equipped with a scanning tunneling microscopy (STM) probe inside a transmission electron microscopy (TEM) system was used to perform the in situ studies on mechanical, electrical, and electrochemical properties of nanomaterials. The nanostructures of titanium dioxide (TiO2) nanotubes are characterized by electron imaging, diffraction, and chemical analysis techniques inside TEM. TiO2 nanotube is one of the candidates as anode materials for lithium ion batteries. It is necessary to study their morphological, mechanical, electrical, and electrochemical properties at atomic level. The synthesis of TiO2 nanotubes showed that the aspect ratio of TiO2 could be controlled by processing parameters, such as anodization time and voltage. Ammonium hydroxide (NH4OH) treated TiO2 nanotubes showed unexpected instability. Observation revealed the nanotubes were disintegrated into nanoparticles and the tubular morphology was vanished after annealing. The nitrogen compounds incorporated in surface defects weaken the nanotube and result in the collapse of nanotube into nanoparticles during phase transformation. Next, the electrical and mechanical properties of TiO2 nanotubes were studied by in situ TEM system. Phase transformation of anatase TiO2 nanotubes into rutile nanoparticles was studied by in situ Joule heating. The results showed that single anatase TiO2 nanotubes broke into ultrafine small anatase nanoparticles. On further increasing the bias, the nanoclusters of anatase particles became prone to a solid state reaction and were grown into stable large rutile nanoparticles. The relationship between mechanical and electrical properties of TiO2 nanotubes was also investigated. Initially, both anatase and amorphous TiO2 nanotubes were characterized by using I-V test to demonstrate the semiconductor properties. The observation of mechanical bending on TiO2 nanotubes revealed that the conductivity would increase when bending deformation happened. The defects on the nanotubes created by deformation helped electron transportation to increase the conductivity. Lastly, the electrochemical properties of amorphous TiO2 nanotubes were characterized by in situ TEM system. The direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes was studied. The results indicated that the lithiation started with the valance reduction of Ti4+ to Ti3+ leading to a LixTiO2 intercalation compound. The continued intercalation of Li ions in TiO2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano islands and identified to be Li2Ti2O4 with cubic structure (a = 8.375 Å). This phase transformation is associated with local inhomogeneities in Li distribution. Based on these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO2 nanotubes.

The Effect of the Cu:Fe''' Ratio Upon the Current Efficiency in the Electrolysis of a Copper Sulfate Solution Containing Iron Sulfate

It is a well-known fact that, in the electrolysis of a CuSO4 solution containing iron sulfate, using insoluble anodes, with the depletion of copper, the point is finally reached where the current efficiency becomes zero. This decrease in current efficiency is due to the oxidation of the ferrous sulfate to the ferric condition at the anode, by the oxygen liberated. The resulting ferric sulfate diffuses over to the cathode and there dissolves copper from the cathode according to the chemical equation Cu + Fe2 (SO4)3 = CuSO4 + 2FeSO4. This copper, which has been deposited at the cathode by the electric current, is thus redissolved by the Fe2(SO4)3. The solution of the copper causes at the same time a formation of FeSO4 which in turn diffuses over to the anode and is there oxidized to Fe2(SO4)3; and so the cycle continues, using electric current without rendering useful work. E. H. Larison has noted that a definite amount of ferric salts must be reduced to the ferrous condition before all the copper will remain on the cathode; he does not state, however, just what this point is. L. Addicks has plotted the relation between current efficiency and ferric sulphate content. The existence of the results scattered the points more or less, although the decrease in current efficiency with increased ferric sulphate content is clearly indicated. E. T.Kern has likewise noted that the smaller the amount of copper in the solution, the greater is the reduction of current efficiency. In this work, therefore, it was desired to determine what amount of ferric iron was permissible in a copper sulfate solution of definite concentration before the current efficiency would drop to zero, and what, if any, was the effect of definite Cu:Fe’’’ratio upon the current efficiency of the electrolysis.

The Effect of the Fe2: Fe3 Ratio upon the Current Efficiency in the Electrolysis of a Copper Sulfate Solution Containing Iron Sulfate

In the treatment of copper ores by hydro-electro-metallurgical methods, not only is copper deposited, but other metals are also dissolved. In practice it has been found* that iron, under certain conditions, causes the copper to deposit on the cathode as a nonadherent precipitate and also that the iron in solution causes a great decrease in current efficiency, es­pecially when the electrolysis is conducted by operating with a higher current density at the cathode than at the anode. The present investigation deals with the effects of the two valences of iron on the current efficiency and endeavors to determine whether or not there is a ratio of the two at which point the efficiency becomes zero or approaches it.

The Effects of Zinc Sulphate, Manganese Sulphate, and Iron Sulphate on the Lead Storage Cell.

The lead storage battery as it is used today is made up of the pasted type plates of lead dioxide, the anode, and sponge lead, the cathode, and wooden or hard rubber separators, which serve to insulate these from one another. In manufacturing these, it is desirable to keep them free from impurities.

Refining of Low Grade Zinc-Gold Precipitates

The purpose of this investigation was to ascertain if advantage could be taken of the copper in the precipitates as a collecting agent of the precious metals in the direct smelting furnace.The products produced to be low grade anode bullion and a slag low in precious metals, high in zinc and lead.

An Investigation of the Anodic Oxidation of Aluminum in a Sulfuric Acid Electrolyte

When aluminum is allowed to stand in air or is heated in air, a thin oxide film is produced on the metal. If aluminum is made the anode in a suitable electrolyte and a current applied, a coating is obtained which is similar to that produced in air, but may be effected much quicker. This film is thicker, harder, more resistant to corrosion and abrasion, and more adhesive than the natural oxide. The film is porous and makes an excellent adsorptive for dyes and pigments.

Experimental study of electric breakdowns in liquid argon at centimeter scale

In this paper we present results on measurements of the dielectric strength of liquid argon near its boiling point and cathode-anode distances in the range of 0.1 mm to 40 mm with spherical cathode and plane anode. We show that at such distances the applied electric field at which breakdowns occur is as low as 40 kV/cm. Flash-overs across the ribbed dielectric of the high voltage feed-through are observed for a length of 300 mm starting from a voltage of 55 kV. These results contribute to set reference for the breakdown-free design of ionization detectors, such as Liquid Argon Time Projection Chambers (LAr TPC).

Table 2 Analytical data of the samples by the "Dipole CHIM" at the Yingezhuang gold deposit

CHIM method involves extracting metal ions of electromobile forms in either anodes or cathodes, facilitated by a man-made electric field. This paper presents two newly developed CHIM alternatives that are electrified by a low voltage dipole. The firstly improved technique enables cationic ions to be extracted in a single cathode, whereas the secondly improved technique allows both anionic and cationic species to be extracted simultaneously in an anode and in a cathode. Compared with the traditional CHIM methods, the innovative techniques developed in this paper are characterized by simple instrumentation, low cost and easy operation in field, and in particular enables simultaneous extraction of anionic and cationic species of elements, from which more information can be derived with higher extraction efficiency. Field tests at several well-known mine areas in China confirm the effectiveness and efficiency of the new techniques in exploring for deeply buried ore bodies.

Extended description of tunnel junctions for distributed modeling of concentrator multi-junction solar cells

One of the key components of highly efficient multi-junction concentrator solar cells is the tunnel junction interconnection. In this paper, an improved 3D distributed model is presented that considers real operation regimes in a tunnel junction. This advanced model is able to accurately simulate the operation of the solar cell at high concentraions at which the photogenerated current surpasses the peak current of the tunnel junctionl Simulations of dual-junction solar cells were carried out with the improved model to illustrate its capabilities and the results have been correlated with experimental data reported in the literature. These simulations show that under certain circumstances, the solar cells short circuit current may be slightly higher than the tunnel junction peak current without showing the characteristic dip in the J-V curve. This behavior is caused by the lateral current spreading toward dark regions, which occurs through the anode/p-barrier of the tunnel junction.

Short, high current electrodynamic tether

An electrodynamic tether experiment, to be carried out in the Russian spacecraft Almaz, is proposed. A 10 km tether would be deployed downwards; the lower 8 km would be nonconductive, the upper 2 km would be conductive, bare, and 2.2 mm in diameter, and would act as a thruster, with power supply at the top. This hybrid arrangement allows for other, onelectrodynamic experiments,reducing costs; it also limits the induced electromotive force, reducing the power to be handled. The current-voltage characteristic of contactors would be measured. With the anode switched off, the wire itself should collect a current over 5 A at day conditions, providing a thrust of 0.11 N at a 0.77 kW power.

Technology of bare tether current collection

The outstanding problem for useful applications of electrodynamic tethers is obtaining sufficient electron current from the ionospheric plasma. Bare tether collectors, in which the conducting tether itself, left uninsulated over kilometers of its length, acts as the collecting anode, promise to attain currents of 10 A or more from reasonably sized systems. Current collection by a bare tether is also relatively insensitive to drops in electron density, which are regularly encountered on each revolution of an orbit. This makes nighttime operation feasible. We show how the bare tether's high efficiency of current collection and ability to adjust to density variations follow from the orbital motion limited collection law of thin cylinders. We consider both upwardly deployed (power generation mode) and downwardly deployed (reboost mode) tethers, and present results that indicate how bare tether systems would perform as their magnetic and plasma environment varies in low earth orbit.

Current-voltage response of a spherical plasma contactor

A theoretical model for a contactor, collecting electrons from an ambient, unmagnetized plasma and emitting a current Iiis discussed. The relation between Ii and the potential bias of the contactor is found to be crucial for the formation of a quasineutral core around the anode and, consequently, for the current colleted. Approximate analytical laws and charts for the current-voltage response are provided.