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At least 1,369 records · Page 76

A class of polysulfide catholytes for lithium-sulfur batteries: energy density, cyclability, and voltage enhancement

Liquid-phase polysulfide catholytes are attracting much attention in lithium-sulfur (Li-S) batteries as they provide a facile dispersion and homogeneous distribution of the sulfur active material in the conductive matrix. However, the organic solvents used in lithium-polysulfide (Li-PS) batteries play an important role and have an impact on the physico-chemical characteristics of polysulfides. For instance, significantly higher voltages (similar to 2.7 V) of the S/S-n(2-) (4 <= n <= 8) redox couple are observed in Li-PS batteries with dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) solvents. Accordingly, high power Li-PS batteries are presented here with the catholyte prepared with NMP solvent and operated with the highly reversible sulfur/long-chain polysulfide redox couple. On the other hand, a remarkable cyclability enhancement of the Li-PS battery is observed with the long-chain, ether-based tetraglyme (TEGDME) solvent. The voltage enhancement and the cyclability enhancement of the Li-PS batteries are attributed to the solvation effect, viscosity, and volatility of the solvents. Finally, highly concentrated polysulfide catholytes are successfully synthesized, with which high energy density Li-PS batteries are demonstrated by employing a multi-walled carbon nanotube (MWCNT) fabric electrode.

Yu, XW↗

Structure of the high voltage phase of layered P2-Na 2/3-z [Mn 1/2 Fe 1/2 ]O 2 and the positive effect of Ni substitution on its stability

A combination of operando X-ray diffraction, pair distribution function (PDF) analysis coupled with electrochemical measurements and Mössbauer spectroscopy elucidates the nature of the phase transitions induced by insertion and extraction of sodium ions in P2-Na 0.67 [Ni y Mn 0.5 + y Fe 0.5 -2 y ]O 2 (y = 0, 0.10, 0.15). When phase transitions are avoided, the optimal cathode material – P2-Na 0.67 Fe 0.2 Mn 0.65 Ni 0.15 O 2 - delivers 25% more energy than the unsubstituted material, sustaining high specific energy (350 Wh kg -1 ) at moderate rates and maintains 80% of the original energy density after 150 cycles - a significant improvement in performance vs. the unsubstituted analogue. The crystal structure of the high voltage phase is solved for the first time by X-ray PDF analysis of P2-Na 0.67 -z Fe0.5Mn 0.5 O 2 (where z~0.5), revealing that migration of the transition metals – particularly Fe 3+ - into tetrahedral sites in the interlayer space occurs at high potential. This results in new short range order between two adjacent layers. Although the transition metal migration is reversible as proven by electrochemical performance, it induces a large disfavourable cell polarization. The deleterious high voltage transition is mitigated by substitution of Fe 3+ by Mn 4+ /Ni 2+ , giving rise to better cycling performance. Moreover, as demonstrated by 57 Fe Mössbauer spectroscopy, the much lower ratio of Fe 4+ O6 to Fe 3+ O 6 observed systematically across the range of Ni content – compared to the values expected from a purely ionic model – suggests redox activity involves the O-2p orbitals owing to their overlap with the transition metal-3d orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward the design of high voltage magnesium–lithium hybrid batteries using dual-salt electrolytes

We report a design of high voltage magnesium-lithium (Mg-Li) hybrid batteries through rational controls of the electrolyte chemistry, electrode materials and cell architectures. Prototype devices with LiFePO4 and LiMn 2 O 4 cathodes exhibit voltages higher than 2.5 V (vs. Mg) and a high specific energy density of 246 Wh/kg under conditions that are amenable for practical applications. The successful demonstrations reported here could be a significant step forward for practical hybrid batteries.

25 ENERGY STORAGE↗

Facile, ethylene glycol-promoted microwave-assisted solvothermal synthesis of high-performance LiCoPO 4 as a high-voltage cathode material for lithium-ion batteries

Olivine-type LiCoPO 4 is considered a promising high-voltage cathode material for next-generation lithium-ion batteries. However, preparing high-performance LiCoPO 4 by a simple approach has been challenging. Herein, we present a facile and rapid (30 min) one-step microwave-assisted solvothermal synthesis route using a 1 : 1 (v/v) water/ethylene glycol (EG) binary solvent mixture and a temperature of 250 °C. Here, the technique delivers high-performance LiCoPO4nanoparticles without additional post-annealing or carbon coating steps. The as-prepared powder consists of single crystalline LiCoPO 4 and features a hexagonal platelet-like morphology with dimensions of 700-800 nm × 400-600 nm × 100-220 nm. Selected area electron diffraction (SAED) experiments reveal that the platelets show the smallest dimension along [010], which is the direction of the lithium diffusion pathways in the olivine crystal structure. Furthermore, the results indicate that the EG co-solvent plays an important role in tailoring the particle size, morphology, and crystal orientation of the material. Co L-edge soft X-ray absorption spectroscopy (XAS) of LiCoPO 4 are presented for the first time and confirm that the material only consists of Co 2+ . Benefiting from the unique morphology, which facilitates Li-ion conduction, electrochemical measurements deliver an initial discharge capacity of 137 mA h g -1 at 0.1 C, a remarkably stable capacity retention of 68% after 100 cycles at 0.5 C, and a specific energy density of 658 W h kg -1 based on its capacity and voltage, which is the best performance of LiCoPO 4 obtained from microwave-assisted solvothermal synthesis to date.

36 MATERIALS SCIENCE↗

Single-crystal based studies for correlating the properties and high-voltage performance of Li[Ni x Mn y Co 1₋x₋y ]O 2 cathodes

Safe and stable cycling of lithium-ion battery cathodes at high voltages is essential for meeting next-generation energy storage demands, yet the lack of fundamental understanding of the correlation of a material's properties and reactivities largely hinders current progress. Here, we demonstrate how single-crystal samples with well-controlled physical characteristics can be used to unambiguously establish the relationships among specific properties, surface chemistry and electrochemical performance, enabling rational design of better performing cathode materials. Layered Li[Ni x Mn y Co 1₋x₋y ]O 2 (NMC) crystals, with four different particle shapes of an octahedron (Oct), truncated octahedron (T-Oct), polyhedron (Poly) and platelet (Plate), were prepared to vary the presence of (104), (001) and (012) family facets on the surface. This represents the first experimental verification of NMC morphologies that were theoretically calculated in the past. Systematic studies on the impact of isolated physical properties reveal the important roles of the Ni content, particle size and facet on surface stability and electrochemical performance. We show that compared to (012) surface dominated samples, high-voltage cycling stability was much improved on the (001) dominated Plate sample, suggesting that replacing the (012) surface with lower energy (001) and/or (104) surfaces can be effective in stabilizing NMCs during high energy applications. Our study moreover provides insights into how tailoring a material's surface properties can be used as an important route in balancing cathode capacity and stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An interface stabilized perovskite solar cell with high stabilized efficiency and low voltage loss

Stabilization of the crystal phase of inorganic/organic lead halide perovskites is critical for their high performance optoelectronic devices. However, due to the highly ionic nature of perovskite crystals, even phase stabilized polycrystalline perovskites can undergo undesirable phase transitions when exposed to a destabilizing environment. While various surface passivating agents have been developed to improve the device performance of perovskite solar cells, conventional deposition methods using a protic polar solvent, mainly isopropyl alcohol (IPA), results in a destabilization of the underlying perovskite layer and an undesirable degradation of device properties. We demonstrate the hidden role of IPA in surface treatments and develop a strategy in which the passivating agent is deposited without destabilizing the high quality perovskite underlayer. This strategy maximizes and stabilizes device performance by suppressing the formation of the perovskite δ-phase and amorphous phase during surface treatment, which is observed using conventional methods. Our strategy also effectively passivates surface and grain boundary defects, minimizing non-radiative recombination sites, and preventing carrier quenching at the perovskite interface. This results in an open-circuit-voltage loss of only ~340 mV, a champion device with a power conversion efficiency of 23.4% from a reverse current–voltage scan, a device with a record certified stabilized PCE of 22.6%, and enhanced operational stability. In addition, our perovskite solar cell exhibits an electroluminescence external quantum efficiency up to 8.9%.

14 SOLAR ENERGY↗

Imaging of voltage-controlled switching of magnetization in highly magnetostrictive epitaxial Fe–Ga microstructures

The magnetoelectric behavior of epitaxial Fe–Ga microstructures on top of a (001)-oriented PMN–PT piezoelectric substrate is imaged with magnetic X-ray microscopy. Additionally, the micron-scale strain distribution in PMN–PT is characterized by X-ray microdiffraction and examined with respect to the results of the Fe–Ga magnetoelectric switching. The magnetic reorientation of Fe–Ga is found to be strongly correlated with size, shape, and crystallographic orientation of the microstructures. In the case of square-shaped structures, size dictates the influence of the strain distribution on both the initialization of the ground state and on the magnetic reorientation during application of voltage. On the other hand, elliptical microstructures demonstrate completely different magnetic responses depending on the relative orientation of their long axis with respect to the crystallographic directions of the PMN–PT. This study demonstrates that engineering the behavior of highly magnetostrictive epitaxial microdevices is possible. It further elucidates that voltage-induced actuation can be largely tuned to achieve the desired type of magnetic switching ranging from vortex circulation reversal, domain wall motion, to a large rotation of magnetization. Because of the outstanding properties of the investigated material system, the reported findings are expected to be of great interest for the realization of next-generation energy-efficient magnetic memory and logic devices.

42 ENGINEERING↗

Manganese-rich high entropy oxides for lithium-ion batteries:materials design approaches to address voltage fade

Lithium- and manganese-rich oxides are of interest as lithium-ion battery cathode materials as Mn is earth abundant, low cost, and can deliver high capacity. Herein, a high entropy strategy was used to prepare Mn rich high entropy oxide (HEO) materials by including four additional metals (Ni, Co, Fe and Al) in the compositions using a mild co-precipitation method. Two HEOs (Li x Ni 0.1 Mn 0.6 Co 0.1 Al 0.1 Fe 0.1 O y , where x = 1.5 for HEO-L and x = 0.5 for HEO-H) with layered and spinel-layered hybrid structures were investigated where the morphology, elemental composition, structure, atomic level phase distribution, and electrochemistry were determined. The HEO-L samples involve a Li 2 TMO 3 layered structure with ~39% stacking faults. HEO-H is a hybrid structure comprised of 80 wt% spinel and 20 wt% LiMO 2 layered structure. The high entropy manganese-rich HEO-L showed higher capacity and 93% retention of the average voltage after 100 cycles while HEO-H showed higher capacity retention and near 100% average voltage retention. Finally, operando X-ray absorption spectroscopy revealed that the Ni, Co, and Mn are redox active in both materials while the Fe center remains at the Fe 3+ oxidation state throughout cycling, where the changes in the oxidation states for both materials during discharge were consistent with the delivered electrochemical capacity rationalizing the observed electrochemistry.

25 ENERGY STORAGE↗

High voltage and high current density vertical GaN power diodes

We report on the realization of a GaN high voltage vertical p-n diode operating at > 3.9 kV breakdown with a specific on-resistance < 0.9 mΩ.cm 2 . Diodes achieved a forward current of 1 A for on-wafer, DC measurements, corresponding to a current density > 1.4 kA/cm 2 . An effective critical electric field of 3.9 MV/cm was estimated for the devices from analysis of the forward and reverse current-voltage characteristics. Furthermore this suggests that the fundamental limit to the GaN critical electric field is significantly greater than previously believed.

30 DIRECT ENERGY CONVERSION↗

Unidirectional anisotropy in the spin pumping voltage in yttrium iron garnet/platinum bilayers

Detailed measurements of the dc voltage generated in a thin Pt layer deposited on films of yttrium iron garnet (YIG) have been carried out to study the spin pumping effect produced by magnetostatic (MS) modes excited by a microwave field. In relatively thick YIG films the modes are far apart so that one can identify clearly the spin pumping voltage in V{sub SP} produced by each MS mode. We have discovered that when the sputter deposition of the thin Pt layer is made on the YIG film magnetized by a static magnetic field, V{sub SP} exhibits a strong unidirectional anisotropy.

36 MATERIALS SCIENCE↗

Current-voltage-time characteristics of the reactive Ar/N{sub 2} high power impulse magnetron sputtering discharge

The discharge current and voltage waveforms have been measured in a reactive high power impulse magnetron sputtering (HiPIMS) Ar/N{sub 2} discharge with a Ti target for 400 {mu}s long pulses. We observe that the current waveform in the reactive Ar/N{sub 2} HiPIMS discharge is highly dependent on the pulse repetition frequency, unlike the non-reactive Ar discharge. The current is found to increase significantly as the frequency is lowered. This is attributed to an increase in the secondary electron emission yield during the self-sputtering phase, when the nitride forms on the target at low frequencies. In addition, self-sputtering runaway occurs at lower discharge voltages when nitrogen is added to the discharge. This illustrates the crucial role of self-sputtering in the behavior of the reactive HiPIMS discharge.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The influence of the extraction voltage on the energetic electron population of an electron cyclotron resonance ion source plasma

An influence of the extraction voltage on the high energy slope of bremsstrahlung radiation spectra has been reported in ECRIS experiments, which is not well understood so far. In order to provide more detailed data on this effect, we have measured bremsstrahlung radiation spectra accompanying especially the evolution of highly charge ions (i.e., by monitoring the Ar{sup 14+} charge state) as the extraction voltage is changed from 0 to 20 kV, in dedicated experiments at the Frankfurt 14 GHz-ECRIS.

43 PARTICLE ACCELERATORS↗

Glow-to-arc transition events in H{sub 2}-Ar direct current pulsed plasma: Automated measurement of current and voltage

The glow-to-arc transition phenomena (arcing) observed in plasma reactors used in materials processing was studied through the arcs characteristic current and voltage waveforms. In order to capture these arcs signals, a LABVIEW based automated instrumentation system (ARCVIEW) was developed, including the integration of an oscilloscope equipped with proper current and voltage probes. The system also allows capturing the process parameters at the arc occurrence moments, which were used to map the arcs events conditions. Experiments in H{sub 2}-Ar DC pulsed plasma returned signals data from 215 arcs events, which were analyzed through software routines. According to the results, an anti-arcing system should react in the time order of few microseconds to prevent most of the damage caused by the undesired arcing phenomena.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Tungsten oxide proton conducting films for low-voltage transparent oxide-based thin-film transistors

Tungsten oxide (WO{sub x}) electrolyte films deposited by reactive magnetron sputtering showed a high room temperature proton conductivity of 1.38 Multiplication-Sign 10{sup -4} S/cm with a relative humidity of 60%. Low-voltage transparent W-doped indium-zinc-oxide thin-film transistors gated by WO{sub x}-based electrolytes were self-assembled on glass substrates by one mask diffraction method. Enhancement mode operation with a large current on/off ratio of 4.7 Multiplication-Sign 10{sup 6}, a low subthreshold swing of 108 mV/decade, and a high field-effect mobility 42.6 cm{sup 2}/V s was realized. Our results demonstrated that WO{sub x}-based proton conducting films were promising gate dielectric candidates for portable low-voltage oxide-based devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Generation of high-voltage pulses with subnanosecond front rise times in open discharge

The investigation results for plasma switching devices of high-voltage pulses with pulse rise times less than 1 ns are presented. The approach is based on using conditions suitable for bringing a gas discharge chamber in a state with high conductivity due to generation of an electron beam owing to photoelectron emission from the device cathode. It is shown that in co-axial geometry pulses, switching time 0.45 ns on an active load R{sub L} = 50 {Omega} at voltage U = 20 kV can be achieved. It is shown with the method of doubled impulses that such a device can regenerate the acceptable electric strength during 10 {mu}s. It is indicated of the principle possibility of working in the pulse-periodical regime to the repetition rate of 100 kHz.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Accumulated destructive effect of nanosecond repetitive voltage pulses on the insulated coatings of Fe-based nanocrystalline ribbon

Fe-based nanocrystalline ribbon is widely employed in pulsed power devices and accelerators. A temperature accumulation model is put forward to explain the accumulated destructive effect of discharge plasma bombardment on the TiO{sub 2} coatings of nanocrystalline ribbon under 50 Hz/100 ns voltage pulses. Experimental results revealed that the plasma channel expansion caused by air breakdown in the coating crack heated the coating repetitively, and the coating temperature was increased and accumulated around the crack. The fact that repetitive voltage pulses were more destructive than a single pulse with the same amplitude was caused by the intensified coating ablation under the temperature accumulation effect.

36 MATERIALS SCIENCE↗

An accurate online calibration system based on combined clamp-shape coil for high voltage electronic current transformers

Electronic transformers are widely used in power systems because of their wide bandwidth and good transient performance. However, as an emerging technology, the failure rate of electronic transformers is higher than that of traditional transformers. As a result, the calibration period needs to be shortened. Traditional calibration methods require the power of transmission line be cut off, which results in complicated operation and power off loss. This paper proposes an online calibration system which can calibrate electronic current transformers without power off. In this work, the high accuracy standard current transformer and online operation method are the key techniques. Based on the clamp-shape iron-core coil and clamp-shape air-core coil, a combined clamp-shape coil is designed as the standard current transformer. By analyzing the output characteristics of the two coils, the combined clamp-shape coil can achieve verification of the accuracy. So the accuracy of the online calibration system can be guaranteed. Moreover, by employing the earth potential working method and using two insulating rods to connect the combined clamp-shape coil to the high voltage bus, the operation becomes simple and safe. Tests in China National Center for High Voltage Measurement and field experiments show that the proposed system has a high accuracy of up to 0.05 class.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗