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At least 307 records · Page 17

An Oxygen‐Scavenger Sulfide Coating Enabling Long‐Term Stable Nickel‐Rich Cathodes

Oxygen release is a major issue associated with layer-structured metal oxide cathodes in lithium batteries, which can further cause a series of problems, such as irreversible phase transition, microcracking, and electrolyte decomposition. Eventually, these issues jointly result in cell performance degradation and safety hazards. Thus, it is very significant to tackle oxygen release for achieving long-term stable cyclability, but very challenging. Although intensive efforts have been invested to date, there still lacks a feasible solution. In this study, nanoscale ZrS 2 coatings are applied on prefabricated LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes directly via atomic layer deposition (ALD). Very encouragingly, we reveal that this ALD-deposited conformal ZrS 2 nanocoating can serve as an exceptional oxygen scavenger and then convert into a stable sulfate (Zr(SO 4 ) 2 ) coating. Such an in situ conversion is very beneficial and effective for protecting the electrolyte from decomposition. In addition, the resultant Zr(SO 4 ) 2 coating further inhibits undesirable reactions, stabilizes the interface between NMC811 and the electrolyte, suppresses microcracking, mitigates transition metal dissolution, and maintains the structural stability of the NMC811 cathode. Consequently, the ZrS 2 -coated NMC811 cathode has demonstrated extraordinary performance. Thus, this study advances the understanding of interface engineering while paving a new technical pathway for commercializing NMC811 cathodes.

Nickel-rich cathodes↗

Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

Our study demonstrates a direct electrodeposition of UO 2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO 2 (NTf 2 ) 2 )] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM + NTf 2 – ). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO 2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. The UO 2 deposit was characterized by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fuel cell water management via reduced anode reactant pressure

A method is provided for operation of a fuel cell with improved water management by maintaining reduced anode pressure relative to cathode pressure, relative to atmospheric pressure, or both. Typically, the fuel cell comprises a membrane electrode assembly comprising nanostructured thin film cathode catalyst.

30 DIRECT ENERGY CONVERSION↗

High-Performance Polymer Solar Cells Based on a Wide-Bandgap Polymer Containing Pyrrolo[3,4- f ]benzotriazole-5,7-dione with a Power Conversion Efficiency of 8.63%

A novel donor–acceptor type conjugated polymer based on a building block of 4,8-di(thien-2-yl)-6-octyl-2-octyl-5H-pyrrolo[3,4-f]benzotriazole-5,7(6H)-dione (TZBI) as the acceptor unit and 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)­benzo­[1,2-b:4,5-b']dithiophene as the donor unit, named as PTZBIBDT, is developed and used as an electron-donating material in bulk-heterojunction polymer solar cells. The resulting copolymer exhibits a wide bandgap of 1.81 eV along with relatively deep highest occupied molecular orbital energy level of -5.34 eV. Based on the optimized processing conditions, including thermal annealing, and the use of a water/alcohol cathode interlayer, the single-junction polymer solar cell based on PTZBIBDT:PC71BM ([6,6]-phenyl-C71-butyric acid methyl ester) blend film affords a power conversion efficiency of 8.63% with an open-circuit voltage of 0.87 V, a short circuit current of 13.50 mA cm -2 , and a fill factor of 73.95%, which is among the highest values reported for wide-bandgap polymers-based single-junction organic solar cells. The morphology studies on the PTZBIBDT:PC71BM blend film indicate that a fibrillar network can be formed and the extent of phase separation can be mani­pulated by thermal annealing. These results indicate that the TZBI unit is a very promising building block for the synthesis of wide-bandgap polymers for high-performance single-junction and tandem (or multijunction) organic solar cells.

Lan, Liuyuan↗

Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO 2

The study of the electrochemical behavior (in the presence of N 2 or CO 2 ) of size-controlled naked Cu 5 and Cu 20 nanoclusters, prepared using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques, evidences some relevant results regarding the redox behavior of these sub-nanometre sized copper particles and the effect of CO 2 on them. Cu 20 nanoclusters show anodic redox processes occurring at much lower potential with respect to Cu 5 nanoclusters, which behave relatively similar to much larger Cu particles. However, Cu 5 nanoclusters coordinate effectively CO 2 (hydrogen carbonate) in solution, different from Cu 20 nanoclusters and larger Cu particles. This effect, rather than the redox behavior, is apparently connected to the ability of Cu 5 nanoclusters to reduce CO 2 under cathodic conditions at low overpotential. In conclusion, although preliminary, these results provide rather exciting indications on the possibility of realizing low overpotential electrocatalytic conversion of CO 2 .

36 MATERIALS SCIENCE↗

High electron mobility ZnO film for high-performance inverted polymer solar cells

High-quality ZnO films (ZnO-MS) are prepared via magnetron sputtering deposition with a high mobility of about 2 cm{sup 2}/(V·s) and are used as electron transport layer for inverted polymer solar cells (PSCs) with polymer poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′] dithiophene-co-3-fluorothieno[3,4-b]thiophene-2-carboxylate]:[6,6]-phenyl C71-butyric acid methyl ester as the active layer. A significant improvement of J{sub SC}, about 20% enhancement in contrast to the devices built on sol-gel derived ZnO film (ZnO-Sol), is found in the ZnO-MS based device. High performance ZnO-MS based PSCs exhibit power conversion efficiency (PCE) up to 8.55%, which is much better than the device based on ZnO-Sol (PCE = 7.78%). Further research on cathode materials is promising to achieve higher performance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Preliminary experimental investigation of a complex dual-band high power microwave source

In order to promote the power conversion efficiency of a magnetically insulated transmission line oscillator (MILO) and obtain microwaves in dual bands, an axially extracted C-band virtual cathode oscillator (VCO) with multiple resonant cavities is introduced to partially utilize the load current of an S-band MILO. The formed novel dual-band high power microwave source called MILO and VCO is investigated with simulation and experimentally. A dual-band radiation antenna is designed to effectively radiate microwaves generated by the MILO and the VCO, respectively, while avoiding them being influenced by the microwave reflection and diffraction. The preliminary experimental results measured by the dual-band diagnostic system show that both the MILO and the VCO operate normally under repeated shots. A microwave of 2.1 GHz, 1.70 GW is generated from the MILO and a 0.37 GW microwave at frequencies of 4.1 GHz and 3.8 GHz is generated from the VCO under the condition of about 440 kV and 35 kA. Compared with a single MILO (10.6%), a MILO and VCO achieves higher total power and efficiency (13.4%) in both S and C bands, indicating that the load current of the MILO partially couples into the beam-wave interaction in the VCO and then contributes to the output microwaves. However, more works are needed regarding the spectrum purification of the VCO and promotion of the output power of both the MILO and the VCO.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Surface Regulating of a Double–Perovskite Electrode for Protonic Ceramic Fuel Cells to Enhance Oxygen Reduction Activity and Contaminants Poisoning Tolerance

Protonic ceramic fuel cells (PCFCs) are one of the most efficient energy conversion devices. However, the performance of current PCFCs is greatly limited by the sluggish oxygen reduction reaction (ORR) kinetics and the fast degradation of cathode due to contaminants poisoning (such as Cr species and steam). In this work, we report a surface regulating of a double perovskite PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ (PBSCF) cathode by a Pr 0.9 Fe 0.7 Co 0.3 O 3 (PFC) catalyst coating to enhance the ORR activity and stability. When tested in direct contact with Cr in the air with 3% H 2 O at 650 °C, the polarization resistance (Rp) of the PFC-PBSCF electrode increases from $\approx$0.39 to 0.45 Ω cm 2 after 100 h operation; in contrast, the R p of a PBSCF electrode increases from 0.63 to 0.82 Ω cm 2 . Further, a PCFC with the PFC-PBSCF cathode demonstrates an excellent peak power density ($\approx$1.08 W cm -2 at 650 °C) and significantly enhanced durability (degradation rate of 0.03 % h -1 ), much better than those of the cells with a PBSCF cathode ($\approx$0.75 W cm -2 and degradation rate of 0.12 % h -1 ). Raman spectroscopy and density functional theory calculations indicate that the PFC catalyst coating diminishes the formation of Cr species, such as (Ba 1-x Sr x )CrO 4 , on the cathode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced PEM Electrolyzer Membrane for Hydrogen Crossover Mitigation

An unintended reaction in the electrochemical conversion of water to hydrogen in proton exchange membrane (PEM) electrolyzers is the crossover of hydrogen from the anode to the oxygen-containing cathode through the membrane, creating hydrogen losses and safety concerns. Efforts to date have focused on embedding platinum catalysts in perfluorosulfonic (PFSA) membranes to convert H 2 to protons. The objective of this project is to design and develop hydrocarbon (HC) proton exchange membranes (PEMs) that can help overcome the risk of high H 2 crossover in current PEM electrolyzer (ELX) stacks by designing and optimizing the gas recombination catalyst (GRC) within the membrane and membrane electrode assembly (MEA) structure.

08 HYDROGEN↗

Long-Life Lithium-Sulfur Batteries with a Bifunctional Cathode Substrate Configured with Boron Carbide Nanowires

Developing high-energy-density lithium–sulfur (Li–S) batteries relies on the design of electrode substrates that can host a high sulfur loading and still attain high electrochemical utilization. Herein, a new bifunctional cathode substrate configured with boron-carbide nanowires in situ grown on carbon nanofibers (B 4 C@CNF) is established through a facile catalyst-assisted process. The B 4 C nanowires acting as chemical-anchoring centers provide strong polysulfide adsorptivity, as validated by experimental data and first-principle calculations. Meanwhile, the catalytic effect of B 4 C also accelerates the redox kinetics of polysulfide conversion, contributing to enhanced rate capability. As a result, a remarkable capacity retention of 80% after 500 cycles as well as stable cyclability at 4C rate is accomplished with the cells employing B 4 C@CNF as a cathode substrate for sulfur. Moreover, the B 4 C@CNF substrate enables the cathode to achieve both high sulfur content (70 wt%) and sulfur loading (10.3 mg cm -2 ), delivering a superb areal capacity of 9 mAh cm -2 . In addition, Li–S pouch cells fabricated with the B 4 C@CNF substrate are able to host a high sulfur mass of 200 mg per cathode and deliver a high discharge capacity of 125 mAh after 50 cycles.

25 ENERGY STORAGE↗

Experimental investigation of a relativistic magnetron with diffraction output on a repetitive short pulse generator

An experimental investigation of a relativistic Magnetron with Diffraction Output (MDO) on a short voltage pulse generator, which has maximum repetition rate of 100 Hz and plateau of 2.5 ns, is detailed in this paper. Compared to the conversional solid cathode, a direct Density Modulation Cathode is capable for desired microwave radiation. When applied voltage is 200 kV and axial magnetic field is ∼0.12 T, the MDO radiates 120 MW of microwave with 2.3 GHz of central frequency. Power conversion efficiency reaches 22%. Pulse duration is 3 ns. At repetition rates of 50 Hz and 100 Hz, output microwave powers range from 90 MW to 120 MW. Life time is up to 10{sup 4} shots.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A red-light-powered silicon nanowire biophotochemical diode for simultaneous CO 2 reduction and glycerol valorization

A bias-free photochemical diode, in which a p-type photocathode is connected to an n-type photoanode to harness light for driving photoelectrochemical reduction and oxidation pairs, serves as a platform for realizing light-driven fuel generation from CO 2 . However, the conventional design, in which cathodic CO 2 reduction is coupled with the anodic oxygen evolution reaction (OER), requires substantial energy input. Here we present a photochemical diode device that harnesses red light (740 nm) to simultaneously drive biophotocathodic CO 2 -to-multicarbon conversion and photoanodic glycerol oxidation as an alternative to the OER to overcome the above thermodynamic limitation. The device consists of an efficient CO 2 -fixing microorganism, Sporomusa ovata, interfaced with a silicon nanowire photocathode and a Pt–Au-loaded silicon nanowire photoanode. This photochemical diode operates bias-free under low-intensity (20 mW cm –2 ) red light irradiation with ~80% Faradaic efficiency for both the cathodic and anodic products. Finally, this work provides an alternative photosynthetic route to mitigate excessive CO 2 emissions and efficiently generate value-added chemicals from CO 2 and glycerol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local ionic transport enables selective PGM-free bipolar membrane electrode assembly

Bipolar membranes in electrochemical CO 2 conversion cells enable different reaction environments in the CO 2 -reduction and O 2 -evolution compartments. Under ideal conditions, water-splitting in the bipolar membrane allows for platinum-group-metal-free anode materials and high CO 2 utilizations. In practice, however, even minor unwanted ion crossover limits stability to short time periods. Here we report the vital role of managing ionic species to improve CO 2 conversion efficiency while preventing acidification of the anodic compartment. Through transport modelling, we identify that an anion-exchange ionomer in the catalyst layer improves local bicarbonate availability and increasing the proton transference number in the bipolar membranes increases CO 2 regeneration and limits K + concentration in the cathode region. Through experiments, we show that a uniform local distribution of bicarbonate ions increases the accessibility of reverted CO 2 to the catalyst surface, improving Faradaic efficiency and limiting current densities by twofold. Using these insights, we demonstrate a fully platinum-group-metal-free bipolar membrane electrode assembly CO 2 conversion system exhibiting <1% CO 2 /cation crossover rates and 80-90% CO 2 -to-CO utilization efficiency over 150 h operation at 100 mA cm -2 without anolyte replenishment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnesium ion mobility in post-spinels accessible at ambient pressure

We propose that Ti-containing post-spinels may offer a practically-accessible route to fast multivalent ion diffusion in close-packed oxide lattices, with the caveat that substantial thermodynamic driving forces for conversion reactions exist. First-principles modeling of a new mixed V/Ti post-spinel phase reveals a possible route to ambient-pressure oxide cathodes exhibiting fast Mg diffusion.

36 MATERIALS SCIENCE↗

The phototron: A light to RF energy conversion device

The phototron, a photoelectric device that converts light to radio frequency energy, is described. It is a vacuum tube, free electron, device that is mechanically similar to a reflex klystron with the hot filament cathode replaced by a large area photocathode. The device can operate either with an external voltage source used to accelerate the photoelectrons or with zero bias voltage; in which case the photokinetic energy of the electrons sustains the R.F. oscillations in the tuned R.F. circuit. One basic design of the phototron was tested. Frequencies as high as about 1 GHz and an overall efficiency of about 1% in the biased mode were obtained. In the unbiased mode, the frequencies of operation and efficiences are considerably lower. Success with test model suggests that considerable improvements are possible through design refinements. One such design refinement is the reduction of the length of the electron flight path.

Freeman, J. W.↗

CO 2 Electrolysis Using Metal-Supported Solid Oxide Cells with Infiltrated Pr 0.5 Sr 0.4 Mn 0.2 Fe 0.8 O 3-$δ$ Catalyst

Electrochemical conversion of CO 2 to CO is demonstrated with symmetric-structured metal supported solid oxide cells (MS-SOC). Perovskite Pr 0.5 Sr 0.4 Mn 0.2 Fe 0.8 O 3-δ (PSMF) and Pr 6 O 11 catalysts were infiltrated into the MS-SOC cathode and anode, using 3 cycles with firing at 850 °C and 8 cycles with firing at 800 °C, respectively. Upon reduction during operation, the perovskite PSMF was transformed to Ruddlesden–Popper structure with a highly efficient electrocatalytic activity. The impact of operating temperature (600–800 °C) and overpotential (0–1.8 V) on the CO 2 conversion was investigated. The highest CO 2 conversion of 57.2% was achieved at 750 °C and 1.8 V. During extended operation for 150 h at 750 °C and 1.2 V, a cell demonstrated relatively stable performance, with initial current density of 535 mA cm -2 and CO 2 conversion of 23%. Degradation mechanisms were studied by posttest characterization.

25 ENERGY STORAGE↗