Tailoring Ion Ordering in Perovskite Oxide for High-Temperature Oxygen Evolution Reaction.

Perovskites exhibit excellent high-temperature oxygen evolution reaction (OER) activities as the anodes of solid oxide electrolysis cells (SOECs). However, the relationship between ion ordering and OER performances is rarely investigated. Herein, a series of PrBaCo2-x Fex O5+δ perovskites with tailored ion orderings are constructed. Physicochemical characterizations and density functional theory calculations confirm that the oxygen bulk migration and surface transport capacities as well as the OER activities are promoted by the A-site cation ordering, but weakened by the oxygen vacancy ordering. Hence, SOEC with the A-site-ordered and oxygen-vacancy-disordered PrBaCo2 O5+δ anode exhibits the highest performance of 3.40 A cm-2 at 800 °C and 2.0 V. This work sheds light on the critical role of ion orderings in the high-temperature OER performance and paves a new way for screening novel anode materials of SOECs.

Orderly retire China's coal-fired power capacity via capacity payments to support renewable energy expansion.

The energy-only-market implemented in China cannot strongly support large-scale renewable energy expansion because the renewable energy expansion may disorderly phase out non-renewable power capacity. However, non-renewable power capacity, particularly the coal-fired power capacity in China, can provide vital power system adequacy needed by renewable energy expansion. We introduce capacity payments to orderly retire current coal-fired power capacity by transforming some of it into reserve capacity in order to support renewable energy expansion. Using generation and transmission expansion results from the SWITCH-China model, this paper proposes an orderly retirement path based on the assumption of implementing capacity payments. Our results show that roughly 100-200 gigawatts (GW) of coal-fired power capacity can continue to serve through 2050, and most of it is used as reserve capacity. Capacity payments of 400-700 billion yuan are needed to achieve this retirement path, and a higher adequacy requirement needs higher payments.

Improved Phase Stability and Enhanced Luminescence of Calcite Phase LuBO3:Ce3+ through Ga3+ Incorporation.

The application of LuBO3:Ce3+ (LBO:Ce) crystal as an excellent scintillation material has been limited due to its poor phase stability at high temperature or high pressure, so improving the phase stability is essential for promoting its development. Ga stabilized LuBO3:Ce3+ (LGBO:Ce) is synthesized by solid-state reaction at 1200 °C. Powder X-ray diffraction patterns and Raman spectra at ambient pressure show that all the samples are pure calcite phase. In situ high-pressure synchrotron radiation XRD patterns illustrate that calcite phase LGBO:Ce exhibits more excellent phase stability than that of LBO:Ce under high pressure due to the superior compressibility of the [GaO6] octahedral unit. The optical band gap of LGBO decreases from 5.58 to 4.64 eV after introducing 10% Ga, which leads to the decreased nonradiative transition and about double luminescence intensity as expected. More interestingly, the charge transition from O2- to Ce4+ is observed at about 290 nm in the absorption spectra. The X-ray photoelectron spectroscopy spectra indicate the ratio of Ce4+/Ce3+ increases with increasing concentration of Ga3+, which can be attributed to the variation of energy separation between the 4f ground state of Ce3+ and the Fermi energy level position. In contrast to the enhancement of PL intensity, the integrated X-ray excited luminescence intensity decreases after Ga3+ incorporation attributing to the result of both decreased effective atomic number and ionization energy between 5d1 level and conduction band. The thermal luminescence spectra show that after the incorporation of Ga3+ the oxygen vacancy and intrinsic defects in LBO remain unchanged but that the concentration of oxygen vacancy significantly reduces. The mechanism of Ga3+ incorporation on phase stability and luminescence properties of LBO:Ce has been proposed and discussed systematically.

Thermal and temporal stability of the nitridated Ru/B4C multilayer for high-flux monochromator application.

A nitridated Ru/B4C multilayer with period of 3.0 nm and 80 bilayers were fabricated to study thermal and temporal stability. The multilayer was annealed from room temperature to 490°C, and the in situ X-ray measurements showed that the reflectivity remains mostly unchanged up to 300°C. An essential drop of the reflectivity occurred at 490°C with significantly increased interface roughness. A new layered structure with larger thickness than the original multilayer started to appear at 400°C. The nitridated Ru/B4C multilayer remains intact after two years of storage in air, which demonstrated a very good temporal stability.

In Situ Observation of Thermal Proton Transport through Graphene Layers.

Protons can penetrate through single-layer graphene, but thicker graphene layers (more than 2 layers), which possess more compact electron density, are thought to be unfavorable for penetration by protons at room temperature and elevated temperatures. In this work, we developed an in situ subsecond time-resolved grazing-incidence X-ray diffraction technique, which fully realizes the real-time observation of the thermal proton interaction with the graphene layers at high temperature. By following the evolution of interlayer structure during the protonation process, we demonstrated that thermal protons can transport through multilayer graphene (more than 8 layers) on nickel foil at 900 °C. In comparison, under the same conditions, the multilayer graphenes are impermeable to argon, nitrogen, helium, and their derived ions. Complementary in situ transport measurements simultaneously verify the penetration phenomenon at high temperature. Moreover, the direct transport of protons through graphene is regarded as the dominant contribution to the penetration phenomenon. The thermal activation, weak interlayer interaction between layers, and the affinity of the nickel catalyst may all contribute to the proton transport. We believe that this method could become one of the established approaches for the characterization of the ions intercalated with 2D materials in situ and in real-time.

Annealing Induced Re-crystallization in CH3NH3PbI3-xClx for High Performance Perovskite Solar Cells.

Using poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) as hole conductor, a series of inverted planar CH3NH3PbI3-xClx perovskite solar cells (PSCs) were fabricated based on perovskite annealed by an improved time-temperature dependent (TTD) procedure in a flowing nitrogen atmosphere for different time. Only after an optimum annealing time, an optimized power conversion efficiency of 14.36% could be achieved. To understand their performance dependence on annealing time, an in situ real-time synchrotron-based grazing incidence X-ray diffraction (GIXRD) was used to monitor a step-by-step gradual structure transformation from distinct mainly organic-inorganic hybrid materials into highly ordered CH3NH3PbI3 crystal during annealing. However, a re-crystallization process of perovskite crystal was observed for the first time during such an annealing procedure, which helps to enhance the perovskite crystallization and preferential orientations. The present GIXRD findings could well explain the drops of the open circuit voltage (Voc) and the fill factor (FF) during the ramping of temperature as well as the optimized power conversion efficiency achieved after an optimum annealing time. Thus, the present study not only illustrates clearly the decisive roles of post-annealing in the formation of solution-processed perovskite to better understand its formation mechanism, but also demonstrates the crucial dependences of device performance on the perovskite microstructure in PSCs.

High-Performance Perovskite Solar Cells Engineered by an Ammonia Modified Graphene Oxide Interfacial Layer.

The introduction of an ammonia modified graphene oxide (GO:NH3) layer into perovskite-based solar cells (PSCs) with a structure of indium-tin oxide (ITO)/poly(3,4-ethylene-dioxythiophene):poly(4-styrenesulfonate) ( PEDOT: PSS)-GO: NH3/CH3NH3PbI3-xClx/phenyl C61-butyric acid methyl ester (PCBM)/(solution Bphen) sBphen/Ag improves their performance and perovskite structure stability significantly. The fabricated devices with a champion PCE up to 16.11% are superior in all the performances in comparison with all the reference devices without the GO:NH3 layer. To understand the improved device performances, synchrotron-based grazing incidence X-ray diffraction (GIXRD), scanning electron microscopy (SEM), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), and UV-visible absorption measurements have been conducted on perovskite films on different substrates. It was found that these improvements should be partially attributed to the improved crystallization and preferred orientation order of peovskite structure, partially to the improved morphology with nearly complete coverage, partially to the enhanced optical absorption caused by the PEDOT: PSS-GO:NH3 layer, and partially to the better matched energy-level-alignment at the perovskite interface. Furthermore, the device was shown to be more stable in the ambient condition, which is clearly associated with the improved peovskite structure stability by the GO:NH3 layer observed by the GIXRD measurements. All these achievements will promote more applications of chemically modified graphene oxide interfacial layer in the PSCs as well as other organic multilayer devices.

Design, construction and management of tailings storage facilities for surface disposal in China: case studies of failures.

Rapid development of China's economy demands for more mineral resources. At the same time, a vast quantity of mine tailings, as the waste byproduct of mining and mineral processing, is being produced in huge proportions. Tailings impoundments play an important role in the practical surface disposal of these large quantities of mining waste. Historically, tailings were relatively small in quantity and had no commercial value, thus little attention was paid to their disposal. The tailings were preferably discharged near the mines and few tailings storage facilities were constructed in mainland China. This situation has significantly changed since 2000, because the Chinese economy is growing rapidly and Chinese regulations and legislation require that tailings disposal systems must be ready before the mining operation begins. Consequently, data up to 2008 shows that more than 12 000 tailings storage facilities have been built in China. This paper reviews the history of tailings disposal in China, discusses three cases of tailings dam failures and explores failure mechanisms, and the procedures commonly used in China for planning, design, construction and management of tailings impoundments. This paper also discusses the current situation, shortcomings and key weaknesses, as well as future development trends for tailings storage facilities in China.

High-Tc ferromagnetism in a Co-doped ZnO system dominated by the formation of a zinc-blende type Co-rich ZnCoO phase.

The modulation of the distribution of magnetic ions embedded in the host is crucial for the functionality of dilute magnetic semiconductors. Through an element-specific structural characterization, we observe the formation and enhancement of an unrevealed Co-doped ZnO phase and consequently magnetic properties from paramagnetism to ferromagnetism are controlled by surface-modification.