Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na...Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.展开更多
Lithium sulfur batteries have attracted much attention due to their high theoretical specific energy and environmental friendliness.However,the practical application is severely plagued by the cycling life issues resu...Lithium sulfur batteries have attracted much attention due to their high theoretical specific energy and environmental friendliness.However,the practical application is severely plagued by the cycling life issues resulting from the uncontrollable generation and growth of Li dendrites.Herein,an innovative 3D flexible self-supporting Li anode protection layer of P-Mn_(3)O_(4-x)is constructed via a facile solvothermal method followed by an annealing process.Benefiting from the rich oxygen vacancies coupled with the 3D flexible self-supporting skeleton,abundant lithiophilic sites and high ionic conductivity are obtained,which succeed in guiding Li+homogeneous adsorption and redistribution,accelerating Li+diffusion rate,inducing Li+uniform deposition and nucleation.DFT calculations and experimental results conclusively demonstrate such a protection mechanism.Meanwhile,the effective anchoring and catalytic nature of polar P-Mn_(3)O_(4-x)can also be applied as an immobilization-diffusion-conversion host to improve polysulfides redox.Taking advantage of these merits,super-stable functions for Li symmetric cell matched with P-Mn_(3)O_(4-x)layer are achieved,which exhibits an ultralong lifespan of>5000 h with an ultralow overpotential of 20 m V,far lower than that of bare Li symmetric cell(overpotential of 800 m V only after 250 h)at high current densities of 5 m A cm^(-2)and high plating/stripping capacity of 10 m A h cm^(-2).Even in Li|P-Mn_(3)O_(4-x)||S full cell at 1 C,a high initial discharge specific capacity of 843.1 m A h g^(-1)is still delivered with ultralow capacity fading rate of 0.07%per cycle after 250 cycles,further confirming the synergistic regulation of P-Mn_(3)O_(4-x)for Li nucleation behavior.This work illustrates a sufficient guarantee of 3D protection layer coupled with oxygen vacancies in guiding Li diffusion and nucleation behavior and provides new guidance for promoting the development of advanced Li-S batteries.展开更多
Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the i...Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.展开更多
Based on the results of drilling,tests and simulation experiments,the shales of the Cretaceous Qingshankou Formation in the Gulong Sag of the Songliao Basin are discussed with respect to hydrocarbon generation evoluti...Based on the results of drilling,tests and simulation experiments,the shales of the Cretaceous Qingshankou Formation in the Gulong Sag of the Songliao Basin are discussed with respect to hydrocarbon generation evolution,shale oil occurrence,and pore/fracture evolution mechanism.In conjunction with a substantial amount of oil testing and production data,the Gulong shale oil enrichment layers are evaluated and the production behaviors and decline law are analyzed.The results are drawn in four aspects.First,the Gulong shales are in the stage of extensive hydrocarbon expulsion when R_(0) is 1.0%-1.2%,with the peak hydrocarbon expulsion efficiency of 49.5%approximately.In the low-medium maturity stage,shale oil migrates from kerogen to rocks and organic pores/fractures.In the medium-high maturity stage,shale oil transforms from adsorbed state to free state.Second,the clay mineral intergranular pores/fractures,dissolution pores,and organic pores make up the majority of the pore structure.During the transformation,clay minerals undergo significant intergranular pore/fracture development between the minerals such as illite and illite/smectite mixed layer.A network of pores/fractures is formed by organic matter cracking.Third,free hydrocarbon content,effective porosity,total porosity,and brittle mineral content are the core indicators for the evaluation of shale oil enrichment layers.Class-I layers are defined as free hydrocarbon content equal or greater than 6.0 mg/g,effective porosity equal or greater than 3.5%,total porosity equal or greater than 8.0%,and brittle mineral content equal or greater than 50%.It is believed that the favourable oil layers are Q2-Q3 and Q8-Q9.Fourth,the horizontal wells in the core area of the light oil zone exhibit a high cumulative production in the first year,and present a hyperbolic production decline pattern,with the decline index of 0.85-0.95,the first-year decline rate of 14.5%-26.5%,and the single-well estimated ultimate recovery(EUR)greater than 2.0×10^(4)t.In practical exploration and production,more efforts will be devoted to the clarification of hydrocarbon generation and expulsion mechanisms,accurate testing of porosity and hydrocarbon content/phase of shale under formation conditions,precise delineation of the boundary of enrichment area,relationship between mechanical properties and stimulated reservoir volume,and enhanced oil recovery,in order to improve the EUR and achieve a large-scale,efficient development of shale oil.展开更多
The Tazhong paleouplift is divided into the upper and the lower structural layers, bounded by the unconformity surface at the top of the Ordovician carbonate rock. The reservoirs in the two layers from different parts...The Tazhong paleouplift is divided into the upper and the lower structural layers, bounded by the unconformity surface at the top of the Ordovician carbonate rock. The reservoirs in the two layers from different parts vary in number, type and reserves, but the mechanism was rarely researched before. Therefore, an explanation of the mechanism will promote petroleum exploration in Tazhong paleouplift. After studying the evolution and reservoir distribution of the Tazhong paleouplift, it is concluded that the evolution in late Caledonian, late Hercynian and Himalayan periods resulted in the upper and the lower structural layers. It is also defined that in the upper structural layer, structural and stratigraphic overlap reservoirs are developed at the top and the upper part of the paleouplift, which are dominated by oil reservoirs, while for the lower structural layer, lithological reservoirs are developed in the lower part of the paleouplift, which are dominated by gas reservoirs, and more reserves are discovered in the lower structural layer than the upper. Through a comparative analysis of accumulation conditions of the upper and the lower structural layers, the mechanism of enrichment differences is clearly explained. The reservoir and seal conditions of the lower structural layer are better than those of the upper layer, which is the reason why more reservoirs have been found in the former. The differences in the carrier system types, trap types and charging periods between the upper and the lower structural layers lead to differences in the reservoir types and distribution. An accumulation model is established for the Tazhong paleouplift. For the upper structural layer, the structural reservoirs and the stratigraphic overlap reservoirs are formed at the upper part of the paleouplift, while for the lower structural layer, the weathering crust reservoirs are formed at the top, the reef-flat reservoirs are formed on the lateral margin, the karst and inside reservoirs are formed in the lower part of the paleouplift.展开更多
Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions dur...Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.展开更多
Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of ...Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.展开更多
With exhaustion of fossil fuels and the deterioration of global environment,widespread and intensive researches have been concentrated on clean and sustainable alternative energy sources,such as metal-air batteries[1]...With exhaustion of fossil fuels and the deterioration of global environment,widespread and intensive researches have been concentrated on clean and sustainable alternative energy sources,such as metal-air batteries[1],fuel cells[2]and water splitting devices[3].Electrocatalytic oxidation of water to O2(oxygen evolution reaction,OER)is a vital chemical process involved in energy storage and conversion from renewable sources in form of molecular fuels such as H2 via water electrolysis,which has attracted a great amount of research efforts in the past few years[4,5].Nowadays,RuO2 and IrO2 are widely used as typical excellent OER electrocatalysts.However,their high-cost and scarce nature restricts the broadly commercial application of those materials[6,7].Hence,there is an urgent demand to develop low cost,highly efficient,and superb stable OER catalysts.展开更多
Recently measured high gamma ray values in the Yanchang Formation of the Upper Triassic in the Ordos Basin have added an interesting and controversial twist to the study of the formation’s uranium enrichment and gene...Recently measured high gamma ray values in the Yanchang Formation of the Upper Triassic in the Ordos Basin have added an interesting and controversial twist to the study of the formation’s uranium enrichment and genesis.High uranium and thorium contents in the tuffaceous layer cause high gamma ray values in the Yanchang Formation.Petrographic studies,major elements,rare earth elements(REEs),and trace elements have been systematically analyzed to determine the composition,geochemical environment,and diagenetic processes of the layer.The observed color of the tuffaceous layer in the study area varies from yellow to yellowish brown.The tuff consists of matrix supported with sub-rounded to sub-angular lithic fragments.These lithic fragments probably derived from pre-existing rocks and incorporated into the tuffaceous layer during volcanic eruption.Quartz,plagioclase,and biotite were observed in well to poorly sorted form,in addition to framboidal pyrite and organic laminae.Measured ratios of SiO_2/Al_2O_3 ranged from 3.277 to 6.105 with an average of 3.738.The ratio of TiO_2/Al_2O_3 varied from 0.037 to 0.201 with an average of 0.061,indicating that the sediments of the tuffaceous layer originated from an intermediate magma.REE distribution patterns show sharp negative Eu anomalies,indicating a reducing environment,which is suitable for uranium deposition.A reducing environment was confirmed by black shale in the base of the Yanchang Formation.Such black shale has high organic matter content that can take kerogene from mudstone and provide a reducing environment for uranium enrichment in the tuffaceous layer.Moreover,negative Eu anomalies and the REE patterns indicate a subduction-related volcanic arc environment as the magma source of the tuffaceous layers.High values of Rb,Ba,and Sr might be the result of fluid phase activities;low values of Hf and Eu indicate the involvement of crustal material during diagenesis of the tuff.Discrimination diagrams(Th/Yb vs Ta/Yb,Th/Hf vs Ta/Hf)suggest an active continental margin as the tectonic setting of source volcanoes.Plots of Nb versus Y,Rb versus Y+Nb,TiO_2 versus Zr,and Th/Yb versus Nb/Yb of the tuffaceous content point to calc-alkaline continental arc-related magmatism.We concluded that uranium enrichment in the tuffaceous layer was supported by oxidation–reduction.展开更多
Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen...Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen evolution reaction(OER)due to their layered structure combined with versatile com-positions.Furthermore,reducing the thickness of platelet LDH crystals to nanometer or even molecular scale via cleavage or delamination provides an important clue to enhance the activity.In this review,recent progresses on rational design of LDH nanosheets are reviewed,including direct synthesis via traditional coprecipitation,homogeneous precipitation,and newly developed topochemical oxidation as well as chemical exfoliation of parent LDH crystals.In addition,diverse strategies are introduced to modulate their electrochemical activity by tuning the composition of host metal cations and intercalated counter-anions,and incorporating dopants,cavi-ties,and single atoms.In particular,hybridizing LDHs with conductive components or in situ growing them on conductive substrates to produce freestanding electrodes can further enhance their intrinsic catalytic activity.A brief discussion on future research directions and prospects is also summarized.展开更多
Understanding carbon-supported Pt-catalyzed oxygen reduction reaction(ORR)from the perspective of the active sites is of fundamental and practical importance.In this study,three differently sized carbon nanotube-suppo...Understanding carbon-supported Pt-catalyzed oxygen reduction reaction(ORR)from the perspective of the active sites is of fundamental and practical importance.In this study,three differently sized carbon nanotube-supported Pt nanoparticles(Pt/CNT)are prepared by both atomic layer deposition(ALD)and impregnation methods.The performances of the catalysts toward the ORR in acidic media are comparatively studied to probe the effects of the sizes of the Pt nanoparticles together with their distributions,electronic properties,and local environments.The ALD-Pt/CNT catalysts show much higher ORR activity and selectivity than the impregnation-Pt/CNT catalysts.This outstanding ORR performance is ascribed to the well-controlled Pt particle sizes and distributions,desirable Pt^04f binding energy,and the Cl-free Pt surfaces based on the electrocatalytic measurements,catalyst characterizations,and model calculations.The insights reported here could guide the rational design and fine-tuning of carbon-supported Pt catalysts for the ORR.展开更多
Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly...Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly desirable but still a great challenge at current stage.Herein,a new type of hybrid nanostructure,consisting of two-dimensional(2D) Cerium-doped NiFe-layered double hydroxide nanoflakes directly grown on the 2D Ti3C2Tx MXene surface(denoted as NiFeCe-LDH/MXene),is designed using a facile insitu coprecipitation method.The resultant NiFeCe-LDH/MXene hybrid presents a hierarchical nanoporous structure,high electrical conductivity and strong interfacial junction because of the synergistic effect of Ce doping and MXene coupling.As a result,the hybrid catalyst exhibits an excellent catalytic activity for OER,delivering a low onset overpotential of 197 mV and an overpotential of 260 mV at a current density of 10 mA·cm-2 in the alkaline medium,much lower than its pure LDH counterparts and IrO2 catalyst.Besides,the hybrid catalyst also displays a fast reaction kinetics and a remarkable stable durability.Further theoretic studies using density function theory(DFT) methods reveal that Ce doping could effectively narrow the bandgap of NiFe-LDH and reduce the overpotential in OER process.This work may shed light on the exploration of advanced electrocatalysts for renewable energy conversion and storage systems.展开更多
Many people who live in the low altitude areas are often suffered from hypoxia when they entered the high plateau. This problem may seriously influence the physical and mental state and work efficacy for the travelers...Many people who live in the low altitude areas are often suffered from hypoxia when they entered the high plateau. This problem may seriously influence the physical and mental state and work efficacy for the travelers and workers. Oxygen enrichment of a small space air at high altitude is considered as a simple way to provide lowlanders enriched oxygen for sleeping and resting, improving work efficiency, so we developed an oxygen concentration machine based on the technology of oxygen enrichment membrane. This paper tested 8 healthy male lowlanders (age 21.63±1.77 yr) who have never exposed to plateau performed an incremental exercise on cycle ergometer at sea-level in order to be used as sea-level controls. Two days later, the same subjects were taken to Lhasa (3700 m) by air and exposed to the plateau, performed the same exercise as they did at sea-level. The next day, all subjects were asked to enter the experimental tent which was enriched with oxygen (higher than 24%) by the oxygen concentration machine and sleep for 10 hours at night, then exposed to plateau and performed the same exercise twice at different time (2 hours and 10 hours after oxygen enrichment). During the tests, subjects must cycled continuously at 60 rpm beginning with a 3 min exercise intensity of 0 W followed by incremental increases of 25 W every 3 min until 150 W, pulse oxygen saturation (SpO2) and heart rate (HR) were recorded. After sleeping in an oxygen enrichment of tent air, 2 hours later, the subjects’ load capacity had no difference compared with control group, but significant difference than before (higher SpO2 and lower HR), which indicated that oxygen concentration machine is effective in increasing the oxygen concentration of the air for the tent and sleeping in the oxygen enrichment tent for l0 h might be effective in improving exercise performance during high-altitude hypoxia. At the same time, 10 hours later, when work-load exceeded 125 W, the same effects were also found. The results indicated the effects of oxygen enrichment of tent air could last a certain period of time.展开更多
Compared with noble metal catalyst, Co3O4-based electrocatalysts have attracted considerable interesting as low-cost alternatives for oxygen evolution reaction (OER). However, the poor electrocatalytic activity still ...Compared with noble metal catalyst, Co3O4-based electrocatalysts have attracted considerable interesting as low-cost alternatives for oxygen evolution reaction (OER). However, the poor electrocatalytic activity still remains a huge challenge. Herein, we demonstrate a feasible approach through oxidation of CoFe layered double hydroxide (CoFe-LDH) to synthesize Fe-doped Co3O4@C nanopmrticles with size of about 30-50 nm. As OER catalyst, the as-synthesized Fe-doped Co3O4@C nanoparticles exhibited superior OER performance with a small overpotential of 260 mV at the current density of 20 mA cm^-2, a small Tafel slope of 70 mV dec^-1 and long-term durability (there was no obviously OER current density degradation for 100 h) in alkaline solution. The present work opens a new avenue to the exploration of cost-effective and excellent electrocatalysts based on transition metal oxide materials to substitute precious metal materials for water splitting.展开更多
Oxygen evolution reaction(OER) is a key process for electrochemical water splitting due to its intrinsic large overpotential. Recently, layered double hydroxides(LDHs), especially Ni Fe-LDH, have been regarded as high...Oxygen evolution reaction(OER) is a key process for electrochemical water splitting due to its intrinsic large overpotential. Recently, layered double hydroxides(LDHs), especially Ni Fe-LDH, have been regarded as highly performed electrocatalysts for OER in alkaline condition. Here we first present a new class of Ni La-LDH electrocatalyst synthesized by an electrochemical process for efficient water splitting. The as-prepared NiL a-LDH nanosheet arrays(NSAs) give remarkable electrochemical activity and durability under alkaline environments, with a low overpotential of 209 mV for OER to deliver a current density of 10 mA cm^-2, surpassing most of previous reported LDHs eletrocatalysts. The presence of NiLa-LDH in this work extends the studies about LDHs-based electrocatalysts, which will benefit the development of electrochemical energy storage and conversion systems.展开更多
Oxygen evolution reaction(OER) plays an indispensable role in developing renewable clean energy resources. One of the critical bottlenecks for the reaction is the development of highly efficient electrocatalyst to dec...Oxygen evolution reaction(OER) plays an indispensable role in developing renewable clean energy resources. One of the critical bottlenecks for the reaction is the development of highly efficient electrocatalyst to decrease the high overpotentials of four-electron transfer process of OER. Recently, layered double hydroxides(LDHs) have been widely investigated among the most promising electrocatalysts for OER due to their high intrinsic activity, excellent stability as well as low-cost. However, it remains unclear how the exposed facet of the LDHs affects their electrocatalytic activity. Here we elucidate the active edge facet of LDHs towards OER by combining the finely control of edge facet ratio coupled with molecular probe method and computational calculation. The LDHs with higher edge facet area ratio show superior activity with low onset potential as well as decreased Tafel slope. The active edge site is further proved by blocking the unsaturated edge sites with cyanate probe anion, of which the adsorption largely inhibits OER activity. Furthermore, based on density functional theory(DFT) calculation, twodimensional map of theoretical overpotentials as a function of Gibbs free energy reveals that the edge(100) facet exhibits a much higher OER activity than basal plane(001) facet.展开更多
The effects of gas composition, temperature, ore to coke ratio and prereduction rate of ore on coke degradation were studied. The results showed that 1% increment in solution loss of coke reduces coke strength by 0.6%...The effects of gas composition, temperature, ore to coke ratio and prereduction rate of ore on coke degradation were studied. The results showed that 1% increment in solution loss of coke reduces coke strength by 0.6%, and the coke degradation is accelerated with the temperature. The higher the temperature, the more coke surface is involved in reactions, and the less negative effect on coke strength is. Hydrogen exerts stronger effect on coke degradation than CO at high temperature. The coke degradation is decreased with the reduction of ore to coke ratio and increase of ore prereduction rate.展开更多
The Nickel-rich layered cathode materials charged to 4.5 V can obtain a specific capacity of more than 200 m Ah g^(-1).However,the nickel-rich layered cathode materials suffer from the severe capacity fade during high...The Nickel-rich layered cathode materials charged to 4.5 V can obtain a specific capacity of more than 200 m Ah g^(-1).However,the nickel-rich layered cathode materials suffer from the severe capacity fade during high-voltage cycling,which is related to the phase transformation and the surface sides reactions caused by the lattice oxygen evolution.Here,the simultaneous construction of a Mg,Ti-based surface integrated layer and bulk doping through Mg,Ti surface treatment could suppress the lattice oxygen evolution of Nirich material at deep charging.More importantly,Mg and Ti are co-doped into the particles surface to form an Mg_(2)TiO_(4) and Mg_(0.5–x)Ti_(2–y)(PO_(4))_(3) outer layer with Mg and Ti vacancies.In the constructed surface integrated layer,the reverse electric field in the Mg_(2)TiO_(4) effectively suppressed the outward migration of the lattice oxygen anions,while Mg_(0.5–x)Ti_(2–y)(PO_(4))_(3) outer layer with high electronic conductivity and good lithium ion conductor could effectively maintained the stability of the reaction interface during highvoltage cycling.Meanwhile,bulk Mg and Ti co-doping can mitigate the migration of Ni ions in the bulk to keep the stability of transition metal–oxygen(M-O)bond at deep charging.As a result,the NCM@MTP cathode shows excellent long cycle stability at high-voltage charging,which keep high capacity retention of 89.3%and 84.3%at 1 C after 200 and 100 cycles under room and elevated temperature of 25 and 55°C,respectively.This work provides new insights for manipulating the surface chemistry of electrode materials to suppress the lattice oxygen evolution at high charging voltage.展开更多
The effect of oxygen partial pressure (Po2) during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistors (TFTs) is investigated. As Po2 increases fr...The effect of oxygen partial pressure (Po2) during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistors (TFTs) is investigated. As Po2 increases from 10% to 30%, it is found that the device shows enhanced bias stress stability with significantly reduced threshold voltage drift under positive gate bias stress. Based on the x-ray photoelectron spectroscopy measurement, the concentration of oxygen vacancies (Or) within the a-IGZO layer is suppressed by increasing Po2. Meanwhile, the low-frequency noise analysis indicates that the average trap density near the channel/dielectric interface continuously drops with increasing Po2. Therefore, the improved interface quality with increasing Po2 during the channel layer deposition can be attributed to the reduction of interface Ov-related defects, which agrees with the enhanced bias stress stability of the a-IGZO TFTs.展开更多
基金funding supports from the National Key R&D Program of China(Grant Nos.2022YFB2404400 and 2019YFA0308500)Beijing Natural Science Foundation(Z190010)National Natural Science Foundation of China(Grant Nos.51991344,52025025,52072400,and 52002394)。
文摘Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.
基金supported by the Natural Science Foundation of Shandong Province(ZR2021MB101,ZR2021ME113,ZR2021ME177,and ZR2021QE096)。
文摘Lithium sulfur batteries have attracted much attention due to their high theoretical specific energy and environmental friendliness.However,the practical application is severely plagued by the cycling life issues resulting from the uncontrollable generation and growth of Li dendrites.Herein,an innovative 3D flexible self-supporting Li anode protection layer of P-Mn_(3)O_(4-x)is constructed via a facile solvothermal method followed by an annealing process.Benefiting from the rich oxygen vacancies coupled with the 3D flexible self-supporting skeleton,abundant lithiophilic sites and high ionic conductivity are obtained,which succeed in guiding Li+homogeneous adsorption and redistribution,accelerating Li+diffusion rate,inducing Li+uniform deposition and nucleation.DFT calculations and experimental results conclusively demonstrate such a protection mechanism.Meanwhile,the effective anchoring and catalytic nature of polar P-Mn_(3)O_(4-x)can also be applied as an immobilization-diffusion-conversion host to improve polysulfides redox.Taking advantage of these merits,super-stable functions for Li symmetric cell matched with P-Mn_(3)O_(4-x)layer are achieved,which exhibits an ultralong lifespan of>5000 h with an ultralow overpotential of 20 m V,far lower than that of bare Li symmetric cell(overpotential of 800 m V only after 250 h)at high current densities of 5 m A cm^(-2)and high plating/stripping capacity of 10 m A h cm^(-2).Even in Li|P-Mn_(3)O_(4-x)||S full cell at 1 C,a high initial discharge specific capacity of 843.1 m A h g^(-1)is still delivered with ultralow capacity fading rate of 0.07%per cycle after 250 cycles,further confirming the synergistic regulation of P-Mn_(3)O_(4-x)for Li nucleation behavior.This work illustrates a sufficient guarantee of 3D protection layer coupled with oxygen vacancies in guiding Li diffusion and nucleation behavior and provides new guidance for promoting the development of advanced Li-S batteries.
基金supported by the National Natural Science Foundation of China(52272253)the"Lingyan"Research and Development Plan of Zhejiang Province(2022C01071)+2 种基金the S&T Innovation 2025 Major Special Programme of Ningbo(2018B10081)the Natural Science Foundation of Ningbo(202003N4030)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022299)。
文摘Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.
基金Supported by the National Natural Science Foundation Project(42090020,42090025)Strategic Research of Oil and Gas Development Major Project of Ministry of Science and TechnologyPetroChina Scientific Research and Technological Development Project(2019E2601).
文摘Based on the results of drilling,tests and simulation experiments,the shales of the Cretaceous Qingshankou Formation in the Gulong Sag of the Songliao Basin are discussed with respect to hydrocarbon generation evolution,shale oil occurrence,and pore/fracture evolution mechanism.In conjunction with a substantial amount of oil testing and production data,the Gulong shale oil enrichment layers are evaluated and the production behaviors and decline law are analyzed.The results are drawn in four aspects.First,the Gulong shales are in the stage of extensive hydrocarbon expulsion when R_(0) is 1.0%-1.2%,with the peak hydrocarbon expulsion efficiency of 49.5%approximately.In the low-medium maturity stage,shale oil migrates from kerogen to rocks and organic pores/fractures.In the medium-high maturity stage,shale oil transforms from adsorbed state to free state.Second,the clay mineral intergranular pores/fractures,dissolution pores,and organic pores make up the majority of the pore structure.During the transformation,clay minerals undergo significant intergranular pore/fracture development between the minerals such as illite and illite/smectite mixed layer.A network of pores/fractures is formed by organic matter cracking.Third,free hydrocarbon content,effective porosity,total porosity,and brittle mineral content are the core indicators for the evaluation of shale oil enrichment layers.Class-I layers are defined as free hydrocarbon content equal or greater than 6.0 mg/g,effective porosity equal or greater than 3.5%,total porosity equal or greater than 8.0%,and brittle mineral content equal or greater than 50%.It is believed that the favourable oil layers are Q2-Q3 and Q8-Q9.Fourth,the horizontal wells in the core area of the light oil zone exhibit a high cumulative production in the first year,and present a hyperbolic production decline pattern,with the decline index of 0.85-0.95,the first-year decline rate of 14.5%-26.5%,and the single-well estimated ultimate recovery(EUR)greater than 2.0×10^(4)t.In practical exploration and production,more efforts will be devoted to the clarification of hydrocarbon generation and expulsion mechanisms,accurate testing of porosity and hydrocarbon content/phase of shale under formation conditions,precise delineation of the boundary of enrichment area,relationship between mechanical properties and stimulated reservoir volume,and enhanced oil recovery,in order to improve the EUR and achieve a large-scale,efficient development of shale oil.
基金supported by the National 973 Key Development Program for Basic Research of China(S/N: 2006CB202308)the National Natural Science Foundation of China(Grant No.40972088)
文摘The Tazhong paleouplift is divided into the upper and the lower structural layers, bounded by the unconformity surface at the top of the Ordovician carbonate rock. The reservoirs in the two layers from different parts vary in number, type and reserves, but the mechanism was rarely researched before. Therefore, an explanation of the mechanism will promote petroleum exploration in Tazhong paleouplift. After studying the evolution and reservoir distribution of the Tazhong paleouplift, it is concluded that the evolution in late Caledonian, late Hercynian and Himalayan periods resulted in the upper and the lower structural layers. It is also defined that in the upper structural layer, structural and stratigraphic overlap reservoirs are developed at the top and the upper part of the paleouplift, which are dominated by oil reservoirs, while for the lower structural layer, lithological reservoirs are developed in the lower part of the paleouplift, which are dominated by gas reservoirs, and more reserves are discovered in the lower structural layer than the upper. Through a comparative analysis of accumulation conditions of the upper and the lower structural layers, the mechanism of enrichment differences is clearly explained. The reservoir and seal conditions of the lower structural layer are better than those of the upper layer, which is the reason why more reservoirs have been found in the former. The differences in the carrier system types, trap types and charging periods between the upper and the lower structural layers lead to differences in the reservoir types and distribution. An accumulation model is established for the Tazhong paleouplift. For the upper structural layer, the structural reservoirs and the stratigraphic overlap reservoirs are formed at the upper part of the paleouplift, while for the lower structural layer, the weathering crust reservoirs are formed at the top, the reef-flat reservoirs are formed on the lateral margin, the karst and inside reservoirs are formed in the lower part of the paleouplift.
基金supported by the National Research Foundation of Korea grant funded by the Korea government (NRF2021R1A2C1014280)the Fundamental Research Program of the Korea Institute of Material Science (PNK9370)。
文摘Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.
基金supported by the National Research Foundation of Korea (NRF-2022R1C1C1004171)supported by the National Science Foundation (Grant number ACI1548562)。
文摘Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.
基金financially supported by the National Natural Science Foundation of China(U1707603,21521005,21975013,21901017)the National Key Research and Development Program of China(2017YFA0206500,2018YFA0702000)+2 种基金Beijing Natural Science Foundation(2172042)PetroChina Innovation Foundationthe Fundamental Research Funds for the Central Universities。
文摘With exhaustion of fossil fuels and the deterioration of global environment,widespread and intensive researches have been concentrated on clean and sustainable alternative energy sources,such as metal-air batteries[1],fuel cells[2]and water splitting devices[3].Electrocatalytic oxidation of water to O2(oxygen evolution reaction,OER)is a vital chemical process involved in energy storage and conversion from renewable sources in form of molecular fuels such as H2 via water electrolysis,which has attracted a great amount of research efforts in the past few years[4,5].Nowadays,RuO2 and IrO2 are widely used as typical excellent OER electrocatalysts.However,their high-cost and scarce nature restricts the broadly commercial application of those materials[6,7].Hence,there is an urgent demand to develop low cost,highly efficient,and superb stable OER catalysts.
基金supported by National Program on Key Basic Research Project (973 Program) (2015CB453002)DREAM Project of MOST China (2016YFC0600404)CASTWAS President Fellowship 2012
文摘Recently measured high gamma ray values in the Yanchang Formation of the Upper Triassic in the Ordos Basin have added an interesting and controversial twist to the study of the formation’s uranium enrichment and genesis.High uranium and thorium contents in the tuffaceous layer cause high gamma ray values in the Yanchang Formation.Petrographic studies,major elements,rare earth elements(REEs),and trace elements have been systematically analyzed to determine the composition,geochemical environment,and diagenetic processes of the layer.The observed color of the tuffaceous layer in the study area varies from yellow to yellowish brown.The tuff consists of matrix supported with sub-rounded to sub-angular lithic fragments.These lithic fragments probably derived from pre-existing rocks and incorporated into the tuffaceous layer during volcanic eruption.Quartz,plagioclase,and biotite were observed in well to poorly sorted form,in addition to framboidal pyrite and organic laminae.Measured ratios of SiO_2/Al_2O_3 ranged from 3.277 to 6.105 with an average of 3.738.The ratio of TiO_2/Al_2O_3 varied from 0.037 to 0.201 with an average of 0.061,indicating that the sediments of the tuffaceous layer originated from an intermediate magma.REE distribution patterns show sharp negative Eu anomalies,indicating a reducing environment,which is suitable for uranium deposition.A reducing environment was confirmed by black shale in the base of the Yanchang Formation.Such black shale has high organic matter content that can take kerogene from mudstone and provide a reducing environment for uranium enrichment in the tuffaceous layer.Moreover,negative Eu anomalies and the REE patterns indicate a subduction-related volcanic arc environment as the magma source of the tuffaceous layers.High values of Rb,Ba,and Sr might be the result of fluid phase activities;low values of Hf and Eu indicate the involvement of crustal material during diagenesis of the tuff.Discrimination diagrams(Th/Yb vs Ta/Yb,Th/Hf vs Ta/Hf)suggest an active continental margin as the tectonic setting of source volcanoes.Plots of Nb versus Y,Rb versus Y+Nb,TiO_2 versus Zr,and Th/Yb versus Nb/Yb of the tuffaceous content point to calc-alkaline continental arc-related magmatism.We concluded that uranium enrichment in the tuffaceous layer was supported by oxidation–reduction.
基金supported in part by the WPIMANA,Ministry of Education,Culture,Sports,Science and TechnologyCREST of the Japan Science and Technology Agency(JST)(Grant No.JPMJCR17N1)the support from JSPS KAKENNHI grant 15H02004 and 18H03869.
文摘Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen evolution reaction(OER)due to their layered structure combined with versatile com-positions.Furthermore,reducing the thickness of platelet LDH crystals to nanometer or even molecular scale via cleavage or delamination provides an important clue to enhance the activity.In this review,recent progresses on rational design of LDH nanosheets are reviewed,including direct synthesis via traditional coprecipitation,homogeneous precipitation,and newly developed topochemical oxidation as well as chemical exfoliation of parent LDH crystals.In addition,diverse strategies are introduced to modulate their electrochemical activity by tuning the composition of host metal cations and intercalated counter-anions,and incorporating dopants,cavi-ties,and single atoms.In particular,hybridizing LDHs with conductive components or in situ growing them on conductive substrates to produce freestanding electrodes can further enhance their intrinsic catalytic activity.A brief discussion on future research directions and prospects is also summarized.
基金financially supported by the Natural Science Foundation of China(21922803 and 21776077)the Shanghai Natural Science Foundation(17ZR1407300 and 17ZR1407500)+3 种基金the Program for the Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learningthe Shanghai Rising-Star Program(17QA1401200)the State Key Laboratory of Organic-Inorganic Composites(oic-201801007)the Open Project of State Key Laboratory of Chemical Engineering(SKLChe-15C03)。
文摘Understanding carbon-supported Pt-catalyzed oxygen reduction reaction(ORR)from the perspective of the active sites is of fundamental and practical importance.In this study,three differently sized carbon nanotube-supported Pt nanoparticles(Pt/CNT)are prepared by both atomic layer deposition(ALD)and impregnation methods.The performances of the catalysts toward the ORR in acidic media are comparatively studied to probe the effects of the sizes of the Pt nanoparticles together with their distributions,electronic properties,and local environments.The ALD-Pt/CNT catalysts show much higher ORR activity and selectivity than the impregnation-Pt/CNT catalysts.This outstanding ORR performance is ascribed to the well-controlled Pt particle sizes and distributions,desirable Pt^04f binding energy,and the Cl-free Pt surfaces based on the electrocatalytic measurements,catalyst characterizations,and model calculations.The insights reported here could guide the rational design and fine-tuning of carbon-supported Pt catalysts for the ORR.
基金supported by the Science Foundation of China University of Petroleum, Beijing (No. 2462017YJRC013)。
文摘Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly desirable but still a great challenge at current stage.Herein,a new type of hybrid nanostructure,consisting of two-dimensional(2D) Cerium-doped NiFe-layered double hydroxide nanoflakes directly grown on the 2D Ti3C2Tx MXene surface(denoted as NiFeCe-LDH/MXene),is designed using a facile insitu coprecipitation method.The resultant NiFeCe-LDH/MXene hybrid presents a hierarchical nanoporous structure,high electrical conductivity and strong interfacial junction because of the synergistic effect of Ce doping and MXene coupling.As a result,the hybrid catalyst exhibits an excellent catalytic activity for OER,delivering a low onset overpotential of 197 mV and an overpotential of 260 mV at a current density of 10 mA·cm-2 in the alkaline medium,much lower than its pure LDH counterparts and IrO2 catalyst.Besides,the hybrid catalyst also displays a fast reaction kinetics and a remarkable stable durability.Further theoretic studies using density function theory(DFT) methods reveal that Ce doping could effectively narrow the bandgap of NiFe-LDH and reduce the overpotential in OER process.This work may shed light on the exploration of advanced electrocatalysts for renewable energy conversion and storage systems.
文摘Many people who live in the low altitude areas are often suffered from hypoxia when they entered the high plateau. This problem may seriously influence the physical and mental state and work efficacy for the travelers and workers. Oxygen enrichment of a small space air at high altitude is considered as a simple way to provide lowlanders enriched oxygen for sleeping and resting, improving work efficiency, so we developed an oxygen concentration machine based on the technology of oxygen enrichment membrane. This paper tested 8 healthy male lowlanders (age 21.63±1.77 yr) who have never exposed to plateau performed an incremental exercise on cycle ergometer at sea-level in order to be used as sea-level controls. Two days later, the same subjects were taken to Lhasa (3700 m) by air and exposed to the plateau, performed the same exercise as they did at sea-level. The next day, all subjects were asked to enter the experimental tent which was enriched with oxygen (higher than 24%) by the oxygen concentration machine and sleep for 10 hours at night, then exposed to plateau and performed the same exercise twice at different time (2 hours and 10 hours after oxygen enrichment). During the tests, subjects must cycled continuously at 60 rpm beginning with a 3 min exercise intensity of 0 W followed by incremental increases of 25 W every 3 min until 150 W, pulse oxygen saturation (SpO2) and heart rate (HR) were recorded. After sleeping in an oxygen enrichment of tent air, 2 hours later, the subjects’ load capacity had no difference compared with control group, but significant difference than before (higher SpO2 and lower HR), which indicated that oxygen concentration machine is effective in increasing the oxygen concentration of the air for the tent and sleeping in the oxygen enrichment tent for l0 h might be effective in improving exercise performance during high-altitude hypoxia. At the same time, 10 hours later, when work-load exceeded 125 W, the same effects were also found. The results indicated the effects of oxygen enrichment of tent air could last a certain period of time.
基金supported by the 973 Program(no.2014CB932104)the National Natural Science Foundation of China(nos:2177060378,U1707603 and 21521005)the Program for Changjiang Scholars,Innovative Research Teams in Universities(no.IRT1205)
文摘Compared with noble metal catalyst, Co3O4-based electrocatalysts have attracted considerable interesting as low-cost alternatives for oxygen evolution reaction (OER). However, the poor electrocatalytic activity still remains a huge challenge. Herein, we demonstrate a feasible approach through oxidation of CoFe layered double hydroxide (CoFe-LDH) to synthesize Fe-doped Co3O4@C nanopmrticles with size of about 30-50 nm. As OER catalyst, the as-synthesized Fe-doped Co3O4@C nanoparticles exhibited superior OER performance with a small overpotential of 260 mV at the current density of 20 mA cm^-2, a small Tafel slope of 70 mV dec^-1 and long-term durability (there was no obviously OER current density degradation for 100 h) in alkaline solution. The present work opens a new avenue to the exploration of cost-effective and excellent electrocatalysts based on transition metal oxide materials to substitute precious metal materials for water splitting.
基金supported by the National Natural Science Foundation of China (21601011 and 21521005)the National Key Research and Development Programme (2017YFA0206804)the Fundamental Research Funds for the Central Universities (buctrc201506 and buctylkxj01)
文摘Oxygen evolution reaction(OER) is a key process for electrochemical water splitting due to its intrinsic large overpotential. Recently, layered double hydroxides(LDHs), especially Ni Fe-LDH, have been regarded as highly performed electrocatalysts for OER in alkaline condition. Here we first present a new class of Ni La-LDH electrocatalyst synthesized by an electrochemical process for efficient water splitting. The as-prepared NiL a-LDH nanosheet arrays(NSAs) give remarkable electrochemical activity and durability under alkaline environments, with a low overpotential of 209 mV for OER to deliver a current density of 10 mA cm^-2, surpassing most of previous reported LDHs eletrocatalysts. The presence of NiLa-LDH in this work extends the studies about LDHs-based electrocatalysts, which will benefit the development of electrochemical energy storage and conversion systems.
基金supported by the National Natural Science Foundation of China (21871021, 21922501 and 21521005)the Beijing Natural Science Foundation (2192040)the Fundamental Research Funds for the Central Universities (XK1802-6 and XK1803-05)。
文摘Oxygen evolution reaction(OER) plays an indispensable role in developing renewable clean energy resources. One of the critical bottlenecks for the reaction is the development of highly efficient electrocatalyst to decrease the high overpotentials of four-electron transfer process of OER. Recently, layered double hydroxides(LDHs) have been widely investigated among the most promising electrocatalysts for OER due to their high intrinsic activity, excellent stability as well as low-cost. However, it remains unclear how the exposed facet of the LDHs affects their electrocatalytic activity. Here we elucidate the active edge facet of LDHs towards OER by combining the finely control of edge facet ratio coupled with molecular probe method and computational calculation. The LDHs with higher edge facet area ratio show superior activity with low onset potential as well as decreased Tafel slope. The active edge site is further proved by blocking the unsaturated edge sites with cyanate probe anion, of which the adsorption largely inhibits OER activity. Furthermore, based on density functional theory(DFT) calculation, twodimensional map of theoretical overpotentials as a function of Gibbs free energy reveals that the edge(100) facet exhibits a much higher OER activity than basal plane(001) facet.
文摘The effects of gas composition, temperature, ore to coke ratio and prereduction rate of ore on coke degradation were studied. The results showed that 1% increment in solution loss of coke reduces coke strength by 0.6%, and the coke degradation is accelerated with the temperature. The higher the temperature, the more coke surface is involved in reactions, and the less negative effect on coke strength is. Hydrogen exerts stronger effect on coke degradation than CO at high temperature. The coke degradation is decreased with the reduction of ore to coke ratio and increase of ore prereduction rate.
基金supported by the National Natural Science Foundation of China(51902108,51762006,51964013)the Special Projects for Central Government to Guide Local Technological Development(GUIKE ZY20198008)+2 种基金the Guangxi InnovationDriven Development Subject(GUIKE AA19182020,GUIKE AA19254004)the Guangxi Technology Base and Talent Subject(GUIKE AD18126001,GUIKE AD20999012,GUIKE AD20297086)the Special Fund for Guangxi Distinguished Expert。
文摘The Nickel-rich layered cathode materials charged to 4.5 V can obtain a specific capacity of more than 200 m Ah g^(-1).However,the nickel-rich layered cathode materials suffer from the severe capacity fade during high-voltage cycling,which is related to the phase transformation and the surface sides reactions caused by the lattice oxygen evolution.Here,the simultaneous construction of a Mg,Ti-based surface integrated layer and bulk doping through Mg,Ti surface treatment could suppress the lattice oxygen evolution of Nirich material at deep charging.More importantly,Mg and Ti are co-doped into the particles surface to form an Mg_(2)TiO_(4) and Mg_(0.5–x)Ti_(2–y)(PO_(4))_(3) outer layer with Mg and Ti vacancies.In the constructed surface integrated layer,the reverse electric field in the Mg_(2)TiO_(4) effectively suppressed the outward migration of the lattice oxygen anions,while Mg_(0.5–x)Ti_(2–y)(PO_(4))_(3) outer layer with high electronic conductivity and good lithium ion conductor could effectively maintained the stability of the reaction interface during highvoltage cycling.Meanwhile,bulk Mg and Ti co-doping can mitigate the migration of Ni ions in the bulk to keep the stability of transition metal–oxygen(M-O)bond at deep charging.As a result,the NCM@MTP cathode shows excellent long cycle stability at high-voltage charging,which keep high capacity retention of 89.3%and 84.3%at 1 C after 200 and 100 cycles under room and elevated temperature of 25 and 55°C,respectively.This work provides new insights for manipulating the surface chemistry of electrode materials to suppress the lattice oxygen evolution at high charging voltage.
基金financial support of the National Natural Science Foundation of China(No.50876112)the Fundamental Research Funds for the Central Universities (No.2009QH13)the Program of International S&T Cooperation (No.2009DFR60180,No.2010DFR60610)
基金Supported by the National Basic Research Program of China under Grant Nos 2010CB327504,2011CB922100 and2011CB301900the National Natural Science Foundation of China under Grant Nos 11104130 and 61322112+2 种基金the Natural Science Foundation of Jiangsu Province under Grant Nos BK2011556 and BK2011050the Priority Academic Program Development of Jiangsu Higher Education Institutionsand the NUPTSF Grant Nos NY213069 and NY214028
文摘The effect of oxygen partial pressure (Po2) during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide (a-IGZO) thin film transistors (TFTs) is investigated. As Po2 increases from 10% to 30%, it is found that the device shows enhanced bias stress stability with significantly reduced threshold voltage drift under positive gate bias stress. Based on the x-ray photoelectron spectroscopy measurement, the concentration of oxygen vacancies (Or) within the a-IGZO layer is suppressed by increasing Po2. Meanwhile, the low-frequency noise analysis indicates that the average trap density near the channel/dielectric interface continuously drops with increasing Po2. Therefore, the improved interface quality with increasing Po2 during the channel layer deposition can be attributed to the reduction of interface Ov-related defects, which agrees with the enhanced bias stress stability of the a-IGZO TFTs.