The direct carbonylation of methanol, without any halide in the feed as apromoter, is presented. A series of Mo catalysts supported on activated carbon, γ-Al_2O_3 and SiO_2were prepared. The results show that the sup...The direct carbonylation of methanol, without any halide in the feed as apromoter, is presented. A series of Mo catalysts supported on activated carbon, γ-Al_2O_3 and SiO_2were prepared. The results show that the support greatly affects the Mo catalyst in the directvapor-phase carbonylation of methanol, and activated carbon is the best supports of the investigatedsupports. In addition, the relationships between adsorptions of NH_3 and CO and carbonylation ofmethanol were investigated. A novel sulfided Mo/C catalyst had high activity and selectivity for thevapor phase carbonylation of methanol to methyl acetate without the addition of a CH_3I promoter tothe feed. The reaction conditions were optimized at a reaction temperature of 573 K, a methanolconcentration of 23 mol% and a carbon monoxide space velocity of 3,000 L/(kg·h). Under theseoptimal conditions a methanol conversion of 50%, carbonylation selectivity of 80 rnol%, andspace-time yield of 8.0 mol/(kg·h) were obtained. The active phase of this novel sulfided Mo/Ccatalyst is the non-crystalline phase, and the active component is present as MoS_(2.5) on thesurface of the activated carbon.展开更多
Six Ni-Mo catalysts with different metal contents were prepared and characterized by N2 adsorption and X-ray diffi＇actometry. The active phase microstructure of these catalysts was examined by the Raman spectroscopy,...Six Ni-Mo catalysts with different metal contents were prepared and characterized by N2 adsorption and X-ray diffi＇actometry. The active phase microstructure of these catalysts was examined by the Raman spectroscopy, temperature- programmed reduction （TPR）, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Hydrodesulfurization （HDS） activity of catalyst samples were analyzed in a flow fixed-bed microreactor. The sulfidation degree of Mo and the length of the MoS2 slab slightly increased with the amount of metal loaded following sulfidation. This small change is attributed to polymolybdate species observed in all the oxidized catalysts. Weak metal-support interactions, as determined by the TPR technique, increased the NiSx sulfidation phase and MoS2 slab stacking. The HDS activity of the catalyst samples increased with the number of active sites. For high metal loading catalysts, their HDS activity was nearly identical because the sulfur atoms cannot easily approach active sites. This change is caused by the large number of stacked layers in the MoS2 slabs as well as the decrease in the specific surface area and pore volume of the catalyst samples with an increasing metal loading.展开更多
Co-Mo/MgO-Al_(2)O_(3)catalyst was presulfided with ammonium sulfide in aqueous solution and activated with synthesis gas for water gas shift reaction.The assay results indicate that the presulfided Co-Mo/MgO-Al_(2)O_(...Co-Mo/MgO-Al_(2)O_(3)catalyst was presulfided with ammonium sulfide in aqueous solution and activated with synthesis gas for water gas shift reaction.The assay results indicate that the presulfided Co-Mo/MgO-Al_(2)O_(3)catalyst exhibits an excellent catalytic activity and stability.XRD and EPR characterization results show that the O-S exchange might occur during the impregnation,leading to the formation of(NH4)2MoS4(or(NH4)zMoxSy)precursor,which was then thermally decomposed and reduced to MoS2.The higher catalytic performance is attributed to an optimization formation of active Co-Mo sulfides,consisting of well dispersed MoS2 and Co-Mo-S phase due to the redispersion of Co sulfide particles over the edges of newly formed MoS2 crystallites.展开更多
It is difficult to recover chrysocolla from sulfidation flotation which is closely related to the mineral surface composition.In this study,the effects of fluoride roasting on the surface composition of chrysocolla we...It is difficult to recover chrysocolla from sulfidation flotation which is closely related to the mineral surface composition.In this study,the effects of fluoride roasting on the surface composition of chrysocolla were investigated,its impact on sulfidation flotation was explored,and the mechanisms involved in both fluoride roasting and sulfidation flotation were discussed.With CaF_(2)as the roasting reagent,Na_(2)S·9H_(2)O as the sulfidation reagent,and sodium butyl xanthate(NaBX)as the collector,the results of the flotation experiments showed that fluoride roasting improved the floatability of chrysocolla,and the recovery rate increased from 16.87%to 82.74%.X-ray diffraction analysis revealed that after fluoride roasting,approximately all the Cu on the chrysocolla surface was exposed in the form of CuO,which could provide a basis for subsequent sulfidation flotation.The microscopy and elemental analyses revealed that large quantities of"pagoda-like"grains were observed on the sulfidation surface of the fluoride-roasted chrysocolla,indicating high crystallinity particles of copper sulfide.This suggests that the effect of sulfide formation on the chrysocolla surface was more pronounced.X-ray photoelectron spectroscopy revealed that fluoride roasting increased the relative contents of sulfur and copper on the surface and that both the Cu~+and polysulfide fractions on the surface of the minerals increased.This enhances the effect of sulfidation,which is conducive to flotation recovery.Therefore,fluoride roasting improved the effect of copper species transformation and sulfidation on the surface of chysocolla,promoted the adsorption of collectors,and improved the recovery of chrysocolla from sulfidation flotation.展开更多
A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)...A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)S,metallic copper converts chalcopyrite into bornite(Cu_(5)FeS_(4)).However,the introduction of H_(2)S promotes the formation of chalcocite(Cu_(2)S)by altering the oxidation pathway of copper.Electrochemical analysis demonstrates that the presence of H₂S significantly reduces the corrosion potential of copper from 0.251 to−0.223 V(vs SHE),reaching the threshold necessary for the formation of Cu_(2)S.Nevertheless,excessive H_(2)S triggers sulfate reduction via the reaction of 8Cu+H_(2)SO_(4)+3H_(2)S=4Cu_(2)S+4H_(2)O(ΔG=−519.429 kJ/mol at 50℃),leading to inefficient copper utilization.展开更多
CM chondrites contain valuable insights into the formation and evolution of the solar nebula,as well as the secondary aqueous alteration processes that affected their parent bodies.Our study focuses on primary and sec...CM chondrites contain valuable insights into the formation and evolution of the solar nebula,as well as the secondary aqueous alteration processes that affected their parent bodies.Our study focuses on primary and secondary sulfides within the Aguas Zarcas(CM2)chondrite,investigating their formation mechanisms based on their morphology,textures,and compositions.Moreover,we infer the formation temperatures of the sulfides from 230 to 500℃ for primary and from 100 to 135℃ for secondary.We select representative grains and conduct Fe isotope measurements on them.The primary sulfides with δ^(56/54)Fe ranging from -2.44‰ to +0.69‰are associated with sulfidesilicate melt segregation,while secondary sulfides with δ^(56/54)Fe values between -1.83‰ and -0.14‰ are linked to aqueous alteration.Overall,the Ni content of the grains is positively correlated with δ^(56/54)Fe.It might be related to the changes in crystal structure and chemical bond lengths due to the increase in nickel content.Fe isotopes provide a new perspective on sulfide formation and the evolution of a carbonaceous chondrite parent body.展开更多
To address the poor mechanical performance and improve the tribological properties of self-lubricating polyphenylene sulfide/irradiation treated polytetrafluoroethylene(PPS/i-PTFE)blends,different aspect ratio carbon ...To address the poor mechanical performance and improve the tribological properties of self-lubricating polyphenylene sulfide/irradiation treated polytetrafluoroethylene(PPS/i-PTFE)blends,different aspect ratio carbon fibers(i.e.,PSCF:50,SCF:about 429)were introduced as reinforcement fillers.The results showed that the hybriding of PSCF and SCF at certain mass ratios exhibited simultaneous enhancement of mechanical and tribological performance for PPS/i-PTFE blend through the construction of synergistic lubrication and mechanical interlocking network.Specifically,the flexural strength and modulus of PPS/i-PTFE were increased by 125.6% and 389.3%,the friction coefficient and specific wear rate were decreased by 13.9% and 95%,respectively.It was worth noting that PPS composites possessed excellent integrated performance which were able to withstand sliding action under high PV(≥10 MPa·m/s)conditions,as assessed by a customized pin-on-disc tester.This work demonstrated that the formation of intact lubricating film combined with the enhanced thermal and mechanical properties were favorable for improving the tribological properties of PPS-based composites,which makes them suitable for advanced engineering applications.展开更多
Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic condu...Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.展开更多
Sulfide solid electrolytes are considered promising candidates for all-solid-state lithium batteries(ASSLBs)because of their high ionic conductivity and favorable mechanical properties.However,the uncontrolled growth ...Sulfide solid electrolytes are considered promising candidates for all-solid-state lithium batteries(ASSLBs)because of their high ionic conductivity and favorable mechanical properties.However,the uncontrolled growth of lithium dendrites at the lithium metal-electrolytes interface remains a major obstacle to their practical application.In this work,we introduced a scalable three-dimensional(3D)Li-B skeleton structure designed to suppress dendrite formation.The alloy anode demonstrates a lower Young's modulus,which helps alleviate the accumulation of localized stresses at the interface.Additionally,the 3D alloy anode provided a uniform potential distribution,which promoted homogeneous lithium deposition.Benefiting from these structural advantages,symmetric cells with the Li-B alloy achieved a high critical current density of 2.8 mA cm^(-2).Notably,Li-B‖LPSCI‖LVO-NCM ASSLBs exhibited long-term cycling stability,retaining 97.8%of their capacity after 1500 cycles at 2 C.Furthermore,ASSLBs incorporating the Li-B alloy showed cycling stability comparable with Li-In-based cells,while delivering a higher energy density.Overall,this work presents a practical strategy that may accelerate the commercialization of sulfide-based ASSLBs.展开更多
High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instab...High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.展开更多
Microwave roasting self-leaching is an innovative method for recovering gold from high-sulfur refractory gold concentrates,without using deadly toxic cyanide reagents.However,the mechanism of gold self-leaching,which ...Microwave roasting self-leaching is an innovative method for recovering gold from high-sulfur refractory gold concentrates,without using deadly toxic cyanide reagents.However,the mechanism of gold self-leaching,which relies on lixiviants prepared using volatilized sulfur obtained from roasting,has not been fully elucidated.This study employs the response surface methodology to optimize processing parameters,resulting in an increased gold extraction rate of 96.18%.Analytical factorization and the Tafel curve indicate that CuSO_(4) and NH_(3)·H_(2)O significantly influence the self-leaching process.Furthermore,X-ray photoelectron spectroscopy(XPS)analysis reveals that S^(2−),S_(2)^(2−),polysulfides(S_(n)^(2−)),and thiosulfate(S_(2)O_(3)^(2−))are involved in the gold leaching reaction,with S^(2−),S_(2)^(2−),and S_(n)^(2−) serving as primary ligands for gold complexation.The role of S_(2)O_(3)^(2−) in the early stages of the gold-leaching reaction is also noteworthy.The copper–ammonia complex catalyzes the self-leaching gold reaction;however,an improper addition ratio can lead to copper-sulfur compound precipitates,reducing the extraction rate.展开更多
Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,how...Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.展开更多
The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular an...The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular and cellular mechanisms by which quinolinic acid contributes to Huntington's disease pathology remain unknown. In this study, we established in vitro and in vivo models of Huntington's disease by administering quinolinic acid to the PC12 neuronal cell line and the striatum of mice, respectively. We observed a decrease in the levels of hydrogen sulfide in both PC12 cells and mouse serum, which was accompanied by down-regulation of cystathionine β-synthase, an enzyme responsible for hydrogen sulfide production. However, treatment with NaHS(a hydrogen sulfide donor) increased hydrogen sulfide levels in the neurons and in mouse serum, as well as cystathionine β-synthase expression in the neurons and the mouse striatum, while also improving oxidative imbalance and mitochondrial dysfunction in PC12 cells and the mouse striatum. These beneficial effects correlated with upregulation of nuclear factor erythroid 2-related factor 2 expression. Finally, treatment with the nuclear factor erythroid 2-related factor 2inhibitor ML385 reversed the beneficial impact of exogenous hydrogen sulfide on quinolinic acid-induced oxidative stress. Taken together, our findings show that hydrogen sulfide reduces oxidative stress in Huntington's disease by activating nuclear factor erythroid 2-related factor 2,suggesting that hydrogen sulfide is a novel neuroprotective drug candidate for treating patients with Huntington's disease.展开更多
The use of visible-light responsive photocatalysts for removing heavy metal ions in wastewater has received great attention.However,the development of photocatalysts with high activity and recyclability remains a huge...The use of visible-light responsive photocatalysts for removing heavy metal ions in wastewater has received great attention.However,the development of photocatalysts with high activity and recyclability remains a huge challenge.Herein,a recyclable carbon fiber cloth-supported porous CdS nanorod photocatalyst was fabricated by a two-step hydrothermal treatment using AgVO_(3) nanowires as templates.The results indicated that under visible-light illumination,the carbon cloth-supported porous CdS nanorods showed improved photocatalytic activity for the reduction of Cr(Ⅵ),with an apparent rate constant exceeding that of carbon cloth-supported CdS nanospheres by a factor of 1.65 times.Moreover,the carbon cloth-supported porous CdS nanorods can be easily separated and be reused.This brings a new perspective for developing photocatalysts with high efficiency and recyclability for wastewater treatment.展开更多
Reasonable manipulation of component and microstructure is considered as a potential route to realize high-performance microwave absorber.In this paper,micro-sized hexapod-like CuS/Cu_(9)S_(5) composites were synthesi...Reasonable manipulation of component and microstructure is considered as a potential route to realize high-performance microwave absorber.In this paper,micro-sized hexapod-like CuS/Cu_(9)S_(5) composites were synthesized via a facile approach involving the solvothermal method and subsequent sulfuration treatment.The resultant CuS/Cu_(9)S_(5) exhibited superb microwave absorbing capacity with a minimum reflection loss(RLmin)of-59.38 dB at 2.7 mm.The maximum effective absorption bandwidth(EABmax)was 7.44 GHz(10.56-18 GHz)when the thickness was reduced to 2.3 mm.The outstanding microwave absorbing ability of CuS/Cu_(9)S_(5) composites is mainly related to its unique hexapod shape and the formation of heterogeneous interfaces.The unique hexapod shape significantly promotes the multi-reflection of the incident electromagnetic wave(EMW)increasing the attenuation path of EMWs in the material.Hetero-geneous interfaces between CuS/Cu_(9)S_(5) enable powerful interface polarization,contributing to the atten-uation of EMWs propagating in the medium.In addition,the EMW absorption performance of CuS/Cu_(9)S_(5) composites is also inseparable from the conduction loss.This study provides a strong reference for the research of EMW absorbent materials based on transition metal sulfides.展开更多
This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature&l...This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O_(2)-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O_(2)source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.展开更多
Mg-based hydrogen storage materials have attracted much attention due to their high hydrogen content,abundant resources,and environmental friendliness.However,the high dehydrogenation temperature,slow kinetics and poo...Mg-based hydrogen storage materials have attracted much attention due to their high hydrogen content,abundant resources,and environmental friendliness.However,the high dehydrogenation temperature,slow kinetics and poor cycling stability are limiting its practical application.This work demonstrates the improved dehydrogenation kinetics and cycling stability of MgH_(2) modified by a hybrid of metallic Ni and layered MoS_(2)(denoted as“Ni-MoS_(2)”)introduced by ball milling,with Ni as the catalyst for MgH_(2) and MoS_(2) as the support for both Ni and MgH_(2).The onset dehydrogenation temperature of MgH_(2) is reduced to 198℃,and the rehydrogenation begins at a low temperature of 50℃.The MgH_(2)+10 wt%Ni-MoS_(2) composite has a fast dehydrogenation kinetics and can release 6.1 wt% hydrogen in 10 min at a constant temperature of 300℃,with the dehydrogenation activation energy significantly reduced from 151 to 85 kJ mol^(-1).During the cycling,the reversible capacity of the composite first exhibits a gradual increase for the initial 22 cycles and then maintains at 6.1 wt% from the 23th cycle to the 50th cycle.The Ni/MoS_(2) addition does not change the overall thermodynamic properties of MgH_(2) but can weaken the Mg-H bonds in the local regions as evident by theoretical calculation.Microstructure studies reveal that the metallic Ni will react with MgH_(2) to form Mg_(2)NiH_(0.3),which can act as a hydrogen pump,while the layered MoS_(2) serves as a support for the well dispersion of MgH_(2) and Ni.It is believed that the synergy of Mg_(2)NiH_(0.3) and layered MoS_(2) contributes to the significantly enhanced hydrogen storage of MgH_(2).This work provides a promising and simple strategy for enhancing the Mg-based hydrogen storage materials by combination of transition metals and layered materials introduced via simple ball milling.展开更多
Lithium-sulfur(Li-S)batteries exhibit exceptional high theoretical energy density.However,their practical application is hindered by premature termination of discharge,which severely limits the discharge capacity and ...Lithium-sulfur(Li-S)batteries exhibit exceptional high theoretical energy density.However,their practical application is hindered by premature termination of discharge,which severely limits the discharge capacity and achievable energy density even at low discharge rates.This contribution identifies blocked mass transfer as the primary limitation through relaxation analysis.Both X-ray computed tomography and finite element simulation manifest that the preferential solid deposition at the working cathode surface obstructs the mass transfer pathway and triggers premature discharge termination.The Thiele modulus of a thick cathode is utilized to elucidate the disparity between electrochemical reaction and mass transfer rates,underscoring internal diffusion limitations as the root cause.This understanding affords a theoretical framework for optimizing cathode structures.By reducing the Thiele modulus,an enhanced energy density of 436 Wh kg^(-1)is achieved in Li-S pouch cells.This work advances the understanding of multi-phase reactions in Li-S batteries and offers insights to electrochemical systems involving multi-phase conversions.展开更多
Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are co...Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are confronted with intricate interfacial challenges in high-voltage regines(>4.5 V),resulting in inadequate cathode utilization and premature cell degradation.Moreover,contrary to previous studies,coupled with LiNi_(0.85)Co_(0.1)Mn_(0.05)O_(2)cathodes,typical halide(Li_(2)ZrCl_(6))-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability,while typical sulfide(Li_(6)PS_(5)Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability.Herein,this work addresses the high-voltage limitations of Li_(2)ZrCl_(6)and Li_(6)PS_(5)Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition,thereby effectively improving interfacial charge-transfer kinetics and(electro)chemical stability within cathodes.After appropriate interface design,both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities(>195 mA h g^(-1)at0.1 C),improved cycle stabilities(>80%after 600 cycles at 0.5 C),and enhanced rate performances(>115 mA h g^(-1)at 1.0 C).This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.展开更多
The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,whi...The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature.In this regard,photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method.The recently developed copper-and zinc-based multinary metal sulfide(MMS)semiconductor photocatalysts exhibit the advantages of suitable bandgap,wide light-harvesting range,and flexible elemental composition,thus possessing great potential for achieving considerable photocatalytic hydrogen evolution(PHE)performance.Despite great progress has been achieved,the current photocatalysts still cannot meet the commercial application demands,which highlights the mechanisms understanding and optimization strategies for efficient PHE.Herein,the basic mechanisms of PHE,and effective optimization strategies are firstly introduced.Afterwards,the research process and the performance of copper-and zinc-based MMS photocatalysts,are thoroughly reviewed.Finally,the unresolved issues,and challenges hindering the achievement of overall water splitting have been discussed.展开更多
基金This work was supported by the National Nature Science Foundation of China (No.29903003).
文摘The direct carbonylation of methanol, without any halide in the feed as apromoter, is presented. A series of Mo catalysts supported on activated carbon, γ-Al_2O_3 and SiO_2were prepared. The results show that the support greatly affects the Mo catalyst in the directvapor-phase carbonylation of methanol, and activated carbon is the best supports of the investigatedsupports. In addition, the relationships between adsorptions of NH_3 and CO and carbonylation ofmethanol were investigated. A novel sulfided Mo/C catalyst had high activity and selectivity for thevapor phase carbonylation of methanol to methyl acetate without the addition of a CH_3I promoter tothe feed. The reaction conditions were optimized at a reaction temperature of 573 K, a methanolconcentration of 23 mol% and a carbon monoxide space velocity of 3,000 L/(kg·h). Under theseoptimal conditions a methanol conversion of 50%, carbonylation selectivity of 80 rnol%, andspace-time yield of 8.0 mol/(kg·h) were obtained. The active phase of this novel sulfided Mo/Ccatalyst is the non-crystalline phase, and the active component is present as MoS_(2.5) on thesurface of the activated carbon.
基金SINOPEC for its financial support(No.108012/No.108041)
文摘Six Ni-Mo catalysts with different metal contents were prepared and characterized by N2 adsorption and X-ray diffi＇actometry. The active phase microstructure of these catalysts was examined by the Raman spectroscopy, temperature- programmed reduction （TPR）, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Hydrodesulfurization （HDS） activity of catalyst samples were analyzed in a flow fixed-bed microreactor. The sulfidation degree of Mo and the length of the MoS2 slab slightly increased with the amount of metal loaded following sulfidation. This small change is attributed to polymolybdate species observed in all the oxidized catalysts. Weak metal-support interactions, as determined by the TPR technique, increased the NiSx sulfidation phase and MoS2 slab stacking. The HDS activity of the catalyst samples increased with the number of active sites. For high metal loading catalysts, their HDS activity was nearly identical because the sulfur atoms cannot easily approach active sites. This change is caused by the large number of stacked layers in the MoS2 slabs as well as the decrease in the specific surface area and pore volume of the catalyst samples with an increasing metal loading.
文摘Co-Mo/MgO-Al_(2)O_(3)catalyst was presulfided with ammonium sulfide in aqueous solution and activated with synthesis gas for water gas shift reaction.The assay results indicate that the presulfided Co-Mo/MgO-Al_(2)O_(3)catalyst exhibits an excellent catalytic activity and stability.XRD and EPR characterization results show that the O-S exchange might occur during the impregnation,leading to the formation of(NH4)2MoS4(or(NH4)zMoxSy)precursor,which was then thermally decomposed and reduced to MoS2.The higher catalytic performance is attributed to an optimization formation of active Co-Mo sulfides,consisting of well dispersed MoS2 and Co-Mo-S phase due to the redispersion of Co sulfide particles over the edges of newly formed MoS2 crystallites.
基金financially supported by the National Natural Science Foundation of China(No.52374259)the Open Fund of the State Key Laboratory of Mineral Processing Science and Technology,China(No.BGRIMM-KJSKL-2023-11)the Major Science and Technology Projects in Yunnan Province,China(No.202302 AF080004)。
文摘It is difficult to recover chrysocolla from sulfidation flotation which is closely related to the mineral surface composition.In this study,the effects of fluoride roasting on the surface composition of chrysocolla were investigated,its impact on sulfidation flotation was explored,and the mechanisms involved in both fluoride roasting and sulfidation flotation were discussed.With CaF_(2)as the roasting reagent,Na_(2)S·9H_(2)O as the sulfidation reagent,and sodium butyl xanthate(NaBX)as the collector,the results of the flotation experiments showed that fluoride roasting improved the floatability of chrysocolla,and the recovery rate increased from 16.87%to 82.74%.X-ray diffraction analysis revealed that after fluoride roasting,approximately all the Cu on the chrysocolla surface was exposed in the form of CuO,which could provide a basis for subsequent sulfidation flotation.The microscopy and elemental analyses revealed that large quantities of"pagoda-like"grains were observed on the sulfidation surface of the fluoride-roasted chrysocolla,indicating high crystallinity particles of copper sulfide.This suggests that the effect of sulfide formation on the chrysocolla surface was more pronounced.X-ray photoelectron spectroscopy revealed that fluoride roasting increased the relative contents of sulfur and copper on the surface and that both the Cu~+and polysulfide fractions on the surface of the minerals increased.This enhances the effect of sulfidation,which is conducive to flotation recovery.Therefore,fluoride roasting improved the effect of copper species transformation and sulfidation on the surface of chysocolla,promoted the adsorption of collectors,and improved the recovery of chrysocolla from sulfidation flotation.
基金financially supported by the National Key Research and Development Program of China (No. 2022YFC2105300)。
文摘A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)S,metallic copper converts chalcopyrite into bornite(Cu_(5)FeS_(4)).However,the introduction of H_(2)S promotes the formation of chalcocite(Cu_(2)S)by altering the oxidation pathway of copper.Electrochemical analysis demonstrates that the presence of H₂S significantly reduces the corrosion potential of copper from 0.251 to−0.223 V(vs SHE),reaching the threshold necessary for the formation of Cu_(2)S.Nevertheless,excessive H_(2)S triggers sulfate reduction via the reaction of 8Cu+H_(2)SO_(4)+3H_(2)S=4Cu_(2)S+4H_(2)O(ΔG=−519.429 kJ/mol at 50℃),leading to inefficient copper utilization.
基金supported by the National Science Foundation of China(Nos.42225202 and 41827802)。
文摘CM chondrites contain valuable insights into the formation and evolution of the solar nebula,as well as the secondary aqueous alteration processes that affected their parent bodies.Our study focuses on primary and secondary sulfides within the Aguas Zarcas(CM2)chondrite,investigating their formation mechanisms based on their morphology,textures,and compositions.Moreover,we infer the formation temperatures of the sulfides from 230 to 500℃ for primary and from 100 to 135℃ for secondary.We select representative grains and conduct Fe isotope measurements on them.The primary sulfides with δ^(56/54)Fe ranging from -2.44‰ to +0.69‰are associated with sulfidesilicate melt segregation,while secondary sulfides with δ^(56/54)Fe values between -1.83‰ and -0.14‰ are linked to aqueous alteration.Overall,the Ni content of the grains is positively correlated with δ^(56/54)Fe.It might be related to the changes in crystal structure and chemical bond lengths due to the increase in nickel content.Fe isotopes provide a new perspective on sulfide formation and the evolution of a carbonaceous chondrite parent body.
基金financially supported by the National Natural Science Foundation of China(No.52103040)China Postdoctoral Science Foundation(No.2020M673217)the Fundamental Research Funds for the Central Universities(No.2023SCU12022)。
文摘To address the poor mechanical performance and improve the tribological properties of self-lubricating polyphenylene sulfide/irradiation treated polytetrafluoroethylene(PPS/i-PTFE)blends,different aspect ratio carbon fibers(i.e.,PSCF:50,SCF:about 429)were introduced as reinforcement fillers.The results showed that the hybriding of PSCF and SCF at certain mass ratios exhibited simultaneous enhancement of mechanical and tribological performance for PPS/i-PTFE blend through the construction of synergistic lubrication and mechanical interlocking network.Specifically,the flexural strength and modulus of PPS/i-PTFE were increased by 125.6% and 389.3%,the friction coefficient and specific wear rate were decreased by 13.9% and 95%,respectively.It was worth noting that PPS composites possessed excellent integrated performance which were able to withstand sliding action under high PV(≥10 MPa·m/s)conditions,as assessed by a customized pin-on-disc tester.This work demonstrated that the formation of intact lubricating film combined with the enhanced thermal and mechanical properties were favorable for improving the tribological properties of PPS-based composites,which makes them suitable for advanced engineering applications.
基金financially supported by the National Key Research and Development Program(2022YFE0127400)the National Natural Science Foundation of China(52172040,52202041,and U23B2077)+1 种基金Taishan Scholar Project of Shandong Province(tsqn202211086,ts202208832,tsqnz20221118)the Fundamental Research Funds for the Central Universities(23CX06055A).
文摘Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.52002094)the Guangdong Basic and Applied Basic Research Foundation(Grant Nos.2025A1515011995)+3 种基金the Shenzhen Science and Technology Innovation Program(GXWD20221030205923001)the Shandong Provincial Natural Science Foundation of China(Grant Nos.ZR2024QE525)the Shenzhen Key Laboratory of New Materials Technology(Grant Nos.SYSPG20241211173609003)the State Key Laboratory of Precision Welding&Joining of Materials and Structures(Grant Nos.2024-Z-17,2024-T-08)。
文摘Sulfide solid electrolytes are considered promising candidates for all-solid-state lithium batteries(ASSLBs)because of their high ionic conductivity and favorable mechanical properties.However,the uncontrolled growth of lithium dendrites at the lithium metal-electrolytes interface remains a major obstacle to their practical application.In this work,we introduced a scalable three-dimensional(3D)Li-B skeleton structure designed to suppress dendrite formation.The alloy anode demonstrates a lower Young's modulus,which helps alleviate the accumulation of localized stresses at the interface.Additionally,the 3D alloy anode provided a uniform potential distribution,which promoted homogeneous lithium deposition.Benefiting from these structural advantages,symmetric cells with the Li-B alloy achieved a high critical current density of 2.8 mA cm^(-2).Notably,Li-B‖LPSCI‖LVO-NCM ASSLBs exhibited long-term cycling stability,retaining 97.8%of their capacity after 1500 cycles at 2 C.Furthermore,ASSLBs incorporating the Li-B alloy showed cycling stability comparable with Li-In-based cells,while delivering a higher energy density.Overall,this work presents a practical strategy that may accelerate the commercialization of sulfide-based ASSLBs.
基金supported by the National Key R&D Program of China(2021YFB3800300).
文摘High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.
基金supported by the National Natural Science Foundation of China(No.51974016).
文摘Microwave roasting self-leaching is an innovative method for recovering gold from high-sulfur refractory gold concentrates,without using deadly toxic cyanide reagents.However,the mechanism of gold self-leaching,which relies on lixiviants prepared using volatilized sulfur obtained from roasting,has not been fully elucidated.This study employs the response surface methodology to optimize processing parameters,resulting in an increased gold extraction rate of 96.18%.Analytical factorization and the Tafel curve indicate that CuSO_(4) and NH_(3)·H_(2)O significantly influence the self-leaching process.Furthermore,X-ray photoelectron spectroscopy(XPS)analysis reveals that S^(2−),S_(2)^(2−),polysulfides(S_(n)^(2−)),and thiosulfate(S_(2)O_(3)^(2−))are involved in the gold leaching reaction,with S^(2−),S_(2)^(2−),and S_(n)^(2−) serving as primary ligands for gold complexation.The role of S_(2)O_(3)^(2−) in the early stages of the gold-leaching reaction is also noteworthy.The copper–ammonia complex catalyzes the self-leaching gold reaction;however,an improper addition ratio can lead to copper-sulfur compound precipitates,reducing the extraction rate.
基金financially supported by the National Natural Science Foundation of China(Grants nos.62201411,62371378,22205168,52302150 and 62304171)the China Postdoctoral Science Foundation(2022M722500)+1 种基金the Fundamental Research Funds for the Central Universities(Grants nos.ZYTS2308 and 20103237929)Startup Foundation of Xidian University(10251220001).
文摘Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.
基金supported by the National Natural Science Foundation of China,Nos.82271327 (to ZW),82072535 (to ZW),81873768 (to ZW),and 82001253 (to TL)。
文摘The pathophysiology of Huntington's disease involves high levels of the neurotoxin quinolinic acid. Quinolinic acid accumulation results in oxidative stress, which leads to neurotoxicity. However, the molecular and cellular mechanisms by which quinolinic acid contributes to Huntington's disease pathology remain unknown. In this study, we established in vitro and in vivo models of Huntington's disease by administering quinolinic acid to the PC12 neuronal cell line and the striatum of mice, respectively. We observed a decrease in the levels of hydrogen sulfide in both PC12 cells and mouse serum, which was accompanied by down-regulation of cystathionine β-synthase, an enzyme responsible for hydrogen sulfide production. However, treatment with NaHS(a hydrogen sulfide donor) increased hydrogen sulfide levels in the neurons and in mouse serum, as well as cystathionine β-synthase expression in the neurons and the mouse striatum, while also improving oxidative imbalance and mitochondrial dysfunction in PC12 cells and the mouse striatum. These beneficial effects correlated with upregulation of nuclear factor erythroid 2-related factor 2 expression. Finally, treatment with the nuclear factor erythroid 2-related factor 2inhibitor ML385 reversed the beneficial impact of exogenous hydrogen sulfide on quinolinic acid-induced oxidative stress. Taken together, our findings show that hydrogen sulfide reduces oxidative stress in Huntington's disease by activating nuclear factor erythroid 2-related factor 2,suggesting that hydrogen sulfide is a novel neuroprotective drug candidate for treating patients with Huntington's disease.
文摘The use of visible-light responsive photocatalysts for removing heavy metal ions in wastewater has received great attention.However,the development of photocatalysts with high activity and recyclability remains a huge challenge.Herein,a recyclable carbon fiber cloth-supported porous CdS nanorod photocatalyst was fabricated by a two-step hydrothermal treatment using AgVO_(3) nanowires as templates.The results indicated that under visible-light illumination,the carbon cloth-supported porous CdS nanorods showed improved photocatalytic activity for the reduction of Cr(Ⅵ),with an apparent rate constant exceeding that of carbon cloth-supported CdS nanospheres by a factor of 1.65 times.Moreover,the carbon cloth-supported porous CdS nanorods can be easily separated and be reused.This brings a new perspective for developing photocatalysts with high efficiency and recyclability for wastewater treatment.
基金supported by the National Natural Science Foundation of China(Nos.52377026 and 52301192)the Taishan Scholars and Young Experts Program of Shandong Province(No.tsqn202103057)+3 种基金the Postdoctoral Fellow-ship Program of CPSF under Grant Number(No.GZB20240327)the Shandong Postdoctoral Science Foundation(No.SDCX-ZG-202400275)the Qingdao Postdoctoral Application Research Project(No.QDBSH20240102023)the Qingchuang Talents Induction Program of Shandong Higher Education Institution(Research and Innovation Team of Structural-Functional Polymer Composites).
文摘Reasonable manipulation of component and microstructure is considered as a potential route to realize high-performance microwave absorber.In this paper,micro-sized hexapod-like CuS/Cu_(9)S_(5) composites were synthesized via a facile approach involving the solvothermal method and subsequent sulfuration treatment.The resultant CuS/Cu_(9)S_(5) exhibited superb microwave absorbing capacity with a minimum reflection loss(RLmin)of-59.38 dB at 2.7 mm.The maximum effective absorption bandwidth(EABmax)was 7.44 GHz(10.56-18 GHz)when the thickness was reduced to 2.3 mm.The outstanding microwave absorbing ability of CuS/Cu_(9)S_(5) composites is mainly related to its unique hexapod shape and the formation of heterogeneous interfaces.The unique hexapod shape significantly promotes the multi-reflection of the incident electromagnetic wave(EMW)increasing the attenuation path of EMWs in the material.Hetero-geneous interfaces between CuS/Cu_(9)S_(5) enable powerful interface polarization,contributing to the atten-uation of EMWs propagating in the medium.In addition,the EMW absorption performance of CuS/Cu_(9)S_(5) composites is also inseparable from the conduction loss.This study provides a strong reference for the research of EMW absorbent materials based on transition metal sulfides.
文摘This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O_(2)-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O_(2)source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.
基金supported by the Science and Technology Department of Guangxi Zhuang Autonomous[grant numbers 2025GXNSFFA069003]the National Natural Science Foundation of China[grant numbers 22379030]+1 种基金Bagui Young Scholars Program of Guangxi Zhuang Autonomous Regionthe high-performance computing platform of Guangxi University.
文摘Mg-based hydrogen storage materials have attracted much attention due to their high hydrogen content,abundant resources,and environmental friendliness.However,the high dehydrogenation temperature,slow kinetics and poor cycling stability are limiting its practical application.This work demonstrates the improved dehydrogenation kinetics and cycling stability of MgH_(2) modified by a hybrid of metallic Ni and layered MoS_(2)(denoted as“Ni-MoS_(2)”)introduced by ball milling,with Ni as the catalyst for MgH_(2) and MoS_(2) as the support for both Ni and MgH_(2).The onset dehydrogenation temperature of MgH_(2) is reduced to 198℃,and the rehydrogenation begins at a low temperature of 50℃.The MgH_(2)+10 wt%Ni-MoS_(2) composite has a fast dehydrogenation kinetics and can release 6.1 wt% hydrogen in 10 min at a constant temperature of 300℃,with the dehydrogenation activation energy significantly reduced from 151 to 85 kJ mol^(-1).During the cycling,the reversible capacity of the composite first exhibits a gradual increase for the initial 22 cycles and then maintains at 6.1 wt% from the 23th cycle to the 50th cycle.The Ni/MoS_(2) addition does not change the overall thermodynamic properties of MgH_(2) but can weaken the Mg-H bonds in the local regions as evident by theoretical calculation.Microstructure studies reveal that the metallic Ni will react with MgH_(2) to form Mg_(2)NiH_(0.3),which can act as a hydrogen pump,while the layered MoS_(2) serves as a support for the well dispersion of MgH_(2) and Ni.It is believed that the synergy of Mg_(2)NiH_(0.3) and layered MoS_(2) contributes to the significantly enhanced hydrogen storage of MgH_(2).This work provides a promising and simple strategy for enhancing the Mg-based hydrogen storage materials by combination of transition metals and layered materials introduced via simple ball milling.
基金supported by the National Key Research and Development Program of China(2024YFE0209500)Relevant National Projects,the National Natural Science Foundation of China(22409116)+1 种基金the Seed Fund of Shanxi Research Institute for Clean Energy(SXKYJF015)the Shuimu Tsinghua Scholar Program of Tsinghua University。
文摘Lithium-sulfur(Li-S)batteries exhibit exceptional high theoretical energy density.However,their practical application is hindered by premature termination of discharge,which severely limits the discharge capacity and achievable energy density even at low discharge rates.This contribution identifies blocked mass transfer as the primary limitation through relaxation analysis.Both X-ray computed tomography and finite element simulation manifest that the preferential solid deposition at the working cathode surface obstructs the mass transfer pathway and triggers premature discharge termination.The Thiele modulus of a thick cathode is utilized to elucidate the disparity between electrochemical reaction and mass transfer rates,underscoring internal diffusion limitations as the root cause.This understanding affords a theoretical framework for optimizing cathode structures.By reducing the Thiele modulus,an enhanced energy density of 436 Wh kg^(-1)is achieved in Li-S pouch cells.This work advances the understanding of multi-phase reactions in Li-S batteries and offers insights to electrochemical systems involving multi-phase conversions.
基金supported by the National Key R&D Program of China(2022YFB3803505)National Natural Scientific Foundation of China(U21A2080&22479009)National Related Project and the Fundamental Research Funds for the Central Universities(FRF-TP-22-01C2)。
文摘Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are confronted with intricate interfacial challenges in high-voltage regines(>4.5 V),resulting in inadequate cathode utilization and premature cell degradation.Moreover,contrary to previous studies,coupled with LiNi_(0.85)Co_(0.1)Mn_(0.05)O_(2)cathodes,typical halide(Li_(2)ZrCl_(6))-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability,while typical sulfide(Li_(6)PS_(5)Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability.Herein,this work addresses the high-voltage limitations of Li_(2)ZrCl_(6)and Li_(6)PS_(5)Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition,thereby effectively improving interfacial charge-transfer kinetics and(electro)chemical stability within cathodes.After appropriate interface design,both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities(>195 mA h g^(-1)at0.1 C),improved cycle stabilities(>80%after 600 cycles at 0.5 C),and enhanced rate performances(>115 mA h g^(-1)at 1.0 C).This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.
文摘The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature.In this regard,photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method.The recently developed copper-and zinc-based multinary metal sulfide(MMS)semiconductor photocatalysts exhibit the advantages of suitable bandgap,wide light-harvesting range,and flexible elemental composition,thus possessing great potential for achieving considerable photocatalytic hydrogen evolution(PHE)performance.Despite great progress has been achieved,the current photocatalysts still cannot meet the commercial application demands,which highlights the mechanisms understanding and optimization strategies for efficient PHE.Herein,the basic mechanisms of PHE,and effective optimization strategies are firstly introduced.Afterwards,the research process and the performance of copper-and zinc-based MMS photocatalysts,are thoroughly reviewed.Finally,the unresolved issues,and challenges hindering the achievement of overall water splitting have been discussed.
