With inherent ionic priorities, mixed ion and electron conductor hybrid devices have been proposed for brain-inspired neuromorphic system applications, demonstrating interesting neuromorphic functions. Here, mixed pro...With inherent ionic priorities, mixed ion and electron conductor hybrid devices have been proposed for brain-inspired neuromorphic system applications, demonstrating interesting neuromorphic functions. Here, mixed proton and electron conductor (MPEC) hybrid oxide neuromorphic transistor is proposed by adopting aqueous solution-processed mesoporous silica coating (MSC)-based electrolyte as gate dielec- tric. With optical and electrical synergetic coupling behaviors, the device demonstrates typical synap- tic responses and transition between short-term plasticity and long-term plasticity. With unique field- configurable proton self-modulation behaviors, a pseudo-diode operation mode is demonstrated on the MPEC hybrid transistor. Moreover, the device demonstrates interesting non-associative learning, including habituation and sensitization behavior. The results show that the proposed MPEC hybrid oxide neuromor- phic transistor has great potential in the field of neuromorphic engineering and would have potential in the bionic visual perception platform .展开更多
Despite great advancements in organic mixed ionic-electronic conductors(OMIECs),their applications remain predominantly restricted to three-electrode organic electro-chemical transistors(OECTs),which rely on an additi...Despite great advancements in organic mixed ionic-electronic conductors(OMIECs),their applications remain predominantly restricted to three-electrode organic electro-chemical transistors(OECTs),which rely on an additional electrolyte layer to balance ionic and electronic transport,resulting in indirect coupling of charge carriers.While direct coupling has the potential to greatly simplify device architectures,it remains underexplored in OMIECs due to the inherent imbalance between electronic and ionic conductivities.In this study,we introduce a straightforward approach to achieve balanced OMIECs and employ them as channel materials in two-electrode organic electrochemical memristors.These devices provide clear evidence of direct coupling between electronic and ionic carriers and exhibit exceptional performance in synaptic device applications.Our findings offer new insights into charge carrier transport mechanisms in OMIECs and establish organic electrochemical memristors as a promising new class of organic electronic devices for next-generation neuromorphic applications.展开更多
Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ （SFCTO） was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from ...Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ （SFCTO） was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from 750℃ to 950℃ and different oxygen partial pressure. XRD measurements indicated that the compound was able to form single-phased perovskite structure in which part of Fe was replaced by Cu and Ti. The oxygen desorption and the reducibility of SFCTO powder were characterized by thermogravimetric analysis and temperature programmed reduction analysis, respectively. It was found that SFCTO had good structure stability under low oxygen pressure at high temperature. The addition of Ti increased the reduction temperature of Cu and Fe. Performance tests showed that the oxygen permeation flux through a 1.5 mm thick SFCTO membrane was 0.35-0.96 ml·min ^-1·cm^-2 under air/helium oxygen partial pressure gradient with activation energy of 53.2 kJ·mol^-1. The methane conversion of 85%, CO selectivity of 90% and comparatively higher oxygen permeation flux of 5 ml·min^-1·cm^- 2 were achieved at 850℃, when a SFCTO membrane reactor loaded with Ni-Ce/Al2O3 catalyst was applied for the partial oxidation of methane to syngas.展开更多
In this study,compositionally complex cobaltites with the general formula BaLnCo_(2)O_(6−δ)with three to eight different lanthan-ides at the Ln-site were synthesized using the solid-state reaction method and studied....In this study,compositionally complex cobaltites with the general formula BaLnCo_(2)O_(6−δ)with three to eight different lanthan-ides at the Ln-site were synthesized using the solid-state reaction method and studied.Analysis of entropy metrics and configurational en-tropy calculations indicated that these compounds are medium entropy oxides.All of these crystallize as tetragonal double perovskites from the space group P4/mmm.The unit cell parameters are controlled by the average ionic radius,not the configurational entropy.On the other hand,the oxygen non-stoichiometry is consistently higher than in the case of low entropy double perovskite cobaltites.The total electrical conductivity of all materials in studied conditions is well above 50 S/cm,peaking at 1487 S/cm for BaLa_(1/3)Nd_(1/3)Gd_(1/3)Co_(2)O_(6−δ)at 300℃.The electrical conductivity decreases with the number of substituents.展开更多
Solid-state batteries(SSBs)are considered as the next-generation battery technology,poised to deliver both high energy and enhanced safety.Nonetheless,their transition from laboratory to market is impeded by several c...Solid-state batteries(SSBs)are considered as the next-generation battery technology,poised to deliver both high energy and enhanced safety.Nonetheless,their transition from laboratory to market is impeded by several critical challenges.Among these,the solid–solid interfaces within SSBs represent a bottleneck,characterized by issues such as poor physical contact,side reactions,temporal separation,and sluggish charge carrier transfer.Developing key materials to construct the efficient solid–solid interface is critical for building high-performance SSBs.Organic mixed ionic–electronic conductors(OMIECs)have emerged as a promising alternative to conventional conductors in addressing the abovementioned issues owing to their intrinsic properties,including the capability of conducting both ions and electrons,mechanical flexibility,and structural designability.This review will first elucidate the necessity of the integration of OMIECs in SSBs.Next,a comprehensive exploration of the composition,preparation methods,key advantages,and basic characterizations of OMIECs is presented.This review then delves into recent research progress on OMIECs in SSBs,with a special focus on their application in cathode coating layers,the creation of a 3D mixed conductive framework for Li hosting,and their integration as inner layers in Li anodes.Conclusively,potential future applications and innovative designs of OMIECs are discussed.展开更多
Regulating the nucleation and growth of Li metal is crucial for achieving stable high-energy-density Li metal batteries(LMBs)without dendritic Li growth,severe volume expansion,and“dead Li”accumulation.Herein,we pre...Regulating the nucleation and growth of Li metal is crucial for achieving stable high-energy-density Li metal batteries(LMBs)without dendritic Li growth,severe volume expansion,and“dead Li”accumulation.Herein,we present a modulation layer composed of porous SnP_(0.94)/CoP p-n heterojunction particles(SCP),synthesized applying the Kirkendall effect.The unique heterointerfaces in the SCP induce a fully ionized depletion region and built-in electric field.This provides strong Li affinity,additional adsorption sites,and facilitated electron transfer,thereby guiding dendrite-free Li nucleation/growth with a low Li deposition overpotential.Moreover,the strategic design of the SCP,accounting for its reaction with Li,yields electronically conductive Co,lithiophilic Li-Sn alloy,and ionic conductive Li_(3)P during progressive cycles.The mixed electronic and ionic conductor(MEIC)ensure the long-term stability of the SCP modulation layer.With this layer,the SCP@Li symmetric cell maintains a low overpotential for 750 cycles even at a high current density of 5 mA cm^(-2).Additionally,the LiFePO_(4)//SCP@Li full cell achieves an imperceptible capacity decay of 0.03%per cycle for 800 cycles at 0.5 C.This study provides insight into MEIC heterostructures for high-performance LMBs.展开更多
Lithium metal anodes are of great interest for advanced high-energy density batteries such as lithiumair, lithium-sulfur and solid-state batteries, due to their low electrode potential and ultra-high theoretical capac...Lithium metal anodes are of great interest for advanced high-energy density batteries such as lithiumair, lithium-sulfur and solid-state batteries, due to their low electrode potential and ultra-high theoretical capacity. There are, however, several challenges limiting their practical applications, which include low coulombic efficiency, the uncontrollable growth of dendrites and poor rate capability. Here, a rational design of 3D structured lithium metal anodes comprising of in-situ growth of cobalt-decorated nitrogen-doped carbon nanotubes on continuous carbon nanofibers is demonstrated via electrospinning.The porous and free-standing scaffold can enhance the tolerance to stresses resulting from the intrinsic volume change during Li plating/stripping, delivering a significant boost in both charge/discharge rates and stable cycling performance. A binary Co-Li alloying phase was generated at the initial discharge process, creating more active sites for the Li nucleation and uniform deposition. Characterization and density functional theory calculations show that the conductive and uniformly distributed cobalt-decorated carbon nanotubes with hierarchical structure can effectively reduce the local current density and more easily absorb Li atoms, leading to more uniform Li nucleation during plating. The current work presents an advance on scalable and cost-effective strategies for novel electrode materials with 3D hierarchical microstructures and mechanical flexibility for lithium metal anodes.展开更多
The catalyst function was achieved in two regions in an oxygen permeation membrane reactor： H2 dissociated and reacted with lattice oxygen or oxygen ions to form H20 near the membrane surface. The H20 formed could re...The catalyst function was achieved in two regions in an oxygen permeation membrane reactor： H2 dissociated and reacted with lattice oxygen or oxygen ions to form H20 near the membrane surface. The H20 formed could react with the residual CH4 away from the membrane surface area.展开更多
Mixed oxygen-ionic and electronic conducting membranes of SrFe（Cu）O3-δ were prepared by solid-state reaction method. The crystal structure, oxygen nonstoichiometry, and phase stability of the materials were studied...Mixed oxygen-ionic and electronic conducting membranes of SrFe（Cu）O3-δ were prepared by solid-state reaction method. The crystal structure, oxygen nonstoichiometry, and phase stability of the materials were studied by TGA and XRD. Oxygen permeation fluxes through these membranes were studied at operating temperature ranging from 750 to 950 ℃. Results showed that doping Cu in SrFeO3-δ compound had a significant effect on the formation of single-phased perovskite structure. For SrFe1-xCu2O3-δ series materials, the oxygen nonstoichiometry and the oxygen permeation flux increased considerably with the increase of Cu-doping content （x = 0.1-0.3）. The sintering property of the membrane decreased significantly when the Cu substitution amount reached 40%. SrFe0.7Cu0.3O3-δ showed high oxygen permeation flux, but SrCuO2 and Sr2Fe2O5 phases formed in the compound after oxygen permeation test induced cracks in the membrane.展开更多
Proton-hole mixed conductor, SrCeo.95Yb0.05O3-α(SCYb), has the potential to be used as a membrane for dehydrogenation reactions such as methane coupling due to its high C2-selectivity and its simplicity for fabricati...Proton-hole mixed conductor, SrCeo.95Yb0.05O3-α(SCYb), has the potential to be used as a membrane for dehydrogenation reactions such as methane coupling due to its high C2-selectivity and its simplicity for fabricating reactor systems. In addition, the mixed conducting membrane in the hollow fibre geometry is capable of providing high surface area per unit volume. In this study, mechanism of methane coupling reaction on the SCYb membrane was proposed and the kinetic parameters were obtained by regression of experimental data. A mathematical model describing the methane coupling in the SCYb hollow fibre membrane reactor was also developed. With this mathematical model, various operating conditions such as the operation mode, operation pressure and feed concentrations affecting performance of the reactor were investigated. The simulation results show that the cocurrent flow in the reactor exhibits higher conversion of methane and higher yield of ethylene compared to the countercurrent flow. In order to achieve the highest C2 yield, especially of ethylene, pure methane should be used as feed and the operating pressure be 300 kPa. Air can be used as the source of oxygen for the reaction and its optimum feed velocity is twice of the methane feed velocity. The air pressure in the lumen side should be kept the same as or slightly lower than the pressure of shell side.展开更多
Dense mixed proton and electron conducting membrane made of BaCe0.95Nd0.05O3-δ （BCNd5） was prepared by pressing followed by sintering. X-ray diffraction （XRD） was used to characterize the phase structure of both ...Dense mixed proton and electron conducting membrane made of BaCe0.95Nd0.05O3-δ （BCNd5） was prepared by pressing followed by sintering. X-ray diffraction （XRD） was used to characterize the phase structure of both the powder and the sintered membranes. The microstructure of the sintered membranes was studied by scanning electron microscopy （SEM）. Hydrogen permeation through the BCNd5 membrane was studied using a high temperature permeator. The hydrogen permeation fluxes under wet conditions are higher than those under dry conditions, which is due to H^＋ hopping via surface OH groups. At 925℃, a hydrogen permeation flux of 0.02 mL/min cm^2 was obtained under wet condition, which recommends BCNd5 as a potential material for hydrogen-selective membranes.展开更多
Dense ceramic membranes with protonic and electronic conductivity have attracted considerable interest in recent years.In this paper,the powders of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) were synthesized via the liquid...Dense ceramic membranes with protonic and electronic conductivity have attracted considerable interest in recent years.In this paper,the powders of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) were synthesized via the liquid citrate method,and the membranes of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) were prepared by pressing followed by sintering.X-ray diffraction(XRD) was used to characterize the phase structure of both the powder and sintered membrane.The microstructure of the sintered membranes was studied by scann...展开更多
As a mixed conductor,LaSr3Fe3O10-δ with triple layer perovskite intergrowth structure can be used as an oxygen separation membrane material and cathode material in solid oxide fuell cells.LaSr3Fe3O10-δ was synthesiz...As a mixed conductor,LaSr3Fe3O10-δ with triple layer perovskite intergrowth structure can be used as an oxygen separation membrane material and cathode material in solid oxide fuell cells.LaSr3Fe3O10-δ was synthesized via citrate acid route.Iodine titration method was used to determine the average valence of transition metal Fe and oxygen nonstoichiometry δ.Conductivities of LaSr3Fe3O10-δ were measured in the oxygen partial pressure range from 10-2×105 to 1×105 Pa,by Ac four probe method.Seebeck coefficient...展开更多
Lithium(Li)metal is a potential anode for high-energy-density batteries because of its low potential and ultrahigh capacity.Nevertheless,the Li dendrites formation,the ununiform Li deposition,and the growth of Li dend...Lithium(Li)metal is a potential anode for high-energy-density batteries because of its low potential and ultrahigh capacity.Nevertheless,the Li dendrites formation,the ununiform Li deposition,and the growth of Li dendrites hamper its application,especially under high deposition capacity/high rate.Here,a spatially controlled Li deposition mode with array-oriented morphology is achieved based on the novel mixed ion/electron-conducting Li_(x)Cu_(y)P_(z) arrays constructed on Cu foil,which can be facile fabricated via an in-situ transformation of metal phosphide.Theoretic calculations indicate the excellent lithiophilicity and low Li diffusion barrier of the arrays,especially for the Li_(2)CuP phase,which are conducive to ho-mogenizing the Li nucleation/deposition of Li.Moreover,such mixed conducting arrays promote fast Li+diffusion via the continuous Li+pathways as well as modulate the Li+flux/electric field.Furthermore,the arrays with enlarged specific surface area and open spaces reduce the local current density and alle-viate the volume fluctuation of Li.Consequently,a dendrite-free Li anode is obtained under a high rate(20 mA cm^(–2))or a high deposition capacity(10 mAh cm^(–2)).In addition,even if the negative/positive ratio reduces to only 1.1,the full cells still perform outstanding stability for over 200 cycles.This work empha-sizes the importance of the design of the framework in terms of the intrinsic properties and structure and reveals a pathway for developing Li metal batteries.展开更多
A novel cobalt-free perovskite based on Ba0.5Sr0.5Fe0.8Zn0.2O3-δ （BSFZ） were prepared by EDTA-citric acid method. The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray di...A novel cobalt-free perovskite based on Ba0.5Sr0.5Fe0.8Zn0.2O3-δ （BSFZ） were prepared by EDTA-citric acid method. The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray diffraction （HTXRD）. The thermal expansion coefficient of BSFZ is 10.5×10^-6 K^-1, which is lower than that of cobalt-based perovskite materials. The BSFZ membrane was also used to construct reactors for the partial oxidation of methane （POM） to syngas. Results show that the BSFZ membrane can be operated for the POM reaction for more than 100 h without any fractures. The CO selectivity of 97% is obtained. The steady oxygen permeation flux reaches around 2.5 mL/min cm^2 during POM reaction.展开更多
Monoclinic CeNbO4.25 was prepared by solid state reaction. Complex impedance analysis indicated the presence of grain interior effect along with the grain boundary contribution. The values of ionic transference number...Monoclinic CeNbO4.25 was prepared by solid state reaction. Complex impedance analysis indicated the presence of grain interior effect along with the grain boundary contribution. The values of ionic transference number ti below 423 K were calculated to be about 0.5. The activation energies of ionic conductivity and electronic conductivity were deduced to be 36.0 and 37.2 kJ/mol, re-spectively. The real part of the AC conductivity was frequency dependent. At high frequencies corresponding to the grain interior ef-fect, the non-Debye nature of the AC conductivity was interpreted by the correlated hopping of interstitial oxygen with the electron holes on the basis of the correlated barrier hopping （CBH） model.展开更多
Perovskite-type mixed protonic-electronic conducting membranes have attracted attention because of their ability to separate and purify hydrogen from a mixture of gases generated by industrial-scale steam reforming ba...Perovskite-type mixed protonic-electronic conducting membranes have attracted attention because of their ability to separate and purify hydrogen from a mixture of gases generated by industrial-scale steam reforming based on an ion diffusion mechanism.Exploring cost-effective membrane materials that can achieve both high H_(2) permeability and strong CO_(2)-tolerant chemical stability has been a major challenge for industrial applications.Herein,we constructed a triple phase(ceramic-metal-ceramic)membrane composed of a perovskite ceramic phase BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(3-δ)(BZCYYb),Ni metal phase and a fluorite ceramic phase CeO_(2).Under H_(2) atmosphere,Ni metal in-situ exsolved from the oxide grains,and decorated the grain surface and boundary,thus the electronic conductivity and hydrogen separation performance can be promoted.The BZCYYbNi-CeO_(2)hybrid membrane achieved an exceptional hydrogen separation performance of 0.53 mL min^(-1)cm^(-2) at 800℃ under a 10 vol% H_(2) atmosphere,surpassing all other perovskite membranes reported to date.Furthermore,the CeO_(2) phase incorporated into the BZCYYb-Ni effectively improved the CO_(2)-tolerant chemical stability.The BZCYYbNi-CeO_(2) membrane exhibited outstanding long-term stability for at least 80 h at 700℃ under 10 vol%CO_(2)-10 vol%H_(2).The success of hybrid membrane construction creates a new direction for simultaneously improving their hydrogen separation performance and CO_(2) resistance stability.展开更多
A cobalt-free perovskite-type Ba0.5Sr0.5A10.1Fe0.9O3-δ （BSAF） chemically studied as solid oxide fuel cell （SOFC） cathode. The ductivity, and electrode polarizations in symmetrical cell based is developed and elec...A cobalt-free perovskite-type Ba0.5Sr0.5A10.1Fe0.9O3-δ （BSAF） chemically studied as solid oxide fuel cell （SOFC） cathode. The ductivity, and electrode polarizations in symmetrical cell based is developed and electro- structures, electrical con- on mixed ion conducting electrolyte were investigated, respectively. The temperature dependence of conductivity of BSAF in air shows a typical semiconductor behavior with positive temperature coefficient up to 450℃ where the conductivity reaches 14.0 S/cm while above this temperature the negative temperature coefficient dominates the total conductivity. Electrochemical charac- terizations show desirable polarization resistance of BSAF cathode in a symmetric cell based on mixed ion conducting electrolyte at 650-700℃, A single SOFC with BSAF cathode shows OCV of 1.0 V and maximum output of 420 mW/cm2 at 700 ℃ with humidified hydrogen fuel and static air oxidant.展开更多
Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production...Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production,oxygen transport membranes(OTMs)appear as an alternative technology for the cryogenic distillation of air,the industrially-established process of producing oxygen.Moreover,OTMs could provide oxygen from different sources(air,water,CO_(2),etc.),and they are more flexible in adapting to current processes,producing oxygen at 700^(-1)000℃.Furthermore,OTMs can be integrated into catalytic membrane reactors,providing new pathways for different processes.The first part of this study was focused on electrification on a traditional OTM material(Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)),imposing different electric currents/voltages along a capillary membrane.Thanks to the emerging Joule effect,the membrane-surface temperature and the associated O_(2) permeation flux could be adjusted.Here,the OTM is electrically and locally heated and reaches 900℃on the surface,whereas the surrounding of the membrane was maintained at 650℃.The O_(2)permeation flux reached for the electrified membranes was~3.7 NmL min^(-1)cm^(-2),corresponding to the flux obtained with an OTM non-electrified at 900℃.The influence of depositing a porous Ce_(0.8)Tb_(0.2)O_(2-δ) catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures(830℃)were detected at the same imposed electric power.Finally,the electrification concept was demonstrated in a catalytic membrane reactor(CMR)where the oxidative dehydrogenation of ethane(ODHE)was carried out.ODHE reaction is very sensitive to temperature,and here,we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O_(2) injection into the reaction can be easily fine-tuned.展开更多
BaFeO_(3-δ)-derived perovskites are promising cathodes for intermediate temperature solid oxide fuel cells.The activity of these perovskites depends on the number of oxygen vacancies in their lattice,which can be tun...BaFeO_(3-δ)-derived perovskites are promising cathodes for intermediate temperature solid oxide fuel cells.The activity of these perovskites depends on the number of oxygen vacancies in their lattice,which can be tuned by cationic substitution.Our first-principle calculations show that Ag is a promising substitute for the Fe site,resulting in a reduced oxygen vacancy formation energy compared with the pristine BaFeO_(3-δ).Ag has limited solubility in perovskites,and its introduction generates an Ag metal secondary phase,which influences the cathode performances.In this work,we investigate the matter,using a Ba0:9La0:1Fe_(1-x)AgxO_(3-δ)series of materials as a case study.Acknowledging the limited solubility of Ag in Ba0:9La0:1Fe_(1-x)AgxO_(3-δ),we aim to distinguish the effects of Ag substitution from those of the Ag secondary phase.We observed that Ag substitution increases the number of oxygen vacancies,confirming our calculations,and facilitates the oxygen incorporation.However,Ag substitution lowers the number of holes,in this way reducing the electronic p-type conductivity.On the other hand,Ag metal positively affects the electronic conductivity and helps the redistribution of the electronic charge at the cathode-electrolyte interface.展开更多
基金the National Natural Science Foun-dation of China(Nos.51972316,U22A2075)the Ningbo Key Scientific and Technological Project(No.2021Z116).
文摘With inherent ionic priorities, mixed ion and electron conductor hybrid devices have been proposed for brain-inspired neuromorphic system applications, demonstrating interesting neuromorphic functions. Here, mixed proton and electron conductor (MPEC) hybrid oxide neuromorphic transistor is proposed by adopting aqueous solution-processed mesoporous silica coating (MSC)-based electrolyte as gate dielec- tric. With optical and electrical synergetic coupling behaviors, the device demonstrates typical synap- tic responses and transition between short-term plasticity and long-term plasticity. With unique field- configurable proton self-modulation behaviors, a pseudo-diode operation mode is demonstrated on the MPEC hybrid transistor. Moreover, the device demonstrates interesting non-associative learning, including habituation and sensitization behavior. The results show that the proposed MPEC hybrid oxide neuromor- phic transistor has great potential in the field of neuromorphic engineering and would have potential in the bionic visual perception platform .
基金supported by the National Natural Science Foundation of China(4020969,62405044,and 52173156)Fund by Science Research Project of Hebei Education Department(HY2024050011)+1 种基金Natural Science Foundation of Sichuan Province(25NSFSC1287)Foundation of Yanshan University(1050030 and 8190299).
文摘Despite great advancements in organic mixed ionic-electronic conductors(OMIECs),their applications remain predominantly restricted to three-electrode organic electro-chemical transistors(OECTs),which rely on an additional electrolyte layer to balance ionic and electronic transport,resulting in indirect coupling of charge carriers.While direct coupling has the potential to greatly simplify device architectures,it remains underexplored in OMIECs due to the inherent imbalance between electronic and ionic conductivities.In this study,we introduce a straightforward approach to achieve balanced OMIECs and employ them as channel materials in two-electrode organic electrochemical memristors.These devices provide clear evidence of direct coupling between electronic and ionic carriers and exhibit exceptional performance in synaptic device applications.Our findings offer new insights into charge carrier transport mechanisms in OMIECs and establish organic electrochemical memristors as a promising new class of organic electronic devices for next-generation neuromorphic applications.
基金Supported by the Natural Science Foundation of Guangdong Province （030514） and the Science and Technology Program of Guangdong Province （2004B33401006）.
文摘Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ （SFCTO） was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from 750℃ to 950℃ and different oxygen partial pressure. XRD measurements indicated that the compound was able to form single-phased perovskite structure in which part of Fe was replaced by Cu and Ti. The oxygen desorption and the reducibility of SFCTO powder were characterized by thermogravimetric analysis and temperature programmed reduction analysis, respectively. It was found that SFCTO had good structure stability under low oxygen pressure at high temperature. The addition of Ti increased the reduction temperature of Cu and Fe. Performance tests showed that the oxygen permeation flux through a 1.5 mm thick SFCTO membrane was 0.35-0.96 ml·min ^-1·cm^-2 under air/helium oxygen partial pressure gradient with activation energy of 53.2 kJ·mol^-1. The methane conversion of 85%, CO selectivity of 90% and comparatively higher oxygen permeation flux of 5 ml·min^-1·cm^- 2 were achieved at 850℃, when a SFCTO membrane reactor loaded with Ni-Ce/Al2O3 catalyst was applied for the partial oxidation of methane to syngas.
基金support of these studies from Gdańsk University of Technology by the DEC-3/2/IDUB/Ⅲ.1a/Ra/2023 and DEC-1/1/2024/IDUB/Ⅲ.4c/Tc grants under the Radium and Technetium-‘Excellence Initiative-Research University’programs.
文摘In this study,compositionally complex cobaltites with the general formula BaLnCo_(2)O_(6−δ)with three to eight different lanthan-ides at the Ln-site were synthesized using the solid-state reaction method and studied.Analysis of entropy metrics and configurational en-tropy calculations indicated that these compounds are medium entropy oxides.All of these crystallize as tetragonal double perovskites from the space group P4/mmm.The unit cell parameters are controlled by the average ionic radius,not the configurational entropy.On the other hand,the oxygen non-stoichiometry is consistently higher than in the case of low entropy double perovskite cobaltites.The total electrical conductivity of all materials in studied conditions is well above 50 S/cm,peaking at 1487 S/cm for BaLa_(1/3)Nd_(1/3)Gd_(1/3)Co_(2)O_(6−δ)at 300℃.The electrical conductivity decreases with the number of substituents.
基金supported by the National Key R&D Program of China(grant no.2021YFB3800300)the National Natural Science Foundation of China(grant nos.22179143,22309201,and 22309202)the Jiangsu Funding Program for Excellent Postdoctoral Talent,and the Gusu Leading Talents Program(grant no.ZXL2023190).
文摘Solid-state batteries(SSBs)are considered as the next-generation battery technology,poised to deliver both high energy and enhanced safety.Nonetheless,their transition from laboratory to market is impeded by several critical challenges.Among these,the solid–solid interfaces within SSBs represent a bottleneck,characterized by issues such as poor physical contact,side reactions,temporal separation,and sluggish charge carrier transfer.Developing key materials to construct the efficient solid–solid interface is critical for building high-performance SSBs.Organic mixed ionic–electronic conductors(OMIECs)have emerged as a promising alternative to conventional conductors in addressing the abovementioned issues owing to their intrinsic properties,including the capability of conducting both ions and electrons,mechanical flexibility,and structural designability.This review will first elucidate the necessity of the integration of OMIECs in SSBs.Next,a comprehensive exploration of the composition,preparation methods,key advantages,and basic characterizations of OMIECs is presented.This review then delves into recent research progress on OMIECs in SSBs,with a special focus on their application in cathode coating layers,the creation of a 3D mixed conductive framework for Li hosting,and their integration as inner layers in Li anodes.Conclusively,potential future applications and innovative designs of OMIECs are discussed.
基金supported by the Basic Science Research Program through National Research Foundation of Korea(NRF)grant funded by the Ministry of Education(RS-2020-NR049594)the Ministry of Science and ICT(RS-2022-NR070534).
文摘Regulating the nucleation and growth of Li metal is crucial for achieving stable high-energy-density Li metal batteries(LMBs)without dendritic Li growth,severe volume expansion,and“dead Li”accumulation.Herein,we present a modulation layer composed of porous SnP_(0.94)/CoP p-n heterojunction particles(SCP),synthesized applying the Kirkendall effect.The unique heterointerfaces in the SCP induce a fully ionized depletion region and built-in electric field.This provides strong Li affinity,additional adsorption sites,and facilitated electron transfer,thereby guiding dendrite-free Li nucleation/growth with a low Li deposition overpotential.Moreover,the strategic design of the SCP,accounting for its reaction with Li,yields electronically conductive Co,lithiophilic Li-Sn alloy,and ionic conductive Li_(3)P during progressive cycles.The mixed electronic and ionic conductor(MEIC)ensure the long-term stability of the SCP modulation layer.With this layer,the SCP@Li symmetric cell maintains a low overpotential for 750 cycles even at a high current density of 5 mA cm^(-2).Additionally,the LiFePO_(4)//SCP@Li full cell achieves an imperceptible capacity decay of 0.03%per cycle for 800 cycles at 0.5 C.This study provides insight into MEIC heterostructures for high-performance LMBs.
基金kindly supported by the National Natural Science Foundation of China (No. U1864213)the EPSRC Joint UK-India Clean Energy center (JUICE) (EP/P003605/1)+2 种基金the EPSRC Multi-Scale Modelling project (EP/S003053/1)the Innovate UK for Advanced Battery Lifetime Extension (ABLE) projectthe EPSRC for funding under EP/S000933/1。
文摘Lithium metal anodes are of great interest for advanced high-energy density batteries such as lithiumair, lithium-sulfur and solid-state batteries, due to their low electrode potential and ultra-high theoretical capacity. There are, however, several challenges limiting their practical applications, which include low coulombic efficiency, the uncontrollable growth of dendrites and poor rate capability. Here, a rational design of 3D structured lithium metal anodes comprising of in-situ growth of cobalt-decorated nitrogen-doped carbon nanotubes on continuous carbon nanofibers is demonstrated via electrospinning.The porous and free-standing scaffold can enhance the tolerance to stresses resulting from the intrinsic volume change during Li plating/stripping, delivering a significant boost in both charge/discharge rates and stable cycling performance. A binary Co-Li alloying phase was generated at the initial discharge process, creating more active sites for the Li nucleation and uniform deposition. Characterization and density functional theory calculations show that the conductive and uniformly distributed cobalt-decorated carbon nanotubes with hierarchical structure can effectively reduce the local current density and more easily absorb Li atoms, leading to more uniform Li nucleation during plating. The current work presents an advance on scalable and cost-effective strategies for novel electrode materials with 3D hierarchical microstructures and mechanical flexibility for lithium metal anodes.
基金supported by the Natural Science Foundation of China(Grant No.51304082 and 51174133)the Natural Science Foundation of Jiangsu Province,China(Grant No.BK20130462)+1 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(Grant No.12KJB450001)the Science and Technology Commission of Shanghai Municipality(Grant No.11ZR1412900)
文摘The catalyst function was achieved in two regions in an oxygen permeation membrane reactor： H2 dissociated and reacted with lattice oxygen or oxygen ions to form H20 near the membrane surface. The H20 formed could react with the residual CH4 away from the membrane surface area.
基金Natural Science Foundation of Guangdong Province (No. 030514)the Science and Technology Program of Guangdong Province(No. 2004B33401006)
文摘Mixed oxygen-ionic and electronic conducting membranes of SrFe（Cu）O3-δ were prepared by solid-state reaction method. The crystal structure, oxygen nonstoichiometry, and phase stability of the materials were studied by TGA and XRD. Oxygen permeation fluxes through these membranes were studied at operating temperature ranging from 750 to 950 ℃. Results showed that doping Cu in SrFeO3-δ compound had a significant effect on the formation of single-phased perovskite structure. For SrFe1-xCu2O3-δ series materials, the oxygen nonstoichiometry and the oxygen permeation flux increased considerably with the increase of Cu-doping content （x = 0.1-0.3）. The sintering property of the membrane decreased significantly when the Cu substitution amount reached 40%. SrFe0.7Cu0.3O3-δ showed high oxygen permeation flux, but SrCuO2 and Sr2Fe2O5 phases formed in the compound after oxygen permeation test induced cracks in the membrane.
基金Supported by the National Natural Science Foundation of China(No.20076025).
文摘Proton-hole mixed conductor, SrCeo.95Yb0.05O3-α(SCYb), has the potential to be used as a membrane for dehydrogenation reactions such as methane coupling due to its high C2-selectivity and its simplicity for fabricating reactor systems. In addition, the mixed conducting membrane in the hollow fibre geometry is capable of providing high surface area per unit volume. In this study, mechanism of methane coupling reaction on the SCYb membrane was proposed and the kinetic parameters were obtained by regression of experimental data. A mathematical model describing the methane coupling in the SCYb hollow fibre membrane reactor was also developed. With this mathematical model, various operating conditions such as the operation mode, operation pressure and feed concentrations affecting performance of the reactor were investigated. The simulation results show that the cocurrent flow in the reactor exhibits higher conversion of methane and higher yield of ethylene compared to the countercurrent flow. In order to achieve the highest C2 yield, especially of ethylene, pure methane should be used as feed and the operating pressure be 300 kPa. Air can be used as the source of oxygen for the reaction and its optimum feed velocity is twice of the methane feed velocity. The air pressure in the lumen side should be kept the same as or slightly lower than the pressure of shell side.
基金Natural Science Foundation of Guangdong Province(No.7300769)Program for New Century Excellent Talents in University(No.NECT-07-0307)Fok Ying Tung Education Foundation(No.114019).
文摘Dense mixed proton and electron conducting membrane made of BaCe0.95Nd0.05O3-δ （BCNd5） was prepared by pressing followed by sintering. X-ray diffraction （XRD） was used to characterize the phase structure of both the powder and the sintered membranes. The microstructure of the sintered membranes was studied by scanning electron microscopy （SEM）. Hydrogen permeation through the BCNd5 membrane was studied using a high temperature permeator. The hydrogen permeation fluxes under wet conditions are higher than those under dry conditions, which is due to H^＋ hopping via surface OH groups. At 925℃, a hydrogen permeation flux of 0.02 mL/min cm^2 was obtained under wet condition, which recommends BCNd5 as a potential material for hydrogen-selective membranes.
基金supported by Joint Funds of NSFC-Guangdong(No.U0834004)NSFC(No.20976057)Guangdong Provincial Natural Science Funding(No.06025657)
文摘Dense ceramic membranes with protonic and electronic conductivity have attracted considerable interest in recent years.In this paper,the powders of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) were synthesized via the liquid citrate method,and the membranes of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) were prepared by pressing followed by sintering.X-ray diffraction(XRD) was used to characterize the phase structure of both the powder and sintered membrane.The microstructure of the sintered membranes was studied by scann...
基金supported by the National Natural Science Foundation of China (50672100)the Provincial Education Department of Jiangxi Province ([2006]313)
文摘As a mixed conductor,LaSr3Fe3O10-δ with triple layer perovskite intergrowth structure can be used as an oxygen separation membrane material and cathode material in solid oxide fuell cells.LaSr3Fe3O10-δ was synthesized via citrate acid route.Iodine titration method was used to determine the average valence of transition metal Fe and oxygen nonstoichiometry δ.Conductivities of LaSr3Fe3O10-δ were measured in the oxygen partial pressure range from 10-2×105 to 1×105 Pa,by Ac four probe method.Seebeck coefficient...
基金This work was supported by the National Science Foundation of Tianjin(No.20JCQNJC00500)。
文摘Lithium(Li)metal is a potential anode for high-energy-density batteries because of its low potential and ultrahigh capacity.Nevertheless,the Li dendrites formation,the ununiform Li deposition,and the growth of Li dendrites hamper its application,especially under high deposition capacity/high rate.Here,a spatially controlled Li deposition mode with array-oriented morphology is achieved based on the novel mixed ion/electron-conducting Li_(x)Cu_(y)P_(z) arrays constructed on Cu foil,which can be facile fabricated via an in-situ transformation of metal phosphide.Theoretic calculations indicate the excellent lithiophilicity and low Li diffusion barrier of the arrays,especially for the Li_(2)CuP phase,which are conducive to ho-mogenizing the Li nucleation/deposition of Li.Moreover,such mixed conducting arrays promote fast Li+diffusion via the continuous Li+pathways as well as modulate the Li+flux/electric field.Furthermore,the arrays with enlarged specific surface area and open spaces reduce the local current density and alle-viate the volume fluctuation of Li.Consequently,a dendrite-free Li anode is obtained under a high rate(20 mA cm^(–2))or a high deposition capacity(10 mAh cm^(–2)).In addition,even if the negative/positive ratio reduces to only 1.1,the full cells still perform outstanding stability for over 200 cycles.This work empha-sizes the importance of the design of the framework in terms of the intrinsic properties and structure and reveals a pathway for developing Li metal batteries.
基金supported by Program for New Century Excellent Talents in Chinese Ministry of Education(No.NECT-07-0307)Natural Science Foundation of Guangdong province(No.7300769)+1 种基金Fok Ying Tung Education Foundation(No.114019)New Teacher Fund of Ministry of Education of China(No.20070561032).
文摘A novel cobalt-free perovskite based on Ba0.5Sr0.5Fe0.8Zn0.2O3-δ （BSFZ） were prepared by EDTA-citric acid method. The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray diffraction （HTXRD）. The thermal expansion coefficient of BSFZ is 10.5×10^-6 K^-1, which is lower than that of cobalt-based perovskite materials. The BSFZ membrane was also used to construct reactors for the partial oxidation of methane （POM） to syngas. Results show that the BSFZ membrane can be operated for the POM reaction for more than 100 h without any fractures. The CO selectivity of 97% is obtained. The steady oxygen permeation flux reaches around 2.5 mL/min cm^2 during POM reaction.
基金Project supported by National Natural Science Foundation of China(51062015)the Provincial Education Department of Jiangxi(GJJ12421)
文摘Monoclinic CeNbO4.25 was prepared by solid state reaction. Complex impedance analysis indicated the presence of grain interior effect along with the grain boundary contribution. The values of ionic transference number ti below 423 K were calculated to be about 0.5. The activation energies of ionic conductivity and electronic conductivity were deduced to be 36.0 and 37.2 kJ/mol, re-spectively. The real part of the AC conductivity was frequency dependent. At high frequencies corresponding to the grain interior ef-fect, the non-Debye nature of the AC conductivity was interpreted by the correlated hopping of interstitial oxygen with the electron holes on the basis of the correlated barrier hopping （CBH） model.
基金financially supported by the National Key R&D Program of China(2021YFA1502400)the"Transformational Technologies for Clean Energy and Demonstration"+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA2100000)the National Natural Science Foundation of China(52172005,21905295,22179141)the DNL Cooperation Fund,CAS(DNL202008)the Photon Science Center for Carbon Neutrality and the Major Scientific and Technological Innovation Project of Shandong Province(2020CXGC010402)。
文摘Perovskite-type mixed protonic-electronic conducting membranes have attracted attention because of their ability to separate and purify hydrogen from a mixture of gases generated by industrial-scale steam reforming based on an ion diffusion mechanism.Exploring cost-effective membrane materials that can achieve both high H_(2) permeability and strong CO_(2)-tolerant chemical stability has been a major challenge for industrial applications.Herein,we constructed a triple phase(ceramic-metal-ceramic)membrane composed of a perovskite ceramic phase BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(3-δ)(BZCYYb),Ni metal phase and a fluorite ceramic phase CeO_(2).Under H_(2) atmosphere,Ni metal in-situ exsolved from the oxide grains,and decorated the grain surface and boundary,thus the electronic conductivity and hydrogen separation performance can be promoted.The BZCYYbNi-CeO_(2)hybrid membrane achieved an exceptional hydrogen separation performance of 0.53 mL min^(-1)cm^(-2) at 800℃ under a 10 vol% H_(2) atmosphere,surpassing all other perovskite membranes reported to date.Furthermore,the CeO_(2) phase incorporated into the BZCYYb-Ni effectively improved the CO_(2)-tolerant chemical stability.The BZCYYbNi-CeO_(2) membrane exhibited outstanding long-term stability for at least 80 h at 700℃ under 10 vol%CO_(2)-10 vol%H_(2).The success of hybrid membrane construction creates a new direction for simultaneously improving their hydrogen separation performance and CO_(2) resistance stability.
文摘A cobalt-free perovskite-type Ba0.5Sr0.5A10.1Fe0.9O3-δ （BSAF） chemically studied as solid oxide fuel cell （SOFC） cathode. The ductivity, and electrode polarizations in symmetrical cell based is developed and electro- structures, electrical con- on mixed ion conducting electrolyte were investigated, respectively. The temperature dependence of conductivity of BSAF in air shows a typical semiconductor behavior with positive temperature coefficient up to 450℃ where the conductivity reaches 14.0 S/cm while above this temperature the negative temperature coefficient dominates the total conductivity. Electrochemical charac- terizations show desirable polarization resistance of BSAF cathode in a symmetric cell based on mixed ion conducting electrolyte at 650-700℃, A single SOFC with BSAF cathode shows OCV of 1.0 V and maximum output of 420 mW/cm2 at 700 ℃ with humidified hydrogen fuel and static air oxidant.
基金Financial support by the Spanish Ministry of Science(PID2022139663OB-I00 and CEX2021-001230-S grant funded by MCIN/AE I/10.13039/501100011033)with funding from Next Generation EU(PRTR-C17.I1)within the Planes Complementarios con CCAA(Area of Green Hydrogen and Energy)+2 种基金carried out in the CSIC Interdisciplinary Thematic Platform(PTI+)Transición Energética Sostenible+(PTI-TRANSENER+)the Universitat Politècnica de València(UPV)the support of the Servicio de Microscopía Elcectronica of the UPV。
文摘Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production,oxygen transport membranes(OTMs)appear as an alternative technology for the cryogenic distillation of air,the industrially-established process of producing oxygen.Moreover,OTMs could provide oxygen from different sources(air,water,CO_(2),etc.),and they are more flexible in adapting to current processes,producing oxygen at 700^(-1)000℃.Furthermore,OTMs can be integrated into catalytic membrane reactors,providing new pathways for different processes.The first part of this study was focused on electrification on a traditional OTM material(Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)),imposing different electric currents/voltages along a capillary membrane.Thanks to the emerging Joule effect,the membrane-surface temperature and the associated O_(2) permeation flux could be adjusted.Here,the OTM is electrically and locally heated and reaches 900℃on the surface,whereas the surrounding of the membrane was maintained at 650℃.The O_(2)permeation flux reached for the electrified membranes was~3.7 NmL min^(-1)cm^(-2),corresponding to the flux obtained with an OTM non-electrified at 900℃.The influence of depositing a porous Ce_(0.8)Tb_(0.2)O_(2-δ) catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures(830℃)were detected at the same imposed electric power.Finally,the electrification concept was demonstrated in a catalytic membrane reactor(CMR)where the oxidative dehydrogenation of ethane(ODHE)was carried out.ODHE reaction is very sensitive to temperature,and here,we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O_(2) injection into the reaction can be easily fine-tuned.
基金The authors gratefully acknowledge the Research Grant Council of Hong Kong for support through the projects 16201820,and 16206019.
文摘BaFeO_(3-δ)-derived perovskites are promising cathodes for intermediate temperature solid oxide fuel cells.The activity of these perovskites depends on the number of oxygen vacancies in their lattice,which can be tuned by cationic substitution.Our first-principle calculations show that Ag is a promising substitute for the Fe site,resulting in a reduced oxygen vacancy formation energy compared with the pristine BaFeO_(3-δ).Ag has limited solubility in perovskites,and its introduction generates an Ag metal secondary phase,which influences the cathode performances.In this work,we investigate the matter,using a Ba0:9La0:1Fe_(1-x)AgxO_(3-δ)series of materials as a case study.Acknowledging the limited solubility of Ag in Ba0:9La0:1Fe_(1-x)AgxO_(3-δ),we aim to distinguish the effects of Ag substitution from those of the Ag secondary phase.We observed that Ag substitution increases the number of oxygen vacancies,confirming our calculations,and facilitates the oxygen incorporation.However,Ag substitution lowers the number of holes,in this way reducing the electronic p-type conductivity.On the other hand,Ag metal positively affects the electronic conductivity and helps the redistribution of the electronic charge at the cathode-electrolyte interface.
