The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based...The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based oxide(LLO)materials naturally stand out.Despite their inherent advantages,these materials encounter significant practical hurdles,including low initial Coulombic efficiency(ICE),diminished cycle/rate performance,and voltage fading during cycling,hindering their widespread adoption.In response,we introduce an ionic-electronic dual-conductive(IEDC)surface control strategy that integrates an electronically conductive graphene framework with an ionically conductive heteroepitaxial spinel Li_(4)Mn_(5)O_(12)layer.Prolonged electrochemical and structural analyses demonstrate that this IEDC heterostructure effectively minimizes polarization,mitigates structural distortion,and enhances electronic/ionic diffusion.Density functional theory calculations highlight an extensive Li^(+)percolation network and lower Li^(+)migration energies at the layered-spinel interface.The designed LLO cathode with IEDC interface engineering(LMOSG)exhibits improved ICE(82.9%at 0.1 C),elevated initial discharge capacity(296.7 mAh g^(-1)at 0.1 C),exceptional rate capability(176.5 mAh g^(-1)at 5 C),and outstanding cycle stability(73.7%retention at 5 C after 500 cycles).These findings and the novel dual-conductive surface architecture design offer promising directions for advancing highperformance electrode materials.展开更多
Ionic-electronic coupling serves as the core process enabling the operation of organic mixed ionic-electronic(semi)conductors(OMIECs)based devices,for instance,organic electrochemical transistors(OECTs).Replacing hydr...Ionic-electronic coupling serves as the core process enabling the operation of organic mixed ionic-electronic(semi)conductors(OMIECs)based devices,for instance,organic electrochemical transistors(OECTs).Replacing hydrophobic side chains of conjugated polymers with hydrophilic ethylene glycol/ionic ones is a well-developed approach to enable transistor channels with coupled ionic and electronic transport.Here,in contrast,we introduce a hydrophilic glycol chain-modified photocrosslinker(DtFGDA)for the direct photolithography process and blend it with various representative hydrophobic conjugated polymers.The precise patterning of blended films by direct photolithography is achieved while tremendous enhancements of OECTs performance are attained,with maximum six orders of magnitude higher transconductance,significantly decreased hysteresis,and lower threshold voltage.Through spectroelectrochemical characterization,surprisingly,no obvious variations in polaron absorption peaks are observed in all conjugated polymer/crosslinker blends.An ionic-electronic separated conduction mechanism,which is never reported in OECTs before,is further proposed based on the characterization of the transmission electron microscope,wherein ions primarily migrate within the crosslinker while holes transport within the semiconducting polymer.This work proposes an efficient strategy,which involves incorporating hydrophilic chains into the photocrosslinker necessary for direct photolithography and blending it with hydrophobic semiconducting polymers,achieving synergistic ionic-electronic transport in the blended film.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
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
Solid-state batteries(SSBs)will potentially offer increased energy density and,more importantly,improved safety for next generation lithium-ion(Li-ion)batteries.One enabling technology is solid-state composite cathode...Solid-state batteries(SSBs)will potentially offer increased energy density and,more importantly,improved safety for next generation lithium-ion(Li-ion)batteries.One enabling technology is solid-state composite cathodes with high operating voltage and area capacity.Current composite cathode manufacturing technologies,however,suffer from large interfacial resistance and low active mass loading that with excessive amounts of polymer electrolytes and conductive additives.Here,we report a liquidphase sintering technology that offers mixed ionic-electronic interphases and free-standing electrode architecture design,which eventually contribute to high area capacity.A small amount(~4 wt.%)of lithium hydroxide(LiOH)and boric acid(H_(3)BO_(3))with low melting point are utilized as sintering additives that infiltrate into single-crystal Ni-rich LiNi_(0.8)Mn_(0.1)Co_(0.1)(NMC811)particles at a moderately elevated temperature(~350℃)in a liquid state,which not only enable intimate physical contact but also promote the densification process.In addition,the liquid-phase additives react and transform to ionic-conductive lithium boron oxide,together with the indium tin oxide(ITO)nanoparticle coating,mixed ionic-electronic interphases of composite cathode are successfully fabricated.Furthermore,the liquid-phase sintering performed at high-temperature(~800℃)also enables the fabrication of highly dense and thick composite cathodes with a novel free-standing architecture.The promising performance characteristics of such composite cathodes,for example,delivering an area capacity above 8 mAh·cm^(−2) within a wide voltage window up to 4.4 V,open new opportunities for SSBs with a high energy density of 500 Wh·kg^(−1) for safer portable electronic and electrical transport.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
Solid solutions of Na_(0.5) Bi_(0.5) TiO_(3)(NBT)and BiNi_(0.5) Ti_(0.5) O_(3)(BNiT)were prepared by a solid-state reaction route,and their electrical properties investigated by a combination of impedance spectroscopy...Solid solutions of Na_(0.5) Bi_(0.5) TiO_(3)(NBT)and BiNi_(0.5) Ti_(0.5) O_(3)(BNiT)were prepared by a solid-state reaction route,and their electrical properties investigated by a combination of impedance spectroscopy and electromotive force measurements to explore the possibility of developing mixed ionic-electronic conductors based on NBT.Phase analysis showed that BNiT has a large solid solution limit in NBT(60 mol%based on X-ray diffraction),and the room temperature crystal structure changes from rhombohedral to pseudo-cubic with increasing BNiT content.Neutron diffraction revealed the coexistence of rhombohedral and tetragonal phases when the BNiT content≥40 mol%.Electrically,incorporation of BNiT induces p-type electronic conduction into NBT by hopping of holes between Ni^(2+)(Ni_(Ni)^(x))and Ni^(3+)(Ni·Ni),and therefore changes the electrical conduction mechanism systematically from predominant oxide-ion conduction to mixed ionic-electronic conduction and then to predominant p-type electronic conduction.The total conductivity of the solid solutions showed a“V-shape”variation with increasing BNiT content.Possible mechanisms for the phase evolution and the conductivity-composition relationships are discussed.Achieving high levels of ionic and electronic conductivity simultaneously in NBT by introducing elements with variable oxidation states remains challenging due to the competition between an enhanced electronic component and a suppressed ionic component.Low levels of BNiT incorporation are,however,beneficial to reducing the dielectric loss of NBT for dielectric applications.展开更多
Ionic, electronic and mixed (ionic-electronic) conductivities of blends of poly(2-vinyl pyridine) (P2VP) and poly(ethylene oxide) (PEO) with high molecular weight after doped with LiClO4, TCNQ or LiClO4 and TCNQ were ...Ionic, electronic and mixed (ionic-electronic) conductivities of blends of poly(2-vinyl pyridine) (P2VP) and poly(ethylene oxide) (PEO) with high molecular weight after doped with LiClO4, TCNQ or LiClO4 and TCNQ were investigated. Effects of LiClO4 and TCNQ concentrations on the conductivity of PEO/P2VP/LiClO4 or TCNQ blend were studied. The ionic conductivity of PEO/P2VP/LiClO4 blend increases with increasing PEO content. At a Li/ethylene bride molar ratio of 0.10 and a TCNQ/2-vinyl pyridine molar ratio of 0.5, the mixed conductivity of PEO/P2VP/LiClO4/TCNQ is higher than the total of ionic conductivity of PEO/P2VP/LiClO4 and electronic conductivity of PEO/P2VP/TCNQ when the weight ratio of PEO and P2VP is 6/4 or 5/5. Scanning electron microscopy (SEM) on the broken cross-section of the PEO/P2VP/LiClO4 blend and differential scanning calorimetry (DSC) results show that LiClO4 could act as a compatibilizer in the blend.展开更多
High-performance organic electrochemical transistors(OECTs)with sustainable processes are crucial for bioelectronics and integration applications,but still face challenges in molecular design,as well as solvent-device...High-performance organic electrochemical transistors(OECTs)with sustainable processes are crucial for bioelectronics and integration applications,but still face challenges in molecular design,as well as solvent-device compatibility.Herein,we introduced a unique synthetic protocol focused on regioselective chemistry for the development of a donor-acceptor polymeric mixed ionic-electronic conductor(PMIEC)with a well-defined side chain arrangement and demonstrated the superiority of side chain regioregularity in enhancing OECT performance.Furthermore,we pioneered the utilization of a green solvent,2-methyl tetrahydrofuran(MeTHF),for depositing the active OECT channel layers.We found that the regioregular copolymer exhibited over three times higherμC*of up to 810 F cm^(-1)V^(-1)s^(-1)compared to its regioirregular counterpart,thanks to improved crystallinity,reduced trap density of states(tDOS),and enhanced OECT hole mobility.Notably,this was achieved without the need for additional film posttreatments or specialized polymer fractionation techniques and stood among the highest values reported to date for green-solvent-processed OECTs.Our work represents a significant advancement in sustainable OECTs and highlights the importance of precise control over side chain regioregularity in developing high-performance PMIECs.展开更多
Organic mixed ionic-electronic conductor(OMIEC)polymers with the ability of mixed charge transport have been widely used in organic electronic devices,such as organic thermoelectric transistors(OTEs)and organic electr...Organic mixed ionic-electronic conductor(OMIEC)polymers with the ability of mixed charge transport have been widely used in organic electronic devices,such as organic thermoelectric transistors(OTEs)and organic electrochemical transistors(OECTs).The development of an n-type OMIEC remains a grand challenge.Herein,a double B←N bridged bipyridine unit with strong electron deficiency is used to build acceptor-acceptor type conjugated polymers(PBN-alkyl and PBN-OEG).PBN-OEG with oligoethylene glycol side chains exhibits weaker crystallinity,improved doping efficiency,and superior ion uptake capacity relative to the counterpart polymer with alkyl side chains.As a result,PBN-OEG exhibits a higher conductivity of 1.95 S cm-1,a better power factor of 4.7μW m-1 K-2 in OTEs,and a largeμC*of 2.6 F cm-1 V-1 s-1 in OECTs.Such results demonstrate the great potential of acceptor-acceptor type organoboron polymers for OMIEC materials.展开更多
Significant efforts have been dedicated to developing next-generation optimal electrolytes for high-performance low-temperature solid oxide fuel cells(SOFCs).In this study,we present an innovative co-doping strategy,i...Significant efforts have been dedicated to developing next-generation optimal electrolytes for high-performance low-temperature solid oxide fuel cells(SOFCs).In this study,we present an innovative co-doping strategy,incorporating samarium(Sm^(3+))and copper(Cu^(2+))into ceria(CuxSm_(0.2-x)Ce_(0.8)O_(2),x=0,0.05,0.10,0.15).By leveraging Sm^(3+)and Cu^(2+)to create oxygen vacancies and Cu^(2+)to further induce the controlled electronic characteristics,we engineered a material with enhanced proton conductivity and efficient electronic transfer and ionic transport.Distribution of relaxation times and electrochemical impedance spectroscopy analyses revealed significantly reduced grain boundary resistance and efficient proton conduction over the temperature range of 320℃ to 520℃.Notably,the optimized Cu_(0.1)Sm_(0.1)Ce_(0.8)O_(2)composition achieved a peak power density of 902 mW cm^(−2)with appreciable ionic conductivity of 0.16 S cm^(−1)at 520◦C,demonstrating its potential as a high-performance electrolyte.UV-Vis analysis indicated a reduced band gap,while DC polarization measurements indicated electronic conductivity of 0.019 S cm^(−1),suggesting the material possesses semiconducting properties suitable for the electrochemical applications.Advanced physical characterizations and their analysis provided detailed information of the materials,which are suitable for the fuel cell applications.In addition,the post stability of fuel cell device’s characterizations provided the detail information and evident the stable behavior of the as-prepared optimal Cu_(0.1)Sm_(0.1)Ce_(0.8)O_(2)(10-CSC)material acted as electrolyte.These findings position Cu_(0.1)Sm_(0.1)Ce_(0.8)O_(2)as a promising candidate for intermediate-temperature SOFCs,representing a significant advancement in semiconductor ionic electrolyte materials.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
Silicon(Si)is one of the most promising anodes for enabling all-solid-state batteries(ASSBs)with high energy density and safety.However,the tremendous volume change and sluggish kinetics result in poor electrochemical...Silicon(Si)is one of the most promising anodes for enabling all-solid-state batteries(ASSBs)with high energy density and safety.However,the tremendous volume change and sluggish kinetics result in poor electrochemical performance.Herein,we proposed an ionic/electronic dual-conductive material of Li_(x)Si as a diffusion-rapid and all-active anode for ASSBs.Compared with pure Si anode,the as-fabricated Li_(x)Si showed dramatic promotions of 35 times electronic and 400 times ionic conductivities.The three-dimensional(3D)ionic-electronic transport system of Li_(x)Si enabled rapid kinetics and uniform volume change of electrode materials in the whole electrode,corresponding to a lower volumechange rate.As a result,the ASSBs with LiCoO_(2)cathode exhibited a reversible discharge capacity of 154.4 mAh g−1,corresponding to an initial Coulombic efficiency of 97.3%.Besides,the batteries delivered a high rate capacity of 99.3 mAh g^(−1)at 2 C and long-term cycle stability of 94.0%after 800 cycles at 1 C,which was much better than the pure Si anode.This study sheds light on a new understanding of the importance of ionic conductivity for Si-based anode and might help inspire the design of advanced anode materials for ASSBs.展开更多
The control of ion transport by responding to stimulus is a necessary condition for the existence of life.Bioinspired iontronics could enable anomalous ion dynamics in the nano-confined spaces,creating many efficient ...The control of ion transport by responding to stimulus is a necessary condition for the existence of life.Bioinspired iontronics could enable anomalous ion dynamics in the nano-confined spaces,creating many efficient energy systems and neuromorphic in-sensor computing networks:Unlike tradi-tional electronics based on von Neumann computing architec-ture,the Boolean logic computing based on the iontronics could avoid complex wiring with higher energy efficiency and programmable neuromorphic logic.Here,a systematic summary on the state of art in bioinspired iontronics is pre-sented and the stimulus from chemical potentials,electric fields,light,heat,piezo and magnetic fields on ion dynamics are reviewed.Challenges and perspectives are also addressed in the aspects of iontronic integrated systems.It is believed that comprehensive investigations in bioinspired ionic control will accelerate the development on more efficient energy and information flow for the futuristic human-machine interface.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:22179008,21875022Yibin“Jie Bang Gua Shuai”,Grant/Award Number:2022JB004+2 种基金Beijing Nova Program,Grant/Award Number:20230484241Postdoctoral Fellowship Program of CPSF,Grant/Award Number:GZB20230931Special Support of Chongqing Postdoctoral Research Project,Grant/Award Number:2023CQBSHTB2041。
文摘The burgeoning growth in electric vehicles and portable energy storage systems necessitates advances in the energy density and cost-effectiveness of lithium-ion batteries(LIBs),areas where lithium-rich manganese-based oxide(LLO)materials naturally stand out.Despite their inherent advantages,these materials encounter significant practical hurdles,including low initial Coulombic efficiency(ICE),diminished cycle/rate performance,and voltage fading during cycling,hindering their widespread adoption.In response,we introduce an ionic-electronic dual-conductive(IEDC)surface control strategy that integrates an electronically conductive graphene framework with an ionically conductive heteroepitaxial spinel Li_(4)Mn_(5)O_(12)layer.Prolonged electrochemical and structural analyses demonstrate that this IEDC heterostructure effectively minimizes polarization,mitigates structural distortion,and enhances electronic/ionic diffusion.Density functional theory calculations highlight an extensive Li^(+)percolation network and lower Li^(+)migration energies at the layered-spinel interface.The designed LLO cathode with IEDC interface engineering(LMOSG)exhibits improved ICE(82.9%at 0.1 C),elevated initial discharge capacity(296.7 mAh g^(-1)at 0.1 C),exceptional rate capability(176.5 mAh g^(-1)at 5 C),and outstanding cycle stability(73.7%retention at 5 C after 500 cycles).These findings and the novel dual-conductive surface architecture design offer promising directions for advancing highperformance electrode materials.
基金supported by Sichuan Science and Technology Program(2022NSFSC0877,2023ZYD0161,2023YFSY0064)Chengdu Science and Technology Bureau(2023-YF06-00028-HZ)+1 种基金National Key Research and Development Program of China(2022YFF1202700)National Natural Science Foundation of China(52273316,62273073,92163132,T2422019).
文摘Ionic-electronic coupling serves as the core process enabling the operation of organic mixed ionic-electronic(semi)conductors(OMIECs)based devices,for instance,organic electrochemical transistors(OECTs).Replacing hydrophobic side chains of conjugated polymers with hydrophilic ethylene glycol/ionic ones is a well-developed approach to enable transistor channels with coupled ionic and electronic transport.Here,in contrast,we introduce a hydrophilic glycol chain-modified photocrosslinker(DtFGDA)for the direct photolithography process and blend it with various representative hydrophobic conjugated polymers.The precise patterning of blended films by direct photolithography is achieved while tremendous enhancements of OECTs performance are attained,with maximum six orders of magnitude higher transconductance,significantly decreased hysteresis,and lower threshold voltage.Through spectroelectrochemical characterization,surprisingly,no obvious variations in polaron absorption peaks are observed in all conjugated polymer/crosslinker blends.An ionic-electronic separated conduction mechanism,which is never reported in OECTs before,is further proposed based on the characterization of the transmission electron microscope,wherein ions primarily migrate within the crosslinker while holes transport within the semiconducting polymer.This work proposes an efficient strategy,which involves incorporating hydrophilic chains into the photocrosslinker necessary for direct photolithography and blending it with hydrophobic semiconducting polymers,achieving synergistic ionic-electronic transport in the blended film.
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 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 Natural Science Foundation of Jiangsu Province(No.BK20200800)the National Natural Science Foundation of China(Nos.51902165,12004145,52072323,and 52122211)+2 种基金Natural Science Foundation of Jiangxi Province(Nos.20192ACBL2004 and 20212BAB214032)Nanjing Science&Technology Innovation Project for Personnel Studying AbroadPart of the calculations were supported by the Center for Computational Science and Engineering at Southern University of Science and Technology,and high-performance computing platform of Jinggangshan University.
文摘Solid-state batteries(SSBs)will potentially offer increased energy density and,more importantly,improved safety for next generation lithium-ion(Li-ion)batteries.One enabling technology is solid-state composite cathodes with high operating voltage and area capacity.Current composite cathode manufacturing technologies,however,suffer from large interfacial resistance and low active mass loading that with excessive amounts of polymer electrolytes and conductive additives.Here,we report a liquidphase sintering technology that offers mixed ionic-electronic interphases and free-standing electrode architecture design,which eventually contribute to high area capacity.A small amount(~4 wt.%)of lithium hydroxide(LiOH)and boric acid(H_(3)BO_(3))with low melting point are utilized as sintering additives that infiltrate into single-crystal Ni-rich LiNi_(0.8)Mn_(0.1)Co_(0.1)(NMC811)particles at a moderately elevated temperature(~350℃)in a liquid state,which not only enable intimate physical contact but also promote the densification process.In addition,the liquid-phase additives react and transform to ionic-conductive lithium boron oxide,together with the indium tin oxide(ITO)nanoparticle coating,mixed ionic-electronic interphases of composite cathode are successfully fabricated.Furthermore,the liquid-phase sintering performed at high-temperature(~800℃)also enables the fabrication of highly dense and thick composite cathodes with a novel free-standing architecture.The promising performance characteristics of such composite cathodes,for example,delivering an area capacity above 8 mAh·cm^(−2) within a wide voltage window up to 4.4 V,open new opportunities for SSBs with a high energy density of 500 Wh·kg^(−1) for safer portable electronic and electrical transport.
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sponsored by the National Natural Science Founda-tion of China(Nos.52072239 and 52234010)the Natural Science Foundation of Chongqing,China(No.cstc2021jcyj-msxmX0720)the EPSRC(No.EP/L027348/1).
文摘Solid solutions of Na_(0.5) Bi_(0.5) TiO_(3)(NBT)and BiNi_(0.5) Ti_(0.5) O_(3)(BNiT)were prepared by a solid-state reaction route,and their electrical properties investigated by a combination of impedance spectroscopy and electromotive force measurements to explore the possibility of developing mixed ionic-electronic conductors based on NBT.Phase analysis showed that BNiT has a large solid solution limit in NBT(60 mol%based on X-ray diffraction),and the room temperature crystal structure changes from rhombohedral to pseudo-cubic with increasing BNiT content.Neutron diffraction revealed the coexistence of rhombohedral and tetragonal phases when the BNiT content≥40 mol%.Electrically,incorporation of BNiT induces p-type electronic conduction into NBT by hopping of holes between Ni^(2+)(Ni_(Ni)^(x))and Ni^(3+)(Ni·Ni),and therefore changes the electrical conduction mechanism systematically from predominant oxide-ion conduction to mixed ionic-electronic conduction and then to predominant p-type electronic conduction.The total conductivity of the solid solutions showed a“V-shape”variation with increasing BNiT content.Possible mechanisms for the phase evolution and the conductivity-composition relationships are discussed.Achieving high levels of ionic and electronic conductivity simultaneously in NBT by introducing elements with variable oxidation states remains challenging due to the competition between an enhanced electronic component and a suppressed ionic component.Low levels of BNiT incorporation are,however,beneficial to reducing the dielectric loss of NBT for dielectric applications.
基金Project supported by the National Natural Science Foundation of China.
文摘Ionic, electronic and mixed (ionic-electronic) conductivities of blends of poly(2-vinyl pyridine) (P2VP) and poly(ethylene oxide) (PEO) with high molecular weight after doped with LiClO4, TCNQ or LiClO4 and TCNQ were investigated. Effects of LiClO4 and TCNQ concentrations on the conductivity of PEO/P2VP/LiClO4 or TCNQ blend were studied. The ionic conductivity of PEO/P2VP/LiClO4 blend increases with increasing PEO content. At a Li/ethylene bride molar ratio of 0.10 and a TCNQ/2-vinyl pyridine molar ratio of 0.5, the mixed conductivity of PEO/P2VP/LiClO4/TCNQ is higher than the total of ionic conductivity of PEO/P2VP/LiClO4 and electronic conductivity of PEO/P2VP/TCNQ when the weight ratio of PEO and P2VP is 6/4 or 5/5. Scanning electron microscopy (SEM) on the broken cross-section of the PEO/P2VP/LiClO4 blend and differential scanning calorimetry (DSC) results show that LiClO4 could act as a compatibilizer in the blend.
基金financial support from the National Natural Science Foundation of China(NSFCgrant nos.52203251 and 22275212)+3 种基金the Guangzhou Basic and Applied Basic Research Foundation,China(grant no.202201011508)National Key R&D Program(grant no.2022YFA1206600)Fundamental Research Funds for the Central Universities,Sun Yat-sen University,China(grant no.23yxqntd002)State Key Laboratory of Optoelectronic&Materials and Technologies,Sun Yat-Sen University(grant no.OEMT-2023-KF-03).
文摘High-performance organic electrochemical transistors(OECTs)with sustainable processes are crucial for bioelectronics and integration applications,but still face challenges in molecular design,as well as solvent-device compatibility.Herein,we introduced a unique synthetic protocol focused on regioselective chemistry for the development of a donor-acceptor polymeric mixed ionic-electronic conductor(PMIEC)with a well-defined side chain arrangement and demonstrated the superiority of side chain regioregularity in enhancing OECT performance.Furthermore,we pioneered the utilization of a green solvent,2-methyl tetrahydrofuran(MeTHF),for depositing the active OECT channel layers.We found that the regioregular copolymer exhibited over three times higherμC*of up to 810 F cm^(-1)V^(-1)s^(-1)compared to its regioirregular counterpart,thanks to improved crystallinity,reduced trap density of states(tDOS),and enhanced OECT hole mobility.Notably,this was achieved without the need for additional film posttreatments or specialized polymer fractionation techniques and stood among the highest values reported to date for green-solvent-processed OECTs.Our work represents a significant advancement in sustainable OECTs and highlights the importance of precise control over side chain regioregularity in developing high-performance PMIECs.
基金support from the National Natural Science Foundation of China(Nos.52273201,52473199)J.L.thanks the Jilin Scientific and Technological Development Program(No.20230402070GH)+1 种基金a grant for Distinguished Young Scholars of the National Natural Science Foundation of China(Overseas)A portion of this work is based on the data obtained at BSRF-1W1A.The authors gratefully acknowledge the cooperation of the beamline scientists at the BSRF-1W1A beamline.
文摘Organic mixed ionic-electronic conductor(OMIEC)polymers with the ability of mixed charge transport have been widely used in organic electronic devices,such as organic thermoelectric transistors(OTEs)and organic electrochemical transistors(OECTs).The development of an n-type OMIEC remains a grand challenge.Herein,a double B←N bridged bipyridine unit with strong electron deficiency is used to build acceptor-acceptor type conjugated polymers(PBN-alkyl and PBN-OEG).PBN-OEG with oligoethylene glycol side chains exhibits weaker crystallinity,improved doping efficiency,and superior ion uptake capacity relative to the counterpart polymer with alkyl side chains.As a result,PBN-OEG exhibits a higher conductivity of 1.95 S cm-1,a better power factor of 4.7μW m-1 K-2 in OTEs,and a largeμC*of 2.6 F cm-1 V-1 s-1 in OECTs.Such results demonstrate the great potential of acceptor-acceptor type organoboron polymers for OMIEC materials.
基金The National Natural Science Foundation of China(Grant No.32250410309)Science and Technology Department of Jiangsu Province(Grant Nos.BE2022029 and JSSCRC2021491)+1 种基金Author ANA acknowledges Researchers Supporting Project Number(RSP2025R304)King Saud University,Riyadh,Saudi Arabia.
文摘Significant efforts have been dedicated to developing next-generation optimal electrolytes for high-performance low-temperature solid oxide fuel cells(SOFCs).In this study,we present an innovative co-doping strategy,incorporating samarium(Sm^(3+))and copper(Cu^(2+))into ceria(CuxSm_(0.2-x)Ce_(0.8)O_(2),x=0,0.05,0.10,0.15).By leveraging Sm^(3+)and Cu^(2+)to create oxygen vacancies and Cu^(2+)to further induce the controlled electronic characteristics,we engineered a material with enhanced proton conductivity and efficient electronic transfer and ionic transport.Distribution of relaxation times and electrochemical impedance spectroscopy analyses revealed significantly reduced grain boundary resistance and efficient proton conduction over the temperature range of 320℃ to 520℃.Notably,the optimized Cu_(0.1)Sm_(0.1)Ce_(0.8)O_(2)composition achieved a peak power density of 902 mW cm^(−2)with appreciable ionic conductivity of 0.16 S cm^(−1)at 520◦C,demonstrating its potential as a high-performance electrolyte.UV-Vis analysis indicated a reduced band gap,while DC polarization measurements indicated electronic conductivity of 0.019 S cm^(−1),suggesting the material possesses semiconducting properties suitable for the electrochemical applications.Advanced physical characterizations and their analysis provided detailed information of the materials,which are suitable for the fuel cell applications.In addition,the post stability of fuel cell device’s characterizations provided the detail information and evident the stable behavior of the as-prepared optimal Cu_(0.1)Sm_(0.1)Ce_(0.8)O_(2)(10-CSC)material acted as electrolyte.These findings position Cu_(0.1)Sm_(0.1)Ce_(0.8)O_(2)as a promising candidate for intermediate-temperature SOFCs,representing a significant advancement in semiconductor ionic electrolyte materials.
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This research was made possible as a result of a generous grant from the National Natural Science Foundation of China(NSFCgrant nos.22308303 and 12304029)+1 种基金Beijing Nova Program,China(grant no.20230484376)China First Auto Works(FAW)Group Corp.,Ltd.
文摘Silicon(Si)is one of the most promising anodes for enabling all-solid-state batteries(ASSBs)with high energy density and safety.However,the tremendous volume change and sluggish kinetics result in poor electrochemical performance.Herein,we proposed an ionic/electronic dual-conductive material of Li_(x)Si as a diffusion-rapid and all-active anode for ASSBs.Compared with pure Si anode,the as-fabricated Li_(x)Si showed dramatic promotions of 35 times electronic and 400 times ionic conductivities.The three-dimensional(3D)ionic-electronic transport system of Li_(x)Si enabled rapid kinetics and uniform volume change of electrode materials in the whole electrode,corresponding to a lower volumechange rate.As a result,the ASSBs with LiCoO_(2)cathode exhibited a reversible discharge capacity of 154.4 mAh g−1,corresponding to an initial Coulombic efficiency of 97.3%.Besides,the batteries delivered a high rate capacity of 99.3 mAh g^(−1)at 2 C and long-term cycle stability of 94.0%after 800 cycles at 1 C,which was much better than the pure Si anode.This study sheds light on a new understanding of the importance of ionic conductivity for Si-based anode and might help inspire the design of advanced anode materials for ASSBs.
基金supported by the Beijing Natural Science Foundation[Grant No.IS23040].
文摘The control of ion transport by responding to stimulus is a necessary condition for the existence of life.Bioinspired iontronics could enable anomalous ion dynamics in the nano-confined spaces,creating many efficient energy systems and neuromorphic in-sensor computing networks:Unlike tradi-tional electronics based on von Neumann computing architec-ture,the Boolean logic computing based on the iontronics could avoid complex wiring with higher energy efficiency and programmable neuromorphic logic.Here,a systematic summary on the state of art in bioinspired iontronics is pre-sented and the stimulus from chemical potentials,electric fields,light,heat,piezo and magnetic fields on ion dynamics are reviewed.Challenges and perspectives are also addressed in the aspects of iontronic integrated systems.It is believed that comprehensive investigations in bioinspired ionic control will accelerate the development on more efficient energy and information flow for the futuristic human-machine interface.
