In co-ionic conducting solid oxide fuel cell (SOFC), both oxygen ion (O2) and proton (H+) can transport through the electrolyte, generating steam in both the an-ode and cathode. Thus the mass transport phenomenon in t...In co-ionic conducting solid oxide fuel cell (SOFC), both oxygen ion (O2) and proton (H+) can transport through the electrolyte, generating steam in both the an-ode and cathode. Thus the mass transport phenomenon in the electrodes is quite different from that in conventional SOFC with oxygen ion conducting electrolyte (O-SOFC) or with proton conducting electrolyte (H-SOFC). The generation of steam in both electrodes also affects the concentration over-potential loss and further the SOFC performance. However, no detailed modeling study on SOFCs with co-ionic electrolyte has been reported yet. In this paper, a new mathematical model for SOFC based on co-ionic electrolyte was developed to predict its actual performance considering three major kinds of overpotentials. Ohm's law and the Butler-Volmer formula were used to model the ion conduction and electrochemical reactions, respectively. The dusty gas model (DGM) was employed to simulate the mass transport processes in the porous electrodes. Parametric simulations were performed to investigate the effects of proton transfer number (tH) and current density (jtotal) on the cell performance. It is interesting to find that the co-ionic conducting SOFC could perform better than O-SOFC and H-SOFC by choosing an appropriate proton transfer number. In addition, the co-ionic SOFC shows smaller difference between the anode and cathode concentration overpotentials than O-SOFC and H-SOFC at certain t H values. The results could help material selection for enhancing SOFC performance.展开更多
Development of noble-metal-free materials with remarkable electrocatalytic water-splitting performance in acidic or neutral media has sparked considerable attention in recent years.Herein,we review the latest research...Development of noble-metal-free materials with remarkable electrocatalytic water-splitting performance in acidic or neutral media has sparked considerable attention in recent years.Herein,we review the latest research on design and fabrication of precious-metal-free catalytic materials for overall water electrolysis in non-alkaline environment,especially highlighting several optimizing approaches to enhance the catalytic behavior and to realize effective bifunctional electrocatalysts.All these involved noble-metal-free electrocatalysts are classified into transition-metal oxides(TMOs),transition-metal nitrides(TMNs),transition-metal carbides(TMCs),transition-metal phosphides(TMPs),transition-metal chalcogenides,metal complexes,and metal-free carbons,as shown in the main part.Besides,the paper also offers an introduction of the fundamental electrochemistry of water splitting before entering the subject,as well as a prospective discussion on mechanism understanding,novel catalysts fabrication,and standardized performance measurements/evaluation in the last section.展开更多
Material strain and reconstruction effects are critical for catalysis reactions,but current insights into operando strain effects during reaction and means to master catalyst reconstruction are still lacking.Here,we p...Material strain and reconstruction effects are critical for catalysis reactions,but current insights into operando strain effects during reaction and means to master catalyst reconstruction are still lacking.Here,we propose a facile thermal-induced phase-segregation strategy to simultaneously master material operando strain and reconstruction effects for enhanced oxygen-evolving reaction(OER).Specifically,self-assembled and controllable layered LiCoO_(2)phase and Co_(3)O_(4)spinel can be generated from pristine Li2Co_(2)O_(4)spinel via Li and O volatilization under different temperatures,realizing controllable proportions of two phases by calcination temperature.Combined operando and ex-situ characterizations reveal that obvious tensile strain along(003)plane appears on layered LixCoO_(2)phase during OER,while low-valence Co_(3)O_(4)phase transforms into high-valence CoOOHx,realizing simultaneous operando strain and reconstruction effects.Further experimental and computational investigations demonstrate that both strained LixCoO_(2)phase and reconstructed CoOOHxcompound contribute to the beneficial adsorption of important OH-reactants,while respective roles in activity and stability are uncovered by exploring their latticeoxygen participation mechanism.This work not only reveals material operando strain effects during OER,but also inaugurates a new thermal-induced phase-segregation strategy to artificially master material operando strain and reconstruction effects,which will enlighten rational material design for many potential reactions and applications.展开更多
Thermal management in solid oxide fuel cells(SOFC)is a critical issue due to non-uniform electrochemical reactions and convective fl ows within the cells.Therefore,a 2D mathematical model is established herein to inve...Thermal management in solid oxide fuel cells(SOFC)is a critical issue due to non-uniform electrochemical reactions and convective fl ows within the cells.Therefore,a 2D mathematical model is established herein to investigate the thermal responses of a tubular methanol-fueled SOFC.Results show that unlike the low-temperature condition of 873 K,where the peak temperature gradient occurs at the cell center,it appears near the fuel inlet at 1073 K because of the rapid temperature rise induced by the elevated current density.Despite the large heat convection capacity,excessive air could not eff ectively eliminate the harmful temperature gradient caused by the large current density.Thus,optimal control of the current density by properly selecting the operating potential could generate a local thermal neutral state.Interestingly,the maximum axial temperature gradient could be reduced by about 18%at 973 K and 20%at 1073 K when the air with a 5 K higher temperature is supplied.Additionally,despite the higher electrochemical performance observed,the cell with a counter-fl ow arrange-ment featured by a larger hot area and higher maximum temperature gradients is not preferable for a ceramic SOFC system considering thermal durability.Overall,this study could provide insightful thermal information for the operating condition selection,structure design,and stability assessment of realistic SOFCs combined with their internal reforming process.展开更多
The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of cruc...The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of crucial importance for the rational design of flexible rechargeable Zn-air batteries(ZABs).Considering their good elasticity,high conductivity,and superior thermal and chemical stability,carbon nanotubes have been widely used as a catalyst support in various electrocatalysts,while oxide or metal nanoparticles have been frequently deposited on the carbon nanotube substrate to perform as the active materials.Considering the poor contact between active materials and carbon nanotubes may introduce a challenge for long-term operating stability,in particular in flexible devices,pure carbon electrocatalyst is highly appreciated.Herein,a free-standing air electrode with cobalt nanoparticles encapsulated N-codoped carbon nanotube arrays uniformly grown on the surface of carbon fiber cloth is developed by a two-step in situ growth method.Such a carbon-based electrode shows outstanding activity for both ORR and OER.The flexible ZAB with such air electrode shows superior flexibility and stability working under extreme bending conditions.Moreover,the polarization and round-trip efficiency for the flexible battery is 0.67 V and 64.4%at 2 mA/cm2,respectively,even after being operated for 30 hours.This study provides a feasible way to design all carbon-based free-standing and flexible electrode and enlightens the electrode design for flexible energy conversion/storage devices.展开更多
In response to the shortcomings of cobalt-rich cathodes, iron-based perovskite oxides appear as promising alternatives for solid oxide fuel cells (SOFCs). However, their inferior electrochemical performance at reduced...In response to the shortcomings of cobalt-rich cathodes, iron-based perovskite oxides appear as promising alternatives for solid oxide fuel cells (SOFCs). However, their inferior electrochemical performance at reduced temperatures (<700 ℃) becomes a major bottleneck for future progress. Here, a novel cobalt-free perovskite Ba_(0.75)Sr_(0.25)Fe_(0.875)Ga_(0.125)O_(3−δ) (BSFG) is developed as an efficient oxygen reduction electrode for SOFCs, featuring cubic-symmetry structure, large oxygen vacancy concentration and fast oxygen transport. Benefiting from these merits, cells incorporated with BSFG achieve exceptionally high electrochemical performance, as evidenced by a low polarization area-specific resistance of 0.074 Ω cm^(2) and a high peak power density of 1145 mW cm^(−2) at 600 ℃. Meanwhile, a robust short-term performance stability of BSFG cathode can be ascribed to the stable crystalline structure and favorable thermal expansion behavior. First-principles computations are also conducted to understanding the superior activity and durability toward oxygen reduction reaction. These pave the way for rationally developing highly active and robust cobalt-free perovskite-type cathode materials for reduced-temperature SOFCs.展开更多
Rational construction of carbon-based materials with high-efficiency bifunctionality and low cost as the substitute of precious metal catalyst shows a highly practical value for rechargeable Zn-air batteries(ZABs)yet ...Rational construction of carbon-based materials with high-efficiency bifunctionality and low cost as the substitute of precious metal catalyst shows a highly practical value for rechargeable Zn-air batteries(ZABs)yet it still remains challenging.Herein,this study employs a simple mixing-calcination strategy to fabricate a high-performance bifunctional composite catalyst composed of N-doped graphitic carbon encapsulating Co nanoparticles(Co@NrC).Benefiting from the core-shell architectural and compositional advantages of favorable electronic configuration,more exposed active sites,sufficient electric conductivity,rich defects,and excellent charge transport,the optimal Co@NrC hybrid(Co@NrC-0.3)presents outstanding catalytic activity and stability toward oxygen-related electrochemical reactions(oxygen reduction and evolution reactions,i.e.,ORR and OER),with a low potential gap of 0.766 V.Besides,the rechargeable liquid ZAB assembled with this hybrid electrocatalyst delivers a high peak power density of 168 mW cm^(−2),a small initial discharge-charge potential gap of 0.45 V at 10 mA cm^(−2),and a good rate performance.Furthermore,a relatively large power density of 108 mW cm^(−2) is also obtained with the Co@NrC-0.3-based flexible solid-state ZAB,which can well power LED lights.Such work offers insights in developing excellent bifunctional electrocatalysts for both OER and ORR and highlights their potential applications in metal-air batteries and other energy-conversion/storage devices.展开更多
With a rising energy demand and anabatic environmental crisis arising from the fast growth in human population and society economics,numerous efforts have been devoted to explore and design plentiful multifunctional m...With a rising energy demand and anabatic environmental crisis arising from the fast growth in human population and society economics,numerous efforts have been devoted to explore and design plentiful multifunctional materials for meeting highefficiency energy transfer processes,which happen in various developed energy conversion and storage systems.As a special kind of multi-metal oxides,perovskite with attractive physical and chemical properties,is becoming a rapidly rising star on the horizon of high-performance catalytic materials with substantial research behaviors worldwide.The porous nanostructure in targeted catalysts is favorable to the catalytic activity and thus improves the overall efficiency of these energy-related installations.In this review paper,recent advances made in the porous perovskite nanostructures for catalyzing several anodic or cathodic reactions in fuel cells and metal-air batteries are comprehensively summarized.Plenty of general preparation methods employed to attain porous perovskite-type oxides are provided,followed by a further discussion about the influence of various strategies on structures and catalytic properties of the porous perovskites.Furthermore,deep insights gathered in the future development of porous perovskite-based materials for energy conversion and storage technologies are also provided.展开更多
基金supported by Research Grant Council (RGC) of Hong Kong (PolyU 5238/11E)
文摘In co-ionic conducting solid oxide fuel cell (SOFC), both oxygen ion (O2) and proton (H+) can transport through the electrolyte, generating steam in both the an-ode and cathode. Thus the mass transport phenomenon in the electrodes is quite different from that in conventional SOFC with oxygen ion conducting electrolyte (O-SOFC) or with proton conducting electrolyte (H-SOFC). The generation of steam in both electrodes also affects the concentration over-potential loss and further the SOFC performance. However, no detailed modeling study on SOFCs with co-ionic electrolyte has been reported yet. In this paper, a new mathematical model for SOFC based on co-ionic electrolyte was developed to predict its actual performance considering three major kinds of overpotentials. Ohm's law and the Butler-Volmer formula were used to model the ion conduction and electrochemical reactions, respectively. The dusty gas model (DGM) was employed to simulate the mass transport processes in the porous electrodes. Parametric simulations were performed to investigate the effects of proton transfer number (tH) and current density (jtotal) on the cell performance. It is interesting to find that the co-ionic conducting SOFC could perform better than O-SOFC and H-SOFC by choosing an appropriate proton transfer number. In addition, the co-ionic SOFC shows smaller difference between the anode and cathode concentration overpotentials than O-SOFC and H-SOFC at certain t H values. The results could help material selection for enhancing SOFC performance.
基金M.Ni thanks the funding support(Project Number:PolyU 152214/17E and PolyU 152064/18E)from Research Grant Council,University Grants Committee,Hong Kong SAR。
文摘Development of noble-metal-free materials with remarkable electrocatalytic water-splitting performance in acidic or neutral media has sparked considerable attention in recent years.Herein,we review the latest research on design and fabrication of precious-metal-free catalytic materials for overall water electrolysis in non-alkaline environment,especially highlighting several optimizing approaches to enhance the catalytic behavior and to realize effective bifunctional electrocatalysts.All these involved noble-metal-free electrocatalysts are classified into transition-metal oxides(TMOs),transition-metal nitrides(TMNs),transition-metal carbides(TMCs),transition-metal phosphides(TMPs),transition-metal chalcogenides,metal complexes,and metal-free carbons,as shown in the main part.Besides,the paper also offers an introduction of the fundamental electrochemistry of water splitting before entering the subject,as well as a prospective discussion on mechanism understanding,novel catalysts fabrication,and standardized performance measurements/evaluation in the last section.
基金funded by the Australian Research Council Discovery Projects(DP160104835,Z.Shao)the Guangdong Basic and Applied Basic Research Foundation(2023A1515012878,D.Guan)+1 种基金the PolyU Distinguished Postdoctoral Fellowship Scheme(1-YWBU,D.Guan)the support from the Max Planck-POSTECH-Hsinchu Center for Complex Phase Materials。
文摘Material strain and reconstruction effects are critical for catalysis reactions,but current insights into operando strain effects during reaction and means to master catalyst reconstruction are still lacking.Here,we propose a facile thermal-induced phase-segregation strategy to simultaneously master material operando strain and reconstruction effects for enhanced oxygen-evolving reaction(OER).Specifically,self-assembled and controllable layered LiCoO_(2)phase and Co_(3)O_(4)spinel can be generated from pristine Li2Co_(2)O_(4)spinel via Li and O volatilization under different temperatures,realizing controllable proportions of two phases by calcination temperature.Combined operando and ex-situ characterizations reveal that obvious tensile strain along(003)plane appears on layered LixCoO_(2)phase during OER,while low-valence Co_(3)O_(4)phase transforms into high-valence CoOOHx,realizing simultaneous operando strain and reconstruction effects.Further experimental and computational investigations demonstrate that both strained LixCoO_(2)phase and reconstructed CoOOHxcompound contribute to the beneficial adsorption of important OH-reactants,while respective roles in activity and stability are uncovered by exploring their latticeoxygen participation mechanism.This work not only reveals material operando strain effects during OER,but also inaugurates a new thermal-induced phase-segregation strategy to artificially master material operando strain and reconstruction effects,which will enlighten rational material design for many potential reactions and applications.
基金by the Project of Strategic Importance Funding Scheme from The Hong Kong China Polytechnic University(No.P0035168)the National Natural Science Foundation of China(No.51806241).
文摘Thermal management in solid oxide fuel cells(SOFC)is a critical issue due to non-uniform electrochemical reactions and convective fl ows within the cells.Therefore,a 2D mathematical model is established herein to investigate the thermal responses of a tubular methanol-fueled SOFC.Results show that unlike the low-temperature condition of 873 K,where the peak temperature gradient occurs at the cell center,it appears near the fuel inlet at 1073 K because of the rapid temperature rise induced by the elevated current density.Despite the large heat convection capacity,excessive air could not eff ectively eliminate the harmful temperature gradient caused by the large current density.Thus,optimal control of the current density by properly selecting the operating potential could generate a local thermal neutral state.Interestingly,the maximum axial temperature gradient could be reduced by about 18%at 973 K and 20%at 1073 K when the air with a 5 K higher temperature is supplied.Additionally,despite the higher electrochemical performance observed,the cell with a counter-fl ow arrange-ment featured by a larger hot area and higher maximum temperature gradients is not preferable for a ceramic SOFC system considering thermal durability.Overall,this study could provide insightful thermal information for the operating condition selection,structure design,and stability assessment of realistic SOFCs combined with their internal reforming process.
基金Zongping Shao and Kaiming Liao thank the funding support provide by the National Key R&D Program of China(Grant no.2018YFB0905400)Kaiming Liao thanks the funding support provided by the National Natural Science Foundation of China(Grant no.51802152)the Natural Science Foundation of Jiangsu Province of China(Grant no.BK20170974).A Project Funded by Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘The development of an air electrode that is flexible in physical property and highly active and durable at different geometric status for both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of crucial importance for the rational design of flexible rechargeable Zn-air batteries(ZABs).Considering their good elasticity,high conductivity,and superior thermal and chemical stability,carbon nanotubes have been widely used as a catalyst support in various electrocatalysts,while oxide or metal nanoparticles have been frequently deposited on the carbon nanotube substrate to perform as the active materials.Considering the poor contact between active materials and carbon nanotubes may introduce a challenge for long-term operating stability,in particular in flexible devices,pure carbon electrocatalyst is highly appreciated.Herein,a free-standing air electrode with cobalt nanoparticles encapsulated N-codoped carbon nanotube arrays uniformly grown on the surface of carbon fiber cloth is developed by a two-step in situ growth method.Such a carbon-based electrode shows outstanding activity for both ORR and OER.The flexible ZAB with such air electrode shows superior flexibility and stability working under extreme bending conditions.Moreover,the polarization and round-trip efficiency for the flexible battery is 0.67 V and 64.4%at 2 mA/cm2,respectively,even after being operated for 30 hours.This study provides a feasible way to design all carbon-based free-standing and flexible electrode and enlightens the electrode design for flexible energy conversion/storage devices.
基金This work was financially supported by a startup R&D funding from One-Hundred Young Talents Program of Guangdong University of Technology,China(No.220413180)a Foundation for Youth Innovative Talents in Higher Education of Guangdong Province,China(No.2018KQNCX060)+1 种基金Joint Funds of Basic and Applied Basic Research Foundation of Guangdong Province,China(No.2019A1515110322)grants from Research Grant Council,University Grants Committee,Hong Kong SAR(Nos.PolyU 152214/17E and PolyU 152064/18E).
文摘In response to the shortcomings of cobalt-rich cathodes, iron-based perovskite oxides appear as promising alternatives for solid oxide fuel cells (SOFCs). However, their inferior electrochemical performance at reduced temperatures (<700 ℃) becomes a major bottleneck for future progress. Here, a novel cobalt-free perovskite Ba_(0.75)Sr_(0.25)Fe_(0.875)Ga_(0.125)O_(3−δ) (BSFG) is developed as an efficient oxygen reduction electrode for SOFCs, featuring cubic-symmetry structure, large oxygen vacancy concentration and fast oxygen transport. Benefiting from these merits, cells incorporated with BSFG achieve exceptionally high electrochemical performance, as evidenced by a low polarization area-specific resistance of 0.074 Ω cm^(2) and a high peak power density of 1145 mW cm^(−2) at 600 ℃. Meanwhile, a robust short-term performance stability of BSFG cathode can be ascribed to the stable crystalline structure and favorable thermal expansion behavior. First-principles computations are also conducted to understanding the superior activity and durability toward oxygen reduction reaction. These pave the way for rationally developing highly active and robust cobalt-free perovskite-type cathode materials for reduced-temperature SOFCs.
基金the Theme-based Scheme(project number:T23-601/17-R)from Research Grant Council,University Grants Committee,Hong Kong SAR,China.
文摘Rational construction of carbon-based materials with high-efficiency bifunctionality and low cost as the substitute of precious metal catalyst shows a highly practical value for rechargeable Zn-air batteries(ZABs)yet it still remains challenging.Herein,this study employs a simple mixing-calcination strategy to fabricate a high-performance bifunctional composite catalyst composed of N-doped graphitic carbon encapsulating Co nanoparticles(Co@NrC).Benefiting from the core-shell architectural and compositional advantages of favorable electronic configuration,more exposed active sites,sufficient electric conductivity,rich defects,and excellent charge transport,the optimal Co@NrC hybrid(Co@NrC-0.3)presents outstanding catalytic activity and stability toward oxygen-related electrochemical reactions(oxygen reduction and evolution reactions,i.e.,ORR and OER),with a low potential gap of 0.766 V.Besides,the rechargeable liquid ZAB assembled with this hybrid electrocatalyst delivers a high peak power density of 168 mW cm^(−2),a small initial discharge-charge potential gap of 0.45 V at 10 mA cm^(−2),and a good rate performance.Furthermore,a relatively large power density of 108 mW cm^(−2) is also obtained with the Co@NrC-0.3-based flexible solid-state ZAB,which can well power LED lights.Such work offers insights in developing excellent bifunctional electrocatalysts for both OER and ORR and highlights their potential applications in metal-air batteries and other energy-conversion/storage devices.
基金the funding support(Project Number.PolyU 152214/17E)from Research Grant Council,University Grants Committee,Hong Kong SARthe financial support from National Nature Science Foundation of China under contract No.21878158the National Key Research and Development Program of China under contract No.2018YFB0905402
文摘With a rising energy demand and anabatic environmental crisis arising from the fast growth in human population and society economics,numerous efforts have been devoted to explore and design plentiful multifunctional materials for meeting highefficiency energy transfer processes,which happen in various developed energy conversion and storage systems.As a special kind of multi-metal oxides,perovskite with attractive physical and chemical properties,is becoming a rapidly rising star on the horizon of high-performance catalytic materials with substantial research behaviors worldwide.The porous nanostructure in targeted catalysts is favorable to the catalytic activity and thus improves the overall efficiency of these energy-related installations.In this review paper,recent advances made in the porous perovskite nanostructures for catalyzing several anodic or cathodic reactions in fuel cells and metal-air batteries are comprehensively summarized.Plenty of general preparation methods employed to attain porous perovskite-type oxides are provided,followed by a further discussion about the influence of various strategies on structures and catalytic properties of the porous perovskites.Furthermore,deep insights gathered in the future development of porous perovskite-based materials for energy conversion and storage technologies are also provided.
