Protonic solid oxide electrolysis cells(P-SOECs)are a promising technology for water electrolysis to produce green hydrogen.However,there are still challenges related key materials and anode/electrolyte interface.P-SO...Protonic solid oxide electrolysis cells(P-SOECs)are a promising technology for water electrolysis to produce green hydrogen.However,there are still challenges related key materials and anode/electrolyte interface.P-SOECs with Zr-rich electrolyte,called Zr-rich side P-SOECs,possess high thermodynamically stability under high steam concentrations but the large reaction resistances and the current leakage,thus the inferior performances.In this study,an efficient functional interlayer Ba_(0.95)La_(0.05)Fe_(0.8)Zn_(0.2)O_(3-δ)(BLFZ)in-between the anode and the electrolyte is developed.The electrochemical performances of P-SOECs are greatly enhanced because the BLFZ can greatly increase the interface contact,boost anode reaction kinetics,and increase proton injection into electrolyte.As a result,the P-SOEC yields high current density of 0.83 A cm^(-2) at 600℃ in 1.3 Vamong all the reported Zr-rich side cells.This work not only offers an efficient functional interlayer for P-SOECs but also holds the potential to achieve P-SOECs with high performances and long-term stability.展开更多
In response to the increasing demand of ethylene,electrochemical ethane nonoxidative dehydrogenation(EENDH)to ethylene by protonic ceramic electrolysis cells(PCECs)is developed.However,existing anode materials exhibit...In response to the increasing demand of ethylene,electrochemical ethane nonoxidative dehydrogenation(EENDH)to ethylene by protonic ceramic electrolysis cells(PCECs)is developed.However,existing anode materials exhibit poor proton conductivity and limited catalytic activity.Herein,a novel Sr_(1.95)Fe_(1.4)Co_(0.1)Mo_(0.4)Zr_(0.1)O_(6-δ)(SFCMZ)anode is prepared as PCECs anode for EENDH.Zr doping increases the oxygen vacancies and enhances the proton conductivity of SFCMZ.Moreover,an alloy-oxide heterostructure(Co Fe@SFCMZ)is formed through in-situ exsolution of Co Fe alloy nanoparticles under reduction conditions,generating abundant oxygen vacancies and improving its catalytic activity.Co Fe@SFCMZ cell achieves an electrolysis current density of 0.87 A/cm^(2) at 700℃ under 1.6 V,with an ethane conversion rate of 34.22%and corresponding ethylene selectivity of 93.4%.These results demonstrate that Co Fe@SFCMZ anode exhibits excellent electrocatalytic activity,suggesting promising applications for EENDH.展开更多
This study documents pioneering results in marginal wells in Texas,where the application of RDV-00■restored production through delayed protonic activation catalyzed by reservoir energy.The product,based on RDV■(Vaso...This study documents pioneering results in marginal wells in Texas,where the application of RDV-00■restored production through delayed protonic activation catalyzed by reservoir energy.The product,based on RDV■(Vasoactive Dynamic Reactor)technology,operates via:Controlled protonation of molecular structures;Release of energetic carbocations;Autonomous transformation without external inputs.(a)Case 1(Well#E2-Starr County):Certified as“dry”by RRC(2022)after 48 months at 0 BPD;8 months post-injection of 5 gal RDV-00■(Fluid column:37 bbl;Wellhead pressure:80 psi(vs.0 psi initially)).(b)Case 2(Well#P1-Luling Field):Historical stripper well(0.25-0.5 BPD);23 months of immobilization with 15 gal RDV-00■;Critical results:(1)Initial production:42 BPD(8,400%above baseline);(2)Shut-in wellhead pressure:40 psi(neighboring wells=0-3 psi);(3)Current behavior:Continuous recharge from reservoir(well shut-in due to lack of storage).(c)Technically Significant Observations:(1)First case of self-sustaining reactivation in depleted wells;(2)Mechanism validated by Autonomous pressure generation(0→40-80 psi),and Continuous flow without additional stimulation;(3)No documented precedents in SPE/OnePetro literature to our knowledge.展开更多
The slow oxygen reaction kinetics of air electrodes impair the performance of reversible protonic ceramic electrochemical cells(R-PCECs);hence,it is imperative to design novel air electrodes featuring excellent cataly...The slow oxygen reaction kinetics of air electrodes impair the performance of reversible protonic ceramic electrochemical cells(R-PCECs);hence,it is imperative to design novel air electrodes featuring excellent catalytic activity and endurance.Here,we report an Rb-doped double perovskite PrBa_(0.8)Ca_(0.1)Rb_(0.1)Co_(2)O_(5+δ)(denoted as PBCR_(0.1)C)as an air electrode for R-PCECs,displaying a low polarization resistance of 0.044Ωcm^(2) at 700℃ and excellent stability during exposure to humid air(3 vol%H_(2)O).The high performance is attributed to the high electrical conductivity,high concentration of oxygen vacancies,and fast surface exchange,as verified by the analyses of X-ray photoelectron spectroscopy,thermogravimetric testing,and conductivity tests.The R-PCECs with the PBCR_(0.1)C air electrode demonstrate an encouraging performance at 700℃:a peak power density of 2.32 W cm^(-2) in a fuel cell(FC)mode and an electrolysis current density of-3.55 A cm^(-2) at 1.3 V in an electrolysis(EL)mode.At 30 vol%steam concentration,a Faraday efficiency of 87.80%and a corresponding H_(2) production rate of 3.05 mL min^(-1) cm^(-2) at a current density of-0.5 A cm^(-2) at 650℃.Additionally,the durability of the cell in the FC mode(120 h),EL mode(120 h),and cycling FC/EL mode(100 h)at 650℃ suggests the great potential of PBCR_(0.1)C as the highly reactive and robust air electrodes of R-PCECs.展开更多
Despite their high-energy conversion efficiency that has earned them the label of next-generation energy utilization devices,protonic ceramic fuel cells(PCFCs)have not yet fully fulfilled their potential in terms of l...Despite their high-energy conversion efficiency that has earned them the label of next-generation energy utilization devices,protonic ceramic fuel cells(PCFCs)have not yet fully fulfilled their potential in terms of low-cost integration and environmentally friendly application,which remain significant concerns that heavily influence their progress towards commercial viability.A pragmatic way of cell recycling is extremely helpful for addressing these concerns.Herein,we unveil a novel concept of reusable PCFCs,and propose a comprehensive recycling scheme for discarded PCFCs.In this research,a recycled cell with a recycled single perovskite cathode exhibited a peak power density(PPD)of 1.10 W cm^(-2)at 700℃,comparable to a pristine cell of 1.05 W cm^(-2).Metal ion rearrangement and phase evolution during the recycling processes were investigated,which were demonstrated to be in high relevance to the performance of recycled cells.This research constitutes a pioneering exploration of the mechanisms underlying recycling efforts and offers valuable insights into the material recycling of solid-state functional devices used for energy conversion and storage.展开更多
The proton ceramic electrochemical cell(PCEC),distinguished by its robust all-solid-state construction,emerges as a particularly promising contender in the realm of hydrogen production technologies.However,inadequate ...The proton ceramic electrochemical cell(PCEC),distinguished by its robust all-solid-state construction,emerges as a particularly promising contender in the realm of hydrogen production technologies.However,inadequate water-storage capability(hydration)and limited proton mobility within conventional PCEC oxygen electrodes hinder the efficiency of water splitting to oxygen,thereby restricting the broader application of PCECs.Here,we report a Ni-doped perovskite oxygen electrode Sr_(2)Fe_(1.4)Ni_(0.1)Mo_(1.5)O_(6-δ)(SFNM),where the incorporation of nickel can effectively amplify the concentration of oxygen vacancies while synergistically enhancing the hydration interaction between water molecules and the perovskite lattice.The enhanced hydration capacity facilitates proton-defect formation and lowers the energy barrier for proton migration.Benefiting from these synergistic enhancements,SFNM demonstrates a substantially reduced polarization resistance of approximately 0.078Ωcm^(2)at700℃under humidified conditions(pH_(2)O=0.1 atm).A PCEC utilizing the SFNM electrode achieves a remarkable current density of 2.60 A cm^(2)with an applied voltage of 1.3 V at 700℃.Furthermore,the PCEC exhibits favorable stability over a duration of 200 h.These outstanding results emphasize the potential of Ni doping to substantially improve both the hydration efficiency and proton mobility within perovskite electrode materials,positioning them as excellent candidates for high-performance PCECs.展开更多
PrBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(PrBSCF) has attracted much research interest as a potential triple ionic and electronic conductor(TIEC) electrode for protonic ceramic fuel cells(PCFCs). The chemical formula...PrBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(PrBSCF) has attracted much research interest as a potential triple ionic and electronic conductor(TIEC) electrode for protonic ceramic fuel cells(PCFCs). The chemical formula for Pr BSCF is AA'B_(2)O_(5+δ), with Pr(A-site) and Ba/Sr(A'-site) alternately stacked along the c-axis. Due to these structural features, the bulk oxygen ion diffusivity is significantly enhanced through the disorder-free channels in the PrO layer;thus, the A site cations(lanthanide ions) play a pivotal role in determining the overall electrochemical properties of layered perovskites. Consequently, previous research has predominantly focused on the electrical properties and oxygen bulk/surface kinetics of Ln cation effects,whereas the hydration properties for PCFC systems remain unidentified. Here, we thoroughly examined the proton uptake behavior and thermodynamic parameters for the hydration reaction to conclusively determine the changes in the electrochemical performances depending on LnBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(LnBSCF,Ln=Pr, Nd, and Gd) cathodes. At 500 ℃, the quantitative proton concentration of PrBSCF was 2.04 mol% and progressively decreased as the Ln cation size decreased. Similarly, the Gibbs free energy indicated that less energy was required for the formation of protonic defects in the order of Pr BSCF < Nd BSCF < Gd BSCF. To elucidate the close relationship between hydration properties and electrochemical performances in LnBSCF cathodes, PCFC single cell measurements and analysis of the distribution of relaxation time were further investigated.展开更多
Reversible protonic ceramic cells(RePCCs)hold promise for efficient energy storage,but their practicality is hindered by a lack of high-performance air electrode materials.Ruddlesden-Popper perovskite Sr_(3)Fe_(2)O_(7...Reversible protonic ceramic cells(RePCCs)hold promise for efficient energy storage,but their practicality is hindered by a lack of high-performance air electrode materials.Ruddlesden-Popper perovskite Sr_(3)Fe_(2)O_(7−δ)(SF)exhibits superior proton uptake and rapid ionic conduction,boosting activity.However,excessive proton uptake during RePCC operation degrades SF’s crystal structure,impacting durability.This study introduces a novel A/B-sites co-substitution strategy for modifying air electrodes,incorporating Sr-deficiency and Nb-substitution to create Sr_(2.8)Fe_(1.8)Nb_(0.2)O_(7−δ)(D-SFN).Nb stabilizes SF’s crystal,curbing excessive phase formation,and Sr-deficiency boosts oxygen vacancy concentration,optimizing oxygen transport.The D-SFN electrode demonstrates outstanding activity and durability,achieving a peak power density of 596 mW cm^(−2)in fuel cell mode and a current density of−1.19 A cm^(−2)in electrolysis mode at 1.3 V,650℃,with excellent cycling durability.This approach holds the potential for advancing robust and efficient air electrodes in RePCCs for renewable energy storage.展开更多
For protonic ceramic fuel cells,it is key to develop material with high intrinsic activity for oxygen activation and bulk proton conductivity enabling water formation at entire electrode surface.However,a higher water...For protonic ceramic fuel cells,it is key to develop material with high intrinsic activity for oxygen activation and bulk proton conductivity enabling water formation at entire electrode surface.However,a higher water content which benefitting for the increasing proton conductivity will not only dilute the oxygen in the gas,but also suppress the O_(2)adsorption on the electrode surface.Herein,a new electrode design concept is proposed,that may overcome this dilemma.By introducing a second phase with high-hydrating capability into a conventional cobalt-free perovskite to form a unique nanocomposite electrode,high proton conductivity/concentration can be reached at low water content in atmosphere.In addition,the hydronation creates additional fast proton transport channel along the two-phase interface.As a result,high protonic conductivity is reached,leading to a new breakthrough in performance for proton ceramic fuel cells and electrolysis cells devices among available air electrodes.展开更多
Perovskite oxides with diverse composition and structure have exhibited grand advances in boosting the oxygen reduction and evolution reaction(ORR/OER),which are essential for the reversible protonic ceramic electroch...Perovskite oxides with diverse composition and structure have exhibited grand advances in boosting the oxygen reduction and evolution reaction(ORR/OER),which are essential for the reversible protonic ceramic electrochemical cell(R-PCEC)toward the sustainable hydrogen production and utilization.However,enhancement of their activity and stability remains challenging.Herein,we develop the Ta-regulated BaCo_(0.7)Fe_(0.3)O_(3-δ)perovskite oxygen electrode(Ba(Co_(0.7)Fe_(0.3))_(1-x)Ta_xO_(3-δ))with abundant oxygen defects and achieve the simultaneous enhancement in the electrocatalytic activity and stability toward ORR and OER.As-fabricated R-PCEC with(Ba(Co_(0.7)Fe_(0.3))_(0.9)Ta_(0.1)O_(3-δ))(BCFT10)oxygen electrode performs high power density of 1.47 W·cm^(-2)at 650℃in fuel cell mode,and the current density is up to-2.11 A·cm^(-2)at 1.4 V at 650℃in electrolysis mode,as well as the good stability in both the fuel cell and electrolysis modes.Importantly,the cell also demonstrates a stable cycling operation between fuel cell and electrolysis mode,suggesting a great potential of BCFT10 as oxygen electrode material for R-PCECs.展开更多
Reversible protonic ceramic electrochemical cells(R-PCECs)demonstrate great feasibility for efficient energy storage and conversion.One critical challenge for the development of R-PCECs is the design of novel air elec...Reversible protonic ceramic electrochemical cells(R-PCECs)demonstrate great feasibility for efficient energy storage and conversion.One critical challenge for the development of R-PCECs is the design of novel air electrodes with the characteristics of high catalytic activity and acceptable durability.Here,we report a donor doping of Hf into the B-site of a cobalt-based double perovskite with a nominal formula of PrBa_(0.8)Ca_(0.2)Co_(1.9)Hf_(0.1)O_(5tδ)(PBCCHf_(0.1)),which is naturally reconfigured to a double perovskite PrBa_(0.8-x)Ca_(0.2)Co_(1.9)Hf_(0.1)-xO5tδ(PBCCHf_(0.1)-x)backbone and nano-sized BaHfO3(BHO)on the surface of PBCCHf_(0.1)x.The air electrode demonstrates enhanced catalytic activity and durability(a stable polarization resistance of 0.269Ωcm2 for~100 h at 600℃),due likely to the fast surface exchange process and bulk diffusion process.When employed as an air electrode of R-PCECs,a cell with PBCCHf_(0.1) air electrode demonstrates encouraging performances in modes of the fuel cell(FC)and electrolysis(EL)at 600℃:a peak power density of 0.998 W cm^(-2)and a current density of1.613 A cm^(-2)at 1.3 V(with acceptable Faradaic efficiencies).More importantly,the single-cell with PBCCHf_(0.1) air electrode demonstrates good cycling stability,switching back and forth from FC mode to EL mode0.5 A cm^(-2)for 200 h and 50 cycles.展开更多
Solid oxide fuel cells(SOFCs)and electrolysis cells(SOECs)are promising energy conversion devices,on whose basis green hydrogen energy technologies can be developed to support the transition to a carbon-free future.As...Solid oxide fuel cells(SOFCs)and electrolysis cells(SOECs)are promising energy conversion devices,on whose basis green hydrogen energy technologies can be developed to support the transition to a carbon-free future.As compared with oxygen-conducting cells,the operational temperatures of protonic ceramic fuel cells(PCFCs)and electrolysis cells(PCECs)can be reduced by several hundreds of degrees(down to low-and intermediatetemperature ranges of 400–700C)while maintaining high performance and efficiency.This is due to the distinctive characteristics of charge carriers for proton-conducting electrolytes.However,despite achieving outstanding lab-scale performance,the prospects for industrial scaling of PCFCs and PCECs remain hazy,at least in the near future,in contrast to commercially available SOFCs and SOECs.In this review,we reveal the reasons for the delayed technological development,which need to be addressed in order to transfer fundamental findings into industrial processes.Possible solutions to the identified problems are also highlighted.展开更多
Highly active and stable electrocatalysts are mandatory for developing high-performance and longlasting fuel cells.The current study demonstrates a high oxygen reduction reaction(ORR)electrocatalytic activity of a nov...Highly active and stable electrocatalysts are mandatory for developing high-performance and longlasting fuel cells.The current study demonstrates a high oxygen reduction reaction(ORR)electrocatalytic activity of a novel spinel-structured LaFe_(2)O_(4)via a self-doping strategy.The LaFe_(2)O_(4)demonstrates excellent ORR activity in a protonic ceramic fuel cell(PCFC)at temperature range of 350-500℃.The high ORR activity of LaFe_(2)O_(4)is mainly attributed to the facile release of oxide and proton ions,and improved synergistic incorporation abilities associated with interplay of multivalent Fe^(3+)/Fe^(2+)and La^(3+)ions.Using LaFe_(2)O_(4)as cathode over proton conducting BaZr_(0.4)Ce_(0.4)Y_(0.2)O_(3)(BZCY)electrolyte,the fuel cell has delivered a high-power density of 806 mW/cm^(2)operating at 500℃.Different spectroscopic and calculations methods such as UV-visible,Raman,X-ray photoelectron spectroscopy and density functional theory(DFT)calculations were performed to screen the potential application of LaFe_(2)O_(4)as cathode.This study would help in developing functional cobalt-free ORR electrocatalysts for low temperature-PCFCs(LT-PCFCs)and solid oxide fuel cells(SOFCs)applications.展开更多
Protonic ceramic fuel cells(PCFCs)have been attracting increasing attention because of their advances in high-efficiency power generation in an intermediate-temperature range,as compared to the high-temperature solid ...Protonic ceramic fuel cells(PCFCs)have been attracting increasing attention because of their advances in high-efficiency power generation in an intermediate-temperature range,as compared to the high-temperature solid oxide fuel cells(SOFCs).The greatest difference between PCFCs and SOFCs is the specific requirement of protonic(H+)conductivity at the PCFC cathode,in addition to the electronic(e^(-))and oxide-ion(O^(2-))conductivity.The development of a triple H^(+)/e^(-)/O^(2-)conductor for PCFC cathode is still challenging.Thus,the most-widely used cathode material is based on the mature e^(-)/O^(2-)conductor.However,this leads to insufficient triple phase boundary(TPB),i.e.,reaction area.Herein,an efficient strategy that uses a~100 nm-thick proton conductive functional layer(La_(0.5)Sr_(0.5)CoO_(3-δ),LSC55)in-between the typical La_(0.8)Sr_(0.2)CoO_(3-δ)cathode(a mature e-/O^(2-)conductor,LS C 82)and B aZr_(0.4)Ce_(0.4)Y_(0.1)Yb_(0.)1O_(3-δ)elec trolyte(11 mm in diameter,20μm in thickness)is proposed to significantly enhance the reaction area.Reasonably,the ohmic resistance and polarization resistance are both decreased by 47%and 62%,respectively,compared with that of PCFCs without the functional layer.The power density of the PCFC with such a functional layer can be raised by up to 2.24 times,superior to those described in previous reports.The enhanced PCFC performances are attributed to the well-built TPB and enhanced reaction area via the functional layer engineering strategy.展开更多
BaZr1-xScxO3-0.5x (x=0.07,0.10,0.13,0.16) powders were prepared by solid-state reaction method,and ZnO was used as sintering aid.Samples with different amount of ZnO additive were sintered at 1450·C for 6 h in ai...BaZr1-xScxO3-0.5x (x=0.07,0.10,0.13,0.16) powders were prepared by solid-state reaction method,and ZnO was used as sintering aid.Samples with different amount of ZnO additive were sintered at 1450·C for 6 h in air.Single cubic perovskite phase proton conductors were obtained.Conductivity was measured by electrochemical workstation.It was shown that Sc doping could increase conductivity through enhancing the carrier concentration in the material,but excessive Sc content might decrease the carrier concentration because of its charge compensation.ZnO had an influence on carrier concentration and mobility and affected the electrical conductivity.2 mol% ZnO and 13 mol% ScO1.5 doped sample showed the highest DC conductivity of 3.6×10-3 S·cm-1 tested at 800·C in wet hydrogen atmosphere.展开更多
Reversible protonic ceramic cells(RPCCs) show great potential as new-generation energy conversion and storage devices. However, the mature development of RPCCs is seriously hindered by the inactivity and poor stabilit...Reversible protonic ceramic cells(RPCCs) show great potential as new-generation energy conversion and storage devices. However, the mature development of RPCCs is seriously hindered by the inactivity and poor stability of air electrodes exposed to concentrated vapor under operating conditions. Herein, we report a high-entropy air electrode with the composition BaCo_(0.2)Fe_(0.2)Zr_(0.2)Sn_(0.2)Pr_(0.2)O_(3-δ)(BCFZSP), which shows integrated electronic, protonic and oxygenic conduction in a single perovskite phase and excellent structural stability in concentrated steam. Such triple conduction can spread the electrochemically active sites of the air electrode to the overall electrode surface, thus optimizing the kinetics of the oxygen reduction and evolution reactions(0.448 Ω cm^(2) of polarization resistance at 550℃). As-prepared RPCCs with a BCFZSP air electrode at 600℃ achieved a peak power density of 0.68 W/cm^(2) in fuel-cell mode and a current density of 0.92 A/cm^(2) under a 1.3 V applied voltage in electrolysis mode. More importantly, the RPCCs demonstrate an encouragingly high stability during 120 h of reversible switching between the fuelcell and electrolysis modes. Given their excellent performance, high-entropy perovskites can be promising electrode materials for RPCCs.展开更多
A deep-learning-based framework is proposed to predict the impedance response and underlying electrochemical behavior of the reversible protonic ceramic cell(PCC) across a wide variety of different operating condition...A deep-learning-based framework is proposed to predict the impedance response and underlying electrochemical behavior of the reversible protonic ceramic cell(PCC) across a wide variety of different operating conditions.Electrochemical impedance spectra(EIS) of PCCs were first acquired under a variety of opera ting conditions to provide a dataset containing 36 sets of EIS spectra for the model.An artificial neural network(ANN) was then trained to model the relationship between the cell operating condition and EIS response.Finally,ANN model-predicted EIS spectra were analyzed by the distribution of relaxation times(DRT) and compared to DRT spectra obtained from the experimental EIS data,enabling an assessment of the accumulative errors from the predicted EIS data vs the predicted DRT.We show that in certain cases,although the R^(2)of the predicted EIS curve may be> 0.98,the R^(2)of the predicted DRT may be as low as~0.3.This can lead to an inaccurate ANN prediction of the underlying time-resolved electrochemical response,although the apparent accuracy as evaluated from the EIS prediction may seem acceptable.After adjustment of the parameters of the ANN framework,the average R^(2)of the DRTs derived from the predicted EIS can be improved to 0.9667.Thus,we demonstrate that a properly tuned ANN model can be used as an effective tool to predict not only the EIS,but also the DRT of complex electrochemical systems.展开更多
Due to the high local concentration of substrates in confined space, porous solid Bronsted acids have been extensively explored for efficient acid-catalyzed reaction. However, the porous structures with strong Bronste...Due to the high local concentration of substrates in confined space, porous solid Bronsted acids have been extensively explored for efficient acid-catalyzed reaction. However, the porous structures with strong Bronsted acids lack long-term stability due to chemical hydrolysis. Moreover, the products inhibition effect in confined rigid cavities severely obstructs subsequent catalysis. Here, tubular Bronsted acid catalyst with unique recognition of protons was presented by self-assembly of p H-responsive aromatic amphiphiles. The responsive assembly could mechanically transfer hydrogen ions from low-concentration acidic solution into tubular defined pores, thereby producing effective catalytic activity for Mannich reactions in mildly acidic solution. Notably, the tubular catalyst unfolded into flat sheets upon addition of triethylamine for efficient release of products, which could be recovered by subsequent acidification and the catalytic activity still remained. Therefore, the porous Bronsted acid with reversible assembly provides a new strategy for mass synthesis through increasing conversion times.展开更多
Protonic ceramic electrolysis cell(PCEC)is a promising technology for production of pure dry hydrogen due to the low operating temperature and high efficiency.One of the obstacles for commercialization of PCEC technol...Protonic ceramic electrolysis cell(PCEC)is a promising technology for production of pure dry hydrogen due to the low operating temperature and high efficiency.One of the obstacles for commercialization of PCEC technology is the poor performance and insufficient long-term durability of the oxygen electrode.In this study,we address the above challenge by designing a LaCoO_(3)(LC)catalyst infiltrated porous BaZr_(0.8)Y_(0.2)O_(3)−δ(BZY20)backbone electrode(LC-BZY20).The performance and durability of the LC-BZY20 electrode are investigated on symmetrical cells using electrochemical impedance spectroscopy(EIS).The total electrode polarization resistance(RP)values of the electrode are 0.56,1.24,2.18,and 2.90Ωcm2 in 3vol%humidified synthetic air at 600,550,500,and 450℃,respectively,indicating good electrochemical performance of the LC-BZY20 electrode.Furthermore,the LC-BZY20 electrode displays good stability,without significant performance degradation when tested at 600℃ in 10vol%humidified air for 900h.We further study the influence of oxygen partial pressure(PO_(2))and steam partial pressure(P_(H_(2)O))on the response of the EIS data,and propose a set of chemical and electrochemical processes involved in the steam splitting reaction in the LC-BZY20 electrode.展开更多
Reversible protonic ceramic electrochemical cells(R-PCECs)are ideal,high-effi ciency devices that are environmentally friendly and have a modular design.This paper studies BaFe_(0.6)Zr_(0.1)Y_(0.3)O_(3−δ)(BFZY3)as a ...Reversible protonic ceramic electrochemical cells(R-PCECs)are ideal,high-effi ciency devices that are environmentally friendly and have a modular design.This paper studies BaFe_(0.6)Zr_(0.1)Y_(0.3)O_(3−δ)(BFZY3)as a cobalt-free perovskite oxygen electrode for high-performance R-PCECs where Y ions doping can increase the concentration of oxygen vacancies with a remarkable increase in catalytic performance.The cell with confi guration of Ni-BZCYYb/BZCYYb/BFZY3 demonstrated promising performance in dual modes of fuel cells(FCs)and electrolysis cells(ECs)at 650℃with low polarization resistance of 0.13Ωcm^(2),peak power density of 546.59 mW/cm^(2)in FC mode,and current density of−1.03 A/cm^(2)at 1.3 V in EC mode.The alternative operation between FC and EC modes for up to eight cycles with a total of 80 h suggests that the cell with BFZY3 is exceptionally stable and reversible over the long term.The results indicated that BFZY3 has considerable potential as an air electrode material for R-PCECs,permitting effi cient oxygen reduction and water splitting.展开更多
基金financial support from the JSPS KAKENHI Grant-in-Aid for Scientific Research(B),No.21H02035KAKENHI Grant-in-Aid for Challenging Research(Exploratory),No.21K19017+2 种基金KAKENHI Grant-in-Aid for Transformative Research Areas(B),No.21H05100National Natural Science Foundation of China,No.22409033 and No.22409035Basic and Applied Basic Research Foundation of Guangdong Province,No.2022A1515110470.
文摘Protonic solid oxide electrolysis cells(P-SOECs)are a promising technology for water electrolysis to produce green hydrogen.However,there are still challenges related key materials and anode/electrolyte interface.P-SOECs with Zr-rich electrolyte,called Zr-rich side P-SOECs,possess high thermodynamically stability under high steam concentrations but the large reaction resistances and the current leakage,thus the inferior performances.In this study,an efficient functional interlayer Ba_(0.95)La_(0.05)Fe_(0.8)Zn_(0.2)O_(3-δ)(BLFZ)in-between the anode and the electrolyte is developed.The electrochemical performances of P-SOECs are greatly enhanced because the BLFZ can greatly increase the interface contact,boost anode reaction kinetics,and increase proton injection into electrolyte.As a result,the P-SOEC yields high current density of 0.83 A cm^(-2) at 600℃ in 1.3 Vamong all the reported Zr-rich side cells.This work not only offers an efficient functional interlayer for P-SOECs but also holds the potential to achieve P-SOECs with high performances and long-term stability.
基金financially supported by the National Natural Science Foundation of China(Nos.52272190 and 22178023)the National Key R&D Program of China(No.2021YFB4001401)。
文摘In response to the increasing demand of ethylene,electrochemical ethane nonoxidative dehydrogenation(EENDH)to ethylene by protonic ceramic electrolysis cells(PCECs)is developed.However,existing anode materials exhibit poor proton conductivity and limited catalytic activity.Herein,a novel Sr_(1.95)Fe_(1.4)Co_(0.1)Mo_(0.4)Zr_(0.1)O_(6-δ)(SFCMZ)anode is prepared as PCECs anode for EENDH.Zr doping increases the oxygen vacancies and enhances the proton conductivity of SFCMZ.Moreover,an alloy-oxide heterostructure(Co Fe@SFCMZ)is formed through in-situ exsolution of Co Fe alloy nanoparticles under reduction conditions,generating abundant oxygen vacancies and improving its catalytic activity.Co Fe@SFCMZ cell achieves an electrolysis current density of 0.87 A/cm^(2) at 700℃ under 1.6 V,with an ethane conversion rate of 34.22%and corresponding ethylene selectivity of 93.4%.These results demonstrate that Co Fe@SFCMZ anode exhibits excellent electrocatalytic activity,suggesting promising applications for EENDH.
文摘This study documents pioneering results in marginal wells in Texas,where the application of RDV-00■restored production through delayed protonic activation catalyzed by reservoir energy.The product,based on RDV■(Vasoactive Dynamic Reactor)technology,operates via:Controlled protonation of molecular structures;Release of energetic carbocations;Autonomous transformation without external inputs.(a)Case 1(Well#E2-Starr County):Certified as“dry”by RRC(2022)after 48 months at 0 BPD;8 months post-injection of 5 gal RDV-00■(Fluid column:37 bbl;Wellhead pressure:80 psi(vs.0 psi initially)).(b)Case 2(Well#P1-Luling Field):Historical stripper well(0.25-0.5 BPD);23 months of immobilization with 15 gal RDV-00■;Critical results:(1)Initial production:42 BPD(8,400%above baseline);(2)Shut-in wellhead pressure:40 psi(neighboring wells=0-3 psi);(3)Current behavior:Continuous recharge from reservoir(well shut-in due to lack of storage).(c)Technically Significant Observations:(1)First case of self-sustaining reactivation in depleted wells;(2)Mechanism validated by Autonomous pressure generation(0→40-80 psi),and Continuous flow without additional stimulation;(3)No documented precedents in SPE/OnePetro literature to our knowledge.
文摘The slow oxygen reaction kinetics of air electrodes impair the performance of reversible protonic ceramic electrochemical cells(R-PCECs);hence,it is imperative to design novel air electrodes featuring excellent catalytic activity and endurance.Here,we report an Rb-doped double perovskite PrBa_(0.8)Ca_(0.1)Rb_(0.1)Co_(2)O_(5+δ)(denoted as PBCR_(0.1)C)as an air electrode for R-PCECs,displaying a low polarization resistance of 0.044Ωcm^(2) at 700℃ and excellent stability during exposure to humid air(3 vol%H_(2)O).The high performance is attributed to the high electrical conductivity,high concentration of oxygen vacancies,and fast surface exchange,as verified by the analyses of X-ray photoelectron spectroscopy,thermogravimetric testing,and conductivity tests.The R-PCECs with the PBCR_(0.1)C air electrode demonstrate an encouraging performance at 700℃:a peak power density of 2.32 W cm^(-2) in a fuel cell(FC)mode and an electrolysis current density of-3.55 A cm^(-2) at 1.3 V in an electrolysis(EL)mode.At 30 vol%steam concentration,a Faraday efficiency of 87.80%and a corresponding H_(2) production rate of 3.05 mL min^(-1) cm^(-2) at a current density of-0.5 A cm^(-2) at 650℃.Additionally,the durability of the cell in the FC mode(120 h),EL mode(120 h),and cycling FC/EL mode(100 h)at 650℃ suggests the great potential of PBCR_(0.1)C as the highly reactive and robust air electrodes of R-PCECs.
基金financially supported by the Research Startup Project for High-Level Talent Attraction in Inner Mongolia Agricultural University(No.NDYB2023-40)the Natural Science Research Fund for Colleges and Universities in Anhui Province(No.2022AH050309)+3 种基金The Scientific Research Foundation of Education Department of Anhui Province of China(No.KJ2021ZD0043)the University Synergy Innovation Program of Anhui Province of China(No.GXXT-2022-010)the High-Level Talent Project of Talent Development Fund of Inner Mongoliathe Start-Up Funding from Inner Mongolia University of Technology(No.YLXKZX-NGD-039)
文摘Despite their high-energy conversion efficiency that has earned them the label of next-generation energy utilization devices,protonic ceramic fuel cells(PCFCs)have not yet fully fulfilled their potential in terms of low-cost integration and environmentally friendly application,which remain significant concerns that heavily influence their progress towards commercial viability.A pragmatic way of cell recycling is extremely helpful for addressing these concerns.Herein,we unveil a novel concept of reusable PCFCs,and propose a comprehensive recycling scheme for discarded PCFCs.In this research,a recycled cell with a recycled single perovskite cathode exhibited a peak power density(PPD)of 1.10 W cm^(-2)at 700℃,comparable to a pristine cell of 1.05 W cm^(-2).Metal ion rearrangement and phase evolution during the recycling processes were investigated,which were demonstrated to be in high relevance to the performance of recycled cells.This research constitutes a pioneering exploration of the mechanisms underlying recycling efforts and offers valuable insights into the material recycling of solid-state functional devices used for energy conversion and storage.
基金financially supported by the National Key R&D Program of China(No.2022YFB4002501)the National Natural Science Foundation of China(No.52202208)
文摘The proton ceramic electrochemical cell(PCEC),distinguished by its robust all-solid-state construction,emerges as a particularly promising contender in the realm of hydrogen production technologies.However,inadequate water-storage capability(hydration)and limited proton mobility within conventional PCEC oxygen electrodes hinder the efficiency of water splitting to oxygen,thereby restricting the broader application of PCECs.Here,we report a Ni-doped perovskite oxygen electrode Sr_(2)Fe_(1.4)Ni_(0.1)Mo_(1.5)O_(6-δ)(SFNM),where the incorporation of nickel can effectively amplify the concentration of oxygen vacancies while synergistically enhancing the hydration interaction between water molecules and the perovskite lattice.The enhanced hydration capacity facilitates proton-defect formation and lowers the energy barrier for proton migration.Benefiting from these synergistic enhancements,SFNM demonstrates a substantially reduced polarization resistance of approximately 0.078Ωcm^(2)at700℃under humidified conditions(pH_(2)O=0.1 atm).A PCEC utilizing the SFNM electrode achieves a remarkable current density of 2.60 A cm^(2)with an applied voltage of 1.3 V at 700℃.Furthermore,the PCEC exhibits favorable stability over a duration of 200 h.These outstanding results emphasize the potential of Ni doping to substantially improve both the hydration efficiency and proton mobility within perovskite electrode materials,positioning them as excellent candidates for high-performance PCECs.
基金supported by the National Research Foundation (NRF) grant funded by the Korea government (NRF2022R1C1C1007619, NRF-2021M3H4A1A01002921, NRF2021M3I3A1084292)supported by the KIST Institutional Program (Project No. 2E32592-23-069)。
文摘PrBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(PrBSCF) has attracted much research interest as a potential triple ionic and electronic conductor(TIEC) electrode for protonic ceramic fuel cells(PCFCs). The chemical formula for Pr BSCF is AA'B_(2)O_(5+δ), with Pr(A-site) and Ba/Sr(A'-site) alternately stacked along the c-axis. Due to these structural features, the bulk oxygen ion diffusivity is significantly enhanced through the disorder-free channels in the PrO layer;thus, the A site cations(lanthanide ions) play a pivotal role in determining the overall electrochemical properties of layered perovskites. Consequently, previous research has predominantly focused on the electrical properties and oxygen bulk/surface kinetics of Ln cation effects,whereas the hydration properties for PCFC systems remain unidentified. Here, we thoroughly examined the proton uptake behavior and thermodynamic parameters for the hydration reaction to conclusively determine the changes in the electrochemical performances depending on LnBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(LnBSCF,Ln=Pr, Nd, and Gd) cathodes. At 500 ℃, the quantitative proton concentration of PrBSCF was 2.04 mol% and progressively decreased as the Ln cation size decreased. Similarly, the Gibbs free energy indicated that less energy was required for the formation of protonic defects in the order of Pr BSCF < Nd BSCF < Gd BSCF. To elucidate the close relationship between hydration properties and electrochemical performances in LnBSCF cathodes, PCFC single cell measurements and analysis of the distribution of relaxation time were further investigated.
基金supported by the Research Grants Council,University Grants Committee,Hong Kong SAR(Project Number:N_PolyU552/20)supported by the National Nature Science Foundation of China(22209138)Guangdong Basic and Applied Basic Research Foundation(2021A1515110464).
文摘Reversible protonic ceramic cells(RePCCs)hold promise for efficient energy storage,but their practicality is hindered by a lack of high-performance air electrode materials.Ruddlesden-Popper perovskite Sr_(3)Fe_(2)O_(7−δ)(SF)exhibits superior proton uptake and rapid ionic conduction,boosting activity.However,excessive proton uptake during RePCC operation degrades SF’s crystal structure,impacting durability.This study introduces a novel A/B-sites co-substitution strategy for modifying air electrodes,incorporating Sr-deficiency and Nb-substitution to create Sr_(2.8)Fe_(1.8)Nb_(0.2)O_(7−δ)(D-SFN).Nb stabilizes SF’s crystal,curbing excessive phase formation,and Sr-deficiency boosts oxygen vacancy concentration,optimizing oxygen transport.The D-SFN electrode demonstrates outstanding activity and durability,achieving a peak power density of 596 mW cm^(−2)in fuel cell mode and a current density of−1.19 A cm^(−2)in electrolysis mode at 1.3 V,650℃,with excellent cycling durability.This approach holds the potential for advancing robust and efficient air electrodes in RePCCs for renewable energy storage.
基金supported from the National Key R&D Program of China(No.2022YFB4002502)National Natural Science Foundation of China under(No.22278203,22279057)+4 种基金the Jiangsu Funding Program for Excellent Postdoctoral Talentthe Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)support from the Max Planck-POSTECH-Hsinchu Center for Complex Phase Materialssupport from the Fulbright Foundation Global Scholars Programthe U.S.Army Research Office under grant number W911NF-17-5401-0051
文摘For protonic ceramic fuel cells,it is key to develop material with high intrinsic activity for oxygen activation and bulk proton conductivity enabling water formation at entire electrode surface.However,a higher water content which benefitting for the increasing proton conductivity will not only dilute the oxygen in the gas,but also suppress the O_(2)adsorption on the electrode surface.Herein,a new electrode design concept is proposed,that may overcome this dilemma.By introducing a second phase with high-hydrating capability into a conventional cobalt-free perovskite to form a unique nanocomposite electrode,high proton conductivity/concentration can be reached at low water content in atmosphere.In addition,the hydronation creates additional fast proton transport channel along the two-phase interface.As a result,high protonic conductivity is reached,leading to a new breakthrough in performance for proton ceramic fuel cells and electrolysis cells devices among available air electrodes.
基金financially supported by the National Key R&D Program of China(No.2022YFB4002201)the National Natural Science Foundation of China(Nos.52072362 and 52302119)+3 种基金Jilin Province Science and Technology Development Plan Funding Project(Nos.SKL202302039 and 20220201112GX)Jiangsu Province Innovation Support Program(No.BE2023092-2)Youth Innovation Promotion Association CAS(No.2021223)Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(No.RERU2022008)。
文摘Perovskite oxides with diverse composition and structure have exhibited grand advances in boosting the oxygen reduction and evolution reaction(ORR/OER),which are essential for the reversible protonic ceramic electrochemical cell(R-PCEC)toward the sustainable hydrogen production and utilization.However,enhancement of their activity and stability remains challenging.Herein,we develop the Ta-regulated BaCo_(0.7)Fe_(0.3)O_(3-δ)perovskite oxygen electrode(Ba(Co_(0.7)Fe_(0.3))_(1-x)Ta_xO_(3-δ))with abundant oxygen defects and achieve the simultaneous enhancement in the electrocatalytic activity and stability toward ORR and OER.As-fabricated R-PCEC with(Ba(Co_(0.7)Fe_(0.3))_(0.9)Ta_(0.1)O_(3-δ))(BCFT10)oxygen electrode performs high power density of 1.47 W·cm^(-2)at 650℃in fuel cell mode,and the current density is up to-2.11 A·cm^(-2)at 1.4 V at 650℃in electrolysis mode,as well as the good stability in both the fuel cell and electrolysis modes.Importantly,the cell also demonstrates a stable cycling operation between fuel cell and electrolysis mode,suggesting a great potential of BCFT10 as oxygen electrode material for R-PCECs.
基金the financial support from the National Natural Science Foundation of China(Nos.22179039)the Introduced Innovative R&D Team of Guangdong(No.2021ZT09L392)+3 种基金the Fundamental Research Funds for the Central Universities(2022ZYGXZR002)Zijin Mining Group Co.,Ltd(5405-ZC-2023-00008)the Pearl River Talent Recruitment Program(2019QN01C693)the Natural Science Foundation of Guangdong Province(No.2022A1515011785).
文摘Reversible protonic ceramic electrochemical cells(R-PCECs)demonstrate great feasibility for efficient energy storage and conversion.One critical challenge for the development of R-PCECs is the design of novel air electrodes with the characteristics of high catalytic activity and acceptable durability.Here,we report a donor doping of Hf into the B-site of a cobalt-based double perovskite with a nominal formula of PrBa_(0.8)Ca_(0.2)Co_(1.9)Hf_(0.1)O_(5tδ)(PBCCHf_(0.1)),which is naturally reconfigured to a double perovskite PrBa_(0.8-x)Ca_(0.2)Co_(1.9)Hf_(0.1)-xO5tδ(PBCCHf_(0.1)-x)backbone and nano-sized BaHfO3(BHO)on the surface of PBCCHf_(0.1)x.The air electrode demonstrates enhanced catalytic activity and durability(a stable polarization resistance of 0.269Ωcm2 for~100 h at 600℃),due likely to the fast surface exchange process and bulk diffusion process.When employed as an air electrode of R-PCECs,a cell with PBCCHf_(0.1) air electrode demonstrates encouraging performances in modes of the fuel cell(FC)and electrolysis(EL)at 600℃:a peak power density of 0.998 W cm^(-2)and a current density of1.613 A cm^(-2)at 1.3 V(with acceptable Faradaic efficiencies).More importantly,the single-cell with PBCCHf_(0.1) air electrode demonstrates good cycling stability,switching back and forth from FC mode to EL mode0.5 A cm^(-2)for 200 h and 50 cycles.
文摘Solid oxide fuel cells(SOFCs)and electrolysis cells(SOECs)are promising energy conversion devices,on whose basis green hydrogen energy technologies can be developed to support the transition to a carbon-free future.As compared with oxygen-conducting cells,the operational temperatures of protonic ceramic fuel cells(PCFCs)and electrolysis cells(PCECs)can be reduced by several hundreds of degrees(down to low-and intermediatetemperature ranges of 400–700C)while maintaining high performance and efficiency.This is due to the distinctive characteristics of charge carriers for proton-conducting electrolytes.However,despite achieving outstanding lab-scale performance,the prospects for industrial scaling of PCFCs and PCECs remain hazy,at least in the near future,in contrast to commercially available SOFCs and SOECs.In this review,we reveal the reasons for the delayed technological development,which need to be addressed in order to transfer fundamental findings into industrial processes.Possible solutions to the identified problems are also highlighted.
基金Project supported by the National Natural Science Foundation of China(51772080,11604088,51706093)Jiangsu Provence Talent Program(JSSCRC2021491)。
文摘Highly active and stable electrocatalysts are mandatory for developing high-performance and longlasting fuel cells.The current study demonstrates a high oxygen reduction reaction(ORR)electrocatalytic activity of a novel spinel-structured LaFe_(2)O_(4)via a self-doping strategy.The LaFe_(2)O_(4)demonstrates excellent ORR activity in a protonic ceramic fuel cell(PCFC)at temperature range of 350-500℃.The high ORR activity of LaFe_(2)O_(4)is mainly attributed to the facile release of oxide and proton ions,and improved synergistic incorporation abilities associated with interplay of multivalent Fe^(3+)/Fe^(2+)and La^(3+)ions.Using LaFe_(2)O_(4)as cathode over proton conducting BaZr_(0.4)Ce_(0.4)Y_(0.2)O_(3)(BZCY)electrolyte,the fuel cell has delivered a high-power density of 806 mW/cm^(2)operating at 500℃.Different spectroscopic and calculations methods such as UV-visible,Raman,X-ray photoelectron spectroscopy and density functional theory(DFT)calculations were performed to screen the potential application of LaFe_(2)O_(4)as cathode.This study would help in developing functional cobalt-free ORR electrocatalysts for low temperature-PCFCs(LT-PCFCs)and solid oxide fuel cells(SOFCs)applications.
基金financially supported by China Post-doctoral Science Foundation(No.2022M710856)Guangzhou Postdoctoral Research Project(No.62104380)+2 种基金the Outstanding Youth Project of Natural Science Foundation of Guangdong Province(No.2022B1515020020)the Funding by Science and Technology Projects in Guangzhou(Nos.202206050003 and 202201010603)Guangdong Engineering Technology Research Center for Hydrogen Energy and Fuel Cells。
文摘Protonic ceramic fuel cells(PCFCs)have been attracting increasing attention because of their advances in high-efficiency power generation in an intermediate-temperature range,as compared to the high-temperature solid oxide fuel cells(SOFCs).The greatest difference between PCFCs and SOFCs is the specific requirement of protonic(H+)conductivity at the PCFC cathode,in addition to the electronic(e^(-))and oxide-ion(O^(2-))conductivity.The development of a triple H^(+)/e^(-)/O^(2-)conductor for PCFC cathode is still challenging.Thus,the most-widely used cathode material is based on the mature e^(-)/O^(2-)conductor.However,this leads to insufficient triple phase boundary(TPB),i.e.,reaction area.Herein,an efficient strategy that uses a~100 nm-thick proton conductive functional layer(La_(0.5)Sr_(0.5)CoO_(3-δ),LSC55)in-between the typical La_(0.8)Sr_(0.2)CoO_(3-δ)cathode(a mature e-/O^(2-)conductor,LS C 82)and B aZr_(0.4)Ce_(0.4)Y_(0.1)Yb_(0.)1O_(3-δ)elec trolyte(11 mm in diameter,20μm in thickness)is proposed to significantly enhance the reaction area.Reasonably,the ohmic resistance and polarization resistance are both decreased by 47%and 62%,respectively,compared with that of PCFCs without the functional layer.The power density of the PCFC with such a functional layer can be raised by up to 2.24 times,superior to those described in previous reports.The enhanced PCFC performances are attributed to the well-built TPB and enhanced reaction area via the functional layer engineering strategy.
基金financially supported by the National Natural Science Foundation of China (No.50872090)Guizhou Province-University Scientific and Technological Cooperation Program (No.[2011]7002)
文摘BaZr1-xScxO3-0.5x (x=0.07,0.10,0.13,0.16) powders were prepared by solid-state reaction method,and ZnO was used as sintering aid.Samples with different amount of ZnO additive were sintered at 1450·C for 6 h in air.Single cubic perovskite phase proton conductors were obtained.Conductivity was measured by electrochemical workstation.It was shown that Sc doping could increase conductivity through enhancing the carrier concentration in the material,but excessive Sc content might decrease the carrier concentration because of its charge compensation.ZnO had an influence on carrier concentration and mobility and affected the electrical conductivity.2 mol% ZnO and 13 mol% ScO1.5 doped sample showed the highest DC conductivity of 3.6×10-3 S·cm-1 tested at 800·C in wet hydrogen atmosphere.
基金financially supported by the National Natural Science Foundation of China (Nos. 22078022, 22178023, 22179007)China Postdoctoral Science Foundation (No. 2021M690379)。
文摘Reversible protonic ceramic cells(RPCCs) show great potential as new-generation energy conversion and storage devices. However, the mature development of RPCCs is seriously hindered by the inactivity and poor stability of air electrodes exposed to concentrated vapor under operating conditions. Herein, we report a high-entropy air electrode with the composition BaCo_(0.2)Fe_(0.2)Zr_(0.2)Sn_(0.2)Pr_(0.2)O_(3-δ)(BCFZSP), which shows integrated electronic, protonic and oxygenic conduction in a single perovskite phase and excellent structural stability in concentrated steam. Such triple conduction can spread the electrochemically active sites of the air electrode to the overall electrode surface, thus optimizing the kinetics of the oxygen reduction and evolution reactions(0.448 Ω cm^(2) of polarization resistance at 550℃). As-prepared RPCCs with a BCFZSP air electrode at 600℃ achieved a peak power density of 0.68 W/cm^(2) in fuel-cell mode and a current density of 0.92 A/cm^(2) under a 1.3 V applied voltage in electrolysis mode. More importantly, the RPCCs demonstrate an encouragingly high stability during 120 h of reversible switching between the fuelcell and electrolysis modes. Given their excellent performance, high-entropy perovskites can be promising electrode materials for RPCCs.
基金funding from the National Natural Science Foundation of China,China(12172104,52102226)the Shenzhen Science and Technology Innovation Commission,China(JCYJ20200109113439837)the Stable Supporting Fund of Shenzhen,China(GXWD2020123015542700320200728114835006)。
文摘A deep-learning-based framework is proposed to predict the impedance response and underlying electrochemical behavior of the reversible protonic ceramic cell(PCC) across a wide variety of different operating conditions.Electrochemical impedance spectra(EIS) of PCCs were first acquired under a variety of opera ting conditions to provide a dataset containing 36 sets of EIS spectra for the model.An artificial neural network(ANN) was then trained to model the relationship between the cell operating condition and EIS response.Finally,ANN model-predicted EIS spectra were analyzed by the distribution of relaxation times(DRT) and compared to DRT spectra obtained from the experimental EIS data,enabling an assessment of the accumulative errors from the predicted EIS data vs the predicted DRT.We show that in certain cases,although the R^(2)of the predicted EIS curve may be> 0.98,the R^(2)of the predicted DRT may be as low as~0.3.This can lead to an inaccurate ANN prediction of the underlying time-resolved electrochemical response,although the apparent accuracy as evaluated from the EIS prediction may seem acceptable.After adjustment of the parameters of the ANN framework,the average R^(2)of the DRTs derived from the predicted EIS can be improved to 0.9667.Thus,we demonstrate that a properly tuned ANN model can be used as an effective tool to predict not only the EIS,but also the DRT of complex electrochemical systems.
基金supported by the Natural Science Foundation of China (No. 21871299)Guangdong Natural Science Funds for Distinguished Young Scholar (No. 2019B151502051)+4 种基金the Fundamental Research Funds for the Central Universities (No.19lgzd21)Guangdong Basic and Applied Basic Research Foundation (No. 2022A1515110991)China Postdocroral Science Foundation (No. 2021M701569)the Open Project of State Key Laboratory of Supramolecular Structure and Materials (Jilin University)the Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University)
文摘Due to the high local concentration of substrates in confined space, porous solid Bronsted acids have been extensively explored for efficient acid-catalyzed reaction. However, the porous structures with strong Bronsted acids lack long-term stability due to chemical hydrolysis. Moreover, the products inhibition effect in confined rigid cavities severely obstructs subsequent catalysis. Here, tubular Bronsted acid catalyst with unique recognition of protons was presented by self-assembly of p H-responsive aromatic amphiphiles. The responsive assembly could mechanically transfer hydrogen ions from low-concentration acidic solution into tubular defined pores, thereby producing effective catalytic activity for Mannich reactions in mildly acidic solution. Notably, the tubular catalyst unfolded into flat sheets upon addition of triethylamine for efficient release of products, which could be recovered by subsequent acidification and the catalytic activity still remained. Therefore, the porous Bronsted acid with reversible assembly provides a new strategy for mass synthesis through increasing conversion times.
基金support from the China Scholarship Council(CSC201807040049)from DTU Energy.The authors would like to thank H.Henriksen for his help with cell testing.
文摘Protonic ceramic electrolysis cell(PCEC)is a promising technology for production of pure dry hydrogen due to the low operating temperature and high efficiency.One of the obstacles for commercialization of PCEC technology is the poor performance and insufficient long-term durability of the oxygen electrode.In this study,we address the above challenge by designing a LaCoO_(3)(LC)catalyst infiltrated porous BaZr_(0.8)Y_(0.2)O_(3)−δ(BZY20)backbone electrode(LC-BZY20).The performance and durability of the LC-BZY20 electrode are investigated on symmetrical cells using electrochemical impedance spectroscopy(EIS).The total electrode polarization resistance(RP)values of the electrode are 0.56,1.24,2.18,and 2.90Ωcm2 in 3vol%humidified synthetic air at 600,550,500,and 450℃,respectively,indicating good electrochemical performance of the LC-BZY20 electrode.Furthermore,the LC-BZY20 electrode displays good stability,without significant performance degradation when tested at 600℃ in 10vol%humidified air for 900h.We further study the influence of oxygen partial pressure(PO_(2))and steam partial pressure(P_(H_(2)O))on the response of the EIS data,and propose a set of chemical and electrochemical processes involved in the steam splitting reaction in the LC-BZY20 electrode.
基金support from the National Key Research&Development Project(2022YFB4002201)National Natural Science Foundation of China(Nos.52172199,52072135,52002121)+1 种基金Hubei Province(2023BAB115)Jiangsu Province(BZ2022027).
文摘Reversible protonic ceramic electrochemical cells(R-PCECs)are ideal,high-effi ciency devices that are environmentally friendly and have a modular design.This paper studies BaFe_(0.6)Zr_(0.1)Y_(0.3)O_(3−δ)(BFZY3)as a cobalt-free perovskite oxygen electrode for high-performance R-PCECs where Y ions doping can increase the concentration of oxygen vacancies with a remarkable increase in catalytic performance.The cell with confi guration of Ni-BZCYYb/BZCYYb/BFZY3 demonstrated promising performance in dual modes of fuel cells(FCs)and electrolysis cells(ECs)at 650℃with low polarization resistance of 0.13Ωcm^(2),peak power density of 546.59 mW/cm^(2)in FC mode,and current density of−1.03 A/cm^(2)at 1.3 V in EC mode.The alternative operation between FC and EC modes for up to eight cycles with a total of 80 h suggests that the cell with BFZY3 is exceptionally stable and reversible over the long term.The results indicated that BFZY3 has considerable potential as an air electrode material for R-PCECs,permitting effi cient oxygen reduction and water splitting.
