Surface manipulation of a triple-conducting cathode for protonic ceramic fuel cells to enhance oxygen reduction activity and CO_(2) tolerance

One of the main obstacles limiting the performance of protonic ceramic fuel cells(PCFCs) is the sluggish kinetics of the oxygen reduction reaction(ORR) at reduced temperatures.Here,the surface manipulation of a triple-conducting cathode BaCe_(0.5)Pr_(0.3)Y_(0.2)O_(3-δ)(BCPY) by an efficient catalyst coating PrNi_(0.5)Co_(0.5)O_(3-δ)(PNC) to enhance the ORR activity and CO_(2) tolerance is reported.The developed PNC-coated BCPY cathode achieves the polarization resistance of 0.25 and 1.00 Ω cm^(2) at 600 and 500 ℃,respectively,approximately 1/5 of that for the pristine BCPY cathode(0.99 and 4.79 Ω cm^(2)),while maintaining an excellent CO_(2) tolerance.The single cell on a BaZr_(0.8)Yb_(0.2)O_(3-δ) electrolyte also exhibits a high peak power density of 0.79 W cm^(-2)at 700 ℃ and a stable operation for 200 h at 600 ℃.Such high ORR activity is mainly attributed to the synergistic effect of BCPY support and PNC nanoparticles.Namely,BCPY provides a tripleconducting path(mainly protons),and PNC nanoparticles facilitates surface oxygen exchange and steam adsorption/desorption processes due to the enriched surface oxygen vacancies.This study will provide a new design strategy for developing high-performance PCFCs cathode.

High-entropy perovskite oxide BaCo_(0.2)Fe_(0.2)Zr_(0.2)Sn_(0.2)Pr_(0.2)O_(3-δ) with triple conduction for the air electrode of reversible protonic ceramic cells

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.

Highly active and durable triple conducting composite air electrode for low-temperature protonic ceramic fuel cells

Protonic ceramic fuel cells(PCFCs)are more suitable for operation at low temperatures due to their smaller activation energy(Ea).Unfortunately,the utilization of PCFC technology at reduced temperatures is limited by the lack of durable and high-activity air electrodes.A lot number of cobalt-based oxides have been developed as air electrodes for PCFCs,due to their high oxygen reduction reaction(ORR)activity.However,cobalt-based oxides usually have more significant thermal expansion coefficients(TECs)and poor thermomechanical compatibility with electrolytes.These characteristics can lead to cell delamination and degradation.Herein,we rationally design a novel cobalt-containing composite cathode material with the nominal composition of Sr_(4)Fe_(4)Co_(2)O_(13)+δ(SFC).SFC is composed of tetragonal perovskite phase(Sr_(8)Fe_(8)O_(23)+δ,I4/mmm,81 wt.%)and spinel phase(Co_(3)O_(4),Fd3m,19 wt.%).The SFC composite cathode displays an ultra-high oxygen ionic conductivity(0.053 S·cm^(-1)at 550℃),superior CO_(2)tolerance,and suitable TEC value(17.01×10^(-6)K^(-1)).SFC has both the O_(2)^(-)/e^(-)conduction function,and the triple conducting(H^(+)/O_(2)^(-)/e^(-))capability was achieved by introducing the protonic conduction phase(BaZr_(0.2)Ce_(0.7)Y_(0.1)O_(3-δ),BZCY)to form SFC+BZCY(70 wt.%:30 wt.%).The SFC+BZCY composite electrode exhibits superior ORR activity at a reduced temperature with extremely low area-specific resistance(ASR,0.677Ω·cm^(2)at 550℃),profound peak power density(PPD,535 mW·cm^(-2)and 1.065 V at 550℃),extraordinarily long-term durability(>500 h for symmetrical cell and 350 h for single cell).Moreover,the composite has an ultra-low TEC value(15.96×10^(-6)K^(-1)).This study proves that SFC+BZCY with triple conducting capacity is an excellent cathode for low-temperature PCFCs.

A comprehensive review of recent progresses in cathode materials for Proton-conducting SOFCs

Solid oxide fuel cells(SOFCs)are widely recognized as efficient energy sources that have the potential to shape the future of energy development.Among various types of SOFCs,the low-temperature operation of protonconducting SOFCs(H–SOFCs)offers distinct advantages for wide commercialization compared to oxygen-ion conducting SOFCs(O–SOFCs).However,the commercialization of H–SOFCs is hindered by several challenges,including slow oxygen reduction kinetics and long-term instability of cathode materials.The electrochemical performance of the cathode system in H–SOFCs is limited by the poor proton conductivity of the cathode material and the scarcity of surface reaction sites.Additionally,the presence of undesirable phases induced by elements such as Cr and CO_(2)adversely affects the chemical stability and catalytic activity of the cathode.Thermal stress arising from the mismatch in coefficient of thermal expansion between the cathode and electrolyte further adds to the challenges.Therefore,this comprehensive review presents underlying mechanisms and potential solutions to overcome the challenges in H–SOFCs,leading to higher efficiency and wider commercialization of H–SOFCs.

K-doped BaCo_(0.4)Fe_(0.4)Zr_(0.2)O_(3−δ) as a promising cathode material for protonic ceramic fuel cells

Slow oxygen reduction reaction(ORR)involving proton transport remains the limiting factor for electrochemical performance of proton-conducting cathodes.To further reduce the operating temperature of protonic ceramic fuel cells(PCFCs),developing triple-conducting cathodes with excellent electrochemical performance is required.In this study,K-doped BaCo_(0.4)Fe_(0.4)Zr_(0.2)O_(3−δ)(BCFZ442)series were developed and used as the cathodes of the PCFCs,and their crystal structure,conductivity,hydration capability,and electrochemical performance were characterized in detail.Among them,Ba_(0.9)K_(0.1)Co_(0.4)Fe_(0.4)Zr_(0.2)O_(3−δ)(K10)cathode has the best electrochemical performance,which can be attributed to its high electron(e^(−))/oxygen ion(O^(2−))/H^(+)conductivity and proton uptake capacity.At 750℃,the polarization resistance of the K10 cathode is only 0.009Ω·cm^(2),the peak power density(PPD)of the single cell with the K10 cathode is close to 1 W·cm^(−2),and there is no significant degradation within 150 h.Excellent electrochemical performance and durability make K10 a promising cathode material for the PCFCs.This work can provide a guidance for further improving the proton transport capability of the triple-conducting oxides,which is of great significance for developing the PCFC cathodes with excellent electrochemical performance.