A robust fluorine-containing ceramic cathode for direct CO_(2) electrolysis in solid oxide electrolysis cells

Stro ntium-doped lanthanum ferrite(LSF)is a potential ceramic cathode for direct CO_(2) electrolysis in solid oxide electrolysis cells(SOECs),but its application is limited by insufficient catalytic activity and stability in CO_(2)-containing atmospheres.Herein,a novel strategy is proposed to enhance the electrolytic performance as well as chemical stability,achieved by doping F into the O-site of the perovskite LSF.Doping F does not change the phase structure but reduces the cell volume and improves the chemical stability in a CO_(2)-rich atmosphere.Importantly,F doping favors oxygen vacancy formation,increases oxygen vacancy concentration,and enhances the CO_(2) adsorption capability.Meanwhile,doping with F greatly improves the kinetics of the CO_(2) reduction reaction.For example,kchem increases by 78%from3.49×10^(-4) cm s^(-1) to 6.24×10^(-4) cm s^(-1),and Dchem doubles from 4.68×10^(-5) cm^(2) s^(-1) to 9.45×10^(-5)cm^(2) s^(-1).Consequently,doping F significantly increases the electrochemical performance,such as reducing R_(p) by 52.2%from 0.226Ωcm^(2) to 0.108Ωcm^(2) at 800℃.As a result,the single cell with the Fcontaining cathode exhibits an extremely high current density of 2.58 A cm^(-2) at 800℃and 1.5 V,as well as excellent durability over 200 h for direct CO_(2) electrolysis in SOECs.

High-temperature electrocatalysis and key materials in solid oxide electrolysis cells

Solid oxide electrolysis cells(SOECs)can convert electricity to chemicals with high efficiency at ~600-900℃,and have attracted widespread attention in renewable energy conversion and storage.SOECs operate in the inverse mode of solid oxide fuel cells(SOFCs)and therefore inherit most of the advantages of SOFC materials and energy conversion processes.However,the external bias that drives the electrochemical process will strongly change the chemical environments in both in the cathode and anode,therefore necessitating careful reconsideration of key materials and electrocatalysis processes.More importantly,SOECs provide a unique advantage of electrothermal catalysis,especially in converting stable low-carbon alkanes such as methane to ethylene with high selectivity.Here,we review the state-of-the-art of SOEC research progress in electrothermal catalysis and key materials and provide a future perspective.

Materials of solid oxide electrolysis cells for H_(2)O and CO_(2) electrolysis:A review

Reliable and economical energy storage technologies are urgently required to ensure sustainable energy supply.Hydrogen(H_(2))is an energy carrier that can be produced environmentfriendly by renewable power to split water(H_(2)O)via electrochemical cells.By this way,electric energy is stored as chemical energy of H_(2),and the storage can be large-scale and economical.Among the electrochemical technologies for H_(2)O electrolysis,solid oxide electrolysis cells(SOECs)operated at temperatures above 500℃have the benefits of high energy conversion efficiency and economic feasibility.In addition to the H_(2)O electrolysis,SOECs can also be employed for CO_(2) electrolysis and H2O–CO_(2) co-electrolysis to produce value-added chemicals of great economic and environmental significance.However,the SOEC technology is not yet fully ready for commercial deployment because of material limitations of the key components,such as electrolytes,air electrodes,and fuel electrodes.As is well known,the reactions in SOEC are,in principle,inverse to the reactions in solid oxide fuel cells(SOFCs).Component materials of SOECs are currently adopted from SOFC materials.However,their performance stability issues are evident,and need to be overcome by materials development in line with the unique requirements of the SOEC materials.Key topics discussed in this review include SOEC critical materials and their optimization,material degradation and its safeguards,future research directions,and commercialization challenges,from both traditional oxygen ion(O_(2)−)-conducting SOEC(O-SOEC)and proton(H^(+))-conducting SOEC(H-SOEC)perspectives.It is worth to believe that H_(2)O or/and CO_(2) electrolysis by SOECs provides a viable solution for future energy storage and conversion.

Novel Perovskite Oxide Hybrid Nanofibers Embedded with Nanocatalysts for Highly Efficient and Durable Electrodes in Direct CO_(2) Electrolysis

The unique characteristics of nanofibers in rational electrode design enable effec-tive utilization and maximizing material properties for achieving highly efficient and sustainable CO_(2) reduction reactions( CO_(2)RRs)in solid oxide elec-trolysis cells(SOECs).However,practical appli-cation of nanofiber-based electrodes faces chal-lenges in establishing sufficient interfacial contact and adhesion with the dense electrolyte.To tackle this challenge,a novel hybrid nanofiber electrode,La_(0.6)Sr_(0.4)Co_(0.15)Fe_(0.8)Pd_(0.05)O_(3-δ)(H-LSCFP),is developed by strategically incorporating low aspect ratio crushed LSCFP nanofibers into the excess porous interspace of a high aspect ratio LSCFP nanofiber framework synthesized via electrospinning technique.After consecutive treatment in 100% H_(2) and CO_(2) at 700°C,LSCFP nanofibers form a perovskite phase with in situ exsolved Co metal nanocatalysts and a high concentration of oxygen species on the surface,enhancing CO_(2) adsorption.The SOEC with the H-LSCFP electrode yielded an outstanding current density of 2.2 A cm^(-2) in CO_(2) at 800°C and 1.5 V,setting a new benchmark among reported nanofiber-based electrodes.Digital twinning of the H-LSCFP reveals improved contact adhesion and increased reaction sites for CO_(2)RR.The present work demonstrates a highly catalytically active and robust nanofiber-based fuel electrode with a hybrid structure,paving the way for further advancements and nanofiber applications in CO_(2)-SOECs.

Orthorhombic Y_(0.95-x)Sr_(x)Co_(0.3)Fe_(0.7)O_(3-δ) anode for oxygen evolution reaction in solid oxide electrolysis cells

Cubic perovskite oxides usually suffer from delamination and Sr^(2+) segregation for catalyzing oxygen evolution reaction (OER) at the anodes of solid oxide electrolysis cells (SOECs). It is crucial to develop alternative and efficient anode materials for SOECs. Herein, a series of novel Y_(0.95-x)Sr_(x)Co_(0.3)Fe_(0.7)O_(3-δ) (YSCF-x) orthorhombic perovskite oxides in the Pnma (62) space group are synthesized as anode materials of SOECs. Physicochemical characterizations and density functional theory calculations reveal that the partial substitution of Y^(3+) by Sr^(2+) increases the oxygen vacancy concentration and mobility as well as improves the electrical conductivity, which contributes to the excellent OER activity of YSCF-x. At 800 °C, the current density of SOEC with YSCF-0.05-Ce0.8Sm0.2O2-δ anode can reach 1.32 A cm^(−2) at 1.6 V, about twice that of SOEC with Y_(0.95-x)Sr_(x)Co_(0.3)Fe_(0.7)O_(3-δ)-Ce_(0.8)Sm_(0.2)O_(2-δ) anode. This work paves a new avenue for the design of advanced anode materials of SOECs.

Degradation of solid oxide electrolysis cells: Phenomena,mechanisms, and emerging mitigation strategies——A review

Solid oxide electrolysis cell(SOEC) is a promising electrochemical device with high efficiency for energy storage and conversion.However,the degradation of SOEC is a significant barrier to commercial viability.In this review paper,the typical degradation phenomena of SOEC are summarized,with great attention into the anodes/oxygen electrodes,including the commonly used and newly developed anode materials.Meanwhile,mechanistic investigations on the electrode/electrolyte interfaces are provided to unveil how the intrinsic factor,oxygen partial pressure pO2,and the electrochemical operation conditions,affect the interracial stability of SOEC.At last,this paper also presents some emerging mitigation strategies to circumvent long-term degradation,which include novel infiltration method,development of new anode materials and engineering of the microstructure.

Exsolved materials for CO_(2)reduction in high-temperature electrolysis cells

Electrochemical reduction of CO_(2)into valuable fuels and chemicals has become a contemporary research area,where the heterogeneous catalyst plays a critical role.Metal nanoparticles supported on oxides performing as active sites of electrochemical reactions have been the focus of intensive investigation.Here,we review the CO_(2)reduction with active materials prepared by exsolution.The fundamental of exsolution was summarized in terms of mechanism and models,materials,and driven forces.The advances in the exsolved materials used in hightemperature CO_(2)electrolysis were catalogued into tailored interfaces,synergistic effects on alloy particles,phase transition,reversibility and electrochemical switching.

Electrochemical performance and stability of Sr-doped LaMnO_(3)-infiltrated yttria stabilized zirconia oxygen electrode for reversible solid oxide fuel cells

Porous Sr-doped lanthanum manganite–yttria stabilized zirconia(LSM–YSZ)oxygen electrode is prepared by an infiltration process for a reversible solid oxide fuel cell(RSOFC).X-ray diffraction and SEM analysis display that perovskite phase LSM submicro particles are evenly distributed in the porous YSZ matrix.Polarization curves and electrochemical impedance spectra are conducted for the RSOFC at 800 and 850C under both SOFC and SOEC modes.At 850℃,the single cell has the maximum power density of~726 mW/cm^(2)under SOFC mode,and electrolysis voltage of 1.35 V at 1 A/cm^(2)under SOEC mode.Fuel cell/water electrolysis cycle shows the cell has good performance stability during 6 cycles,which exhibits the LSM–YSZ oxygen electrode has high electrochemical performance and good stability.The results suggest that netw ork-like LSM–YSZ electrode made by infiltration process could be a promising oxygen electrode for high temperature RSOFCs.

Enhancing cathode performance for CO2 electrolysis with Ce0.9M0.1O2-δ（M=Fe, Co, Ni） catalysts in solid oxide electrolysis cell

Electrochemical conversion with solid oxide electrolysis cells is a promising technology for CO2 utilization and simultaneously store renewable energy.In this work,Ce0.9M0.1O2-δ(CeM,M=Fe,Co,Ni)catalysts are infiltrated into La0.6Sr0.4Cr0.5Fe0.5O3-δ-Gd0.2Ce0.8O2-δ(LSCr Fe-GDC)cathode to enhance the electrochemical performance for CO2 electrolysis.CeCo-LSCrFe-GDC cell obtains the best performance with a current density of 0.652 A cm^-2,followed by CeFe-LSCrFe-GDC and CeNi-LSCrFe-GDC cells with the value of 0.603 and 0.535 A cm^-2,respectively,about 2.44,2.26 and 2.01 times higher than that of the LSCrFe-GDC cell at1.5 V and 800℃.Electrochemical impedance spectra combined with distributions of relaxed times analysis shows that both CO2 adsorption process and the dissociation of CO2 at triple phase boundaries are accelerated by Ce M catalysts,while the latter is the key rate-determining step.

Co/Fe oxide and Ce_(0.8)Gd_(0.2)O_(2-δ) composite interlayer for solid oxide electrolysis cell

A composite interlayer comprised of gadolinia doped ceria（GDC） and Co/Fe oxide was prepared and investigated for solid oxide electrolysis cell with yttrium stabilized zirconia（YSZ） electrolyte and LaSrCoFeO（LSCF） anode. The interlayer was constructed of a base layer of GDC and a top layer of discrete CoO/FeCoOparticles. The presence of the GDC layer drastically alleviated the undesired reactions between LSCF and YSZ, and the presence of Co/Fe oxide led to further performance improvement. At 800 °C and 45% humidity, the cell with 70% Co/Fe-GDC interlayer achieved 0.98 A/cmat 1.18 V, 14% higher than the cell without Co/Fe oxide. Electrochemical impedance spectroscopy（EIS） revealed that with higher Co/Fe content, both the ohmic resistance and the polarization resistance of the cell were reduced. It is suggested that Co/Fe oxide can react with the Sr species segregated from LSCF and Sr（Co,Fe）O, a compound with high catalytic activity and electronic conductivity. The Sr-capturing ability of Co/Fe oxide in combination with the Sr-blocking ability of GDC layer can effectively suppress the undesired reaction between LSCF and YSZ, and consequently improve the cell performance.

Advances in component and operation optimization of solid oxide electrolysis cell

Considering the earth powered by intermittent renewable energy in the coming future,solid oxide electrolysis cell(SOEC)will play an indispensable role in efficient energy conversion and storage on demand.The thermolytic and kinetic merits grant SOEC a bright potential to be directly integrated with electrical grid and downstream chemical synthesis process.Meanwhile,the scientific community are still endeavoring to pursue the SOEC assembled with better materials and operated at a more energy-efficient way.In this review article,at cell level,we focus on the recent development of electrolyte,cathode,anode and buffer layer materials for both steam and CO_(2)electrolysis.On the other hand,we also discuss the next generation SOEC operated with the assistant of other fuels to further reduce the energy consumption and enhance the productivity of the electrolyzer.And stack level,the sealant,interconnect and stack operation strategies are collectively covered.Finally,the challenges and future research direction in SOECs are included.

Parametric Study of Operating Conditions on Performances of a Solid Oxide Electrolysis Cell

The operating conditions greatly affect the electrolysis performance and temperature distribution of solid oxide electrolysis cells(SOECs).However,the temperature distribution in a cell is hard to determine by experiments due to the limitations of in-situ measurement methods.In this study,an electrochemical-flow-thermal coupling numerical cell model is established and verified by both current-voltage curves and electrochemical impedance spectroscopy(EIS)results.The electrolysis performance and temperature distribution under different working conditions are numerically analyzed,including operating temperature,steam and hydrogen partial pressures in the fuel gas,inlet flow rate and inlet temperature of fuel gas.The results show that the electrolysis performance improves with increasing operating temperature.Increasing steam partial pressure improves electrolysis performance and temperature distribution uniformity,but decreases steam conversion rate.An inappropriately low hydrogen partial pressure reduces the diffusion ability of fuel gas mixture and increases concentration impedance.Although increasing the flow rate of fuel gas improves electrolysis performance,it also reduces temperature distribution uniformity.A lower airflow rate benefits temperature distribution uniformity.The inlet temperature of fuel gas has little influence on electrolysis performance.In order to obtain a more uniform temperature distribution,it is more important to preheat the air than the fuel gas.

Solid Oxide Electrolysis of H_(2)O and CO_(2) to Produce Hydrogen and Low‑Carbon Fuels

Solid oxide electrolysis cells(SOECs)including the oxygen ion-conducting SOEC(O-SOEC)and the proton-conducting SOEC(H-SOEC)have been actively investigated as next-generation electrolysis technologies that can provide high-energy conversion efficiencies for H_(2)O and CO_(2) electrolysis to sustainably produce hydrogen and low-carbon fuels,thus providing higher-temperature routes for energy storage and conversion.Current research has also focused on the promotion of SOEC critical components to accelerate wider practical implementation.Based on these investigations,this perspective will summarize the most recent progress in the optimization of electrolysis performance and long-term stability of SOECs,with an emphasis on material developments,technological approaches and improving strategies,such as nano-composing,surface/interface engineering,doping and in situ exsolution.Existing technical challenges are also analyzed,and future research directions are proposed to achieve SOEC technical maturity and economic feasibility for diverse conversion applications.

Thermodynamic Analysis of Solid Oxide Fuel Cell Based Combined Cooling,Heating,and Power System Integrated with Solar-Assisted Electrolytic Cell

Syngas fuel such as hydrogen and carbon monoxide generated by solar energy is a promising method to use solar energy and overcome its fluctuation effectively.This study proposes a combined cooling,heating,and power system using the reversible solid oxide fuel cell assisted by solar energy to produce solar fuel and then supply energy products for users during the period without solar radiation.The system runs a solar-assisted solid oxide electrolysis cell mode and a solid oxide fuel cell mode.The thermodynamic models are constructed,and the energetic and exergetic performances are analyzed.Under the design work conditions,the SOEC mode’s overall system energy and exergy efficiencies are 19.0%and 20.5%,respectively.The electrical,energy and exergy efficiencies in the SOFC mode are 51.4%,71.3%,and 45.2%,respectively.The solid oxide fuel cell accounts for 60.0%of total exergy destruction,caused by the electrochemical reactions’thermodynamic irreversibilities.The increase of operating temperature of solid oxide fuel cell from 800℃to 1050℃rises the exergy and energy efficiencies by 11.3%and 12.3%,respectively.Its pressure from 0.2 to 0.7 MPa improves electrical efficiency by 13.8%while decreasing energy and exergy efficiencies by 5.2%and 6.0%,respectively.

Energy,Exergy,and Exergoeconomic Analysis of Solar-Driven Solid Oxide Electrolyzer System Integrated with Waste Heat Recovery for Syngas Production

Syngas fuel generated by solar energy integrating with fuel cell technology is one of the promising methods for future green energy solutions to carbon neutrality.This paper designs a novel solar-driven solid oxide electrolyzer system integrated with waste heat for syngas production.Solar photovoltaic and parabolic trough collecter together drive the solid oxide electrolysis cell to improve system efficiency.The thermodynamic models of components are established,and the energy,exergy,and exergoeconomic analysis are conducted to evaluate the system’s performance.Under the design work conditions,the solar photovoltaic accounts for 88.46%of total exergy destruction caused by its less conversion efficiency.The exergoeconomic analysis indicates that the fuel cell component has a high exergoeconomic factor of 89.56%due to the large capital investment cost.The impacts of key parameters such as current density,operating temperature,pressure and mole fraction on system performances are discussed.The results demonstrate that the optimal energy and exergy efficiencies are achieved at 19.04%and 19.90%when the temperature,pressure,and molar fraction of H_(2)O are 1223.15 K,0.1 MPa,and 50%,respectively.

Development of catalytic combustion and CO_(2)capture and conversion technology

Changes are needed to improve the efficiency and lower the CO_(2)emissions of traditional coal-fired power generation,which is the main source of global CO_(2)emissions.The integrated gasification fuel cell(IGFC)process,which combines coal gasification and high-temperature fuel cells,was proposed in 2017 to improve the efficiency of coal-based power generation and reduce CO_(2)emissions.Supported by the National Key R&D Program of China,the IGFC for nearzero CO_(2)emissions program was enacted with the goal of achieving near-zero CO_(2)emissions based on(1)catalytic combustion of the flue gas from solid oxide fuel cell(SOFC)stacks and(2)CO_(2)conversion using solid oxide electrolysis cells(SOECs).In this work,we investigated a kW-level catalytic combustion burner and SOEC stack,evaluated the electrochemical performance of the SOEC stack in H2O electrolysis and H2O/CO_(2)co-electrolysis,and established a multiscale and multi-physical coupling simulation model of SOFCs and SOECs.The process developed in this work paves the way for the demonstration and deployment of IGFC technology in the future.

A highly active and stable Sr_(2)Fe_(1.5)Mo(0.5)O_(6)‑δ‑Ce_(0.8)Sm_(0.2)O_(1.95)ceramic fuel electrode for efficient hydrogen production via a steam electrolyzer without safe gas

High temperature steam(H_(2)O)electrolysis via a solid oxide electrolysis cell is an efficient way to produce hydrogen(H_(2))because of its high energy conversion efficiency as well as simple and green process,especially when the electrolysis process is combined with integrated gasification fuel cell technology or derived by renewable energy.However,about 60%-70%of the electricity input is consumed to overcome the large oxygen potential gradient but not for electrolysis to split H_(2)O to produce H_(2)due to the addition of safe gas such as H_(2)in the fuel electrode.In this work,Sr_(2)Fe_(1.5)Mo_(0.5)O_(6)-δ-Ce_(0.8)Sm_(0.2)O_(1.95)(SFM-SDC)ceramic composite material has been developed as fuel electrode to avoid the use of safe gas,and the open circuit voltage(OCV)has been effectively lowered from 1030 to 78 mV when the feeding gas in the fuel electrode is shifted from 3%H_(2)O-97%H_(2)to 3%H_(2)O-97%N_(2),reasonably resulting in a significantly increased electrolysis efficiency.In addition,it is also demonstrated that the electrolysis current density is greatly enhanced by increasing the humidity in the fuel electrode and the working temperature.A considerable electrolysis current density of−0.54 A/cm^(2)is obtained at 800°C and 0.4 V for the symmetrical electrolyzer by exposing SFM-SDC fuel electrode to 23%H_(2)O-77%N_(2),and durability test at 800°C for 35 h demonstrates a relatively stable electrochemical performance for steam electrolysis under the same operation condition without safe gas and a constant electrolysis current density of−0.060 A/cm2.Our findings achieved in this work indicate that SFM-SDC is a highly promising fuel electrode for steam electrolysis.

In-situ exsolution of cobalt nanoparticles from La_(0.5)Sr_(0.5)Fe_(0.8)Co_(0.2)O_(3-δ) cathode for enhanced CO_(2) electrolysis performance

Solid oxide electrolysis cell(SOEC)is a promising technology for CO_(2) conversion and renewable energy storage with high efficiency.It is highly desirable to develop catalytically active cathodes for CO_(2) electrolysis.Herein,cathode materials with different structural stabilities are designed by Nb substitution on La_(0.5)Sr_(0.5)Fe_(0.8)Co_(0.2)O_(3-δ)(LSFC82)to obtain La_(0.5)Sr_(0.5)Fe_(0.7)Co_(0.2)Nb_(0.1)O_(3-δ)(LSFCN721)and La_(0.5)Sr_(0.5)Fe_(0.8)Co_(0.1)Nb_(0.1)O_(3-δ)(LSFCN811),respectively.LSFC82-Sm_(0.2)Ce_(0.8)O_(2-δ)(SDC)cathode with inferior structural stability(ability to maintain the structure)shows desirable CO_(2) electrolysis performance with the generated current density of 1.80 A cm^(-2)2 at 1.6 V and stable performance during 110 h operation at 1.2 V and 800℃.However,LSFC82 particles are collapsed into pieces after stability test with the generation of Co nanoparticles simultaneously.The frameworks of LSFCN721 and LSFCN811 particles maintain well because of the high-valent niobium,but Co exsolution,ox-ygen vacancy content and the corresponding CO_(2) electrolysis performance are restricted.This work confirms that Co nanoparticles can be exsolved from LSFC82-SDC cathode during CO_(2) electrolysis,providing references for constructing metallic nanoparticles decorated-perovskite cathodes for SOECs.

Preparation of Sr_2Fe_(1-x)Sc_xMoO_(6-δ) nanopowders and its electrical conductivity

Double-perovskite Sr2Fe1-xScxMoO6-δ （x=0, 0.05, 0.1, 0.2, 0.3, 0.4） powders applied to the cathode of solid oxide electrolysis cells were synthesized by the sol-gel citrate combustion method. Initial powders were calcined at different temperatures under different atmosphere （air, H2（4 vol.%）/Ar）, and the effects of the preparation process on the structure and the morphology of the powders were investigated by thermal analysis （TG/DSC）, X-ray diffraction （XRD）, scanning electron microscopy （SEM） and surface area analysis. The electric conductiv-ity of the materials was measured by electrochemical work station using wafers prepared by dry pressing. It was found that the formation of perovskite structure was related to the content of Sc and combustion improver （NH4NO3）, pH value, calcining temperature and atmosphere. A single perovskite phase of Sr2Fe1-xScxMoO6-δ could be formed after 3 h calcining in reducing atmosphere of H2 （4 vol.%）/Ar at 1100 oC. The electrical property indicated that, this material had a potential to be used in medium/high temperature solid oxide fuel cells or electrolysis cells.