A general descriptor for guiding the electrolysis of CO_(2)in molten carbonate

Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.

Electrochemical preparation of the Fe-Ni36 Invar alloy from a mixed oxides precursor in molten carbonates

The Fe-Ni36 alloy was prepared via the one-step electrolysis of a mixed oxides precursor in a molten Na2CO3-K2CO3 eutectic melt at 750℃,where porous Fe_(2)O_(3)-NiO pellets served as the cathode and the Ni10 Cu11 Fe alloy was an inert anode.During the electrolysis,Ni O was preferentially electro-reduced to Ni,then Fe_(2)O_(3)was reduced and simultaneously alloyed with nickel to form the Fe-Ni36 alloy.Different cell voltages were applied to optimize the electrolytic conditions,and a relatively low energy consumption of 2.48 k W·h·kg^(-1) for production of Fe Ni36 alloy was achieved under 1.9 V with a high current efficiency of 94.6%.The particle size of the alloy was found to be much smaller than that of the individual metal.This process provides a low-carbon technology for preparing the Fe-Ni36 alloy via molten carbonates electrolysis.

The capacitive performances of carbon obtained from the electrolysis of CO_(2) in molten carbonates: Effects of electrolysis voltage and temperature

The electrochemical reduction of CO2 to capacitive carbon in molten Li2 CO3–Na2 CO3–K2 CO3 is an effective strategy for capturing and utilizing CO2. This paper reports the effects of the cell voltages and operating temperatures(450–650 °C) of the molten salt electrolysis on the capacitive performance of electrolytic carbon. The electrolytic carbon delivers excellent specific capacitance when the cell voltage is 4.5 V and the temperature of molten salt is 450 °C. The carbon obtained at 450 °C and under 4.5 V delivers a specific capacitance of 550 F g^(-1) at 0.2 A g^(-1) in 1 M aqueous H2 SO4, and the capacity retention rate is73% after 10000 cycles. The specific capacitance of the electrolytic carbon increases as the electrolysis temperature decreases, and the optimal cell voltage is 4.5 V.

MICROSTRUCTURE CHARACTERIZATION OF LiCoO_2 COATINGS FOR MOLTEN CARBONATE FUEL CELLS COMPONENTS

The sol-gel process, sing aqueous solutions, is used for dip coating ontosubstrates of 316L stainless steel. A suitable coating of Li CoO_2 is achieved by varying thethickness and heat treating at 650 deg C for 3 h. Thermal analysis, X-ray diffraction analysis andSEM are carried out to characterize the microstructure of the coatings. The results show that thecoating transforms from an amorphous gel to crystalline phases above 350 deg C, and show a porousstructure. The phase transition mechanism is discussed.

Study and performance test of 10 kW molten carbonate fuel cell power generation system

The use of high-temperature fuel cells as a power technology can improve the efficiency of electricity generation and achieve near-zero emissions of carbon dioxide.This work explores the performance of a 10 kW high-temperature molten carbonate fuel cell.The key materials of a single cell were characterized and analyzed using X-ray diffraction and scanning electron microscopy.The results show that the pore size of the key electrode material is 6.5 lm and the matrix material is a-LiAlO_(2).Experimentally,the open circuit voltage of the single cell was found to be 1.23 V.The current density was greater than 100 mA/cm^(2)at an operating voltage of 0.7 V.The 10 kW fuel cell stack comprised 80 single fuel cells with a total area of 2000 cm^(2)and achieved an open circuit voltage of greater than 85 V.The fuel cell stack power and current density could reach 11.7 kW and 104.5 mA/cm2 at an operating voltage of 56 V.The influence and long-term stable operation of the stack were also analyzed and discussed.The successful operation of a 10 kW high-temperature fuel cell promotes the large-scale use of fuel cells and provides a research basis for future investigations of fuel cell capacity enhancement and distributed generation in China.

Advance on Molten Carbonate Fuel Cell and Research on Some Key Problems

The paper is a summary of researches on molten carbonate fuel cell. On the same time, several key technology difficulties are discussed. Combining with our recent studies, the accessements to these problems are given out and they will be references for future works.

Performance Evaluation of a Molten Carbonate Fuel Cell-Graphene Thermionic Converter-Thermally Regenerative Electrochemical Cycles Hybrid System

A combined system model is proposed including a molten carbonate fuel cell(MCFC),a graphene thermionic converter(GTIC)and thermally regenerative electrochemical cycles(TRECs).The expressions for power output,energy efficiency of the subsystems and the couple system are formulated by considering several irreversible losses.Energy conservation equations between the subsystems are achieved leaned on the first law of thermodynamics.The optimum operating ranges for the combined system are determined compared with the MCFC system.Results reveal that the peak power output density(POD)and the corresponding energy efficiency are 28.22%and 10.76%higher than that of the single MCFC system,respectively.The effects of five designing parameters on the power density and energy efficiency of the MCFC/GTIC/TRECs model are also investigated and discussed.

A Reliable Reference Electrode in Molten Carbonate and Its Applications

A Ag|AgCl reference electrode which can be used in molten carbonate media has been described in this paper.It consists of a silver wire immersed in a solution of AgCl(1mol%) in (Li 0.62 ,K 0.38 ) 2CO 3,with a zirconia junction.The main properties of reference electrode,such as reproducibility ,stability and reversibility, were checked.The results have demonstrated that the reference electrode is reliable.With such reference electrode catalysis of various electrode materials to oxygen reduction in molten alkali carbonate media was investigated.It is found that as catalysts for oxygen reduction oxidized nickel niobium alloy is superior to nickel oxide.

Hardware Materials in Molten Carbonate Fuel Cell:A Review

The high-temperature molten carbonate fuel cell is an ultra-clean and highly efficient power generator. It is operated at - 550-650 ℃, which is considered optimal in facilitating fast fuel cell reaction kinetics, utilizing waste heat efficiently, and allowing use of commercial construction materials. Commercial MW-size （mega watt） power plants of FuelCell Energy products have already been deployed worldwide. Metallic hardware materials are extensively utilized and may experience high-temperature reducing and oxidizing atmospheres in the presence of molten alkali carbonate electrolyte. Material selections are founded on many decades of focused research and development and field experience. Results to date show that the baseline stack module materials meet 5-year life goal and BOP （balance of plant） construction materials meet 20-year life goal. Material durability is well understood, and solutions are available to further extend the durability. This paper will review hardware materials experience and development approaches that would further reduce cost and extend life.

Multi-objective optimization of molten carbonate fuel cell system for reducing CO2 emission from exhaust gases

The aim of this paper is to investigate the implementation of a molten carbonate fuel cell （MCFC） as a CO2 separator. By applying multi-objective optimization （MOO） using the genetic algorithm, the optimal values of operating load and the corresponding values of objective functions are obtained. Objective functions are minimiza- tion of the cost of electricity （COE） and minimization of CO2 emission rate. CO2 tax that is accounted as the pollution-related cost, transforming the environmental objective to the cost function. The results show that the MCFC stack which is fed by the syngas and gas turbine exhaust, not only reduces CO2 emission rate, but also produces electricity and reduces environmental cost of the system.

The Corrosion Behavior of Ni-Y Binary Alloys in Air and in Molten (0.62Li,0.38K)_2CO_3 Mixture at 650℃

The corrosion behavior of pure Ni and of binary Ni-Y alloys containing 1wt%,3wt%,5wt% Y,respectively,was investigated in air and in the eutectic (0.62Li,0.38K)2CO3 mixture at 650 ℃.The alloys are two-phase composed of γ-Ni solid solution and intermetallic compound Ni17Y2.The experimental results indicated that the corrosion of Ni-Y alloys in air and in molten salts,respectively,produced an external NiO scale with a small amount of Y2O3 and an internal oxidation region composed of Ni and Y2O3 resulting from the oxidation of the intermetallic phase Ni17Y2.The presence of yttrium in the alloy had a positive effect on the lithiation reaction of NiO during immersion in the melt.

Anodic Oxidation of Nickel in Molten(Li_(0.62),K_(0.38))_2CO_3

The anodic oxidation of nickel in molten (Li 0.62 ,K 0.38 ) 2CO 3 was investigated by means of cyclic voltammetry, X ray diffraction and X ray photoelectron spectroscopy. The results indicate that two reactions are involved in the anodic process: one is Ni+O 2- =NiO+2e -, the other reaction is Ni(Ⅱ)=Ni(Ⅲ)+e -.

Catalytic action of rare earth oxide(La_(2)O_(3),CeO_(2),Pr_(6)O_(11))on electrochemical oxidation of activated carbon in molten KOH-NaOH

The oxidation of anode carbon fuel directly affects the electrochemical performance of molten hydroxide direct carbon fuel cell(MHDCFC).In general,the anode carbon fuel can be oxidized at high temperature,thus the direct carbon fuel cell(DCFC)can show great electrochemical performance.In this study,rare earth oxides(La_(2)O_(3),CeO_(2),Pr_(6)O_(11))were prepared by the method of precipitation.Activated carbon was prepared by pretreatment of lignite.Rare earth oxides and activated carbon were mixed as anode carbon fuel,and rare earth oxides were used to catalyze the electrochemical oxidation of anode carbon fuel.The results show that CeO_(2)has better electrocatalytic activity compared with La_(2)O_(3)and Pr_(6)O_(11) in the MHDCFC.The electrochemical test results show that the current density(at 0.4 V)increases from 81.02 to 112.90 mA/cm^(2)and the maximum power density increases from 34.78 to 47.05 mW/cm^(2)at 450℃,when the mass fraction of CeO_(2)is increased from 0 to 40%.When the mass fraction of CeO_(2)is 30%,the current density(82.55 mA/cm^(2)at 0.4 V)at 400℃is higher than that(81.02 mA/cm^(2)at 0.4 V)without CeO_(2)at 450℃.The electrochemical oxidation mechanism of CeO_(2)catalyzed anode carbon fuel is discussed.