Pulsed electrolysis of carbon dioxide by large-scale solid oxide electrolytic cells for intermittent renewable energy storage

CO_(2) electrolysis with solid oxide electrolytic cells(SOECs)using intermittently available renewable energy has potential applications for carbon neutrality and energy storage.In this study,a pulsed current strategy is used to replicate intermittent energy availability,and the stability and conversion rate of the cyclic operation by a large-scale flat-tube SOEC are studied.One hundred cycles under pulsed current ranging from -100 to -300 mA/cm^(2) with a total operating time of about 800 h were carried out.The results show that after 100 cycles,the cell voltage attenuates by 0.041%/cycle in the high current stage of−300 mA/cm^(2),indicating that the lifetime of the cell can reach up to about 500 cycles.The total CO_(2) conversion rate reached 52%,which is close to the theoretical value of 54.3% at -300 mA/cm^(2),and the calculated efficiency approached 98.2%,assuming heat recycling.This study illustrates the significant advantages of SOEC in efficient electrochemical energy conversion,carbon emission mitigation,and seasonal energy storage.

Determining the Boundary of Molten Electrolyte and Aluminum in Electrolytic Cells by Detecting Their Vertical Distribution of Potential

Aluminum production is a high energy consumption process so that maintaining fundamental compositions in balance and optimal conditions are essential.The molten electrolyte and melted aluminum are primary materials and their boundary needs to be monitored from time to time.An automatic measurement technic is presented in the paper to substitute for the traditional manual measurement work that is dull,poor efficiency and dangerous for operators.The boundary forming mechanism is analyzed,the vertical profile of electric potential is simulated,an automatic instrument is developed to sense the potential distribution,and a strategy is provided to identify the boundary according to the potential curves.Finally,some practical results are compared with manual measurements,which shows good consistency.

Optimization of operating conditions and structure parameters of zinc electrolytic cell based on numerical simulation for electrolyte flow

The physical and mathematical model of an operating electrowinning cell was established, and the flow of electrolyte was numerically simulated by the commercial software Fluent. The results indicate that there are two circulations at the surface flow where part of electrolyte backflows to the inlet from the side of cell, and the rest flows directly to the outlet, and the separation of two circulations with opposite direction occurs at the 20th pair of anode-cathode. This phenomenon was observed in the real operation. The electrolyte flows into the space between anode and cathode from the side portion of the cell. Meanwhile, the interelectrode effective flow rate （IEFR） is put forward to describe quantitively the flow field characteristics and is defined as the ratio of electrolyte flow between the anode and cathode to the total flow area. The influences of structure parameters and operating conditions on IEFR, such as the inlet angle, the volumetric flow rate, the inlet position and the height of steel baffles were simulated. The inlet position has a significant influence on the IEFR and its optimal value is 0.9 m below free surface. The inlet angle should be in the range from -10° to 10°. IEFR is in linear proportion with the volumetric flow rate, and the height of the steel baffle has little influence on the flow field.

Recent developments in electrocatalysts and future prospects for oxygen reduction reaction in polymer electrolyte membrane fuel cells

The main difficulty in the extensive commercial use of polymer electrolyte membrane fuel cells （PEMFCs） is the use of noble metals such as Pt-based electrocatalyst at the cathode, which is essential to ease the oxygen reduction reaction （ORR） in fuel cells （FCs）. To eliminate the high loading of Pt-based electrocatalysts to minimize the cost, extensive study has been carried out over the previous decades on the non-noble metal catalysts. Development in enhancing the ORR performance of FCs is mainly due to the doped carbon materials, Fe and Co-based electrocatalysts, these materials could be considered as probable substitutes for Pt-based catalysts. But the stability of these non-noble metal electrocatalysts is low and the durability of these metals remains unclear. The three basic reasons of instability are： （i） oxidative occurrence by H2O2, （ii） leakage of the metal site and （iii） protonation by probable anion adsorption of the active site. Whereas leakage of the metal site has been almost solved, more work is required to understand and avoid losses from oxidative attack and protonation. The ORR performance such as stability tests are usually run at low current densities and the lifetime is much shorter than desired need. Therefore, improvement in the ORR activity and stability afe the key issues of the non-noble metal electrocatalyst. Based on the consequences obtained in this area, numerous future research directions are projected and discussed in this paper. Hence, this review is focused on improvement of stability and durability of the non-noble metal electrocatalyst.

Multi-objective optimization of the cathode catalyst layer micro-composition of polymer electrolyte membrane fuel cells using a multi-scale,two-phase fuel cell model and data-driven surrogates

Polymer electrolyte membrane fuel cells(PEMFCs)are considered a promising alternative to internal combustion engines in the automotive sector.Their commercialization is mainly hindered due to the cost and effectiveness of using platinum(Pt)in them.The cathode catalyst layer(CL)is considered a core component in PEMFCs,and its composition often considerably affects the cell performance(V_(cell))also PEMFC fabrication and production(C_(stack))costs.In this study,a data-driven multi-objective optimization analysis is conducted to effectively evaluate the effects of various cathode CL compositions on Vcelland Cstack.Four essential cathode CL parameters,i.e.,platinum loading(L_(Pt)),weight ratio of ionomer to carbon(wt_(I/C)),weight ratio of Pt to carbon(wt_(Pt/c)),and porosity of cathode CL(ε_(cCL)),are considered as the design variables.The simulation results of a three-dimensional,multi-scale,two-phase comprehensive PEMFC model are used to train and test two famous surrogates:multi-layer perceptron(MLP)and response surface analysis(RSA).Their accuracies are verified using root mean square error and adjusted R^(2).MLP which outperforms RSA in terms of prediction capability is then linked to a multi-objective non-dominated sorting genetic algorithmⅡ.Compared to a typical PEMFC stack,the results of the optimal study show that the single-cell voltage,Vcellis improved by 28 m V for the same stack price and the stack cost evaluated through the U.S department of energy cost model is reduced by$5.86/k W for the same stack performance.

Recent research progress on quasi-solid-state electrolytes for dye-sensitized solar cells

Dye-sensitized solar cells （DSSCs） are the most promising, low cost and most extensively investigated solar cells. They are famous for their clean and efficient solar energy conversion. Nevertheless this, long-time sta- bility is still to be acquired. In recent years research on solid and quasi-solid state electrolytes is extensively in- creased. Various quasi-solid electrolytes, including composites polymer electrolytes, ionic liquid electrolytes, thermoplastic polymer electrolytes and thermosetting polymer electrolytes have been used. Performance and stability of a quasi-solid state electrolyte are between liquid and solid electrolytes. High photovoltaic performances of QS-DSSCs along better long-term stability can be obtained by designing and optimizing quasi-solid electrolytes. It is a prospective candidate for highly efficient and stable DSSCs.

Study on Influencing Factors of Methane Production Efficiency of Microbial Electrolytic Cell with CO_(2) as Carbon Source

Reducing CO_(2) to produce methane through microbial electrolytic cell(MEC)is one of the important methods of CO_(2) resource utilization.In view of the problem of low methanogenesis rate and weak CO_(2) conversion rate in the reduction process,theflowfield environment of the cathode chamber is changed by changing the upper gas cir-culation rate and the lower liquid circulation rate of the cathode chamber to explore the impact on the reactor startup and operation and products.The results showed that under certain conditions,the CO_(2) consumption and methane production rate could be increased by changing the upper gas recirculation rate alone,but the increase effect was not obvious,but the by-product hydrogen production decreased significantly.Changing the lower liquid circulation rate alone can effectively promote the growth of biofilm,and change the properties of biofilm at the later stage of the experiment,with the peak current density increased by 16%;The methanogenic rate decreased from the peak value of 0.561 to 0.3 mmol/d,and the CO_(2) consumption did not change signifi-cantly,which indicated that CO_(2) was converted into other organic substances instead of methane.The data after coupling the upper gas circulation rate with the lower liquid circulation rate is similar to that of only changing the lower liquid circulation rate,but changing the upper gas circulation rate can alleviate the decline of methane pro-duction rate caused by the change of biofilm properties,which not only improves the current density,but also increases the methane production rate by 0.05 mmol/d in the stable period.This study can provide theoretical and technical support for the industrial application scenario offlowfield regulation intervention of microbial elec-trolytic cell methanogenesis.

Effects of Freeze/Thaw Cycles and Gas Purging Method on Polymer Electrolyte Membrane Fuel Cells

At subzero temperature, the startup capability and performance of polymer electrolyte membrane fuel cell PEMFC deteriorates markedly. The object of this work is to study the degradation mechanism of key compo- nents of PEMFC—membrane-electrode assembly MEA and seek feasible measures to avoid degradation. The ef- fect of freezethaw cycles on the structure of MEA is investigated based on porosity and SEM measurement. The performance of a single cell was also tested before and after repetitious freezethaw cycles. The experimental results indicated that the performance of a PEMFC decreased along with the total operating time as well as the pore size distribution shifting and micro configuration changing. However, when the redundant water had been removed by gas purging, the performance of the PEMFC stack was almost resumed when it experienced again the same subzero temperature test. These results show that it is necessary to remove the water in PEMFCs to maintain stable per- formance under subzero temperature and gas purging is proved to be the effective operation.

Designing physical experiment about characters of fuel cells

Currently, proton exchange membrane fuel cells are the most widely used fuel cell technology, In this article the function of fuel cells is briefly introduced. Certain characters of fuel cells are investigated through measuring the relation between electric current, voltage and product. A series of physics experiments using fuel cells is designed.

Atomic layer deposition of ultrathin layered TiO_2 on Pt/C cathode catalyst for extended durability in polymer electrolyte fuel cells

This study shows the preparation of a TiO2 coated Pt/C（TiO2/Pt/C） by atomic layer deposition（ALD）,and the examination of the possibility for TiO2/Pt/C to be used as a durable cathode catalyst in polymer electrolyte fuel cells（PEFCs）. Cyclic voltammetry results revealed that TiO2/Pt/C catalyst which has 2 nm protective layer showed similar activity for the oxygen reduction reaction compared to Pt/C catalysts and they also had good durability. TiO2/Pt/C prepared by 10 ALD cycles degraded 70% after 2000 Accelerated degradation test, while Pt/C corroded 92% in the same conditions. TiO2 ultrathin layer by ALD is able to achieve a good balance between the durability and activity, leading to TiO2/Pt/C as a promising cathode catalyst for PEFCs. The mechanism of the TiO2 protective layer used to prevent the degradation of Pt/C is discussed.

Activities of FeO in CaO-SiO2-Al2O3-MgO-FeO slags

Activities of FeO in CaO-SiO2-Al2O3-MgO-FeO slags were determined at 1673 K by electrochemical of the solid electrolyte cell： Mo [Mo＋MoOu[ZrO2（MgO）[Fe＋（CaO-SiO2-Al2O3-MgO-FeO）＋Ag[Fe. The influences of slag compositions and basicity on FeO activities were analyzed. The results reveal that, for slags of fixed （%CaO）/（%SiO2） ratio, MgO and Al2O3 content, there was an increase of FeO activities with increase of FeO content. For slags with constant {（%CaO）＋ （%MgO）}/（%SiO2） ratio, fixed FeO and A1203 content, FeO activities decreased when MgO content increased from 5% to 10%, and increased with the increase of MgO content when it was over 10%. The FeO activities increased when （%CaO）/（%SiO2） ratio changed from 1.03 to 1.30 in the slags of constant MgO, FeO and Al2O3 content.

Carbon matrix effects on the micro-structure and performance of Pt nanowire cathode prepared by decal transfer method

High performance cathode for polymer electrolyte membrane fuel cell was prepared by depositing Pt nanowires in a carbon matrix coated on a substrate, and using decal transfer method to fabricate the membrane electrode assembly. The effects of carbon and ionomer contents on the electrode micro-structure and fuel cell performance are investigated by physical characterization and single cell testing. The Pt nanowires are gradient distributed across the cathode thickness, and more Pt exists near the membrane. Both the carbon and ionomer contents can affect the Pt nanowires distribution and aggregation. In addition, the carbon loading dominates the transport distance of gas and proton, and the ionomer content affects the triple phase boundaries and porosity in the cathode. The optimal structure of Pt nanowire cathode is obtained at 0.10 mg·cm^-2 carbon loading and 10 wt% ionomer.

Two-step pyrolysis of ZIF-8 functionalized with ammonium ferric citrate for efficient oxygen reduction reaction

Zeolitic imidazolate frameworks（ZIFs） are widely employed in catalyst synthesis as parental materials for electrochemical energy storage and conversion. Herein, we have demonstrated a facile synthesis of highly efficient catalyst for oxygen reduction reaction in both alkaline and acidic medium, which is derived from ZIF-8 functionalized with ammonium ferric citrate via two-step pyrolysis in Ar and NHatmosphere.The results reveal that the catalytic activity improvement after NH3 pyrolysis benefits from mesoporedominated morphology and high utilization of Fe-containing active sites. The optimum catalyst shows excellent performance in zinc-air battery and polymer electrolyte membrane fuel cell tests.

Fuel cell performance assessment for closed-loop renewable energy systems

Fuel cells and electrolysis are promising candidates for future energy production from renewable energy sources. Usually, polymer electrolyte fuel cell systems run on hydrogen and air, while the most of electrolysis systems vent out oxygen as unused by-product. Replacing air with pure oxygen, fuel cell electrochemical performance, durability and system efficiency can be significantly increased with a further overall system simplification and increased reliability. This work, which represents the initial step for pure H;/O;polymer electrolyte fuel cell operation in closed-loop systems, focuses on performance validation of a single cell operating with pure H;/O;under different relative humidity（RH） levels, reactants stoichiometry conditions and temperature. As a result of this study, the most convenient and appropriate operative conditions for a polymer electrolyte fuel cell stack integrated in a closed loop system were selected.

High-loading Pt-alloy catalysts for boosted oxygen reduction reaction performance

To improve performance of membrane electrode assembly(MEA)at large current density region,efficient mass transfer at the cathode is desired,for which a feasible strategy is to lower catalyst layer thickness by constructing high loading Pt-alloy catalysts on carbon.But the high loading may induce unwanted par-ticle aggregation.In this work,H-PtNi/C with 33%(mass)Pt loading on carbon and monodisperse distri-bution of 3.55 nm PtNi nanoparticles,was prepared by a bimodal-pore route.In electrocatalytic oxygen reduction reaction(ORR),H-PtNi/C displays an activity inferior to the low Pt loading catalyst L-PtNi/C(13.3%(mass))in the half-cell.While in H_(2)-0_(2) MEA,H-PtNi/C delivers the peak power density of 1.51 W·cm^(-2) and the mass transfer limiting current density of 4.4 A·cm^(-2),being 21%and 16%higher than those of L-PtNi/C(1.25 W·cm^(-2),3.8 A·cm^(-2))respectively,which can be ascribed to enhanced mass trans-fer brought by the thinner catalyst layer in the former.In addition,the same method can be used to pre-pare PtFe alloy catalyst with a high-Pt loading of 36%(mass).This work may lead to a range of catalyst materials for the large current density applications,such as fuel cell vehicles.

MEASUREMENT OF THE THERMODYNAMIC PROPERTIES OF Fe_(2)Ti_(3)O_(9) AND Fe_(2)TiO_(5)

The thermodynamic properties of Fe_(2)Ti_(3)O_(9) and Fe_(2)TiO_(5) were measured by means of the following solid state electrolyte cells:Pt,Fe+"FeO"||ZrO_(2)(CaO)||FeTiO_(3)+Fe_(2)Ti_(3)O_(9)+Fe_(2)O_(3),Pt Pt,Fe+"FeOM"||ZrO_(2)(CaO)||FeTiO_(3)+Fe_(2)TiO_(5)+TiO_(2),Pt From the experimental data,the Gibbs energies of formation of Fe_(2)Ti_(3)O_(9) and Fe_(2)TiO_(5) were obtained:△G^(0)_(pr)(kJ·mol^(-1))=3459.7-0.847T,(1053K<T<1153K) △G^(0)_(pb)(kJ·mol^(-1))=-1700.2-0.465T,(1173K<T<1273K) Experimental results fit approximately to those of estimation.

High-quality and deeply excavated PtPdNi nanocubes as efficient catalysts toward oxygen reduction reaction

The oxygen reduction reaction(ORR)on the cathode of a polymer electrolyte fuel cell requires the use of a catalyst based on Pt,one of the most expensive metals on the earth.A number of strategies,including optimization of a different metal into the core,have been investigated to enhance the activity of a Pt-based catalyst and thus reduce the loading of Pt.By dedicating to compounding high catalytic activity Pt_(2.7)Pd_(0.3)Ni concave cubic with high index crystal face,the paper shows that concave structures can offer more active site and high level of catalytic activity and if mixed with other metal,decrease the proportion of Pt and improve its mass activity.The paper also makes an exploration into the theory and conditions behind the formation of Pt_(2.7)Pd_(0.3)Ni concave cubic structure,and investigates the difference it demonstrates by modifying the reactive conditions.The results of the oxygen reduction performance of the electrochemical test are as follows:the concave cube-shaped Pt-Pd-Ni catalyst has a mass activity of 1.28 A mg_(Pt)^(–1) at 0.9 V,its highest mass activity is 8.20 times that of commercial Pt/C,and its specific activity is 8.68 times of that commercial Pt/C.And the Pt-Pd-Ni ternary nanocage has excellent structural invariance.After the stability test,there is no obvious structural change and performance degradation in the nanostructure.

Numerical Analysis of Temperature Distributions in Single Cell of Polymer Electrolyte Fuel Cell when Operated in Elevated Temperature Range

Abstract： The purpose of this study is to analyze the temperature distribution on the interface between the polymer electrolyte membrane and catalyst layer at the cathode in single cell of polymer electrolyte fuel cell when operated in elevated temperature range than usual. In this study, the interface between the polymer electrolyte membrane and catalyst layer at the cathode is named as reaction surface. This study has considered the 1D multi-plate heat transfer model estimating the temperature distribution on the reaction surface and verified with the 3D numerical simulation model solving many governing equations on the coupling phenomena of the polymer electrolyte fuel cell. The 3D numerical simulation model coverers a half size of actual cell including three straight parts and two turn-back corners, which can display the essential phenomena of single cell. The results from both models/simulations agreed well. The effects of initial operation temperature, flow rate, and relative humidity of supply gas on temperature distribution on the reaction surface have been investigated. Though the effect of flow rate of supply gas on temperature distribution on reaction surface has been small, low relative humidity of supply gas has caused higher temperature on the reaction surface compared to high relative humidity of the supply gas. The temperature rise of reaction surface from initial operation temperature has increased with the increasing in initial operation temperature of cell.

Theoretical On-Board Hydrogen Redox Electric Power Generator for Infinite Cruising Range Fuel Cell Vehicles

The development of hydrogen redox electric power generators for infinite cruising range electric vehicles represents a true technological breakthrough. Such systems consist of a polymer electrolyte membrane hydrogen electrolytic cell equipped with an electrostatic-induction potential-superposed water electrolytic cell that provides a stoichiometric H2-O2 fuel mixture during operation of the vehicle. This generator functions with zero power input, zero matter input and zero emission due to the so-called ＂zero power input＂ electrostatic-to-chemical energy conversion occurring in the electrolytic cell. Here, theoretical simulations were performed to verify the target performance of such generators, assuming a pair of FC （fuel cell） and electrolytic cell stacks, both of which are commercially available.

DETERMINATION OF ACTIVITY OF AI IN SOLID Cu-Al ALLOYS

Activities and activity coefficients of Al in solid Cu-AI alloys have been determined by means of solid electorlyte galvanic cells Al(a_1 , in alloy), Al_2O_3 | ZrO_2· Y_2O_3 | Ni, NiO and Al(a_1 , in alloy), Al_2O_3 | Na, βAl_2O_3 | Al(a_2 , in alloy), Al_2O_3