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.

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.

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.

Study on Biological Pathway of Carbon Dioxide Methanation Based on Microbial Electrolysis Cell

Realization of CO_(2) resource utilization is the main development direction of CO_(2) reduction.The CO_(2) methana-tion technology based on microbial electrolysis cell(MEC)has the characteristics of ambient temperature and pressure,green and low-carbon,which meets the need of low-carbon energy transition.However,the lack of the system such as the change of applied voltage and the reactor amplification will affect the methane production efficiency.In this research,the efficiency of methane production with different applied voltages and different types of reactors was carried out.The results were concluded that the maximum methane production rate of the H-type two-chamber microbial electrolysis cells(MECs)at an applied voltage of 0.8 V was obtained to be 1.15 times higher than that of 0.5 V;under the same conditions of inoculated sludge,the reactor was amplified 2.5 times and the cumulative amount of methane production was 1.04 times higher than the original.This research can provide a theoretical basis and technical reference for the early industrial application of CO_(2) methanation tech-nology based on MEC.

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 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.

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.

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.

Impact of Separator Thickness on Temperature Distribution in Single Polymer Electrolyte Fuel Cell Based on 1D Heat Transfer

It is known from the New Energy and Industry Technology Development Organization (NEDO) roam map Japan, 2017 that the polymer electrolyte fuel cell (PEFC) power generation system is required to operate at 100°C for application of mobility usage from 2020 to 2025. This study aims to clarify the effect of separator thickness on the distribution of the temperature of reaction surface (Treact) at the initial temperature of cell (Tini) with flow rate, relative humidity (RH) of supply gases as well as RH of air surrounding cell of PEFC. The distribution of Treact is estimated by means of the heat transfer model considering the H2O vapor transfer proposed by the authors. The relationship between the standard deviation of Treact-Tini and total voltage obtained in the experiment is also investigated. We can know the effect of the flow rate of supply gas as well as RH of air surrounding cell of PEFC on the distribution of Treact-Tini is not significant. It is observed the wider distribution of Treact-Tini provides the reduction in power generation performance irrespective of separator thickness. In the case of separator thickness of 1.0 mm, the standard deviation of Treact-Tini has smaller distribution range and the total voltage shows a larger variation compared to the other cases.

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.

Study of Bi_2O_3-based Rare Earth Solid Electrolyte Used in Fuel Cell

Solid ceramic electrolyte materials (Bi_2O_3)_(0.75)(Y_2O_3)_(0.25) and(Bi_2O_3)_(0.65)(Gd_2O_3 )_(0.35)were synthesized.Their crystal structure, XPS spectra and the change of ionic conductivity versus temperature were measured.A Bi_2O_3-based rare earth solid electrolyte fuel cell with ZrO_2-Y_2O_3 protection film was made.

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.

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-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.

Study on Electrolytes (CeO_2 )_( 0.7-x) (MO) _x (La_2O_3)_(0.3)(M=Mg,Ca, Sr)

Solid electrolytes(CeO2)0.7-x(MO)x (La2O3) 0.3(M = Mg,Ca,Sr)were synthesized.Their crystal structure,conductivity, XPS spectrum,ionic transferance number and the V-1 curve of the obtained fuel cell were measured.(CeO2)0.7z (La2O3)0.3 doped with Ca2+,Mg2+,and Sr2+can perform the oxygen ionic electrolyte,and so enhance the open voltage and power output of the fuel cell.

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

Synthesis of dual-doped non-precious metal electrocatalysts and their electrocatalytic activity for oxygen reduction reaction

The pyrolyzed carbon supported ferrum polypyrrole （Fe-N/C） catalysts are synthesized with or without selected dopants, p-toluenesulfonic acid （TsOH）, by a facile thermal annealing approach at desired temperature for optimizing their activity for the oxygen reduction reaction （ORR） in O2-saturated 0.1 mol/L KOH solution. The electrochemical techniques such as cyclic voltammetry （CV） and rotating disk electrode （RDE） are employed with the Koutecky-Levich theory to quantitatively obtain the ORR kinetic constants and the reaction mechanisms. It is found that catalysts doped with TsOH show significantly improved ORR activity relative to the TsOH-free one. The average electron transfer numbers for the catalyzed ORR are determined to be 3.899 and 3.098, respectively, for the catalysts with and without TsOH-doping. The heat-treatment is found to be a necessary step for catalyst activity improvement, and the catalyst pyrolyzed at 600℃ gives the best ORR activity. An onset potential and the potential at the current density of -1.5 mA/cm2 for TsOH-doped catalyst after pyrolysis are 30 mV and 170 mV, which are more positive than those without pyrolized. Furthermore, the catalyst doped with TsOH shows higher tolerance to methanol compared with commercial Pt/C catalyst in 0.1 mol/L KOH. To understand this TsOH doping and pyrolyzed effect, X-ray diffraction （XRD）, scanning electron microscope （SEM） and X-ray photoelectron spectroscopy （XPS） are used to characterize these catalysts in terms of their structure and composition. XPS results indicate that the pyrrolic-N groups are the most active sites, a finding that is supported by the correspondence between changes in pyridinic-N content and ORR activity that occur with changing temperature. Sulfur species are also structurally bound to carbon in the forms of C-Sn-C, an additional beneficial factor for the ORR.

Phosphorus induced activity-enhancement of Fe-N-C catalysts for high temperature polymer electrolyte membrane fuel cells

Fe-N-C materials with atomically dispersed Fe–N_(4) sites could tolerate the poisoning of phosphate,is regarded as the most promising alternative to costly Pt-based catalysts for the oxygen reduction in high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs).However,they still face the critical issue of insufficient activity in phosphoric acid.Herein,we demonstrate a P-doping strategy to increase the activity of Fe-N-C catalyst via a feasible one-pot method.X-ray absorption spectroscopy and electron microscopy with atomic resolution indicated that the P atom is bonded with the N in Fe–N_(4) site through C atoms.The as prepared Fe-NCP catalyst shows a half-wave potential of 0.75 V(vs.reversible hydrogen electrode(RHE),0.1 M H_(3)PO_(4)),which is 60 and 40 mV higher than that of Fe-NC and commercial Pt/C catalysts,respectively.More importantly,the Fe-NCP catalyst could deliver a peak power density of 357 mW·cm^(−2)in a high temperature fuel cell(160℃),exceeding the non-noble-metal catalysts ever reported.The enhancement of activity is attributed to the increasing charge density and poisoning tolerance of Fe–N_(4) caused by neighboring P.This work not only promotes the practical application of Fe-N-C materials in HT-PEMFCs,but also provides a feasible P-doping method for regulating the structure of single atom site.