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.

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.

High-Performance Quasi-Solid-State Pouch Cells Enabled by in situ Solidification of a Novel Polymer Electrolyte

Conventional lithium-ion batteries(LIBs)with liquid electrolytes are challenged by their big safety concerns,particularly used in electric vehicles.All-solid-state batteries using solid-state electrolytes have been proposed to significantly improve safety yet are impeded by poor interfacial solid–solid contact and fast interface degradation.As a compromising strategy,in situ solidification has been proposed in recent years to fabricate quasi-solid-state batteries,which have great advantages in constructing intimate interfaces and cost-effective mass manufacturing.In this work,quasi-solid-state pouch cells with high loading electrodes(≥3 m Ah cm^(-2))were fabricated via in situ solidification of poly(ethylene glycol)diacrylate-based polymer electrolytes(PEGDA-PEs).Both single-layer and multilayer quasi-solid-state pouch cells(2.0 Ah)have demonstrated stable electrochemical performance over500 cycles.The superb electrochemical stability is closely related to the formation of robust and compatible interphase,which successfully inhibits interfacial side reactions and prevents interfacial structural degradation.This work demonstrates that in situ solidification is a facile and cost-effective approach to fabricate quasi-solid-state pouch cells with both excellent electrochemical performance and safety.

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.

Heterostructured nickel-cobalt metal alloy and metal oxide nanoparticles as a polysulfide mediator for stable lithium-sulfur full batteries with lean electrolyte

Batteries that utilize low-cost elemental sulfur and light metallic lithium as electrodes have great potential in achieving high energy density.However,building a lithium-sulfur(Li-S)full battery by controlling the electrolyte volume generally produces low practical energy because of the limited electrochemical Li-S redox.Herein,the high energy/high performance of a Li-S full battery with practical sulfur loading and minimum electrolyte volume is reported.A unique hybrid architecture configured with Ni-Co metal alloy(NiCo)and metal oxide(NiCoO_(2))nanoparticles heterogeneously anchored in carbon nanotube-embedded selfstanding carbon matrix is fabricated as a host for sulfur.This work demonstrates the considerable improvement that the hybrid structure's high conductivity and satisfactory porosity promote the transport of electrons and lithium ions in Li-S batteries.Through experimental and theoretical validations,the function of NiCo and NiCoO_(2) nanoparticles as an efficient polysulfide mediator is established.These particles afford polysulfide anchoring and catalytic sites for Li-S redox reaction,thus improving the redox conversion reversibility.Even at high sulfur loading,the nanostructured Ni-Co metal alloy and metal oxide enable to have stable cycling performance under lean electrolyte conditions both in half-cell and full-cell batteries using a graphite anode.

Mitigated reaction kinetics between lithium metal anodes and electrolytes by alloying lithium metal with low-content magnesium

Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.

12.6μm-Thick Asymmetric Composite Electrolyte with Superior Interfacial Stability for Solid-State Lithium-Metal Batteries

Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.

High-performance and robust high-temperature polymer electrolyte membranes with moderate microphase separation by implementation of terphenyl-based polymers

Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.

Simulation of Flow Field of Molten Salt in Neodymium Metal Electrolytic Cell Using Vortex-Flow Function Method

With the applications of Nd-Fe-B material extending in recent years, the materials of neodymium metal and other rare earth metal alloy confront the increased demand and the high quality request at the same time.These factors stimulated greatly to perfect the producing craft of RE metals and improve the equipments.The rare earth electrolysis cell is developing towards large-scale way.Notwithstanding the present electrolysis cell of Nd metal, include 6 kA and 10 kA cell, exists some insurmountable problems during operation and these problems lead to lower electric efficiency and higher operating costs.So it is significant to study the physical fields of rare earth electrolysis cell.In this paper,a numerical flow mode is established using vortex- flowing function method and the fluid flow field of 3000A Nd electrolysis cell is computed using MATLAB.The results of the study will be important reference in theory for improving and enlarging rare earth fluoride system cell.

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.

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 components of PEMFC-membrane-electrode assembly (MEA) and seek feasible measures to avoid degradation. The effect of freeze/thaw 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 freeze/thaw 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 performance under subzero temperature and gas purging is proved to be the effective operation.

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.

Achieving long-cycling sodium-ion full cells in ether-based electrolyte with vinylene carbonate additive

Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.

Numerical simulation on electrolyte flow field in 156 kA drained aluminum reduction cells

Based on the commercial CFD software CFX-4.3, two-phase flow of electrolyte in 156 kA drained aluminum reduction cells with a new structure was numerically simulated by multi-fluid model and k-ε turbulence model. The results show that the electrolyte flow in the drained cells is more even than in the conventional cells. Corresponding to center point feeding, the electrolyte flow in the drained cells is more advantageous to the release of anode gas, the dissolution and diffusion of alumina, and the gradient reduction of the electrolyte density and temperature. The average velocity of the electrolyte is 8.3 cm/s, and the maximum velocity is 59.5 cm/s. The average and maximum velocities of the gas are 23.2 cm/s and 61.1 cm/s, respectively. The cathode drained slope and anode cathode distance have certain effects on the electrolyte flow.

Effect of imidazole based polymer blend electrolytes for dye-sensitized solar cells in energy harvesting window glass applications

The exploration of polymer electrolyte in the field of dye sensitized solar cell(DSSC) can contribute to increase the invention of renewable energy applications. In the present work, the influence of imidazole on the poly(vinylidene fluoride)(PVDF)–poly(methyl methacrylate)(PMMA)–Ethylene carbonate(EC)–KI–I2 polymer blend electrolytes has been evaluated. The different weight percentages of imidazole added into polymer blend electrolytes have been prepared by solution casting. The prepared films were characterized by Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD), thermogravimetric analysis(TGA), UV–visible spectra, photoluminescence spectra and impedance spectroscopy. The surface roughness texture of the film was analyzed by atomic force microscopy(AFM). The ionic conductivity of the optimized polymer blend electrolyte was determined by impedance measurement, which is 1.95 × 10-3 S·cm-1 at room temperature. The polymer electrolyte containing 40 wt% of imidazole content exhibits the highest photo-conversion efficiency of 3.04%under the illumination of 100 m W·cm-2. Moreover, a considerable enhancement in the stability of the DSSC device was demonstrated.

Effect of electromagnetic force and anode gas on electrolyte flow in aluminum electrolysis cell

Based on the commercial computational fluid dynamics software CFX-4.3, electrolyte flow fields in a 156 kA pre-baked anode aluminum electrolysis cell were investigated in three different cases where the electrolyte melt was driven by different kinds of force, i.e. electromagnetic force only, the anode gas drag force only and both of the former two forces. The results show that when electromagnetic force was introduced only, most of the electrolyte moves horizontally; when anode gas drag force was introduced only, the electrolyte flows mainly around each anode with small circulation; when electromagnetic force and anode gas drag force were both introduced together, the structure of the electrolyte flow fields and the velocity of electrolyte are similar to that of the case where only anode gas drag force is used. The electrolyte flow fields are mainly determined by the anode gas drag force.

Pt Deposition on Anode Enhances the Performance of Dye-Sensitized Solar Cell with Non-Cross-Linked Gel Electrolyte

We fabricated dye-sensitized solar cells with non-cross-linked fluorinated gel electrolyte. The application of fluorinated gel to electrolyte is a challenging issue at present. The gelation of the electrolyte is of importance in order to solve the problem in the durability of the cell. We investigated, in this article, the effect of Pt deposition on the anode of the cell. The Pt was deposited by means of a DC sputtering technique. The studies showed that the deposition time strongly affected both open voltage and short-circuit current of the cell. The adaptive thickness of the Pt layer was determined to be 10 nm for the non-cross-linked fluorinated gel electrolyte cells.

Characteristic Analysis of the Solid Oxide Fuel Cell with Proton Conducting Ceramic Electrolyte

An electrolyte model for the solid oxide fuel cell (SOFC) with proton conducting perovskite electrolyte is developed in this study, in which four types of charge carriers including proton, oxygen vacancy (oxide ion), free electron and electron hole are taken into consideration. The electrochemical process within the SOFC with hydrogen as the fuel is theoretically analyzed. With the present model, the effects of some parameters, such as the thickness of electrolyte, operating temperature and gas composition, on the ionic transport (or gas permeation) through the electrolyte and the electrical performance, i.e., the electromotive force (EMF) and internal resistance of the cell, are investigated in detail. The theoretical results are tested partly by comparing with the experimental data obtained from SrCe0.95M0.05O3-α, (M=Yb, Y) cells.

Polymer Electrolyte Membrane Fuel Cells (PEMFC) in Automotive Applications: Environmental Relevance of the Manufacturing Stage

This study presents a state of the art of several studies dealing with the environmental impact assessment of fuel cell (FC) vehicles and the comparison with their conventional fossil-fuelled counterparts, by means of the Life Cycle As-sessment (LCA) methodology. Results declare that, depending on the systems characteristics, there are numerous envi-ronmental advantages, but also some disadvantages can be expected. In addition, the significance of the manufac-turing process of the FC, more specifically the Polymer Electrolyte Membrane Fuel Cell (PEMFC) type, in terms of environmental impact is presented. Finally, CIEMAT’s role in HYCHAIN European project, consisting of supporting early adopters for hydrogen FCs in the transport sector, is