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At least 199 records · Page 11

Robust highly durable solid oxide fuel cell cathodes – Improved materials compatibility & self-regulating surface chemistry

Solid oxide fuel cells (SOFCs) are electrochemical conversion devices that directly transform hydrogen or hydrocarbon fuels to electricity, with energy efficiencies as high as 90%, coupled with reduced emissions. Several factors, however, remain to be addressed when considering scale-up of SOFC technology, including the need to overcome decreased performance due to sluggish rates of the oxygen reduction reaction (ORR) at the cathode under reduced temperatures and susceptibility to degradation in performance from surface poisoning e.g. from chromia, while limiting the use of critical raw materials (lanthanides and transition metals) present in high performing mixed ionic electronic conducting electrodes like (La,Sr)CoO 3 (LSC). In this project we explored the key descriptors for determining ORR activity in SOFC electrodes and tried to recover performance degradation by applying them to SOFC electrodes. In order to do this, we first selected a model mixed ionic electronic conducting (MIEC) oxide, Pr-doped CeO 2 (Pr 0.1 Ce 0.9 O 2-δ , PCO), which is a chemically stable fluorite and free of inherent poison sources (e.g. Sr segregation in LSC) that potentially react with external impurities such as Cr-species vaporized from the interconnect. The three approaches originally planned in this project are as follows: 1) evaluation of scavenger exsolution characteristics, 2) study of scavengers gettering efficacy following Cr and Si poisoning and 3) integration of new compositions into porous electrodes. Among them, exceptional progress has been made in 2) and 3), especially understanding the role of surface infiltrants in impacting electrode performance and degradation of PCO materials. We found that the Smith acidity scale for binary oxides serves as a powerful descriptor for tuning and predicting the oxygen exchange kinetics on MIEC PCO surfaces. As a result, with infiltration with binary oxides, ranging from strongly basic (Li 2 O) to strongly acidic (SiO 2 ) onto the surface of porous PCO, it was possible to systematically vary the chemical surface exchange coefficient (k chem ) by 6 orders of magnitude! L i2 O increased k chem by nearly 1,000 times over that of pristine PCO, while SiO 2 decreased k chem by nearly the same factor. Strikingly, although the pre-exponential of k chem scales linearly with the acidity of the infiltrated binary oxide, there is nearly no change in the activation energy. With this insight, we attributed the origin of these dramatic changes in k chem values to the systematic increase and decrease in the surface electron density induced by infiltrated binary oxides. More interestingly, although both Cr 2 O 3 and SiO 2 were determined to be acidic by Smith, suggesting that this feature could likely be the primary reason that these compounds serve to poison the ORR on SOFC cathodes, the effect of poisoning could be subsequently tuned by adding multiple infiltrants and controlling their relative surface acidities. We also systematically examined the effect of serial infiltration of basic and acidic oxides. It turned out that serial infiltration of Li not only recovers approximately 20-fold degraded k chem of PCO by acidic Cr 2 O 3 but its k chem is enhanced even beyond that of the non-infiltrated PCO by more than three orders of magnitude. This was further verified with a screen-printing PCO symmetric cell in terms of the electrode performance (area-specific resistance, ASR) related to approach 3). These observations point to acidity as a key descriptor not only in tuning and predicting the ORR activity of SOFC cathodes that largely determines the overall performance of SOFC, but in mitigating and reactivating poisoned electrode performance. This work provides novel guidelines for making the electrode performance much more active and robust in SOFCs, which can further be applied to all applications requiring oxygen exchange reaction, such as electrolyzers, permeation membranes and gas sensors.

30 DIRECT ENERGY CONVERSION↗

Optimization of metal-supported solid oxide electrolysis cells with infiltrated catalysts

We report metal-supported solid oxide electrolysis cells (MS-SOECs) are being developed for steam-to-hydrogen electrolysis, especially for utilization of dynamic or intermittent electrical power from renewable sources. Various aspects of the electrocatalyst processing and composition, and metal support structure were explored. Catalyst materials, infiltration temperature and infiltration cycles were optimized for high performance and durability. Numerous catalyst materials were screened for both oxygen and steam electrodes. The oxygen catalyst had moderate impact on both initial cell performance and durability. Reducing Ni content in the steam electrode had little effect on durability, but reduced initial performance. Ex-situ XRD analysis and cell assessment of catalyst infiltration temperature revealed that the optimal range is 750–850 °C. The best cell performance and durability was achieved with LSCF-SDC oxygen electrocatalyst and SDC-Ni (60:40 vol%) steam electrocatalyst infiltrated 11 times at 800 °C and operated at 700 °C. At low steam content, a significant mass transport limitation on the steam side results in limiting current behavior. Thinner and more porous metal supports were implemented, and found to improve steam mass transport at low steam content, relevant for SOECs operating under high H 2 recycle rate or high steam utilization.

08 HYDROGEN↗

FCET Solid Oxide Fuel Cell Testing and Development (CRADA 526) (Final Report)

Pacific Northwest National Laboratory (PNNL) tested electrolyte coatings from Fuel Cell Enabling Technologies, Inc. (FCET) for use in solid oxide fuel cells (SOFCs). The key technology held by FCET is a process to deposit thin layers of oxide materials, less than 1 μm in thickness. The range of possible materials that can be deposited with their method is broad, but this project focused on the gadolinium-doped ceria (GDC) and yttria-stabilized zirconia (YSZ) electrolytes for SOFCs. Thin, gas tight electrolyte membranes have been a long-sought target in SOFC research. The thinner the electrolyte, the lower the cell resistance, and the higher performance of the cell (or the lower the operating temperature). A YSZ thickness of 1 μm would be a step change from the state-of-the-art, tape-cast electrolytes (~10 μm). An in-house prototype SOFC stack from FCET was first tested. The sealing geometry of the prototype stack was determined to be problematic, and testing shifted to button cells. Anode-supported solid oxide electrolysis cell (SOEC) button cells without an electrolyte layer were produced at PNNL and sent to FCET for coating with electrolyte. Three cells were tested with a gadolinium-doped ceria (GDC) electrolyte applied via spin coating. GDC was chosen for its conductivity at lower temperatures than YSZ. All three cells failed during initial reduction under hydrogen at 600°C. Testing then shifted to YSZ, which is the standard SOFC electrolyte. Several button cells were coated with YSZ and examined with scanning electron microscopy (SEM). A promising coating of ~1 mm thickness was observed under SEM. A similarly coated button cell was tested and failed similarly to previous tests during reduction at 600°C. The YSZ coating appeared dense and uniform in SEM analysis. The roughness of the underlying Ni/YSZ anode is on the order of 1 μm, and that may have compromised the gas-tightness of the coating. Further development is warranted to understand and refine the coating process. Thin YSZ applied via this spin-coating technique could be used as a low-cost, drop-in replacement in large-scale SOFC manufacturing processes, improving cell performance and lowering the cost per watt of SOFCs.

30 DIRECT ENERGY CONVERSION↗

System for operating solid oxide fuel cell generator on diesel fuel

A system is provided for operating a solid oxide fuel cell generator on diesel fuel. The system includes a hydrodesulfurizer which reduces the sulfur content of commercial and military grade diesel fuel to an acceptable level. Hydrogen which has been previously separated from the process stream is mixed with diesel fuel at low pressure. The diesel/hydrogen mixture is then pressurized and introduced into the hydrodesulfurizer. The hydrodesulfurizer comprises a metal oxide such as ZnO which reacts with hydrogen sulfide in the presence of a metal catalyst to form a metal sulfide and water. After desulfurization, the diesel fuel is reformed and delivered to a hydrogen separator which removes most of the hydrogen from the reformed fuel prior to introduction into a solid oxide fuel cell generator. The separated hydrogen is then selectively delivered to the diesel/hydrogen mixer or to a hydrogen storage unit. The hydrogen storage unit preferably comprises a metal hydride which stores hydrogen in solid form at low pressure. Hydrogen may be discharged from the metal hydride to the diesel/hydrogen mixture at low pressure upon demand, particularly during start-up and shut-down of the system.

Singh, Prabhu↗

Optimal Operation of Solid-Oxide Electrolysis Cell Systems Considering Synergistic Chemical and Physical Degradation

This poster summarizes work on synergistic degradation of Solid-Oxide Cells under physical and chemical degradation. We present operational insights that extend the useful life of SOCs while maintaining high efficiencies and economic viability. We also provide insights on how often the SOC must be replaced to ensure the reliability of the process. All these decisions are made through a dynamic optimization framework that utilizes new models for degradation that were developed as a part of the IDAES project.

Giridhar, Nishant↗

Development of Low Cost, Robust and Durable Cathode Materials to Support Solid Oxide Fuel Cell Commercialization (Final Technical Report)

The project is aimed at addressing critical issues related to chromia-poisoning in the cathode of solid oxide fuel cells. A technical hurdle to the commercialization of solid oxide fuel cells is that chromia sources from the metallic interconnect and the balance of plant (BoP) components will cause chromia-poisoning to the cathode performance. This presents a significant challenge since it is very difficult to eliminate chromia sources in the cathode environment. One aspect of the current project is to evaluate whether SFM (Sr 2 Fe 1.5 Mo 0.5 O 6-δ ) that we have recently developed as redox-stable mixed conducting oxide possesses tolerance to chromia-poisoning. The second focus of this project is to evaluate coating on the cathode materials to mitigate chromia poisoning effect. Both thermodynamic evaluation and experimental approaches have been applied to enhance the knowledge base and fundamental understanding of chromia-tolerance of cathode for solid oxide fuel cells. low cost, robust and durable cathode material to support SOFC commercialization.

30 DIRECT ENERGY CONVERSION↗

Precision surface modification of solid oxide fuel cells via layer-by-layer surface sol–gel deposition

While solid oxide fuel cells (SOFCs) are a promising technology for a clean and sustainable future, their commercialization is hindered by limited durability and performance. Here, we report our findings on the application of a layer-by-layer surface sol–gel (SSG) coating of catalysts to dramatically enhance the electro-catalytic activity and durability of SOFC cathodes. The SSG process is capable of penetrating and preserving complex backbone microstructures of porous electrodes, creating highly conformal coatings of controlled morphology, while tailoring the composition of the surface to improve catalytic properties and durability. For example, the application of an SSG coating of PrO x to a La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ (LSCF) cathode has reduced the polarization resistance from 1.136 to 0.117 Ω cm 2 at 600 °C and the degradation rate from 1.13 × 10 –3 to 2.67 × 10 –4 Ω cm 2 h –1 at 650 °C. In addition, a continuous improvement in electrode performance is demonstrated as the thickness of the coating is increased, corresponding to the linear addition of catalyst. Furthermore, this first application of the SSG technique to SOFC systems opens the door for the controlled surface modification of porous components in electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phase field simulation of anode microstructure evolution of solid oxide fuel cell through Ni(OH) 2 diffusion

Microstructure evolution in a solid oxide fuel cell anode is strongly affected by operating condition. The detailed mesoscale evolution mechanism under operating condition is still under debate. Here we develop a phase-field model to simulate microstructure evolution through formation and diffusion of gaseous Ni(OH)2. We studied the coarsening kinetics and redistribution of Ni under different steam distributions and compare it to that under pure hydrogen condition. Overall, the results suggest that although the presence of a steady gradient of steam leads to redistribution of Ni, Ni(OH) 2 formation and diffusion do not significantly change the Ni coarsening rate under strictly humid conditions, contrary to commonly reported hypotheses. It is concluded that competing mechanisms other than Ni(OH) 2 diffusion must be responsible for the experimentally observed Ni redistribution and enhanced coarsening under humid conditions.

25 ENERGY STORAGE↗

Ethanol-fueled metal supported solid oxide fuel cells with a high entropy alloy internal reforming catalyst

High-performance metal supported solid oxide fuel cells (MS-SOFC) with an integrated high entropy alloy (HEA) internal reforming catalyst (IRC) are demonstrated for transportation applications using ethanol and methanol as fuels. Addition of the HEA IRC dramatically improves cell performance and stability when using ethanol/water blend fuel. Absence of carbon deposition predicted by thermodynamic calculations is confirmed by Raman spectroscopy analysis of posttest anodes. Optimal catalyst processing (deposition technique, loading, firing temperature) and cell operation conditions (flow rates, temperature, fuel compositions) are explored. Infiltrated HEA reforming catalyst provides a highly porous structure and low catalyst loading (6 mg cm –2 ). The designed structure and catalysts achieve small mass transport resistances in the fuel electrode (26.2 s m –1 ) and oxygen electrode (41.6 s m –1 ). The best ethanol concentration (60:40 v% ethanol: water) provides 0.83 W cm –1 at 700 °C, without carbon deposition. The ethanol-fueled MS-SOFC is operated for 500 h, including five thermal cycles. As a result, cell evolution is similar to that reported previously for hydrogen fuel; nickel aggregation and chromia deposition were the major observed changes, and carbon formation can be avoided even after long-term operation.

30 DIRECT ENERGY CONVERSION↗

Intermediate Temperature Proton‐Conducting Solid Oxide Electrolysis Cells with Improved Performance and Durability

Technical understanding: A high-performance and stable intermediate temperature proton-conducting solid oxide electrolysis cell (PCEC) will add significantly to the hydrogen roadmap of EERE. However, the low electrocatalytic activity of the air electrode and the instability of the electrolyte are technical barriers. In this research, we utilized computational fluid dynamic modeling and materials/microstructure engineering to investigate the complex reaction chain and to improve the performance and reliability of the protonic ceramic electrochemical cells. An active and stable Pr 1.8 Ba 0.2 NiO 4+δ -BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb) scaffold conformal coating electrode was rationally designed where the robust Pr 1.8 Ba 0.2 NiO 4+δ functions both as a catalytic active and a protective layer. The PCECs with porosity-optimized scaffold conformal coating electrodes demonstrate 1.46 Acm -2 under 1.3 V at 600°C, which is among the highest in recent years. The final optimization by computational fluid dynamic modeling and conformal coating technique was applied to evolve the PCEC air electrode from Pr 2 NiO 4+δ to Pr 1.8 Ba 0.2 NiO 4+δ -BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ scaffold conformal coating. The electrolysis current was boosted from 0.445A/cm 2 to 1.46A/cm 2 at 600°C and 1.3V. A superior low degradation rate of 1mV/kh was achieved in a 5000-hour of operation. Technical effectiveness and economic feasibility: The effectiveness of this TCO conformal coating on electrolyte backbone as air electrode has been proven by long-term demonstration. Based on the highly conductive BZCYYb electrolyte and the TCO steam electrode PNO, this project rationally took advantage of the existent materials to structure a PCEC device with high TRL and low risk. The solution infiltration method used to structure the conformal coating is a standard method used by the solid oxide cell community. Very minimal adoption is needed in the current SOC fabrication process. It is a cost-effective, scalable method for manufacturing, and brings up remarkable impact on the current technical status of PCEC. Benefit to the public: The findings in the research showed the industry that the severe challenge in PCEC can be overcome in a practical way. A various energy-hydrogen ecosystem is not beyond reach. The success of this technology provides sustainable and affordable H 2 to society. It will stimulate investment from the governmental and private sectors in response to the device manufacture and deployment, and the related infrastructure construction. It will generate high-pay domestic jobs and environmental benefits to the general public in the United States.

08 HYDROGEN↗

Techno-Economic Analysis of a Thermally Integrated Solid Oxide Fuel Cell and Compressed Air Energy Storage Hybrid System

Natural-gas-fueled solid oxide fuel cell (SOFC) systems have the potential for high-efficiency conversion of carbon to power due to the underlying electrochemical conversion process while readily facilitating carbon capture through the separation of the fuel and oxidant sources. Compressed air energy storage (CAES) technology can potentially store significant quantities of energy for later use with a high round-trip efficiency and lower cost when compared with state-of-the-art battery technology. The base load generation capability of SOFC can be coupled with CAES technology to provide a potentially flexible, low-carbon solution to meet the fluctuating electricity demands imposed by the increasing share of intermittent variable renewable energy (VRE) production. SOFC and CAES can be hybridized through thermal integration to maximize power output during periods of high electrical demand and then store power when either demand is low or renewable generation reduces power prices. The techno-economics of a low-carbon hybrid SOFC and CAES system was developed and investigated in the present study. The proposed hybrid system was found to be cost-competitive with other power-generating base-load facilities when power availability was considered. The hybrid system shows increased resilience to changes in a high VRE grid market scenario.

25 ENERGY STORAGE↗

Rare Earth Nickelate Electrodes Containing Heavily Doped Ceria for Reversible Solid Oxide Fuel Cells

The electrochemical performance of composite rare-earth nickelate-rare-earth doped ceria oxygen electrodes, with a high level of rare-earth doping in ceria are reported. Additionally, the chemical stability of these compositions is reported at both the sintering (1240 ?C) and operating temperature (800 ?C). Specifically, a lanthanum nickelate La2NiO4+d (LNO) ?? 50 mol% lanthanum doped ceria (LDC50) oxygen electrode and a neodymium nickelate Nd2NiO4+d (NNO) ?? 50 mol% neodymium doped ceria (NDC50) oxygen electrode are tested in solid oxide fuel cell (SOFC) and solid oxide electrolysis cell (SOEC) modes and compared to a composite (La0.75Sr0.25)0.95MnO3±d (LSM)-8 mol% yttria stabilized zirconia (YSZ) electrode. The LNO–LDC50 oxygen electrode reaches a current density which is approximately three times that of the LSM-YSZ electrode in SOFC mode at 0.7 V and approximately two times the LSM-YSZ electrode at 1.2 V in SOEC mode. Similarly the NNONDC50 oxygen electrode reaches a current density which is approximately two times and approximately one and a half times that of LSM-YSZ at 0.7 V and 1.2 V respectively. Oxygen surface exchange results for LNO and NNO are also reported which show different oxygen exchange kinetics during oxidation versus reduction steps.

solid oxide electrolysis, solid oxide fuel cell (S↗

High spatial resolution temperature profile measurements of solid-oxide fuel cells

Temperature gradients resulting from local electrochemical reactions, current distribution and geometry of gas flow channels in solid oxide fuel cells (SOFCs) create thermal stresses, localized thermophysical property gradients and uneven property evolution, contributing to SOFC degradation. This paper presents a new method to perform temperature measurements (up to 800°C) at high spatial resolutions to monitor the operation of SOFCs. Using femtosecond laser irradiation, distributed fiber sensors were hardened for high temperature environment applications. Distributed fiber sensors were embedded in interconnected plates using an additive manufacturing method to perform temperature measurements with 4-mm spatial resolution during the operation of a planar fuel cell. The measurement revealed the impact of various H 2 fuel concentrations and current loads have on temperature profiles of the SOFC tested. Temperature variation on the anode side was found to be less than 5°C, and 3°C on the cathode side. The measurements were compared to results from a multiphysics fuel cell performance model simulating similar conditions. These simulations predicted similar temperature gradients, indicating the experimental data obtained is reasonable. The model also predicts that the effect of the embedded sensor has on the local temperature will be minimal and that the gradient of temperature in the gas channels will be captured despite the separation between the sensor and the gas flow. Finally, the high spatial resolution data harnessed by these distributed fiber sensors provides experimental support for model-based design and optimization to improve the operational efficiency and longevity of solid oxide fuel cells and fuel cell assemblies.

25 ENERGY STORAGE↗

A stable high-humidity bubbler design to supply steam for solid oxide electrolysis cells

A stable steam supply is required for the operation of solid oxide electrolysis cells. Heated water bubblers are the most common method due to the simplicity and inherent safety of the method, however, several design challenges hinder effective implementation. Here, a stable and validated bubbler design is presented, capable of achieving very high steam concentrations, relatively high flow rates, and continuous operation. A piping and instrumentation diagram and bill of materials are provided to enable easy duplication. Critical design parameters are discussed, including safety considerations and materials requirements, which are applicable to any bubbler design. The practical implementation of bubblers is also presented, including methods to prevent condensation instability and reduce backpressure to achieve a stable steam supply. The 3″ x 6″ (7.6 cm × 15.2 cm) bubbler achieves up to 98% steam balance hydrogen at 200 sccm and up to 1 slpm at 96% steam.

08 - HYDROGEN↗

Microstructure-Based Modeling of Inner Oxygen Pressure in Solid Oxide Electrolysis Cells

One major degradation mechanism during long-term operation of solid oxide electrolysis cells (SOECs) is delamination of oxygen electrodes (OEs). The driving force for the electrode delamination could be the generated high inner oxygen pressure near the electrode-electrolyte interface during operation. However, the effects of transport properties and electrode thickness on the inner oxygen partial pressure are not well understood. Here, a microstructure-based electrochemical model which includes the conduction of electrons and oxygen ions coupled with Butler-Volmer-type chemical reactions at triple-phase-boundaries (TPBs), is employed to investigate the oxygen pressure in lanthanum strontium manganate (LSM)-based SOECs. The model is applied to both two-dimensional (2D) prototype microstructures and three-dimensional (3D) realistic microstructures, and the oxygen pressure is analyzed as a function of transport properties and electrode thickness under both potentiostatic and galvanostatic operations. The simulation results suggest strategies to suppress electrode delamination. The simulation results are compared to an analytical solution, and the discrepancies are attributed to the Butler-Volmer-type kinetics included in the microstructure-based model.

Xue, Fei↗

Optimization of metal-supported solid oxide fuel cells with a focus on mass transport

Performance of symmetric-architecture metal-supported solid oxide fuel cells was improved significantly by optimizing the catalyst infiltration process and metal support structure. Optimization of component structure and processing parameters was performed during tape-casting and fabrication of button cells. Mass transport of oxygen in the metal support was identified as a major limitation. To overcome this limitation, pore former loading and thickness of the metal support (130–250 μm) were optimized. The catalyst infiltration process was also improved by studying the impact of firing temperature (400 °C–900 °C) and infiltration cycle numbers (1–15). The maximum power density of the optimized cell was 0.9 W cm –2 at 700°C using hydrogen as a fuel, a three-fold increase over the baseline cell performance. The degradation rate of optimized cells at 550 °C, 600 °C, and 700 °C was 2%, 4.5%, and 5.5% per 100 h, respectively. Here, the phenomena of mass transport, catalyst coarsening, and chromium poisoning on the catalyst were analyzed by electrochemical impedance spectroscopy and scanning electron microscopy.

13 HYDRO ENERGY↗