bluuebunny/crossref_metadata_2025 huggingface dataset:
Investigation of La0.65Ca0.35FeO3−δ
as a Co-Free Cathode for Protonic Ceramic Fuel Cells with Yb-Doped BaZrO3 Electrolyte
Authors: Watanabe Konosuke , Shimada Hiroyuki , Yamaguchi Yuki , Nomura Katsuhiro , Sumi Hirofumi , Kagomiya Isao , Mizutani Yasunobu
Published: September 2023

In protonic ceramic fuel cells (PCFCs), the use of cobalt-free cathodes is expected to reduce manufacturing costs and improve durability performance. However, cobalt-free cathodes generally tend to have poor power generation performance due to their lower catalytic activity than cobalt-containing cathodes. Therefore, based on a previous study in which higher power generation performance was obtained with SOFCs using La0.65Ca0.35FeO3−δ
(LCaF) than with SOFCs using La0.6Sr0.4Co0.2Fe0.8O3-δ
(LSCF) containing cobalt, we focused on LCaF as a cobalt-free cathode. In this study, we attempted to apply cathodes with LCaF to anode-supported PCFCs using a BaZr0.8Yb0.2O3-δ
(BZYb) electrolyte in order to improve the power generation performance and durability of PCFCs.

The proton-conducting oxides used for composite cathodes were investigated. BZYb, which is the same as the electrolyte, was used, but the adhesion between the electrolyte and the cathode was poor. When, BaZr0.1Ce0.7Y0.1Yb0.1O3-δ
(BZCYYb), which has good sinterability compared with BZYb, was therefore used, reading to improvement in the adhesion. Moreover, process parameters such as composite ratio and sintering temperature were also optimized. As a result, a maximum power density of 0.4 W cm-2 at an operating temperature of 600 °C was obtained for PCFCs using a composite cathode of LCaF and BZCYYb at a weight ratio of 6:4 sintered at 1100 °C, which is equivalent to PCFCs using a cathode with LSCF. In addition, the voltage drop rate of PCFCs using a composite cathode of LCaF and BZCYYb in the constant current durability test (0.26 A cm-2) at an operating temperature of 600 °C was 4% per 1000 hours, less than 1/10 that of PCFCs using a cathode with LSCF. Based on these results, LCaF is one of the candidate materials of cobalt-free cathode for PCFCs.

Acknowledgements: This work is based on the results obtained from a project (JPNP20003) commissioned by the New Energy and Industrial Technology Development Organization (NEDO), Japan.
Reforming of Exotic, but Environmental-Friendly Electrolyte Material Ca12Al14O33
Authors: Toda Yoshitake , Tomeno Satoru
Published: September 2023

Recently, lowering industrial CO2 emission is required in worldwide. Acquirement of the CO2 molecule decomposition technique is the most important step for business continuity especially in high temperature material manufacturing such as steel, cement and glass due to the processes necessarily entail CO2 emission. For this reason, we focused on direct electrolysis of CO2 by solid oxide electrolysis cell (SOEC) from the limited options because of its high energy efficiency, compatibility with decomposition targets of gas phase and effective utilization of waste heat. Nevertheless, in the case of our company that manufacturing glass in worldwide, it was roughly estimated that a total of at least 1 km2 surface area of SOEC would be needed to achieve zero-carbon emission. Thus, from these viewpoints, we considered it might be helpful to add robust and environmental-friendly materials to current group of materials that can be applicable for SOEC.

The complex oxide Ca12Al14O33 (C12A7) which was reported by A. R. West et al. in 1988 as having the potential for electrolyte applications only consists of abundant atoms in earth’s crust1. C12A7 have unique crystal structure which is characterized positively charged zeolite-like lattice framework with 12 crystallographic cages of ~0.4 nm in diameter per unit cell. The 1/6 cages are randomly occupied by remaining oxide ions (O2-) to maintain charge neutrality. The intra-cage oxide ions work as ion carrier and then C12A7 work as oxide ion conducting electrolyte. Negative point of C12A7 as an electrolyte is its low, 1/10 or less of that of 8YSZ, ionic conductivity.

In this study, we try to substitute constituent elements of C12A7 for other elements having larger valence than Ca2+ and/or Al3+. This attempt was expected to increase the charge of lattice framework and concentration of intra-cage oxide ion. We found that some additional elements can modify ionic conductivity of C12A7.

[1] M. Lacerda, J. T. S. Irvine, F. P. Glasser, A. R. West Nature
332 525-526 (1988).
Preparation of Ni/YSZ Catalysts for Application of Solid Oxide Electrolysis Cell Methanation
Authors: Horiguchi Genki , Yamaguchi Toshiaki , Tateno Hiroyuki , Bagarinao Katherine Develos , Kishimoto Haruo , Mochizuki Takehisa
Published: September 2023

Co-electrolysis of CO2 and steam using solid oxide electrolysis cells (SOECs) is a major focus of the CO2 conversion. Furthermore, SOECs have the potential to drive high value-added products with reduced carbon footprint. For example, the syngas (mixture of CO and H2) can be produced by SOEC-driven co-electrolysis of CO2 and steam, and utilized in the Fischer-Tropsch (FT) process for the synthesis of artificial hydrocarbon. The artificial hydrocarbons would be environmentally friendly fuels when CO2 is obtained from carbon capture and storage (CCS) technology. The Ni-based cermet, such as Ni with yttria-stabilized zirconia (Ni/YSZ), is a typical material of SOEC device, and Ni has been found to be an active catalyst for CH4 production (methanation). Therefore, use of the Ni/YSZ has potential to directly convert CO2 and H2O to CH4. In the catalytic process, the activity, selectivity and durability of the Ni/YSZ catalyst are significantly influenced by the structural property of Ni and YSZ, which is varied by the Ni loading and calcination conditions in addition to the studied reaction conditions. The preparation of Ni/YZS catalyst with high performance in co-electrolysis and methanation is still challenging.

Herein, the preparation of the Ni/YSZ catalysts with enhanced activity in SOEC methanation was studied. The Ni/YSZ catalysts were prepared by wet impregnation, one of the catalyst preparation methods, and characterized by several conventional methods. Effects of Ni loading and calcination conditions on the performance of Ni/YSZ catalysts were examined by CO2 methanation. A Ni/YZS catalyst gave a high CO2 conversion of 86% and a high methane selectivity at around 300 ºC under ambient pressure. With Ni/YSZ prepared using the optimized method, we are planning to prepare tubular cells and evaluate their activity in SOEC methanation.
The Effect of Operating Temperature on Galvanostatic Operation of Solid Oxide Electrolysis Cells
Authors: Bilalis Vasileios , Li Bowen , Frandsen Henrik Lund , Chen Ming
Published: September 2023

The purpose of this work is to study the degradation of Nickel Yttrium Stabilized Zirconia (Ni-YSZ) supported Solid Oxide Electrolysis Cells at different temperatures during galvanostatic steam electrolysis.

Four long-term experiments (>=700 h) electrolysis tests are carried out in galvanostatic mode (i.e. constant current), at a current density of 1 A/cm2 and testing temperatures of 925, 850, 800 and 750 oC. The cells’ performance and degradation are comprehensively analyzed via operando Electrochemical Impedance Spectroscopy (EIS). To quantify the degradation, EIS data from Nyquist, Bode and Distribution of Relaxation Times (DRT) plots are utilized in conjunction with complex-non-linear-least-square (CNLS) fitting on suitable equivalent circuit models (ECM).

The durability tests show that increasing the operational temperature has significantly beneficial effect on the long-term performance of the cells. More specifically, the cells operated at 850 oC and 925 oC not only did not reach 1.3 V during operation but they also have considerable low voltage degradation rates.

To highlight the beneficial effect of increasing the operational temperature, one more durability test at 925oC and 1.25 A/cm2 is conducted. It is showed that even at higher current density the cell shows superior performance compared to lower temperatures and lower current densities.

The results obtained from the CNLS fitting of the EIS data revealed that the observed degradation is attributed mainly to the increase of fuel electrode’s resistance and the corresponding increase of fuel electrode’s overpotential. At higher temperatures, the increase of fuel electrode’s resistance and overpotential is significantly lower during operation. The data from the CNLS fitting are used in order to approximate the time evolution of the different overpotentials of the cell.

In addition, the first and last EIS measurements under current of each of the durability tests are used for fitting to an ECM which contains Transmission Line Model (TLM) elements. The physical parameters obtained by the TLM fitting are compared with the results of the microstructure analysis. More specifically, post-mortem analysis of the cells using Scanning Electron Microscopy (SEM) and Energy-dispersive X-ray spectroscopy (EDS) provide extra info about the microstructure changes in the Ni-YSZ and the depleted layer of Ni close to the electrode/electrolyte interface.

The findings of this work highlight the significance of preserving a low fuel electrode overpotential during SOEC operation by increasing the operational temperature and therefore, by improving the reaction kinetics. It is suggested that Ni coarsening does not have a detrimental effect on long-term performance and that the overpotential-driven degradation mechanisms, such as Ni migration, mainly determine the life time of a SOEC.
(Invited) Current Status of SOFC Deployment and Technology Developments in Korea
Authors: Song Rak-Hyun
Published: September 2023

In Korea, the supply of stationary fuel cells for power generation is being promoted by the mandatory RPS program. The deployment of fuel cells in Korea began in 2012. Currently, fuel cells of about 880 MW have been supplied. Among them, the amount of SOFC system is about 220 MW, and the SOFC installation started in 2014. About 40 MW in 2021 and 50 MW in 2022 were installed. The deployment of residential SOFCs has just begun, and a small number of systems have been deployed. In Korea, fuel cell deployment is accelerated by the mandatory supply amount allocated to power generation companies by the RPS policy, and in addition, the clean energy supply promotion regulation granted to public buildings partially contributes to fuel cell supply. Several Korean companies have developed the SOFC and SOEC technologies under the national program, and major projects are the development of a 200 kW SOFC and a 20 kW SOEC systems. The 2~8kW class SOFC products have been developed already and are in deployment. In Korea, SOEC demonstration is being also promoted to store electricity generated from renewable energy, and about 1.5MW SOEC is scheduled to be demonstrated by 2024. The Korean government enacted the Hydrogen Law in 2019, and under this law, development and deployment of hydrogen and fuel cell-related technologies are in progress. In addition, a hydrogen roadmap was established as an implementation plan to encourage achievement of the deployment targets. In this talk, the achievements of the SOFC R&D and deployment, and national hydrogen roadmap in Korea are introduced in more detail.
Reliable Lab-Scale Evaluation for Enhanced SOFCs Electrode Performance - Influence of Electronic Transport
Authors: Kim Jae Jin , Vu Anh , Cronauer Donald , Carter John , Maroni Victor , Hock Adam , Ingram Brian J.
Published: September 2023

Understanding and optimizing electrochemically active zone for oxygen reduction reaction (ORR) in solid oxide fuel cells (SOFCs) cathodes are indispensable to maximize device’s performance. For a mixed ionic and electronic conducting electrode, the range of this zone depends on the oxygen surface exchange and solid-state oxygen/electron transport properties of electrode materials and the oxygen gas transport through porous electrode. This implies that electrode microstructure, including surface area, porosity, and tortuosity, needs to be carefully designed and controlled to maximize electrochemically active electrode volume. This aspect is also critical to realize valid characterization of the electrode’s electrochemical activities. For instance, when a material’s electronic conductivity is low or the electrical contact points are spaced beyond a critical distance, the electrode polarization resistance measured by electrochemical impedance spectroscopy will be controlled by the sheet resistance not the oxygen exchange resistance. In this presentation, we will discuss our synthesis approach of lanthanum strontium cobalt ferrite (LSCF) and spinel powders by using co-precipitation with a continuous stirred-tank reactor, in order to precisely control powder’s chemistry and morphology (ultimately, electrode microstructure). And, we will discuss the influence of electrode microstructure and current collecting method on electronic conduction in porous electrode and, eventually, on electrochemical performance and its reliable evaluation in a lab-scale button cell configuration.

This work was supported by the US Department of Energy (DOE), Office of Fossil Energy, (Office of Fossil Energy & Carbon Management), “Solid Oxide Fuel Cell Manufacturing in Support of Office of Fossil Energy” program through Argonne National Laboratory under FWP No. 27327.1.
Recent Developments of the International Future Lab of Hydrogen Economy: Using Artificial Intelligence (AI) Based Machine Learning (ML) in r-SOC Development
Authors: Peksen Murat , Steinrücken Benjamin , Spliethoff Hartmut
Published: September 2023

The International Future Laboratory for Hydrogen Economy at the Technical University of Munich (TUM) has established a research-network model researching in the field of electrically assisted gasification, reversible solid oxide cells, and biocatalytic synthesis of hydrogen. Using experimental and numerical data, the current study elucidates the progress on reversible solid oxide cell technologies. Advanced artificial intelligence (AI)-based machine learning approaches are utilized to evaluate and optimize SOC-relevant processes. The SOC research is giving particular attention to the integrated approach of traditional numerical methods such as CFD and accelerated modern AI methods. The complex thermochemistry of syngas-containing auxiliary components has been assessed using experimentally validated numerical models. The approach is utilized to create data for the successful construction and training of AI-based machine-learning models. Multi-regression studies shed light on the interactions between process variables to improve and prepare SOC-ready fuel which is essential for successful operation. A recently developed ML model is effectively employed to forecast and optimize the reforming procedures with different fuel constellations including oxygen-containing syngas compositions. Consequently, the results contribute to better knowledge and qualitative benefits of the preparation of high-quality, pure syngas, improved fuel utilisation furthering sustainable research and r-SOC operation in a safe, consistent manner. Hence, the availability of valuable information early in the process is achieved. Moreover, the approach reduced prohibitive experiments contributing to the sustainable use of resources.
Simulation Assisted Development of SOFC Power Generation
Authors: Cvikl Aleš
Published: September 2023

SOFC Power Generation systems are getting more and more popular in the stationary and marine sector, to move away from traditional internal combustion engines, not only to reduce emissions, but also for higher system efficiency. In this presentation AVL shows how system simulation was initially used for definition of appropriate system architecture, following by correct component selection to fulfill contract efficiency and performance targets. To get the most reliable results at any point of V process development, simulation tool has to be predictive enough in concept phase and it should also offer simple parameterization of components where more data is available, either from component supplier or actual measurements. The complete workflow will be shown to have an idea how AVL is utilizing the software at any point of the V process for SOFC system development.
From Ideal to Stack-like Contacting of an SOC
Authors: Grosselindemann Cedric , Esau Daniel , Dorn Marvin , Bauer Frank Manuel , Wissmeier Lena , Weber Andre
Published: September 2023

The cell performance of a solid oxide cell strongly depends on the testing environment and conditions. In case of an inert testing set-up with ceramic (Al2O3) flow fields and gold (cathode) and nickel (anode) contact grids the losses inside the cell determine the performance [1]. For an electrolyte-supported cell with a nickel / gadolinium-doped ceria (Ni/CGO) fuel electrode and LSCF air electrode, the ideal cell behavior has been characterized by electrochemical impedance spectroscopy (EIS) and the subsequent analysis of the distribution of relaxation times (DRT) considering technically meaningful operating conditions. Furthermore, the deconvolution and quantification of the gas diffusion polarization has been shown with the help of ternary fuel gas mixtures with different gas diffusion coefficients. [2-4]

In this contribution, the electrochemical characterization is now extended to a stack-like contacting of the solid oxide cell with different metallic interconnectors, protective coatings and contact layers. The resulting contact loss is quantified with a method by Kornely et al. [5] using potential probes at the interconnector and the air electrode in order to enable voltage loss measurements. The stack-like contacting leads to gas transport conditions different from the ideal case which is investigated at the fuel and air side with modified gas diffusion coefficients by using gas mixtures containing nitrogen and helium as well [2].

The positive effect of the protective coating towards the cell performance is evaluated by current-voltage characteristics and EIS measurements. Further, the electrode electrochemistry influenced by effects like chromium-poisoning will be shown and compared to the ideal contact set-up [2].

References:

[1] D. Klotz et al., Electrochim. Acta, 227, 110 (2017).

[2] C. Grosselindemann et al., J. Electrochem. Soc., 168, 124506 (2021).

[3] C. Grosselindemann et al., Proceedings of the 15th EFCF, July 5th-8th (2022).

[4] M. Riegraf et al., J. Electrochem. Soc., 166, F865 (2019).

[5] M. Kornely et al., J. Power Sources, 196, 7209-7216 (2011).
Development of High-Entropy Alloy (HEA) Anode for Carbon-Free and Electrochemically-Stable Operation of SOFC on Hydrocarbon Fuels
Authors: Lee Kevin X , Singh Prabhakar , Hu Boxun , Dubey Pawan Kumar Kumar , Belko Seraphim
Published: September 2023

State of the art SOFCs, consisting of Ni base anode, experience excessive localized endothermic cooling and carbon deposition during internal reforming of hydrocarbon fuels. To mitigate the above issues, we developed high-entropy alloy (HEA) anode consisting of optimized mixture of Cu, Ni, Co, Fe and Mn transition metals. Alloys were synthesized using co-precipitation technique and experimentally evaluated for internal reforming and electrochemical activity under SOFC operating conditions. As-synthesized HEA catalysts were also characterized by techniques including N2 adsorption/desorption analysis, SEM, XRD, TPR, TPO and TPD. Compared with standard Ni/YSZ and Ni/GDC anodes, HEA anode containing gadolinium-doped ceria (GDC) showed controlled reforming of methane. Raman spectroscopy and SEM microscopy confirmed the absence of carbon on the HEA/GDC anode.
An Experimental Method to Measure Electrokinetics of Oxygen Electrodes in High Temperature Solid Oxide Electrolyzers through Symmetrical Cell Configuration
Authors: Wen Yeting , Zhang Yongliang , Huang Kevin
Published: September 2023

Using high temperature solid oxide electrolytic cells (SOECs) to make hydrogen from steam has thermodynamic advantages in efficiency and yield over its low temperature water electrolyzer counterparts. However, SOECs generally exhibit faster performance degradation than solid oxide fuel cells (SOFCs), thus presenting a major challenge to the technology scale up for mass production of hydrogen. One leading cause for the degradation is associated with the delamination of oxygen electrode (OE), particularly under high current densities or hydrogen production rate. In this presentation, we show our efforts to determine the experimental conditions under which OE can safely operate without delamination. We first show application of DC-biased electrochemical impedance spectroscopy (EIS) method to three-electrode symmetrical cells (STEC) to delineate OE polarization resistance RP and overpotential h as a function of current density (J) and time (t) under both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) operation modes. From this set of basic data, we extract intrinsic exchange current density (io) of the OE using the “low-field” approximation approach embedded in the classical Butler-Volmer equation. We then correlate the obtained io with time-to-delamination (TTD) defined by the time at which io become zero. We finally establish the analytical relationship between TTD and io for three typical operating current densities ranging from 0.5-1.5 A/cm2, from which the lifetime of SOEC is predicted at a specific H2-producing current density.
Enhancement of Ni-YSZ Fuel Electrode Performance Via Pressurization and GDC Infiltration
Authors: Grimes Jerren , Zhang Yubo , Cox Dalton , Barnett Scott A
Published: September 2023

Solid oxide cell systems are often designed for operation with a pressurized stack. Although the cell performance is expected to improve with pressurization, the details of how pressure affects the performance of various technologically-relevant electrodes are typically not known. Here we investigate the electrochemical characteristics of Ni-YSZ and GDC-infiltrated Ni-YSZ fuel electrodes in Ni-YSZ-supported cells as a function of total pressure P from 1 to 5 atm in H2/H2O fuel mixtures with humidification of 25%, 50%, and 75% and temperatures of 600˚C and 700˚C. Using electrochemical impedance spectroscopy, the two limiting electrode processes are identified: charge transfer reactions and gas diffusion. The charge transfer resistance is significantly reduced for Ni-YSZ:GDC compared to Ni-YSZ for all conditions, with total polarization resistance RP reduced by 30 - 40%. Fitting the data to a power-law dependence, RP ∝ P−n, yields a power law exponent of n = 0.28 for Ni-YSZ and 0.36 for Ni-YSZ:GDC (at 600˚C) and n = 0.32 for Ni-YSZ and 0.39 (at 700˚C). That is, GDC infiltration improved electrode performance more at higher pressure. Increasing the total pressure from 1 to 5 atm results in a 42% and 47% reduction in RP for infiltrated electrodes at 600˚C and 700˚C; these values are averaged for all humidities. Increasing humidity from 25 to 50% at 1 atm resulted in a ~26% reduction in total RP. The Ni-YSZ:GDC electrode at 5 atm had a RP value 63% - 65% lower than that of the Ni-YSZ electrode at 1 atm, a very substantial combined effect. The impact of pressurization on overall cell area-specific resistance is assessed based on the present data combined with prior measurements of oxygen electrode pressurization effects.
Gas Evolution Characterization of NiZn Batteries with Residual Gas Analysis
Authors: Landgraf Niklas , Mandava Pranav , Cox Joshua , Skaggs Pablo , Cornelison David , Moreno Daniel
Published: September 2023

As humanity strives to reduce its impact on the environment, the need for safe, recyclable, and efficient batteries increases. Nickel-Zinc batteries offer a solution to some of the world’s needs with its materials being abundant and recyclable, its ability to discharge at high currents, and its safe and nontoxic materials providing low risk with applications. Nickel-Zinc batteries are rechargeable, have a ZnO anode, a NiOOH cathode, and an aqueous KOH solution as the electrolyte. During cycling, Ni-Zn cells produce and consume H2 and O2 gas. This gassing behavior has not previously been characterized. The goal of this research was to analyze this gassing behavior by measuring the partial pressure vs. time of a cell’s headspace gas during cycling. The headspace gas was leaked into a vacuum chamber and analyzed with an RGA quadrupole mass spectrometer. The primary trend of the H2 gassing was that the cell produced hydrogen during charging and was rapidly consumed at the end of charging, which indicated recombination with oxygen at an internal catalyst coil. The consumption stopped about midway through discharging and began to produce the H2 gas again. The O2 gassing peaked as H2 was consumed and slowly tapered off during the rest of the discharge and charge. The curvature of these partial pressure plots was dependent of the cycle number and charge rate. The eventual goal of this research is to use the gassing data to indicate the different phases of the electrode materials present throughout cycling.

Figure 1
Modulating Ionic Transport and Interface Chemistry Via Surface-Modified Nanoparticle Carrier in Silica-Colloidal Electrolyte for Li-Metal Batteries
Authors: Lim Minhong , Seo Jiyeon , Lee Hongkyung
Published: September 2023

Tailoring the Li+ solvating environment and solid-electrolyte interface (SEI) chemistry is crucial for developing long-life lithium (Li) metal batteries. However, it is hard to reinforce at the same time, fully solvating Li+ for fast ionic transport and forming anion-derived SEI, due to both being strongly related. Here, we report a CA-modified SiO2 dispersed colloidal electrolyte (C-SCE) for modulating the Li+ solvation structure and interface chemistry, simultaneously. SiO2 nanoparticle migration can act as an additive and anion carrier toward the Li surface, tailoring the Li+ solvating environment and SEI chemistry. We further render more active sites for intermolecular hydrogen bonds between neighboring complex anions and solvent molecules, using CA-tethered SiO2 in colloidal electrolytes. Chemisorption of CA can further dissociate the Li+ from anions allowing selective Li+ transport, resulting in a high Li+ transference number (~0.78). Also, SiO2 nanoparticle migration can act as an additive and anion carrier toward the Li surface, SEI chemistry. More ingredients delivered by CA-tethered SiO2 carriers reinforce the SEI via co-implantation of SiO2 and fluorinated components. Furthermore, C-SCE demonstrates Li dendrite suppression and stable cycling stability (>100 cycles at 70% of initial capacity) of LMBs under stringent conditions (lean electrolyte (6 g Ah−1), high loading (4.8 mAh cm−2), thin Li metal (50 µm)).

Figure 1
Li2So4 Coating of Co-Free, Li-Rich Layered Oxide Cathodes through a Carbonate Coating Method for Improving Cycle Performance
Authors: Moon Jung Hyeon , Kang Hyeonmuk , Hwang GyuSeong , Lee Junho , Shin GeunHyeong , Cho EunAe
Published: September 2023

In the continued evolution toward high-performance lithium-ion batteries, cobalt has presented itself as a major obstacle due to its price and accessibility. Thus, Co-Free, Li-rich Layered Oxide Cathodes (CF-LLC) have become a promising cathode candidate for their exclusion of Cobalt and high theoretical capacity. Nevertheless, CF-LLC suffers from LLC issues such as phase transformation and voltage fade. Due to high overpotential from sluggish kinetics, the oxygen plateau of CF-LLC occurs at a higher-than-normal potential, leading to a shortened first cycle charge and lower discharge capacity. To mitigate this, we implemented a sulfate coating of the carbonate precursor; which upon lithiation, presents a Li2SO4 coated LLC (S-CF-LLC). The Li-sulfate coating prevents agglomeration of the primary particles during lithiation, leading to a larger surface area and thus, faster kinetics. The coating also prevents increased degradation from the increased surface area by acting as a protective barrier. The S-CF-LLC was successfully synthesized using a hydrothermal synthesis method with a wet chemical coating step and the synthesis was confirmed using XRD, SEM, XPS, and HR-TEM techniques. Galvanostatic cycling showed that the first cycle improved from 236.1mAhg-1 to 263.5mAhg-1 after coating, owing to the improved kinetics. GITT analysis of the increased diffusion coefficient further confirmed the overall improved kinetics. Moreover, the efficacy of the coating was shown through cycle data after 100 cycles, which showed good coulombic efficiency with a high average of >99%, good capacity retention, and good voltage fade per cycle improvement. Overall, the successfully synthesized S-CF-LLC opens up the possibility of practical cobalt-free high-performance batteries.
Electrochemically Mediated Ammonia Removal and Recovery from Wastewater Using Functional Membranes
Authors: Chen Weikun , Grimberg Stefan , Rogers Shane , Kim Taeyoung
Published: September 2023

Wastewater treatment plants (WWTPs) typically use anaerobic digestion (AD) to treat sludge, but ammonia produced during AD process returns to the headworks of WWTPs. The amount of ammonia in the liquid stream produced after dewatering the stabilized sludge, commonly referred to as dewatering sidestream, could contribute as high as 20% of the overall ammonia loading to WWTPs. Several sidestream treatment technologies are being developed not only to prevent additional ammonia inputs to WWTPs, but also to valorize ammonia for fertilizer production. Electrochemically mediated processes can achieve this goal in two simultaneous steps: (1) ammonium separation from wastewater through a cation-exchange membrane and (2) ammonium-to-ammonia conversion for its recovery by membrane stripping. Although electrochemical reactions in electrodialysis or flow-electrode capacitive deionization have been shown to drive the separation and increase the solution pH, an acid solution must be externally fed in the subsequent stripping process. Here, we demonstrated the use of bipolar membrane electrodialysis (BMED) to separate ammonium while simultaneously producing acid and base streams. Using a three-compartment BMED cell (effective repeating unit area = 29.2 cm2) with a synthetic sidestream containing 50 mM total ammonia nitrogen (TAN), we achieved TAN removal up to 80% with energy consumption less than 10 kWh kg−1 N at a productivity of 34.2 L m−2-repeating unit membrane area h−1 (LMH). The separated ammonia was recovered (>90%) in a subsequent membrane contactor that was fed with acid and base streams produced from the BMED cell. We specifically focused on increasing TAN concentration in the final product stream by changing relative flow rate of acid/base streams, which allowed for concentrating TAN nearly 8 times greater than the feed. These results show the use of BMED coupled with membrane stripping enables ammonia recovery without the need for chemical inputs, representing a promising sidestream treatment technology.
Activated Carbon Electrodes with Enhanced Supercapacitive Swing Adsorption of Carbon Dioxide
Authors: Bilal Muhammad , Landskron Kai
Published: September 2023

Activated carbon electrodes with enhanced supercapacitive swing adsorption of carbon dioxide

The necessity to achieve net-zero emission of anthropogenic CO2 by the end of the twenty first century has recently raised interest among researchers to develop electrochemical CO2 capture technologies due to their high selectivity, low energy consumption, and ease to be powered with renewable electricity. Currently, most of these technologies rely on the use of expensive adsorbing electrode materials, and ion-selective membranes.1 Supercapacitive swing adsorption (SSA) is a technique that only requires activated carbon electrodes, a separator, and an aqueous electrolyte to capture and concentrate CO2 during the capacitive charging and discharging of carbon electrodes, making it attractive from the cost and environmental perspective.2 Recent studies on SSA focused on improving the energetic and adsorptive performance by tuning the electrolyte concentration, composition, and electrode charging protocols.3 However, the adsorption capacity stayed around 100 mmol/kg (compared to ∼1000 mmol/kg for amine scrubbing) even at higher electrolyte concentrations and extended voltage windows.2,4

Herein, we report high surface area activated carbon electrodes derived from biomass, coke, coal, and carbide for SSA. We find a strong correlation between capacitance and CO2 adsorption capacity and quantitatively analyze the energetic and adsorptive performance of different electrode materials. Biomass-derived garlic roots-derived activated carbon (GR-AC) electrodes show 4-fold enhanced adsorption capacity (270 mmol/kg) and 3.2-fold enhanced adsorption rate (84 μmol.kg-1.s-1) compared to state-of-the-art coal-derived carbon. However, GR-AC electrodes showed an energy consumption of 179 kJ/mol. Modifying the activation treatment from KOH-based two-step process to K2CO3-based one-step process yielded micro-mesoporous activated carbon. Warm-pressed electrodes from this carbon showed lower energy consumption (72 kJ/mol) and improved gravimetric/volumetric adsorption capacity (312 mmol/kg and 86 mol/m3). Increasing the voltage window from 1 V to 1.6 V resulted in even higher adsorption capacity (524 mmol/kg at -1.4 V and 578 mmol/kg at -1.6 V) as well as improved gas purity (Figure 1). Cyclic voltammetry and electrochemical impedance spectroscopy confirmed the capacitive-type behavior of electrodes up to 1.4 V.

Figure 1 Voltage response (black) and CO2 concentration changes (blue) at different voltage windows

References

R. Sharifian, R. M. Wagterveld, I. A. Digdaya, C. Xiang, and D. A. Vermaas, Energy Environ. Sci., 14, 781–814 (2021).

S. Zhu, J. Li, A. Toth, and K. Landskron, ACS Appl. Energy Mater., 2, 7449–7456 (2019).

M. Rahimi, A. Khurram, and T. A. Hatton, Chem Soc Rev (2022).

T. B. Binford, G. Mapstone, I. Temprano, and A. C. Forse, Nanoscale (2022).

Figure 1
(General Student Poster Award Winner - 1st Place) Six Practices to Improve Alkaline Electrolyte Preparation
Authors: Marquez-Montes Raul A. , Kawashima Kenta , Son Yoon Jun , Castelino Grace , Miller Nathan , Smith Lettie A. , Chukwuneke Chikaodili E. , Mullins Charles Buddie
Published: September 2023

Alkaline electrolytes represent a critical component of electrochemical energy devices, including alkaline electrolyzers, fuel cells, supercapacitors, and alkaline batteries. In addition, these electrolytes define essential properties of electrocatalytic reactions, such as the oxygen evolution reaction (OER), the hydrogen evolution reaction (HER), and the oxygen reduction reaction (ORR). However, alkaline electrolyte concentrations and compositions are often considered trivial, resulting in misinterpretation of different phenomena and overestimating critical performance metrics. Thus, in an expanding field full of interdisciplinary research groups, there is an urgent need for standardized protocols designed to improve and evaluate the quality of alkaline electrolytes so that electrochemical energy systems can be objectively examined and compared.

In this work, we propose a protocol composed of six steps to prepare, characterize and validate the quality of common alkaline electrolytes. By adapting well-established methods in the literature and validating additional features experimentally, we standardize six general practices: (1) proper alkaline electrolyte handling and preparation, (2) removal of Fe impurities, (3) alkali molarity standardization via pH titrations, (4) electrolyte composition analysis via inductively-coupled plasma mass spectrometry (ICP-MS), (5) statistical quality control assessment and (6) electrolyte validation through electrochemical aging of Ni electrodes in alkaline media. The effects of Fe incorporation for different alkaline electrolytes were examined using Ni and NiFe foam electrodes. Furthermore, ICP-MS measurements were complemented with prolonged cyclic voltammetry tests to confirm the effectiveness of the Fe purification procedure. We believe this work illustrates the importance of standardizing protocols and reporting reliable quality metrics to improve consistency and accuracy in electrochemistry. Furthermore, adopting the practices presented in this work would greatly benefit the evaluation and comparison of electrochemical energy materials and devices operating with alkaline electrolytes.

Figure 1
Electrochemical Biosensor for the Rapid Detection of HIV P24 Protein
Authors: Saha Dipu , Botte Gerardine G
Published: September 2023

Human immunodeficiency virus (HIV) is a deadly virus that propagates rapidly. It leads to acquired immunodeficiency syndrome (AIDS) disease with time. Early detection is one way to decrease the spread of the virus. P24 protein is the capsid protein of HIV available for detection in one’s body two weeks after the virus infection. A nickel-based electrochemical sensor is developed to detect the P24 protein using electrocatalysis. A rotating disk electrode is used to minimize the mass limitations. Also, the sensor is label-free which limits the dependence on immobilization. Cyclic voltammetry (CV), chronoamperometry, and electrochemical impedance spectroscopy (EIS) are used throughout the detection process. The electrochemical method CV is used to produce the catalyst layer on the nickel surface, which paves the way for the other two methods to monitor the current response and resistance of the P24 protein with the nickel surface. The sensor detects the presence of HIV P24 protein in the 1 ms of chronoamperometry. Also, the total assay time is less than other conventional methods. The sensor showed good sensitivity and a lower detection limit of around 70 ng/mL, which makes the sensor more reliable. Also, the sensor showed a linear current response with the increasing concentration of P24 protein. So, this simple biosensor has applications to decrease the infections of HIV.
(Invited, Digital Presentation) Materials Research in Low-Earth Orbit
Authors: Matson Douglas
Published: September 2023

Low-Earth Orbit (LEO) provides a high-quality, long-duration microgravity conditions. We go to space to eliminate gravity-induced systematic measurement error. My work has centered on control of convection during solidification and this talk will summarize some of my recent microgravity test results from onboard the International Space Station. I will also discuss the future trends in space-based physical and biological science from a fundamental and applied perspective.
(Keynote) Electrochemical Devices for Lunar Exploration - JAXA's Concept
Authors: Naito Hitoshi
Published: September 2023

Japan has decided to participate in the space exploration program "ALTEMIS program" proposed by US. One of the manned mission, Lunar surface exploration using rover (vehicle), is also involved in this program and Japan has started to develop it with JAXA and several companies and planned to be operational by the end of the decade, probably in 2029. The ultimate goal of the project is to help humanity live on the moon by 2040, and eventually on Mars. These plans are summarized in Fig. 1.

This project surely supports the resources exploration on the moon as in-situ Resources Utilization(ISRU). The Lunar Cruiser, which alludes to Toyota’s Land Cruiser  SUV, is essentially a fuel-cell-powered mobile laboratory that features living quarters, workstations, and cutting-edge scientific instruments. The pressurized rover is expected to have a “lunar-surface cruising range of more than 10,000 km.” Now, other automobile companies like Honda and Nissan might collaborate with all Japan projects.

They have since then been creating virtual reality visualizations, conducting simulations, telecommunication systems for automatic operation and building full-scale models with photovoltaic power generation, advanced battery, and fuel cell. This presentation mainly focuses the energy and electrical system design.

Figure 1
(Keynote) Parameterize Important Factors for Li Metal Batteries: Cycle Life, Calendar Life and Reactivity
Authors: Meng Shirley , Bao Wurigumula , Lu Bingyu
Published: September 2023

The lithium (Li) metal anode is essential for next-generation high-energy-density lithium metal batteries. The calendar life and reactivity (safety) are equally important to cycle stability for the real application of Li metal anode in different devices. Our recent studies have identified that preventing Li dendrite growth by stacking pressure could improve cycle life by consuming less electrolyte and preventing inactive Li0 accumulation. A similar conclusion is obtained in the study of electrodepositing Li metal anode calendar life and reactivity (safety), in which the porosity of the deposited Li dominates the Li metal corrosion rate and reactivity. The larger the porosity of deposited Li, the faster the corrosion rate/higher reactivity will be. Moreover, all cell components must be considered when it comes to the reactivity (safety) of Li metal batteries because components may react with each other. Our results revealed that dense Li metal anode owns similar reactivity as lithiated graphite/ Li-Si alloy. All results facilitate lithium metal battery design and manufacturing.
Electrochemical Engineering to Optimize the Next Generation of Space Power
Authors: Wagner Mary Elizabeth
Published: September 2023

The increasing democratization of space has sparked new research developments for on-orbit systems. As the technology flown becomes more sophisticated, their power needs increase as well, highlighting the battery as a critical component that ensures a consistent supply of electricity can be fed to the necessary satellite subsystems, independent of solar panel exposure (i.e. during eclipse conditions). However, despite the growth of the industry, space batteries are derived from technology engineered for terrestrial use, and thus are not optimized for all on-orbit challenges. It is the job of the electrochemist to develop batteries designed to meet the unique needs of the space environment. This talk will outline some of the key challenges facing the future of space power, including power requirements for in-space manufacturing, reduced capacity after an extended lifetime in space, and SWAP-C (size, weight, power and cost) considerations for smallsat constellations. Different pathways to optimize electrochemical engineering to meet these needs will be discussed, and recent efforts by the National Reconnaissance Office to support basic research and academic outreach will be highlighted.
(Invited) Bubble Trouble: Simulation of Molten Oxide Electrolysis in Reduced Gravity
Authors: Humbert Matthew , Brooks Geoffrey , Duffy Alan , Hargrave Chad , Rhamdhani Akbar
Published: September 2023

Molten Oxide Electrolysis (MOE) is a leading contender for processing extra-terrestrial minerals because it produces oxygen and liquid metal without the use of consumables. During electrolysis a gravitational field stratifies gas, electrolyte, and metal from each other by density. Processing on the moon, with ~1/6g, or Mars, with ~1/3g, will reduce the buoyancy force slowing bubble velocity and lowering convection intensity. Low thermal conductivity, (~1Wm-1K-1) and high viscosity, (~1Pa⋅s) of molten regolith contribute to thermal and chemical transport being dominated by convection, even as convection velocity decreases. We explore MOE system dynamics in Earth’s (1g), Mars’ (1/3g), and the Moon’s (1/6g) gravity through simulations that include composition and temperature dependent material properties and two phase flow. We implement the level set method to track the interface between the bubble laden flow near the anode and the bubble free flow far from the anode. By grouping bubble dynamics into the material properties of the fluid near the anode we relax the requirements for a fine mesh to track individual bubble-fluid interfaces, and are able to use a mesh that is finer than that required for a bubbly flow mixture model. Thus, all physics can be captured on one mesh. This is particularly relevant because bubble sizes for proposed systems are 1/10 to 1/100 of the system scale. While other simulations have been presented and experiments performed in micro and zero gravity for gas evolving electrolysis systems, none have investigated the downward facing electrode, heat transfer, or species diffusion. The focus of this work is to address this gap in the literature through simulation. Here, multiphysics simulation is supported by inspection of dimensionless groups and observations from other electrolysis systems. This work demonstrates that combining heat and mass transfer with temperature and composition dependent material properties is critical to designing MOE and other electrolysis systems for earth and beyond.
Electrochemical Oxygen Evolution from Metal Oxides Using Perovskite Anodes Towards Lunar Resource Utilization
Authors: Tanaka Seiya , Suzuki Yuta , Fukunaka Yasuhiro , Goto Takuya
Published: September 2023

In-situ resource utilization (ISRU) has been proposed for realizing sustainable lunar development. One of the representative resources on the Moon is lunar regolith, which covers the lunar surface. The chemical composition of lunar regolith resembles the constituents of the Earth: silica (SiO2) is the most abundant oxides in the lunar regolith. Silicon, which can be produced by silica reduction, will be the material for solar cells, and oxygen is essential for manned space exploration. Enormous amounts of silicon and oxygen will be obtainable on the Moon without transportation from the Earth by establishing silicon reduction methods without consumables. However, the conventional silica reduction method consumes vast amounts of carbon, which cannot be mined on the Moon.

For realizing carbon free silica reduction method consistent with the concept of ISRU, molten salt electrolysis processes using perovskite anodes has been researched. In this method, the silica dissolved in molten salts is electrolyzed using voltage with passage of direct current through electrodes, which generate oxygen gas and silicon by the electrochemical process. The perovskite oxides have high electrical conductivity and oxidation resistance. Therefore, the perovskite anodes have been expected as oxygen generation inert anodes.

In this study, we report the characteristics of perovskite-type anodes for oxygen generation measured in the electrolysis experiments. In molten fluoride containing silica at a temperature over 500℃, the measured cyclic voltammograms with a perovskite-type anode show drastically increases of current density at 2.6 V vs K+/K, which was approximately same to the oxygen generation potential in the previous molten salt electrolysis result without the perovskite anodes. The characteristics of perovskite-type anodes for oxygen generation will be discussed from the results of electrochemical measurements and chemical analysis using XRD, SEM, EDX, and ICP-AES analysis.
(Invited) Sodium-ion Batteries – an Energy Storage Solution
Authors: Sayers Ruth
Published: September 2023

Sodium ion batteries offer a sustainable and low cost energy storage solution. In this talk we look at

the fundamental principles behind how they work at a materials, cell and battery pack level, as well

as some of the challenges that Faradion have overcome to successfully commercialise the

technology.

We also look at what the future holds, as global energy demand increases, where are the near and

mid-term opportunities to deploy the technology, as well as the longer term outlook. The

presentation will address the current state of the art in sodium-ion batteries, as well as what the

future holds for the technology.