bluuebunny/crossref_metadata_2025 huggingface dataset:
Li Dendrite Formation on the Side of Cu Current Collector during Charging in Misaligned Pouch-Type Lithium-Ion Batteries
Authors: Choi Seungyeop , Kim Nayeon , Jin Dahee , Roh Youngjoon , Lee Yong Min
Published: September 2023

Not only high-capacity electrode materials but also electrode/cell design greatly governs the electrochemical performance of LIBs. For instance, there are systematic works to unravel the effect of area or capacity ratio between anode and cathode or the electrolyte amount. [1,2,3] Especially, our research group has already reported the effect of electrode misalignment, which can frequently occur during the coin cell assembly, on the electrochemical properties, where Li dendrites formed on the coin cell bottom mainly deteriorated the cell performance. [4] However, considering the commercial cell configurations like pouch-type LIBs, which have insulating polypropylene inner layer, those negative phenomena should be evaluated in misaligned LIB cells.

For this purpose, three pouch-type cells (well-aligned, slightly misaligned, and largely misaligned) using LixNi0.6Co0.2Mn0.2O2 cathode and graphite anode were fabricated in a dry room. Surprisingly, a similar misalignment effect to coin cells was also observed in the pouch-type cell, even though the inner layer of the Al-pouch is insulative. When we disassembled the misaligned cell after precycling, we could observe Li dendrites formed on the side of the Cu current collector (CC) of the anode. That is, the Li ions from the cathode are able to be plated on the metal side of Cu CC of a few micrometer thickness. Thus, even in pouch cells, the electrode misalignment can lead to Li inventory loss. To solve this problem, an insulating coating was applied to the side of the Cu CC, and as a result, the cycle performance of the misaligned cell was improved by suppressing the Li dendrite formation. In addition, the electrochemical characteristics were compared as a function of the lithiation state (SOL, x in LixNi0.6Co0.2Mn0.2O2) using EIS, DC-IR, XRD, etc.

Reference

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Power Sources
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Electrochem. Soc.
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Electrochem. Soc.
, 169 (2022) 023502
Corona Phase Molecular Recognition of Interleukin-6 Family Cytokines Using Nir Single Walled Carbon Nanotube
Authors: Jin Xiaojia , Lee Michael Andrew , Gong Xun , Bakh Naveed Ali , Park Minkyung , Cho Soo-Yeon , Strano Michael S.
Published: September 2023

The Interleukin-6 (IL-6) family of cytokines regulate inflammation and play important roles in numerous biochemical pathways. Understanding the fundamental molecular recognition of these molecules with synthetic substrates is key to new biomedical technologies, including assays and sensors, therapeutics and purification methods. In this work, we use Corona Phase Molecular Recognition (CoPhMoRe) to engineer new carbon nanotubes corona phases and study nanotube binding to IL6. Library screening identifies two CoPhMoRe constructs based on carbon nanotube complexation with a p(AA68-rand-BA
16
-rand-CD
16
) polymer (MK2) and a p(SS80-rand-BS
20
) polymer (P14) corona phases respectively. Both exhibit KD of binding of 8.38 ng/mL and 16.7 μg/mL respectively, with MK2 construct having a response function consistent with two stage binding for IL-6. Comparative binding experiments show that both constructs appear to recognize the axially aligned alpha-helical structures present in the IL-6 and other IL-6 family cytokines. The findings from this study elucidate how nanoparticle interfaces can be designed to lock onto specific protein features, particularly alpha-helical structures, to enable molecular recognition and new types of sensing technologies.
(General Student Poster Award Winner - 2nd Place) Electrochemical Routes for Polymer Upcycling
Authors: Haque Zenifar G. , Ortega Ramos Jessica , Botte Gerardine G
Published: September 2023

Approximately 380 million tons of plastic are produced annually, and it is projected to rise to nearly 1.1 billion by 2050 [1]. The largest fraction of such waste consists of polyethylene (PE) and polypropylene (PP), which commonly require energy-intensive methods to achieve depolymerization (such as pyrolysis and hydrogenolysis) due to their remarkable thermodynamic stability. Electrochemical methods are a promising alternative for polymer upcycling as they can utilize renewable energy to create an external potential, overcoming the thermodynamic constraints that the C-C bond cleavage endothermicity imposes on low-temperature polymer conversion. They also offer improved chemical process control by manipulating the electrode potential and minimizing the use and storage of hazardous reagents. Electrochemistry provides a broad range of opportunities for establishing green routes to converting plastic into valuable products.

Botte's group is investigating electrochemical approaches to convert polyolefins into valuable products like fuels and fatty acids [2]. Our findings indicate that an electrocatalyst in concert with controlled ionic strength and applied potential enable the selective functionalization of polyolefins and their defragmentation towards target molecules regardless of impurities present in the polymer. In this presentation, we will discuss results of the electrochemical functionalization and deconstruction of low-density polyethylene implementing transition metal electrocatalysts.

Acknowledgments: The authors would like to acknowledge the financial support of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Upcycling of Polymers Program, under Award DE-SC0022307

[1] J. E. Rorrer, C. Troyano-Valls, G. T. Beckham, and Y. Román-Leshkov, "Hydrogenolysis of Polypropylene and Mixed Polyolefin Plastic Waste over Ru/C to Produce Liquid Alkanes," ACS Sustainable Chemistry & Engineering, vol. 9, no. 35, pp. 11661-11666, 2021/09/06 2021, doi: 10.1021/acssuschemeng.1c03786.

[2] G. G. Botte, "Process for the Electrochemical Up-Cycling of Plastics (US Pending Patent)," U.S. Patent 63040929, 2020.
Multi-Metal Additive Manufacturing with Submicron Resolution by Electrohydrodynamic Redox 3D Printing
Authors: Nydegger Mirco , Reiser Alain , Spolenak Ralph
Published: September 2023

The ability to design metals with control over the 3D chemistry at a submicron level unlocks unique possibilities for tailoring and programming their properties. Small scale additive manufacturing of metals has recently shown promising results towards the direct synthesis of chemically heterogeneous 3D geometries. However, the fast and reliable deposition of a wide range of device-grade materials as well as the ability the change the chemistry on-the-fly still pose challenges to the field.

Here, we will show how electrohydrodynamic redox (EHD-RP) 3D printing can serve as a toolbox to manufacture multi-metal structures [1]. This technique is based on the dissolution, transfer and re-deposition of metals in solvents using electrochemistry. The on-demand generation of metal ions enables the local modification of the chemical composition in a voxel-by-voxel fashion. The confined electroplating process on the substrates allows feature sizes down to 120 nm, while providing an as-deposited dense microstructure. We’ll focus first on the challenges involved in depositing a large range of metals with EHD-RP [2]. Second, we’ll show how the deposition of metals using different solvents can be combined to manufacture multi-metal structures with a high chemical resolution.

[1] A. Reiser, M. Linden, P. Rohner, A. Marchand, H. Galinski, A. S. Sologubenko, J. M. Wheeler, R. Zenobi, D. Poulikakos, and R. Spolenak. Multi-metal electrohydrodynamic redox 3D printing at the submicron scale. Nat. Commun., 10(1):1-8, 2019.

[2] M. Nydegger, A. Pruška, H. Galinski, R. Zenobi, A. Reiser and R. Spolenak. Additive Manufacturing of Zn with Submicron Resolution and its Conversion into Zn/ZnO core-shell structures. Nanoscale, 2022
Development of Fuel Cell System Using Metal Hydride and Hydrogen Peroxide in Low-Oxygen Environments
Authors: Cheon Hyungjun , Kim Dongmin , Choi Sinwoo , Lee Bongjae , Roh Heesook , Bae Joongmyeon
Published: September 2023

Hydrogen energy is attracting attention as a promising power system due to high energy storage density and environmentally friendly features. For these reasons, fuel cell system using hydrogen energy in unmanned underwater vehicles have been studied. However, in low-oxygen environment, fuel cell system requires an oxygen storage as well as a hydrogen storage. In this study, a fuel cell system using a metal hydride and hydrogen peroxide was designed. The metal hydride can charge and discharge hydrogen at a lower pressure than a high-pressure hydrogen tank and has a high hydrogen storage density. In this system, AB2 type metal hydride is used to store hydrogen. Hydrogen desorption reaction of the metal hydride is an endothermic reaction, and heat supply is required to maintain the temperature of the metal hydride in order to stably supply hydrogen. Therefore, in this system, hydrogen peroxide was used as an oxygen source. Hydrogen peroxide reacts with a metal catalyst to generate oxygen and water. The decomposition reaction of hydrogen peroxide is an exothermic reaction and can supply heat required for the metal hydride. In this system, hydrogen peroxide is decomposed into water and oxygen through a catalytic reaction, and the generated heat is supplied to the metal hydride. Finally, hydrogen and oxygen are supplied to the PEMFC stack to generate power. For system design, in this study, PCT characteristics of AB2 type metal hydride, thermal management method, and hydrogen peroxide decomposition catalyst were studied, and an operation strategy for non-humidified PEMFC operation was proposed. This system generated a power output of about 290 W for 97 hours, and the hydrogen utilization rate of the fuel cell was confirmed to be 92.3%.
Zn-Introduced Platinum-Cobalt Intermetallic Catalyst for Oxygen Reduction Reaction
Authors: Chang HyunWoo , Lee KwangHo , Roh JeongHan , Lee SangJae , Bak Junu , Shin Dongwon , Kim Minjun , Cho EunAe
Published: September 2023

Extensive commercialization of polymer electrolyte membrane fuel cells (PEMFCs) is restricted by high price of Pt which is commonly used to promote the oxygen reduction reaction (ORR). Therefore, reducing the dosage of Pt in the ORR catalysts while maintaining high activity and stability is important key for accelerating PEMFCs’ commercialization. In this study, Zn-introduced PtCo intermetallic nanoparticles supported on Zn-NC substrate (Zn-PtCo/Zn-NC) were synthesized, demonstrating superior activity and durability toward the acidic ORR in half-cell. The Zn-PtCo/Zn-NC catalyst was synthesized via the gas phase reduction method for the deposition of PtCo nanoparticles (NPs) on Zn-NC, and subsequent post-annealing process. During the annealing procedure, diffusion of Zn atoms into PtCo NPs occurred and leaded to enhanced atom-ordering of the intermetallic NPs. In the half-cell configuration, the Zn-PtCo/Zn-NC catalyst showed about 7.3-fold enhancement in the mass activity, compared to that of the commercial Pt/C catalyst. The high activity of the Zn-PtCo/Zn-NC was attributed to the incorporation of Zn atoms and the ordered structure which synergistically enhanced the ligand effects. In addition, the polarization curve of the Zn-PtCo/Zn-NC showed only a negative shift of 9 mV in a half-wave potential after the accelerated durability test (ADT), indicating the excellent stability of the catalyst. The robustness of the Zn-PtCo/Zn-NC was reinforced due to the thermodynamically stable structure of the atom-ordered intermetallic phase. The synthesis strategy presented in this work provides new pathway for developing the electrocatalysts applicable to the energy conversion devices.
Proton Exchange Membrane Fuel Cell Chemical and Mechanical Durability Study of Heteropoly Acid Functionalized Perfluorinated Sulfonic Acid with Expanded Polyteterafluoroethylene Support
Authors: Kim Chuloong (Christoph) , Kuo Mei-Chen , Lindell Matthew , Jiang Ruichun , Gittleman Craig S , Herring Andrew M.
Published: September 2023

The application of proton exchange membrane fuel cells to heavy-duty vehicles has been a new trend for fuel cell society due to high efficiency, power density, faster refueling, and ability to remove auxiliary power units. However, the critical bottleneck for the commercialization and technology transfer from already-commercialized light-duty fuel cell vehicles is the chemical and mechanical durability of the proton exchange membranes. Chemical degradation is initiated by H2O2 which forms ▪OH radicals during the fuel cell operation. The radicals that are formed during the fuel cell operation can be suppressed by adding a radical decomposing catalyst such as cerium, cerium oxide, manganese, manganese oxide, and heteropoly acids. However, those metal oxides and heteropoly acids lack immobilization. We have previously reported the chemical immobilization of silicotungstic acid (HPA), a heteropoly acid with radical decomposing functionality, using dehydrofluorination. This has resulted in improvements in both the chemical durability and proton conductivity, wherein the HPA serves as a proton conductor.

In this study, we applied the chemical anchoring synthesis method to multiple polymers with different binding monomer group ratios and supported with expanded-polyterafluorethylene (e-PTFE) support. We investigated the optimized HPA ratio to the perfluorinated sulfonic acid membrane and studied the chemical and mechanical durability of the composite membrane. The structure-property relationship of composite membranes was studied using scanning electron microscopy (SEM), small angle x-ray scattering, and dynamic mechanical analysis (DMA). The chemical degradation was tested with open-circuit voltage (OCV) and fluoride release rate (FRR) under the accelerated standard condition (AST).
The Effect of Heteroatom-Doped Graphene Supports on the PtNPs Electrocatalytic Activity for ORR
Authors: Chambers Raegan , Erikson Heiki , Tammeveski Kaido
Published: September 2023

There has been a global shift in energy production emphasizing the reduction of fossil fuels by the augmentation of more renewable energy. Proton-exchange membrane fuel cells (PEMFC) and anion-exchange membrane fuel cells (AEMFC) can mitigate a need for fossil fuels and provide an alternative route of hydrogen-based energy production. Fuel cells utilize a catalyst at both the cathode and anode to increase the overall kinetics of the redox reactions and enhance the cell performance.1 Current fuel cell technology employs a platinum based catalyst due to its efficiency and robust performance in both alkaline and acidic environments.1,2 The drawbacks associated with Pt-based catalysts are centered around its economic viability and its affinity towards surface poisoning.1

A catalyst using platinum nanoparticles (PtNPs) loaded onto a graphene support can address some of the aforementioned drawbacks.1 To maximize the electrocatalytic activity of the PtNPs – all aspects of the PtNPs catalyst must be optimized, which includes the optimization of the support material. The effect that the different commercially available heteroatom-doped graphene had on the activity of the PtNPs was investigated during this study. The PtNPs were synthesized using the citrate method, which produces ≤ 5 nm size particles. Our study confirmed that the choice of doped graphene support has an effect on the overall activity of PtNPs. The results were confirmed via a comparison with PtNPs supported on Vulcan XC-72R carbon. All Pt catalysts supported on the doped graphene showed an improvement in the oxygen reduction reaction (ORR) half-wave potentials (E
1/2) over PtNPs on Vulcan XC-72R carbon (Fig. 1A); with the nitrogen-doped graphene exhibiting the greatest improvements in the half-wave potential with the E
1/2 value of 0.85 V vs. RHE as compared to the 0.77 V of the Pt/C. A comparison of the Tafel slopes (Fig. 1B) confirmed that the transfer of the first electron was the rate-determining step for all of the Pt catalysts supported on doped graphene as all Tafel slopes were around -120 mV per decade. This has been confirmed in literature with Pt on various carbon supports.2

Figure 1. A) Comparison of RDE polarization curves for oxygen reduction on Pt/NGr (pink), Pt/SGr (green) and Pt/N-PGr (blue) with Pt/C (black) at 1900 rpm in a O2-saturated 0.1 M HClO4 solution (v= 10 mV s−1). B) Mass transfer corrected Tafel plots derived from A

References:

(1) Holton, O. T.; Stevenson, J. W. The Role of Platinum in Proton Exchange Membrane Fuel Cells. Platin. Met. Rev.
2013, 57 (4), 259–271. https://doi.org/10.1595/147106713X671222.

(2) Hussain, S.; Erikson, H.; Kongi, N.; Sarapuu, A.; Solla-Gullón, J.; Maia, G.; Kannan, A. M.; Alonso-Vante, N.; Tammeveski, K. Oxygen Reduction Reaction on Nanostructured Pt-Based Electrocatalysts: A Review. Int. J. Hydrog. Energy
2020, 45 (56), 31775–31797. https://doi.org/10.1016/j.ijhydene.2020.08.215.

Figure 1
Pulse Waveforms Monitoring Using Supercapacitive Sensing
Authors: Chowdhury Azmal Huda , Jafarizadeh Borzooye , Pala Nezih , Wang Chunlei
Published: September 2023

There is a recent boost of interest in wearable, flexible sensors, and devices for non-invasive monitoring of physiological parameters. Among such flexible sensors, considerable research has been appointed towards flexible pressure sensors. These pressure sensors can detect large and small deformations suitable for applications ranging from e-skin to detecting tiny pulse waveforms from the neck and wrist artery. In order to realize a sensor capable of pressure sensing targeting numerous applications, the recent sensors should have high sensitivity with an extended pressure range, fast response time, and a high signal-to-noise ratio. Pulse waveforms are important cardiovascular biomarkers that bear essential information about cardiovascular health. In order to visualize and extract meaningful information from the pulse waveforms, acquiring high-quality pulse waveforms is the prerequisite. However, building highly sensitive pressure sensors is still challenging while maintaining the sensitivity with a broad pressure sensing range. Targeting these issues, this study presents a facile and cost-effective approach to realize a capacitive pressure sensor based on a supercapacitive sensing mechanism. The sensor could achieve high sensitivity of 2.9kPa-1 with a broad and linear range of around 100kPa. Besides, the sensor has a fast response time of 0.2s and negligible hysteresis. The sensor showed no performance degradation after 5000 cycles. In order to show the practicality, the sensor was used to acquire pulse waveforms from wrist and neck arteries under different conditions. The excellent performance of the sensor was observed as the sensor could detect detailed pulse waveforms under all circumstances. The detailed results will be discussed during the presentation.
Hydrogen Gas Bubble Evolution on Electrocatalytic Nanostructures in Microgravity Environment
Authors: Akay Oemer , Brinkert Katharina , Romero-Calvo Álvaro , Saravanabavan Shaumica , Sokalu Eniola , Giersig Michael
Published: September 2023

Photoelectrochemical (PEC) monolithic devices for oxygen and chemical production are attractive for space applications due to predominant weight and volume constraints as well as a high system tunability. Here, advanced semiconductor-electrocatalyst systems integrate the processes of light absorption, charge separation and catalysis in one device - processes, which are usually carried out e.g., on the International Space Station (ISS) by an electrolyser coupled to external PV cells. Due to the near absence of buoyancy and buoyancy-induced convection in micro gravity, all (photo)electrolyser systems in space naturally have lower efficiencies, as gas bubble desorption and phase separation are severely hindered. We report on a new approach to design the electrocatalyst morphology on a nanoscale in order to modify the physicochemical properties of the photoelectrode and thus allow for continuous gas bubbles desorption and efficient operation of the PEC device in microgravity. Using a rhodium-coated p-InP model photoelectrochemical system, we discuss different Rh electrocatalyst nanotopographies fabricated by shadow nanosphere lithography and report on their characterisation as well as performance in photoelectrochemical measurements realised during 9.2 s of free fall at the Bremen Drop Tower, Center of Applied Space Technology and Microgravity (ZARM). In particular, we elucidate on how the electrocatalyst nanostructures affect the gas bubble size during growth and at detachment from the electrode and conclude on an efficient (photo-)electrode design for hydrogen evolution in microgravity.
(Invited) Leveraging Magnetohydrodynamic Mechanisms for Stable and Efficient Microgravity Electrolysis
Authors: Romero-Calvo Álvaro , Brinkert Katharina
Published: September 2023

Water electrolysis is the fundamental chemical process for oxygen and hydrogen production in space. It is widely employed in modern environmental control and life support systems, propulsion technologies, and high-density energy storage devices. Furthermore, future interplanetary missions are likely to employ water as a commodity acquired and processed by In Situ Resource Utilization (ISRU) methodologies to produce propellants, thereby reducing vehicle launch mass.

The absence of buoyancy results in major technical challenges for the operation of electrolytic cells in low gravity. The need to detach and collect oxygen and hydrogen bubbles has been traditionally addressed by means of forced water recirculation loops. However, this leads to complex, inefficient, and unreliable liquid management devices composed of multiple elements and moving parts. Two distinct magnetohydrodynamic (MHD) mechanisms may instead be employed to induce phase separation: diamagnetic, and Lorentz forces. The former arises in the presence of strong, inhomogeneous magnetic fields and results in a magnetic buoyancy effect. The latter is a consequence of the imposition of a magnetic field to the current generated between two electrodes. Both approaches can potentially lead to a new generation of electrolytic cells with minimum or no moving parts, hence enabling the human deep space operations with minimum mass and power penalties.

Dedicated microgravity experiments are required to study these novel magnetically enhanced electrolysis concepts. This presentation introduces the fundamentals of both methods and discusses the experimental design and results from several experimental campaigns at ZARM’s drop tower and Blue Origin’s New Shepard. The performance of representative electrolytic cells subject to different MHD regimes is addressed from an electrochemical and fluid dynamic perspectives. It is demonstrated that the MHD force effectively detaches and collects gas bubbles in microgravity while increasing the current density and improving the stability of the electrolytic cell. Ultimately, this opens the door for the development of highly-efficient space electrolytic cells with applications to human and robotic space exploration.
(Invited) The Electrostatic Levitation Furnace Onboard the International Space Station for Container-Less Material Processing and Thermophysical Property Measurements at Extremely High Temperature
Authors: Ishikawa Takehiko , Koyama Chihiro , Oda Hirohisa , Shimonishi Rina , Ito Tsuyoshi
Published: September 2023

Electrostatic levitation is one of the container-less processing methods which utilizes Coulomb force between a charged sample and surrounding electrodes. Contrary to the other methods, electrostatic levitation cannot create a potential minimum, so high-speed feedback position control is necessary. Because of this technical difficulty, development of this method was behind to other methods, such as electromagnetic levitation, or acoustic levitation. Samples can be levitated even in ground. However, to levitate samples against gravity, huge electric field and huge surface charge on the sample are required. This creates some limitations in ground experiments. Firstly, Oxides samples are hard to levitate due to low surface charge. Secondly, experiment in inert gas environment is impossible to prevent electric discharge among electrodes. These limitations can be easily solved in microgravity. Oxides sample cane be levitated and melted. Metals and alloys can be processed in inert gas to suppress evaporation.

The electrostatic levitation furnace on the International Space Station (ISS-ELF) developed by Japan Aerospace Exploration Agency, was launched to the ISS in 2015. Then, Installation to the MSPR (multi-purpose Small Payload Rack) was conducted in the next year. Since then, a variety of oxide/ metal samples have been levitated and melted in the facility. The ISS-ELF has a capability to measure thermophysical property of extremely high temperature melts. Density, Surface tension, and viscosity can be measured by this facility. Status of thermophysical property measurements is described in this presentation.
Numerical Modeling of a Pressurized Solid Oxide Fuel Cell for Electric Aircraft
Authors: Nakajima Hironori , Yamashita Jin , Okai Keiichi , Kojima Takayuki
Published: September 2023

Electric aircraft have attracted attention to reducing carbon dioxide emissions and fuel consumption. Compared with conventional aircraft, distributed propulsion with electric motors is expected to increase the efficiency of the propulsion systems for the above purpose. Furthermore, the application of solid oxide fuel cell (SOFC) – gas turbine (GT) hybrid systems to their electric power sources is promising for higher efficiency. We have thus developed a three-dimensional numerical model of a planar SOFC pressurized for the combination with a GT for the optimal design and operation of practical cells. A software package with the finite element method (COMSOL Multiphysics 5.4) is employed to analyze the current and temperature distributions in a cell. Exchange current densities under pressurized conditions are experimentally evaluated using a symmetric test cell for the electrochemical kinetics in the model.
Application of Water-Based Ferrofluid for Water Electrolysis
Authors: Iwamoto Yuhiro , Chimura Kotaro , Ido Yasushi , Ishii Yosuke , Jeyadevan Balachandran
Published: September 2023

A combination of renewable energies and water electrolysis has been attracting much attention as an environmentally-friendly method to produce hydrogen, which has been expected as promising future energy storage and carrier media. And micro-gravity induces the adsorption of gas-bubbles on the surface of electrodes and this leads the declination of water electrolysis. In the present study, a new method which has the potential to dramatically enhance the water electrolysis efficiency was proposed by utilizing the magnetic buoyancy. Using water-based ferrofluids as an electrolyte and directly electrolyzing them in the presence of inhomogeneous magnetic fields enhance the desorption of gas-bubbles adsorbed on electrodes.

When non-magnetic bodies are placed in the ferrofluid and are exposed to an inhomogeneous magnetic field, the magnetic buoyancy force acts on the non-magnetic bodies. Because the gradient of the magnetic field gives the magnetic buoyancy force, the non-magnetic body moves as the non-magnetic body is ejected from the magnetic field. When the water-based ferrofluid is used as an electrolyte and magnets are placed nearby electrodes, the magnetic buoyancy force acts on the bubbles (H2 and O2) generated from the surface of the electrodes, resulting in the water electrolysis enhancement.

However, the effect of the magnetic fields on the water electrolysis using the ferrofluid is not well understood. In the present study, to understand the effect of the magnetic field on the water electrolysis, the chronoamperometry measurements in the presence of the magnetic field was carried out. The results showed that the water electrolysis is found to be enhanced by increasing the magnetic field intensity due to the magnetic buoyancy force. The present study showed that our proposed method has a great potential to enhance the water electrolysis substantially.

In addition, we investigated the effect of magnetic field strength on the water electrolysis process by a dynamic impedance method. The Nyquist plot was obtained by the dynamic impedance method. The tested electrolyte was a water-based ferrofluid adding Na2SO4 with 0.1 mol/L. When the magnetic field intensity increases, Z
Re decreases, which represents that the resistance in the water electrolysis becomes smaller. The equivalent circuit fits the experimental data well, resulting in that it is possible to divide the whole resistance into the charge-transfer and solution resistances. The charge-transfer resistance dramatically decreases with the magnetic field strength, while the solution resistance doesn't change. This phenomenon explains that the magnetic buoyancy sufficiently enhances the bubble desorption, resulting in the water electrolysis enhancement.
(Invited) Effect of Gaseous Tritium Environments on Betavoltaic Device Longevity
Authors: Ellis Brian , Patel Jayesh , Kaloni Thaneshwor , Torres Edmanuel
Published: September 2023

Direct betavoltaic energy conversion is a specialized energy harvesting technology, converting beta radiation from a radiation source directly into electricity using a semiconductor. Of the most common beta emitting isotopes, tritium betavoltaics hold promise owing to the high specific activity of solid tritium compounds, low shielding requirements and relatively high availability. Betavoltaic devices offer great promise to produce continuous quantities of nanowatt to microwatt power over the course of several years, particularly for low-power sensor, medical, and space applications where sunlight is too sparse for solar cell use or where battery replacement is challenging.

Canadian Nuclear Laboratories (CNL) is currently developing betavoltaic devices based on tritium. CNL has unique facilities to produce, fabricate and test betavoltaic devices. Computational techniques have been used to address challenges of longevity and electron-hole pair generation in semiconductor materials, in particular (In,Ga)P. Long-term studies on test wafers in different tritium-containing environments and the effects on power output and longevity will also be discussed.
(Invited) Electrochemical Conversion of CO2 Into Oxygen/ and C/CO in Molten Carbonate
Authors: Yin Huayi , Wang Dihua
Published: September 2023

The molten salt CO2 capture and electrochemical transformation (MSCC-ET) process has been demonstrated as an effective approach to capturing and converting CO2 into oxygen and C/CO [1-2]. The effective CO2 capture and electrochemical conversion rely on the high-temperature molten carbonate electrolytes and the cost-effective inert oxygen-evolution anode. In recent years, we have focused on the electrolyte engineering to modulate the reactions at both the cathode and anode as well as the CO2 capture efficiency [3-4]. Besides, we insist on developing iron- and nickel-base oxygen-evolution inert anodes in terms of revealing the fundamental principles and basic guidelines for choosing proper materials and fabrication processes [5]. By doing so, we can prepare functional carbon materials or CO at the cathode with a high current efficiency of over 90%, and produce oxygen at the inert anode. In addition, the kilo-ampere scale electrolyzer was built to produce oxygen, carbon or CO with an energy efficiency of over 50%. Therefore, the molten carbonate CO2 electrolyzer shows its potential to convert CO2 on the Mars to produce oxygen and fuels to support the future exploration of outer space.

References

[1] H. Y. Yin, D. H. Wang*, et al., Capture and electrochemical conversion of CO2 to value-added carbon and oxygen by molten salt electrolysis. Energy & Environmental Science, 2013, 6: 1538-1545.

[2] R. Jiang, M. X. Gao, X. H. Mao, D. H. Wang*. Advancements and potentials of molten salt CO2 capture and electrochemical transformation (MSCC-ET) process, Current Opinion in Electrochemistry, 2019, 17: 38-46.

[3] B. W. Deng, J. J. Tang, X. H. Mao, Y. Q. Song, H. Zhu, W. Xiao, D. H. Wang*. Kinetic and Thermodynamic Characterization of Enhanced Carbon Dioxide Absorption Process with Lithium Oxide-Containing Ternary Molten Carbonate, Environmental Science & Technology, 2016, 50(19): 10588-10595.

[4] Z. S Yang, B. W. Deng, K. F. Du, H. Y. Yin*, D. H. Wang*, A general descriptor for guiding the electrolysis of CO2 in molten carbonate, 2022, in press.

[5] P. L. Wang, K. F. Du, Y. P. Dou, H. Zhu, D. H. Wang*, Corrosion behaviour and mechanism of nickel anode in SO42- containing molten Li2CO3-Na2CO3-K2CO3. Corrosion Science 2022, 166.

Figure 1
(Keynote) Experimental Insights for Extra-Terrestrial Application of Molten Oxide Electrolysis
Authors: Boury Charles , Paras Jonathan , Allanore Antoine
Published: September 2023

Molten oxide electrolysis (MOE) has been considered for several decades for oxygen generation from extra-terrestrial oxides. It consists in the electrolytic decomposition of the rocks or soils, which are mixture of the common earth oxides (silica, iron oxide(s), alumina, magnesia...). Therein the oxides mixture is acting as the electrolyte, in the molten state. The target anodic product is oxygen gas, and the cathodic product is a metal. In one version of MOE, the temperature is high enough to sustain the production of a liquid metal, offering the opportunity to conceive a fully continuous process thanks to periodic tapping of the cathodic product. A key attribute of such approach is the high current density (productivity) that can be anticipated thanks to the high concentration of oxygen and metal present in the electrolyte. This leads to electrochemical engineering questions that are not commonly discussed in other electrolysis methods. This presentation offers to review some of the prior findings related to the underlying thermodynamic of the process, as well as the oxygen evolution and transport phenomena that support the development of MOE. Recent findings combining a container-less method and advanced electrochemical techniques will be presented.
(Invited) Zirconia-Based Hollow Anode Development for Molten Regolith Electrolysis
Authors: Yu Kevin , Chi Ike , West William C , Reidy Lorlyn P , Faber Katherine T
Published: September 2023

Molten regolith electrolysis (MRE) is a promising in-situ resource utilization technique for producing oxygen and molten metal alloys from lunar regolith. However, MRE requires operating temperatures at or above 1600°C to melt lunar regolith and dissociate the molten oxides to enable electrolysis. Anode degradation in this corrosive and oxidizing environment is a major concern for long-term operation on the lunar surface and can be mitigated by a novel hollow anode design with a solid electrolyte shell and porous metallic core as proposed here. The metallic anode will be shielded from the regolith melt by an oxygen ion-conducting zirconia-based ceramic, allowing electron transfer to occur in the interior of the shell. Additionally, bubble formation at a traditional anode surface is avoided, thereby eliminating the concerns of molten regolith splatter and increased ohmic resistance. This work focuses on corrosion studies of dense stabilized zirconia in contact with molten lunar mare and highlands regolith simulants at 1600°C to support hollow anode development. The interactions between zirconia and molten regolith are characterized using SEM/EDS, with an emphasis on elemental analysis to assess reactivity and degradation of zirconia.
Electrochemical and Spectroscopic Study on Electrochemical Processing of Silicon in Fluoride Melt
Authors: Suzuki Yuta , Fukunaka Yasuhiro , Goto Takuya
Published: September 2023

For sustainable space utilization on the Moon and the Mars, it is essential to establish in-situ resources and energy utilization systems in space. Because of the large amount of silica in the regolith which composed of metallic oxides on the Moon and the Mars, the technology development for the covering the silica to silicon and oxygen is indispensable. The silicon can be used as a key material for silicon photovoltaics. Against this background, the authors have studied the electrochemical reduction of silica to silicon in fluoride melt. We propose a one-step process to obtain a silicon film on the cathode by electrolysis using molten salts containing silica. To determine the feasibility of the proposed process, it is necessary to understand the effects of the physicochemical properties such as the coordination structure of Si ions in the fluoride melt since the difference in the melt structure affects the nucleation and growth mechanisms of the silicon electrodeposition. However, there are few reports on the dissolved state of silicon ions in fluoride melt. The author thus clarified the relationship of the electrochemical behavior of coordination structure of Si ions in fluoride melts composed of LiF, KF, and NaF.

The coordination structure of Si ions in the fluoride melt was investigated by high-temperature Raman spectroscopy and quantum chemical calculations based on the density functional theory (DFT). The vibrational modes of the Si ions were detected through high-temperature Raman spectroscopy and the Raman bands were simulated by DFT calculations. We clarified the interaction between Si ions and cation and anion species such as Li+, Na+, K+, O2−, and F−. In addition, the electrochemical behavior of Si ions was investigated by electrochemical measurements. The effect of O2− ions on the dissolution of SiO2 and the electrodeposition process of Si in fluoride molten salts revealed a significant increase in the reduction current of Si ions as well as in the film thickness and current efficiency of deposited Si. The molten fluoride system, which can fabricate Si films from SiO2 at low temperatures, has the potential to develop environmentally friendly and sustainable electrolytic systems.
(Invited, Digital Presentation) Electrochemistry at the Atomic Scale
Authors: Jacob Timo
Published: September 2023

Electrochemistry is at the heart of many important industrial processes or systems, ranging from electrolysis and hydrogen evolution over corrosion, metal deposition up to batteries, fuel cells and photoelectrochemical devices. Here, the interface between the electrolyte and the electrolyte, which can be considered the site where electrocatalytic processes occur, is of particular interest. Due to its complexity and multi-component environment even after many decades of research, our understanding of the properties of this interface is still scarce. In this talk we will discuss how modern theoretical multi-scale methods in conjunction with in-situ experiments on well-defined model systems is capable to unravel the structure and composition of these interfaces as well as the ongoing electrochemical processes.

We will concentrate on metal-ion based energy storage systems, including Li-ion and Mg-ion batteries. In our experimental work we concentrated on realizing and investigating the deposition of these metal ions on model electrodes in order to understand apparent nucleation and growth processes (e.g. dendrite formation/growth). By combining different in-situ structure sensitive techniques we could resolve the initial stages of dendrite formation, which we believe is prerequisite to avoid or control their appearance [1]. The experimental work was accompanied with corresponding theoretical studies [2] on the self-diffusion on transition metal electrodes, battery-relevant materials and finally the dynamics of alloy-based electrocatalysts under operation conditions, showing the importance and urgent need for in-operando experimental studies. Further, we will discuss our recent work on understanding plasma-electrochemical systems and how plasmas are capable to alter the structure and properties of materials [3].

[1] Berger, C.; Ceblin M.; Jacob T., ChemElectroChem
2017, 4, 261.

[2] Gaißmaier, D.; Fantauzzi, D.; Jacob T., J. Chem. Phys.
2019, 150, 041723.

[3] Menezes, P.V.; Elnagar, M.M.; Eckl, M.; Al-Shakran, M.; Menezes, P.W.; Jacob, T., Adv.
Funct. Mater., DOI: 10.1002/adfm.202107058.
Sodium-Ion Cathodes Designed for in-Situ Resource Utilization on the Moon and Mars
Authors: Huddleston William , Dornbusch Donald , Maurel Alexis , Martinez Ana Cristina , Seol Myeonglok , Henry Christopher , Jones Jennifer M. , Yelamanchi Bharat , Chavari Sina Bakhtar , Edmunson Jennifer E. , Sreenivasan Sreeprasad T , Cortes Pedro , MacDonald Eric , Sherrard Cameroun
Published: September 2023

On-demand in-space and on-surface manufacturing of batteries is sought to deliver energy storage devices needed for sustained human presence on the Moon and Mars. In-situ resource utilization (ISRU) is a disruptive approach that reduces the dependence on launch payload weight and volume to maximize long-term sustainability of exploration where resupply may be infeasible or costly. While lithium-ion batteries have seen widespread adoption in mobile devices and electric vehicles, the low abundance of lithium in lunar and martian regolith necessitates selection of an alternative chemistry for batteries derived from ISRU materials. Compared to lithium, sodium and the appropriate redox active cations for sodium-ion batteries are more abundant. However, state-of-the-art sodium-ion cathodes may be more complex in chemistry and use elements that are not feasible to attain by ISRU manufacturing. In this work, candidate sodium-ion cathodes were studied within the elemental abundance limitations on the Moon and Mars and in consideration of requirements for 3D printing and post-printing thermal treatment, such as stability of active material during resin curing and burnout. Cathode composition and processing conditions were varied to explore the balance between specific energy density and cycling performance with elemental abundance, specifically searching for replacement of manganese in layered and tunnel-type cathodes. This study found that a critical manganese content is required to stabilize the orthorhombic tunnel type structure with Pbam symmetry (Na0.44MnO2 type), over the NaTiFeO4 type Pnma symmetry, and that the stability was also a function of sodium content and calcination temperature.
Characterising the Ionic Transport and Thermodynamic Properties of Potassium-Ion Electrolytes
Authors: Dhir Shobhan , Jagger Ben , Maguire Alen , Pasta Mauro
Published: September 2023

The lithium price has increased more than sevenfold since the start of 2021 (as of May 2022), reaching unprecedented price levels and demonstrating significant challenges for the security of supply of lithium for lithium-ion batteries (LIBs)1. With forecasts showing a potential significant lithium supply deficit by 20301, the case for alternative chemistries based on abundant minerals which can fulfil some LIB functions has never been stronger. Sodium-ion batteries (NIBs) and potassium-ion batteries (KIBs) are emerging as promising complementary technologies to lithium-ion batteries (LIBs) due to the availability and low cost of sodium and potassium, and the minerals comprising their leading electrodes2
,
3. KIBs have a significant advantage over NIBs as K+ can reversibly intercalate into the graphite electrodes used in LIBs, thus one of the primary components of KIBs is already available at commercial scale, unlike for NIBs2. The lower charge density of K+ compared to Li+ has also been suggested to result in superior ion transport in the electrolyte with KIBs potentially able to deliver superior rate capability and low-temperature performance. However, a comprehensive characterisation of the ionic transport and thermodynamic properties of nonaqueous K-ion electrolytes, critical to the development of KIBs, has not yet been reported. Here, for the first time, we fully characterise the ionic transport and thermodynamic properties of a nonaqueous K-ion electrolyte4, potassium bis(fluorosulfonyl)imide (KFSI) in 1,2-dimethoxyethane (DME) and compare it with its Li-ion equivalent (LiFSI in DME) over the concentration range 0.25–2 m. This was realised by developing a K metal preparation protocol enabling sufficient K metal stability for electrolyte characterisation. Our results demonstrate that the K-ion electrolyte indeed displays significantly higher salt diffusion coefficients and transference numbers than the Li-ion electrolyte, evidencing the potential for high-power applications of KIBs.

IEA. Global EV Outlook 2022. (IEA, 2022).

Dhir, S., Wheeler, S., Capone, I. & Pasta, M. Outlook on K-Ion Batteries. Chem vol. 6 2442–2460 (2020). doi: 10.1016/j.chempr.2020.08.012

Hosaka, T., Kubota, K., Hameed, A. S. & Komaba, S. Research Development on K-Ion Batteries. Chem. Rev. acs.chemrev.9b00463 (2020) doi:10.1021/acs.chemrev.9b00463.

Dhir, S., Jagger, B., Maguire, A. & Pasta, M. Characterising the Ionic Transport and Thermodynamic Properties of Potassium-ion Electrolytes. Res. Sq. (2022) doi:10.21203/RS.3.RS-2310020/V1.

Figure 1
Cycling Performance of Zinc-Nickel Rechargeable Battery Using Segmentation of Electrolyte
Authors: Morimitsu Masatsugu , Okumura Takuya , Yasuda Mayu
Published: September 2023

An aqueous rechargeable battery (ARB) shows a high safety and a potential of high cycleability, which have been demonstrated with nickel-hydrogen batteries (NHB) used in electrified vehicles such as HEV and PHEV and electronic devices. A zinc-nickel secondary battery (ZNB) is one of the promising candidates of next-generation ARB which could have higher energy density and power density than NHB, although the zinc anode for secondary uses is still suffering from the issues on dendrite growth and non-uniform redistribution of zinc and zinc oxide, because they result in an internal short circuit and a poor capacity retention.

In this paper, we introduce a novel zinc anode with segmentation of electrolyte (SoE) developed in our recent works. The concept of SoE is to segment the space of the electrolyte between the anode and the cathode. The electrolyte is KOH solutions containing zincate ions that are the intermediate of redox reaction between zinc and zinc oxide, and SoE gives the limited space for zincate ions, within which they can move free but the concentration change is suppressed in the limited space so that the non-uniform reaction distribution during charge and discharge is also inhibited.

Our ZNB using SoE technology presented the excellent cycling performance at 1 C of charge-discharge rate for 5,500 cycles, in which the charge and discharge voltages hardly changed and the discharge capacity was 90% or more of the initial one during the cycles [1]. Comparison to ZNB using non-woven separator further indicated that SoE technology is beneficial to improve the cycling performance on cell voltage and capacity retention and ZNB with SoE is unnecessary to use non-woven separator. SoE is expected to solve the zinc anode problems of ZNB, i.e., both zinc dendrite and non-uniform distribution of zinc/zinc oxide, and may be applied to other zinc rechargeable battery such as zinc-air battery.

This work was financially supported by DOWA Holdings, Co. Ltd.

Ref. [1] M. Morimitsu, Patent No. WO-A1-2021/049609.

Figure 1