bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) (Photo)Electrochemical Cells for Hydrogen Production and Carbon Dioxide Utilization
Authors: Minegishi Tsutomu 
Published: July 2022

Photoelectrochemical (PEC) and electrochemical cells can produce hydrogen from water and/or can produce useful chemicals from carbon dioxide, and, thus, are the key technologies for construction of carbon neutral society.
Direct water splitting using photoelectrochemical cell is one of the promising means to produce hydrogen utilizing solar energy. The most important issue for photoelectrode the central of photoelectrochemical cell is narrow bandgap combined with large reaction driving force. Cu(In,Ga)Se2 (CIGS) which is employed as an absorber material in photovoltaic devices is one of the promising photocathode materials because of its long absorption edge of >1000 nm. [1] However, its driving force for water splitting is limited because of relatively shallow valence band maximum (VBM). The solid solution between ZnSe and CIGS (ZnSe-CIGS) is one of the promising candidates of photocathode material for water splitting because of its long absorption edge, ~900 nm, and large driving force, ~1.0 V. [2] In the present study, we investigated introduction of tellurium during ZnSe-CIGS thin films, and found the tellurium introduction increase grain size of ZnSe-CIGS film. The sequential deposition of Ga-rich layer and In-rich layer resulted in formation of composition gradient which facilitate charge separation thorough conduction band minimum (CBM) gradient. The ZnSe-CIGS base photocathode prepared with employing tellurium introduction and composition gradient showed significantly increased incident photon-to-current conversion efficiencies (IPCEs), close to unity. [3]
The electrochemical cell with gas diffusion electrode (GDE) for carbon dioxide reduction reaction (CO2RR) can produce useful chemicals efficiently. Copper species are the catalysts with capable of producing C2 products such as C2H5OH and C2H4. In the present study, Cu2O was examined as an electrocatalyst for CO2RR. A GDE composed of carbon paper coated with Cu2O by electroplating method showed C2H4 production with faradaic efficiency (FE) of >50% and C2H5OH production with FE of >20% under the optimized conditions for >10 hours.
References

H. Kumagai, T. Minegishi, N. Sato, T. Yamada, J. Kubota, K. Domen, J. Mater. Chem. A, 3, 8300 (2015).

H. Kaneko, T. Minegishi, M. Nakabayashi, N. Shibata, K. Domen, Angew.Chem. Int. Ed. 55,15329 (2016).

T. Minegishi, S. Yamaguchi, M. Sugiyama, Appl. Phys. Lett. 119, 123905 (2021).
Pt Current Collectors Artificially Boosting Si-Contaminated Praseodymium Doped Ceria Oxygen Surface Exchange Coefficients
Authors: Ma Yuxi , Burye Theodore , Nicholas Jason 
Published: July 2022

The chemical oxygen surface exchange coefficient (kchem
) values used to quantify and rank oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalyst performance for high-temperature, oxygen-exchange-enabled devices (such as Solid Oxide Fuel Cells, Solid Oxide Electrolysis Cells, oxygen sensors, etc.) are often determined electrically, with the aid of precious metal current collectors. In addition, due to ease of introducing siliceous contaminants during the manufacturing and operation of these devices, the performance of their oxygen exchange catalysts are often impacted by Si surface contaminants.
Here, Curvature Relaxation (KR), Time-of-Flight Secondary Ion Mass Spectroscopy (ToF-SIMS), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and X-Ray Photoelectron Spectroscopy (XPS) analyses performed on Pulsed Laser Deposited thin films of the oxygen exchange catalyst Pr0.1Ce0.9O2-x (PCO) show that siliceous surface phases only a few nanometers thick are capable of 1) reducing the PCO chemical oxygen surface exchange coefficient by approximately 3 orders of magnitude and 2) approximately doubling the activation energy for oxygen incorporation and removal. Further, the results show that unpolarized platinum current collectors dramatically improve the kchem
of Si-contaminated PCO by reducing the Si concentration at the PCO surface and/or diffusing into the PCO; even for PCO thin films only exposed to mild temperatures of 500 oC. This suggests that precious metal current collectors are likely responsible for some of the large kchem
variation reported in the literature for “identical” materials tested under “identical” conditions.

Figure 1
(Invited) Electro-Chemo-Mechanical Effects in Mixed Ionic–Electronic Conductors
Authors: Chen Chia-Chin 
Published: July 2022

Performance and reliability of energy harvesting, storage and conversion devices are closely connected to mechanics as large stress gradients are usually intrinsic. In addition to causing mechanical failure, large stress is suspected to lead to anomalous experimental observations in a wide range of electrochemical cells. However, the standard framework for mixed ion-electron conductors does not capture this electro-chemo-mechanical coupling in stressed solids; it remains a challenge to theoretically predict how external stress would influence the reaction kinetics or electrical transport of solids.
In this contribution, we will present a generalized thermodynamic theory to explain how and mechanics are coupled to ionic and electronic carriers in the presence of stress field. We categorize the carriers into physically-meaningful four types, based on the signs of the charge number (i.e., polarity) and the partial molar volume (i.e., expansion coefficient). Beyond the electrostatic effects discussed in the literature, our work reveals the importance of elastic effects, as demonstrated by simulations of a composite beam bending experiment. The proposed framework not only provides a deeper understanding of stress-driven phenomena in electrochemical materials, but also suggests an unconventional approach to mechanically tune the interfacial electrical properties of mixed-conducting solids.
(Invited, Digital Presentation) Impedance Analysis of Porous Electrodes in Solid Oxide and Polymer Electrolyte Fuel Cells
Authors: Weber Andre 
Published: July 2022

Technical electrodes in fuel cells rely on complex multiphase microstructures that facilitate electronic, ionic and gas transport to active reaction sites distributed in the electrode volume. In such electrodes, material and microstructural properties of the porous electrode likewise determine the cell performance and different losses related to gas diffusion, electronic / ionic transport or the charge transfer at the active reaction sites might dominate the electrode resistance.
Impedance spectroscopy is a powerful tool to evaluate and quantify the losses within a porous electrode. In this contribution it will be shown how impedance spectroscopy, an impedance data analysis by the distribution of relaxation times (DRT) (1,2) and a subsequent transmission line modeling (TLM) can provide physicochemically meaningful information about technical electrodes applied in solid oxide cells (SOC) (3-7) and polymer electrolyte fuel cells (PEFC) (4,5). Limitations in TLM will be discussed and it will be shown that the well-established straight-forward approach of CNLS-fitting might lead to physicochemically incorrect results. Possible countermeasures as a pre-identification of TLM-parameters by means of separate electrical measurements and microstructural analysis or an appropriate selection of operating parameters during impedance analysis will be presented.
An example for the application of TLM in electrode development and microstructural design of the multiphase microstructure will be discussed and examples how the TLM-approach can be used to optimize an electrode in consideration of available materials and producible microstructures will be shown.
(1) S. Dierickx, A. Weber and E. Ivers-Tiffée, Electrochim Acta, 355, p. 136764 (2020).
(2) A. Weber, tm - Technisches Messen, 88 (1), p. 1 (2021).
(3) C. Endler-Schuck, J. Joos, C. Niedrig, A. Weber and E. Ivers-Tiffée, Solid State Ionics, 269, p. 67 (2015).
(4) M. Heinzmann, A. Weber and E. Ivers-Tiffée, J. Power Sources, 402, p. 24 (2018).
(5) M. Heinzmann, A. Weber and E. Ivers-Tiffée, J. Power Sources, 444, p. 227279 (2019).
(6) S. Dierickx, J. Joos, A. Weber and E. Ivers-Tiffée, Electrochim Acta, 265, p. 736 (2018).
(7) S. Dierickx, T. Mundloch, A. Weber and E. Ivers-Tiffée, J. Power Sources, 415, p. 69 (2019).
(Keynote, Digital Presentation) Mixed Electronic-Ionic Conduction in Spinel-Structured Solid Electrolyte-Electrodes for Li-Ion Batteries
Authors: Allen Jan L 
Published: July 2022

Solid Li-ion conducting electrolytes are one pathway towards future, energy-dense, intrinsically-safe solid-state batteries. Thus, it is of interest to study novel fast Li-ion solid electrolyte materials. Here we report the synthesis and characterization of a family of spinel structured oxide solid electrolytes[1]. Further, we will report on the interface and mixed electronic-ionic conductivity of the spinel structured solid solution which is formed upon reaction with spinel structured Li-ion battery electrode materials. We detail the compositions that were explored and give the results of the synthesis, densification and the structural, physical and electrochemical characterization. The properties of the new materials will be compared and contrasted to well-known solid Li electrolytes such as garnet and NASICON structured materials.
References
1. Allen, J.L.; Crear, B.A.; Choudhury, R.; Wang, M.J.; Tran, D.T.; Ma, L.; Piccoli, P.M.; Sakamoto, J.; Wolfenstine, J. Fast Li-Ion Conduction in Spinel-Structured Solids. Molecules
2021, 26, 2625. https://doi.org/10.3390/molecules26092625

Figure 1
(Invited, Digital Presentation) Detailed Chemical Modeling of Solid Electrolyte Interphase Growth and Evolution
Authors: DeCaluwe Steven C. 
Published: July 2022

The solid electrolyte interphase (SEI) is a layer that forms at the anode-electrolyte interphase in lithium ion batteries. The layer forms due to voltage instability of the electrolyte at low anode potentials, but serves to passivate the electrolyte to protect against further uncontrolled decomposition. In theory, the SEI is self-limiting, but in reality, continued growth over the battery’s lifetime leads to capacity fade, poor rate capability, and eventually cell death. Though significant progress in recent years has improved the SEI’s function and stability, poor understanding of its most basic chemistry impedes “rational design” of SEI layers for advanced battery applications. Understanding and quantifying the elementary chemistry of the SEI is made challenging by the layer’s thickness (10s to ~100 nm), chemical sensitivity, mechanical fragility, and complex chemistry (upwards of 100 reactions have been proposed). For these reasons, These factors combine to make studying the fundamental chemistry of SEI growth and evolution a significant challenge. Both the computational tools to model the SEI’s complex chemistry and the experimental data required to validate such models are all too rare.
This talk will provide an overview of recent efforts to model the fundamental electrochemistry of SEI growth and evolution. The simulations are based on a continuum-scale, finite-volume framework, and leverage the open-source software package Cantera to enable efficient simulation of arbitrarily complex electrochemical mechanisms. Simulation results, as in Figure 1, are validated against two operando measurements of the SEI grown on a non-intercalating tungsten anode: depth profiling via neutron reflectometry (NR), and SEI mass uptake data via quartz crystal microbalance with dissipation (QCM-D) taken during cyclic voltammetry cycling. Interrogation of the detailed model results provide insights into the complex phenomena controlling initial SEI growth, and validation against NR and QCM-D data identify prominent reaction pathways and key chemical species present in the SEI. Finally, we will conclude by discussing future steps, includuing transferring mechanistic insights to new scales, geometries, and chemistries, and coupling models with inputs from atomistic simulations.

Figure 1
Hybrid Manufacturing of a Single-Layer Ceramic Fuel Cell Utilizing 3D Printing and Laser Scribing
Authors: Asghar Muhammad Imran , Lund Peter D. 
Published: July 2022

Single-layer ceramic fuel cells are developing as a promising fuel cell technology [1-3]. Since 3D printing can create both the dense and the porous structures with good mechanical and electrochemical properties, it has the potential to revolutionize the manufacturing of fuel cells. We recently reported a 3D printed single-layer ceramic fuel cell fabricated through an extrusion-based 3D printing, which generated a power density of 230 mW/cm2 at 550oC [1]. A comprehensive investigation into the influence of sintering temperatures ranging from 700oC to 1000oC assisted us in optimizing the density of the functional layer for acceptable electrochemical performance while maintaining adequate mechanical properties. We noticed that the performance of the single-layer cells was limited by the mass transport losses due to low porosity of the single-layer. The best printed cell suffered from a high ohmic loss (0.46 Ω.cm2) and a polarization loss (0.32 Ω.cm2) [1]. In this work, we used a hybrid of a 3D printer and a laser scriber to fabricate the patterned single-layer ceramic fuel cells. Interestingly, the performance of the patterned single-layer ceramic fuel cell was 30% better as compared to a conventional single-layer fuel cell without any patterns. The patterned structures on the surfaces of the cell obtained through the laser scribing, considerably improved the electrode processes. In the patterned 3D printed fuel cells, we studied several electrode materials such as CuFe2O4, LSCF, LSC, NiCoAlLi-oxide, and LiNiZn-oxide and synthesized pastes appropriate for extrusion-based 3D printing. The rheological characteristics of the pastes were investigated using several characterization techniques such as dynamic light scattering, viscometry and tensiometry. Electrochemical impedance spectroscopy and current-voltage measurements were used to assess the electrochemical performance of the cells. Furthermore, high-temperature XRD demonstrated the composite materials' excellent structural stability. To further understand the processes in the cells, additional spectroscopic and microscopic investigations (HR-TEM, SEM-EDX, XPS) were performed.

Acknowledgement. Dr. Asghar thanks Academy of Finland (Grant No. 13322738, 13329016) and the Hubei overseas Talent 100 program for their support.

References

[1] M. I. Asghar, P. Mäkinen, S. Virtanen, A. Maitre, M. Borghei and P. D. Lund, P.D., Nanomaterials 11 (2021) 2180.
[2] M. I. Asghar, X. Yao, S. Jouttijärvi, E. Hochreiner, R. Virta and P. D. Lund, Materials International Journal of Hydrogen energy, 45 (2020) 24083.
[3] M. I. Asghar, S. Jouttijärvi, R. Jokiranta, A. Valtavirta and P. D. Lund, Nanoenergy, 53 (2018) 391.

Figure 1
Redox-Active Organic Molecules and Modified Graphene-Based Materials As Active Material Composites for Supercapacitor Applications
Authors: Noor Navid , Lee Hyejin Jin , Rego Arjun , Baker Thomas , Ibarra Espinoza Alejandra , Schouten Anja , Higgins Drew 
Published: July 2022

Green and sustainable energy demand has directed the modern world toward producing clean energy storage devices to cut down fossil fuel consumption. Supercapacitors are energy storage devices that have attracted much attention due to owning outstanding properties. Supercapacitors use two main mechanisms to storge charge: I) electrical double layer II) pseudocapacitance. Graphene-based materials have shown promising performance in supercapacitors due to their high surface area and proper electrical conductivity. One of the challenges of working with graphene is the restacking of the graphene sheets, leading to poor performance and lower capacitance. Studies have used doping graphene with different heteroatoms as one of the techniques to overcome the restacking and enhancement of its electrochemical performance. Moreover, redox-active organic molecules, including anthraquinones, phenols, and phenathrequinones, also can be employed to modify graphene.
In this work we develop composite active material structures consisting of modified graphene-based materials and organic molecules containing redox active functional groups to provide pseudo-capacitance capabilities. By combining these materials, specific capacitance values above 600 F/g were obtained (at cyclic voltammetry scan rates of 50 mV/s) along with good capacitance retention following repeated electrochemical cycling. In this presentation we will discuss the influence of synthesis route and processing parameters and the resulting structures and performance of the active supercapacitor materials. By correlating these results, we provide insight into the energy storage mechanisms and durability considerations pertaining to these hybrid materials.
(Digital Presentation) Heat Transfer Enhancement in Room-Temperature Metal Hydride Storage Systems
Authors: Kuhnert Eveline , Bodner Merit , Stepanov Dmytro , Hacker Viktor 
Published: July 2022

Among the existing methods of short- and long-term storage of renewable energy, reversible metal hydrides (MH) are considered safe and volume efficient. They provide efficient hydrogen storage capacity for various applications, including Low Temperature PEM Fuel Cells (LT PEMFCs) [1]. The heat transfer in the MH reactor has a substantial influence on the efficiency of the storage process. In order to achieve the established goals for tank filling times, enhanced heat transfer techniques will be essential [2]. Therefore, this work investigates technical solutions for thermal conductivity enhancement in MH storage systems. Different tank designs are assessed in terms of their applicability and the effect of different solid matrices in the storage system on the internal heat transfer is studied. With the help of thermal imaging, the impact of the geometry of the solid matrices on the uniformity of gas distribution along the MH bed is analysed. The MH tanks are operated with room temperature (RT) metal hydrides that achieve a hydrogen storage capacity of up to 105 kgH2 m−3 in a wide range of temperatures (from 50 to -40°C). The tests are carried out within a limited pressure range of 1 to 0.1 MPa to reduce the reliance on additional H2 compressors when used in stationary applications.
[1] M. V. Lototskyy et al., „Metal hydride systems for hydrogen storage and supply for stationary and automotive low temperature PEM fuel cell power modules“, Int. J. Hydrog. Energy, Bd. 40, Nr. 35, S. 11491–11497, Sep. 2015.
[2] K. C. Smith, Y. Zheng, T. S. Fisher, T. L. Pourpoint, und I. Mudawar, „Heat Transfer in High-Pressure Metal Hydride Systems“, J. Enhanc. Heat Transf., Bd. 16, Nr. 2, S. 189–203, 2009.
(Invited) Green Hydrogen Technologies: Status and Trends
Authors: Soloveichik Grigorii L. 
Published: July 2022

There is growing societal consensus that hydrogen is an absolutely necessary part of energy portfolio to reach the COP26 goal to secure global net-zero by mid-century. Hydrogen will play a major role in hard to decarbonize sectors such as industrial (production of steel, cement, and chemicals including ammonia) and heavy-duty, long-haul transportation. By different estimations, hydrogen production volume will be anywhere from 240 to 800 million metric tons per year (MMTY). More realistic predictions are in the range 500 – 600 MMTY that is 7 – 8.5 times more than current global hydrogen production, which predominantly uses fossil fuels and emits around 830 MMTY of carbon dioxide. It is assumed that hydrogen produced by water splitting became predominant by 2050.
With less than 0.1% of current global hydrogen production delivered from water electrolysis, electrolytic hydrogen has tremendous potential for growth. Two commercial (alkaline and PEM) and two emerging (SOEC and AEM) will be compared based on current status and trends of technology (catalysts, membranes, system manufacturability, and capital cost). These technologies could benefit from the integration with energy sources (e.g., nuclear power) or downstream utilization (e.g., ammonia production). Suitability of these technologies for exemplary environments with different energy inputs, electricity prices, and capacity factors will be analyzed. In addition, the effect of different pathways for hydrogen delivery (pure and in the form of a hydrogen carrier) on the levelized cost of hydrogen will be considered.
Development of advanced green hydrogen technologies including early stage research will be illustrated with projects funded by DOE Advanced Research Projects Agency (ARPA-E) and Hydrogen and Fuel Cell technologies Office (HFTO), and their role in DOE Hydrogen Program and Hydrogen Earthshot will be discussed.
Water Oxidation to Hydrogen Peroxide on Carbonaceous Materials
Authors: Pangotra Dhananjai , Csepei Lénárd-István , Roth Arne , Sieber Volker , Vieira Luciana 
Published: July 2022

Hydrogen peroxide (H2O2) is one of the most important chemicals used in the chemical industry. It has been widely utilized in pulp and paper manufacturing, chemical synthesis, wastewater management, and disinfection.1 The primary industrial approach to producing H2O2 is via the fossil-based anthraquinone process - an energy-demanding multi-step process requiring high-cost catalysts and generating substantial volumes of waste. Another route to the classic anthraquinone process is the electrochemical production of H2O2 from oxygen (O2) and water (H2O). This electrochemical route based on renewable energy is an appealing “green” alternative.
Our research group has been extensively working on the electrochemical production of H2O2 through anodic water oxidation using various electrode materials, including metal oxides, commercial carbon materials, and boron-doped diamond (BDD). Besides the electrode material, a suitable electrolyte is equally essential to achieve high H2O2 concentrations and production rates. The role of carbonate ions (HCO3
- and CO3
2-) for producing H2O2 has been investigated using commercial carbon fiber paper (CFP). The electrolyte pH was correlated with the activity of CO3
2- ions in enhancing H2O2 production. Thereby, a cyclic mechanism of H2O2 generation involving the oxidation of CO3
2- ions to peroxodicarbonate (C2O6
2-) species has been proposed.2

The role of the CO3
2- ions in enhancing the anodic H2O2 production was further studied in a continuous flow reactor using BDD anodes. The flow rate and setup configuration for 2e- water oxidation to H2O2 have been optimized at current densities up to 700 mA cm-2, with an impressive H2O2 production rate and faradaic efficiency. Additionally, the role of a chemical stabilizer in avoiding the H2O2 decomposition in the flow system has been addressed. The importance of electrolyte composition, pH, operating parameters, and cell setup to enhance the production of H2O2 at the anode was shown. Finally, outstanding H2O2 yields were obtained in continuous flow for at least 30 hours.

References

Perry, S. C.; Pangotra, D.; Vieira, L.; Csepei, L.-I.; Sieber, V.; Wang, L.; Ponce de León, C.; Walsh, F. C., Electrochemical synthesis of hydrogen peroxide from water and oxygen. Nat. Rev. Chem.
2019,
3 (7), 442-458.

Pangotra, D.; Csepei, L.-I.; Roth, A.; Ponce de León, C.; Sieber, V.; Vieira, L., Anodic production of hydrogen peroxide using commercial carbon materials. Appl. Catal. B Environ.
2022,
303, 120848.