bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intercalated Redox-Active Anions in Layered Double Hydroxides: Toward New Electrode Designs
Authors: Gerlach Patrick , Douard Camille , Gaalich Insaf , Sarmet Julien , Leroux Fabrice , Taviot-Guého Christine , Toussaint Gwenaelle , Stevens Philippe , Brousse Thierry 
Published: February 2024

Layered Double Hydroxides (LDHs) are a versatile class of 2D materials, which consist of layered di- and trivalent metal cation hydroxides with intercalated anions (1). They are used in many applications including energy storage electrodes, water purification or drug delivery (2, 3).
In this new study, Anthraquinone-2-sulfonate (AQS) intercalated in the LDH structure of Mg2Al(OH)6, has been investigated and a charge capacity of 100 mAh g-1 has been measured. However, the dissolution of reduced AQS into the aqueous electrolyte occurs from the first reduction leading to a drastic capacity fade upon cycling.
To get around the dissolution issue, we synthesize a new intercalated LDH using ferrocene as the redox active moiety. Electrodes with this new LDH material Mg2Al(OH)6-Fc (Figure 1A) showed more stable cycling when used in combination with aqueous or organic electrolytes. However, the most significant increase in cycle life was achieved by operating this electrode in highly concentrated, highly viscous ionic liquid based electrolytes such as Pyr13TFSI. Over 97 % capacity retention was achieved after 200 cycles with a coulombic efficiency close to 100 % (Figure 1B). The higher stability of redox active anions working at positive redox potentials like ferrocene in the LDH structure is a key parameter to improve cycling ability. Moreover, the limited solubility of the intercalated redox anions into the high concentrated ionic liquid electrolyte is also a key factor for improving cycle life of this new electrode.
Figure 1: A) Schematic structure of Mg2Al(OH)6-Fc, C) Improved cycling stability of Mg2Al(OH)6-Fc based electrodes in ionic liquid electrolyte Pyr13TFSI.

Figure 1
Lignin-Based Electrolytes for Redox Flow Batteries
Authors: Chakraborty Monalisa , Battestini Vives Mariona , Abdelaziz Omar , Hulteberg Christian , Lindstrom Rakel , Khataee Amirreza 
Published: February 2024

Redox flow batteries (RFBs) are promising candidates for long duration energy storage applications thanks to their unique feature of independent scaling of energy and power. Organic electrolytes and an alternative to the present metal-based have been proposed as potentially low-cost and environmentally friendly electrolytes to alleviate the capital costs of RFBs. Lignin, the second most abundant bio-based polymer in nature, demonstrates the advantages of high carbon content, rich in aromatic groups and is a potential electrolyte basefor RFBs [1] [2] [3] [4]. In this work, soda lignin was considered as redox species modified in optimum oxidative conditions. The cyclic voltammetry analysis confirmed its electrochemical reversibility, so that for RFB tests, modified soda lignin was used on the negative side versus ferrocyanide on the positive at highly alkaline media.
Following RFB cycling tests, a substantial improvement was achieved in the charge/discharge capacities and coulombic efficiency of RFB using modified soda lignin compared to pristine. For further performance optimization, it was found that the flow ratehas a substantial influence. This is more likely due to the thixotropic behaviour of the lignin electrolyte. Further explorations are under way of studying different membranes/electrolyte additives and cycling with higher concentration of lignin towards enhancing the RFB performance by improving the conductivity thus voltage efficiencies. Thecurrent approach of introducing bio-based electrolytes could enlighten a new path in the future research direction of organic RFBs and add a valuable point towards the carbon neutralization.
Keywords:
Lignin, Bio-based electrolyte, Organic redox flow battery, Sustainability, Energy storage
Acknowledgement:
The authors acknowledge Miscancell, Hondiusstraat 28, 6827 DE Arnhem, Netherlands for providing the lignin material for this work.
References:
[1] Mukhopadhyay et al., ACS Sustain. Chem. Eng. 6 (2018) 5394-5400.
[2] Berling et al., Electrochem. Comm. 142 (2022) 107339.
[3] Jiao et al., Indus. Crops & Prod. 187 (2022) 115431.
[4] Soloveichik et al., Inter. J. of Bio. Macromol. 229 (2023) 236–246.
Figure:

Figure 1
Solvent-Free Scalable Preparation of Nickel Manganese Sulfide-Based Hybrids for High-Performance Hybrid Supercapacitors
Authors: Lonkar Sunil 
Published: February 2024

Electrochemical energy storage devices with improved energy and power densities are greatly sought to match the rising demand from electronics to transportation industries. On this front, hybrid supercapacitors are emerging as one of the most promising energy storage technologies in recent years. Hence, to achieve this goal, the rational design and development of highly active, cost-effective and high-performance electrode materials using a facile, efficient, and scalable strategy is an important step. In this work, we demonstrate an environmentally benign, solid-state approach to in-situ producing nanohybrids of transition metal dichalcogenide (TMDs) i.e, nickel-manganese (Ni-Mn) sulfide. Furthermore, its hybridization with carbonaceous materials such as graphene is also targeted. The synthesis encompassed solventless mixing of metal salts (Nickel and manganese), elemental sulfur, and carbon precursors under continuous solid-state dispersion and followed by moderate thermo-annealing. The resulting nanohybrids were thoroughly investigated using several techniques. XRD, HRTEM, SEM, Raman, and BET have been applied to obtain information on the nanohybrid’s morphology, structure, and vibrational and spectroscopic properties.
The as-obtained nanostructured hybrid composed of Ni-Mn sulfide and graphene) was used as a positive electrode material (cathode) in hybrid supercapacitors. The electrochemical studies (CV, GCD, EIS) of the as obtained the devices were assessed to evaluate the charge storage performance, charge storage capability, and stabilities. The electrochemical performance of hierarchically structured Ni-Mn-S-based hybrid electrodes using our solvent-less preparation approach paves a new pathway for developing novel metal chalcogenides for high-performance hybrid supercapacitors.
A Kinetic Study of Repassivation of Stainless Steel
Authors: Shehi Armando , Choudhary Sanjay , Kelly Robert G 
Published: February 2024

Pitting of stainless-steel canisters utilized in temporary storage nuclear fuel containers is a complex process that involves changes in relative humidity, temperature, as well as the type and the quantity of deliquescent salts. Prediction of the maximum pit expected to be developed in these canisters is of importance for regulatory agencies as the damage from subsequent stress corrosion cracking (SCC) can affect canisters’ lifespan. Chen and Kelly’s model in predicting the maximum pit expected in these canisters has provided promising results; however, the input parameters utilized in the model have proven to be overconservative.1 The model utilizes the repassivation potentiation (Erp) as one of the parameters to determine the total cathodic current which can greatly affect the predicted maximum pit calculations. We have developed an approach that utilizes a combination of thermodynamic equilibrium calculations, potentiostatic, galvanostatic, and galvanodynamic electrochemical tests, and in-situ electrochemical microscopy experiments to estimate the true Erp of stainless steel 316L in 0.6M NaCl.2,3 However, crevicing of the stainless-steel wire observed in these tests demand further validation of the obtained Erp values.
In this study, the kinetics of the repassivation of stainless steel 316L will be investigated in chloride solutions and various brine compositions representing different relative humidities. A theoretical approach to predicting the chemistry inside of the pit will be presented. The results will be validated utilizing advanced electrochemical methods such as metallic bi-polar Luggin-Harber probe and in-situ microscopy.4 An attempt to expand the results in one-, two-, and three-dimensional stainless steel 316L pits will be shown.
References

Z. Y. Chen and R. G. Kelly, J. Electrochem. Soc., 157, C69 (2010).

A. Shehi, S. Choudhary, and R. . Kelly, in AAMP 2023,, Denver, Colorado (2023).

J. Srinivasan and R. G. Kelly, J. Electrochem. Soc., 163, C768–C777 (2016).

S. Choudhary, K. Marusak, T. Eldred, and R. G. Kelly, J. Electrochem. Soc., 169, 111505 (2022).
Dynamic Change in Throwing Power for the Cu-to-Carbon Steel Galvanic Couple in the Presence of Bentonite
Authors: Li Xuejie , Pan Xinran , Filice Fraser , Zagidulin Dmitrij , Matin Sina , Noël James J. 
Published: February 2024

In galvanic corrosion, the maximum distance from the periphery of the cathode to the anode is often defined as the throwing power. It dictates the surface area of the cathode involved in the galvanic corrosion and is also related to the extent of the accelerated anodic reaction. Therefore, its estimation is of great interest and importance in engineering applications, such as fastener and panel assembly [1], metal coatings [2], buried metallic structures [3], etc. Throwing power may be estimated experimentally by measuring the solution potential variation in close proximity to the electrode surface (Es) or through modelling, such as finite element analysis (FEA), provided the boundary conditions (polarization characteristics) are correctly determined. In this work, we investigated the throwing power for the Cu-to-carbon steel galvanic couple in the presence of bentonite clay, a scenario that could arise in the vicinity of a through-coating defect in the Canadian-designed nuclear waste container. Using a homemade micro-reference electrode array coupled to a Multichannel Microelectrode Analyzer (MMA), Es was measured simultaneously in 10 locations as a function of time in 0.1 M NaCl solution with and without bentonite clay, Fig. 1. Transient potential peaks were found when bentonite clay was added to the solution and are attributed to the increased galvanic activities driven by the reduction of air-formed Cu oxides.
We further investigated this phenomenon using FEA. Boundary conditions were established experimentally under circumstances reflecting the actual surface states, i.e., with or without Cu oxides. Simulations were conducted considering secondary current distribution, using the appropriate boundary conditions. The obtained results match well with the experimental measurements, including the peak and the stable Es. Additionally, the dynamic change of the throwing power due to the evolution of the surface state was investigated through simulation and discussed.

Reference

[1] R.S. Marshall, A. Goff, C. Sprinkle, A. Britos, R.G. Kelly, Estimating the Throwing Power of SS316 when Coupled with AA7075 Through Finite Element Modeling, Corrosion, 76 (2020) 476-484.
[2] J.R. Scully, F. Presuel-Moreno, M. Goldman, R.G. Kelly, N. Tailleart, User-Selectable Barrier, Sacrificial Anode, and Active Corrosion Inhibiting Properties of Al-Co-Ce Alloys for Coating Applications, Corrosion, 64 (2008) 210-229.
[3] L. Liu, J. Li, M. Peng, W. Li, B. Lei, G. Meng, Macro-galvanic corrosion of tower grounding device consisting of graphite and Zn-coated steel in a simulated soil environment, Engineering Failure Analysis, 135 (2022) 106136.

Figure 1
High Temperature Corrosion Behavior of 15-15Ti Cladding Tube Material in Contact with Liquid Lead, Outside, and Cs2MoO4, Inside
Authors: Tarı Doğaç , Retegan Vollmer Teodora , Geers Christine 
Published: February 2024

Lead-Cooled Fast Reactors are one of the emerging new technologies connected to the Generation IV reactor designs. Even though the reactor features are extensive and beneficial, some technical and regulatory difficulties remain that hinder the deployment. One of them is the corrosion behavior of fuel claddings in high burn-up and elevated temperatures, as fuel claddings are a part of accident barriers. In this study, 15-15Ti austenitic steel was the investigated cladding material.
As this cladding would be used in a tube form, corrosion attack from both sides, inside and outside is studied in contact to their respective environments. From the outside of the tube, the proposed coolant liquid lead is the corrosive substance. At the inside of the tube, the major corrosive species in our test setup is, for simplicity reasons, Cs2MoO4. However, this choice has been made from some considerations regarding the fuel evolution upon burn-up.
In a high burn-up situation, the generated fission products would start to accumulate to the gap between the fuel pellet and the cladding tube. These accumulated products are the so-called “Joint-Oxide Gain” (JOG) phases, and they are the corrosive substances in question when discussing the corrosion attack from the inside of a cladding tube. Cs2MoO4 has been identified as one of the main components of JOG phases and thus will be focused on in this study.
A new capsule was designed to investigate the dual-atmosphere corrosion of cladding tubes. Unexposed capsule parts (a) and the basic schematic of the assembled capsule (b) can be seen in the Figure below. The cladding tube material itself is used as the container for JOG as it is filled with Cs2MoO4 and sealed on both ends. This assembly is then placed inside a bigger capsule, which is filled with lead powder to submerge the cladding tube assembly. All assemblies were done in Ar-filled glovebox. The capsules were then exposed to 600-1000 oC for 52 to 168 hours, which was followed by cutting and epoxy embedding to investigate the cross-sections.

Figure 1
Oxidation of Alloy 690 in Simulated Pressurized Water Reactor Primary Coolant – Experiments and Modeling
Authors: Karastoyanov Vasil , Betova Iva , Bojinov Martin S. 
Published: February 2024

During normal operation of the primary loop of a water cooled-water moderated energy reactor (WWER), the associated water chemistry evolves from an initially high-boron high-potassium (beginning-of-cycle, 1200 ppm B and 8 ppm K) to significantly lower concentrations (ca. 400 ppm B and 3.5 ppm K) at the end of the respective campaign. In addition to that, the concentration of Li produced by transmutation of B reaches ca. 0.7 – 0.9 ppm. To the best of our knowledge, the effect of such water chemistry changes on pressurized water reactor (PWR) internals such as Alloy 690 have not been studied yet. Such a study appears relevant also within the frames of a discussion for a possible transition from B-Li to B-K water chemistry in PWRs.
In the present paper, the effect of evolution of primary water chemistry during operation on the corrosion rate and conduction mechanism of oxide films on Alloy 690 is studied by in-situ impedance spectroscopy at 280 °C / 8 MPa during 1-week exposures in an autoclave connected to a re-circulation loop. Impedance measurements were performed in three-electrode mode featuring a Pt sheet counter electrode and a Pd electrode negatively polarized with a current of -10 µA vs. another Pt to approximate the reversible hydrogen electrode (RHE). Spectra were recorded at the corrosion potential in a frequency range 10 kHz – 0.1 mHz using an ac amplitude of 50 mV (rms). At the end of exposure, the samples were polarized in the range of potentials -0.1 to 0.5 V vs. RHE to evaluate the stability of the passive oxide. Separate samples of Alloy 690 were simultaneously exposed in the autoclave and subsequently analyzed by Glow-Discharge Optical Emission Spectroscopy (GDOES) in order to estimate the thickness and the in-depth composition of the formed oxides.
Impedance data were quantitatively interpreted using the Mixed-Conduction Model for Oxide Films (MCM) to estimate the rates of metal oxidation at the alloy/oxide interface, oxide dissolution and restructuring at the film/coolant interface and ion transport in the protective layer. The effect of water chemistry evolution on corrosion rate and conduction mechanism in the oxide on Alloy 690 in primary coolant is discussed on the basis of the obtained parameters.
Acknowledgments: This study is funded by the European Union-NextGenerationEU, through the National Recovery and Resilience Plan of the Republic of Bulgaria, project № BG-RRP-2.004-0002 (BiOrgaMCT).
Understanding the Corrosion of Copper in Nitric Acid By Tuning the Solution Chemistry
Authors: Skaanvik Sebastian A, , Li Xuejie , Winslade Jessica , Henderson Jeffrey D. , Hedberg Jonas , Behazin Mehran , Biesinger Mark , Noël James J. 
Published: February 2024

The used fuel container (UFC) is a key engineered barrier to permanently contain and isolate used nuclear fuels underground in deep geological repositories (DGR) to be implemented in Canada, Sweden and Finland.1,2 Copper is used for corrosion protection in the current design of the UFC. Within a DGR, radiolysis of humid air will result in the formation of nitric acid.3 Recent studies showed that copper corrodes faster in nitric acid when oxygen is present, which will be the case for a short period after the UFC’s emplacement.4 When the oxygen becomes depleted in a DGR, the corrosion of copper will be minimal but can be affected by corrosion products such as Cu+, Cu2+, NO2
- and NO. Previous results suggest that the presence of copper ions in the solution surrounding the copper can activate nitrate as a cathodic reagent.5 A possible mechanism is that Cu+ reacts with nitrate through its oxidation to Cu2+, which then reacts with metallic copper through its comproportionation reaction, accelerating the corrosion process.5 Yet, a precise mechanistic understanding of the role of Cu+, such as the degree to which oxidation of Cu+ occurs in solution, or if Cu+ simply acts as a catalyst for nitrate reduction or decomposition, is missing. As a result, an improved understanding of the influence of solution parameters on the corrosion mechanisms of copper in nitric acid is needed, including the presence of oxidants and Cu+-chelating species such as chloride.
Herein, the interplay between the dissolved redox couples, Cu+/Cu2+ and NO3
-/NO2
- and Cl- is explored, and their effect on the corrosion of copper is studied by linear sweep voltammetry and polarization resistance and Tafel analysis. The interpretation of linear polarization resistance measurements in the presence of multivalent ions and the role of corrosion products are discussed.
1 P. G. Keech, P. Vo, S. Ramamurthy, J. Chen, R. Jacklin and D. W. Shoesmith, Corrosion Engineering, Science and Technology, 49, 2014, 425-430.
2 F. King, L. Ahonen, C. Taxen, U. Vuorinen and L. Werme, Copper corrosion under expected conditions in a deep geologic repository (SKB-TR--01-23), 2001. Sweden.
3 R. P. Morco, J. M. Joseph, D. S. Hall, C. Medri, D. W. Shoesmith and J. C. Wren, Corrosion Engineering, Science and Technology, 52, 2017, 141-147.
4 J. Turnbull, R. Szukalo, M. Behazin, D. Hall, D. Zagidulin, S. Ramamurthy, J. Wren and D. Shoesmith, Corrosion, 74, 2017, 326-336.
5 J. Turnbull, R. Szukalo, D. Zagidulin, M. Biesinger and D. W. Shoesmith, Materials and
Corrosion, 72, 2021, 348–360.
(Invited) Electrolytes for Next-Generation Sodium Metal Batteries
Authors: Thangadurai Venkataraman 
Published: February 2024

Developing reliable and cost-effective electrical energy storage systems (EESs) for portable electronics, electric vehicles, and grid storage applications is vital. Na-ion batteries are the most promising alternative technology owing to their natural abundance and low sodium cost.[1] Solid-state batteries (SSBs) have garnered extensive attention for their ability to suppress the safety hazards of organic liquid electrolytes by replacing them with solid electrolytes.[2] Among the various solid electrolytes being explored, our group mainly focuses on NASICON (Sodium superionic conductor) type silicate and solid polymer electrolytes. Sodium silicates are a class of materials with composition, NaxMxSixOx (M = rare-earth metals, x = integer (1-10)).[3] They have the advantage of low sintering temperature (~1050 °C) and 3D framework structure containing MO6 octahedra and SiO4 tetrahedra providing facile ionic movement.[4] Solid polymer electrolytes (SPE) are known for their flexibility and electrode compatibility. Highly conductive, filler-free composite solid polymer electrolyte films were prepared using poly(vinylidene fluoride), poly(vinyl pyrrolidone) (PVP), and NaPF6.[5] PVP binder played an essential role in improving Na ion conductivity and excellent plating−stripping performance. This talk will present an overview of these solid electrolytes for next-generation sodium metal batteries.

References

[1] C. Zhou, S. Bag, V. Thangadurai, ACS Energy Lett., 2018, 3, 2181–2198.
[2] V. Thangadurai, B. Chen, Chem. Mater., 2022, 34, 6637–6658.
[3] S. Narayanan, S. Butler, S. Reid, S. Bag, V. Thangadurai, US Pat. 2022/0271330 A1, 2022, 2022.
[4] A. Sivakumaran, A. J. Samson, V. Thangadurai, Energy Technol., 2023, 2201323.
[5] A. A. Bristi, A. J. Samson, A. Sivakumaran, S. Butler, V. Thangadurai, ACS Appl. Energy Mater., 2022, 5, 8812–8822.
Self-Powered and Flexible Integrated System Made By Dye Sensitized Solar Cell, Micro-Supercapacitor and Hydrogel-Based Stress Sensor
Authors: Reina Marco , Mogli Giorgio , Speranza Roberto , Zaccagnini Pietro , Arcoraci Davide , Stassi Stefano , Lamberti Andrea 
Published: February 2024

During the last years the development of integrated devices made of a sensor and an energy storage element has found many applications in terms of wearable, implantable and integrated electronics.1,2 The limitation of this system is the periodical need to recharge the energy storage element, making it less suitable for long time remote measurements.
Herein, we propose a self-powered and flexible system made by an energy harvester, an energy storage element, and a 3D printed stress sensor. (See figure 1)
The harvesting of energy is taken over by a dye sensitized solar cell (DSSC). The DSSC have made their way on the market thanks to the simple fabrication, low payback time and the possibility to customize the choice of electrodes and electrolyte.3 The cell counter electrode is made by laser induced graphene (LIG), gaining the advantage of flexibility with respect to the more common FTO-based counter electrode, as well as more cheapness and ease of fabrication.
The solar cell supplies a micro supercapacitor, which is also made by laser induced graphene. LIG supercapacitors are particularly suitable for this application thanks to one-step fabrication (laser writing), flexibility, low costs, high porosity, and lightweight.4,5 The electrodes design has been optimized to obtain a charge balancing and exploiting the whole potential window using a gel-based electrolyte.
The supercapacitor is also connected to a hydrogel based flexible sensor. The energy storage discharge current is measured at the ends of the sensor. When the hydrogel is stretched or compressed the resistance of the path is changed, causing a variation of the current that can be measured to retrieve the variation of the stress intensity.

Figure 1: Scheme of the self-powered system

P. Glynne‐Jones and N. M. White, Sensor Review, 21, 91–98 (2001).

M. Parrilla and K. De Wael, Adv Funct Mater, 31, 2107042 (2021).

T. V Arjunan and T. S. Senthil, Materials Technology, 28, 9–14 (2013).

T. D. Le et al., Adv Funct Mater, 32, 2205158 (2022).

P. Zaccagnini and A. Lamberti, Appl Phys Lett, 120, 100501 (2022).

Figure 1