bluuebunny/crossref_metadata_2025 huggingface dataset:
Evaluation of Adhesion for Better Electrodeposited Cu Foil on Titanium Substrate
Authors: Fung Kuan-Zong , Tsai Shu-Yi , Li Zih-Jhun , Chou Hsing-Mei
Published: February 2024

Titanium metal is known to have good corrosion resistance. For the plating of Cu in many industrial applications, Ti metal is commonly used as the cathode for the reduction of Cu. Under an acidic and high temperature environment, the passivation layer on the surface of the titanium metal tends to react with acidic solution. As a result, the corrosion of the active titanium metal was observed. In this study, the corrosion behavior of commercial pure titanium in acid copper sulfate baths was investigated, and several surface treatments were used to improve the corrosion resistance of titanium passive layer. The microstructure of titanium metal after immersion in acid copper sulfate solution was examined by using SEM and FIB. The pitting corrosion of Ti was clearly observed using SEM. The corrosion mechanism of the titanium metal in the sulfuric acid solution was discussed. In addition, the electrochemical characteristics of commercial pure titanium metal in sulfuric acid solution were also analyzed using the three-pole potential measurement method.
Electrochemistry of Al3+- Catechol System: Kinetics Vs. Thermodynamics (A1-Triple I)
Authors: Gueskine Viktor , Kumar Divyaratan , Vagin Mikhail Yu. , Crispin Xavier
Published: February 2024

Carbonyls, and quinones among them in particular, occupy a place of choice among organic reversible redox systems for electrocatalysis [1] and energy storage [2]. Their electrochemical behavior is marked by coupled proton and electron transfer (CPET) [3-5]. We have studied this subject in the context of flow batteries [6] and hydrogen carriers [7]. On the other hand, metal ion – catecholate (o-dioxolene) binding [8] attracts attention in different and rather independent domains, including active materials for metal-ion and redox flow batteries [2]. Redox transformations of o-dioxolene-metal complexes are therefore coupled to competitive binding with metal ion and proton at the electrochemical timescale, raising the complexity in the system above that of CPET. These effects have not received proper attention e.g. in aqueous metal-ion battery research.

The subject of this communication is the electrochemistry of Al3+ - catechol system in aqueous solution. We discuss the conditions and measurable electrochemical signatures of complex formation, as well as the role of buffer. We explain why our observations are contrasting those on catechol containing polymers proposed for universal metal-ion batteries [9, 10] by considering which reactions attain equilibrium and which are obeying kinetics only.

[1] K. Tammeveski et al. J. Electroanal. Chem. 2001,
515
, 101; DOI: 10.1016/S0022-0728(01)00633-7

[2] B. Häupler et al. Adv. Energy Mater. 2015,
5
, 1402034; DOI: 10.1002/aenm.201402034

[3] M. Quan et al. J. Am. Chem. Soc. 2007,
129
, 12847; DOI: 10.1021/ja0743083

[4] J. Wang et al. J. Electroanal. Chem. 2007,
601
, 107; DOI: 10.1016/j.jelechem.2006.10.036

[5] Q. Lin et al. J. Phys. Chem. C 2015,
119
, 1489; DOI: 10.1021/jp511414b

[6] H. Ghorbani Shiraz et al. J. Energy Chem. 2022,
73
, 292; DOI: 10.1016/j.jechem.2022.06.015

[7] M. Vagin et al. Adv. Funct. Mat. 2020,
30
, 2007009; DOI: 10.1002/adfm.202007009

[8] R. Maskey et al. Encycl. Inorg. Bioinorg. Chem.; DOI: 10.1002/9781119951438.eibc2810

[9] N. Patil et al. ACS Appl.
Energy Mater. 2019, 2, 3035; DOI: 10.1021/acsaem.9b00443

[10] K. Pirnat et al. Macromolecules 2019, 52, 8155; DOI: 10.1021/acs.macromol.9b01405
A High-Performance Phenazine-Based Cathode for Aqueous Organic Zinc-Ion Battery
Authors: Vallayil Priya , Sankararaman Sethuraman , Ramanujam Kothandaraman
Published: February 2024

Aqueous Zinc-ion batteries are very appealing for massive energy storage applications due to their inherent safety, low cost, and longevity. Nevertheless, the lack of positive electrode material (cathode) caused by the slow diffusion of Zn2+ inside solid inorganic frameworks is impeding their advancement. Organic electrode materials have recently been endorsed as a less-toxic and environment-benign substitute for traditional inorganic electrode materials. Even though, its performance is hampered by the poor rate capability and limited cycle life caused by cathode material deterioration during Zn2+ insertion/de-insertion. An efficient charge-discharge in aqueous zinc ion batteries, even at high current densities with good capacity retention, is made possible by the stability of aromatic organic heterocyclic cathode materials with the necessary intermolecular spacing. Herein, we describe a strategy to utilize a commercially available redox-active organic molecule (ROM), Phenazine (PNZ) derivative, which can offer efficient and reversible Zn2+ storage due to its high molecular symmetry with low molecular weight. The use of a cation exchange membrane and optimization of volume of the electrolyte and conductive carbon enabled the PNZ electrode to provide a better specific capacity value of 247 mAh g-1 (90% of the theoretical capacity of PNZ) at 1 A g-1 with a good capacity retention of 75 % over 300 cycles. These results indicated that exceptional water insolubility in small organic molecules like PNZ would make them a desirable electrode material for AZIBs. In contrast to conventional design ideas for organic electrode materials such as having a larger molecular weight or adding certain polar functional groups to the organic molecular bulk, our research offered fresh and insightful recommendations for the creation of simpler organic electrodes.

Fig. 1. Cyclic performance with charge-discharge plots of PNZ/Katjen black carbon Zinc coin cells with Nafion 212 membrane a) capacity vs. voltage plot b) cycle number vs. capacity plot.

Figure 1
Interlaced Micro-Fibrous Hard Carbon As Superior Anode for Na-Ion Battery: Insights into the Sodium Storage Mechanism and Solid Electrolyte Interface
Authors: Verma Bharat , Sil Anjan
Published: February 2024

Hard carbon has been proved to be a promising negative electrode material for sodium-ion battery (SIBs) application. In this study, we have synthesized carbonaceous anode material by pyrolysis of tissue paper waste at different temperatures ranging from 800° to 1400°C. The tissue paper pyrolyzed at 1400°C has shown highest desodiation capacity of 350 mAhg-1 at 20 mAg-1 with stable cyclic performance and 70% capacity retention after 400 cycles at 200 mAg-1. The morphology, structure and surface chemistry of the cycled hard carbon electrodes were examined by ex-situ FE-SEM, XRD, Raman and XPS. The characterization results obtained reveal the detailed insights of the solid electrolyte interface and sodium storage mechanism of the hard carbon. The parameters of diffusion kinetics were evaluated by Electrochemical Impedance Spectroscopy (EIS) and CV analysis at different sweep rates. The results obtained in the study establish tissue paper waste as a promising precursor material to synthesize carbonaceous anode for SIBs by a simple one-step pyrolysis process.
Water-in-Polymer Salt Electrolyte for Dendrite-Free Zn- Lignin Battery
Authors: Kumar Divyaratan , Crispin Xavier , Khan Ziyauddin
Published: February 2024

Zn-ion batteries are considered to be a promising option for low-cost and sustainable secondary batteries. However, one of the current challenges facing this technology is hydrogen evolution and dendritic growth during Zn deposition. To address these issues, a new strategy is to use "water-in-salt" electrolyte (WISE), which refers to super concentrated aqueous electrolytes. This helps to broaden the electrochemical stability window (ESW), suppress the hydrogen evolution reaction (HER), and impede dendritic growth. In this paper, we propose the idea of using "water-in-polymer salt" electrolyte (WIPSE) to address the challenges facing Zn-ion batteries and move this technology towards becoming one of the most affordable, environmentally friendly, and sustainable options. Specifically, we suggest using a lignin-carbon electrode, which is highly promising and has great potential for achieving these goals. The findings suggest reversible Zn deposition and dissolution, leading to dendrite free Zn deposition. The sustainable Zn-lignin battery exhibited remarkable performance, with a maximum energy of 23 Wh/Kg and a maximum power of 610 W/kg, low self-discharge and 82% retention in capacity after 8000 cycles. Given its improved environmental impact and cost-effectiveness, the Zn-lignin battery holds a promising position in the battery market.

References:

Kumar et al., Advanced Sustainable Systems, 7, 2023, 2200433.

Khan et al., Journal of Power Sources, 524, 2022, 231103.

Khan et al, Advanced Energy and Sustainability Research 3, 2022, 2100165.
Breaking the Passivity Wall of Metals: Exempli Gratia Non-Aqueous Ti–Air Battery
Authors: Durmus Yasin Emre , Kaltenberg Marcel , Kungl Hans , Tempel Hermann , Ein-Eli Yair , Eichel Rüdiger-A.
Published: February 2024

In recent years, metal–air batteries have been gaining much attention as one crucial line of development as promising energy storage devices due to possessing high theoretical specific energies and energy densities while utilizing cost-effective, safe, and environmentally friendly electrode materials. Among various possible metal–air configurations, mostly Zn–, Fe–, and Al–air have been the research focus for many decades. Up to now, Ti has not been considered as an active anode material, although it is a light metal that can possibly transfer up to 4 electrons. The reason behind this is that the electrochemical behavior of Ti is known for its passivity in various media and, also, it is conceptually mistaken as an expensive metal.

Herein, we report a novel non-aqueous primary Ti–air battery utilizing 1-ethyl-3-methylimidazolium oligofluorohydrogenate (EMIm(HF)2.3F) room temperature ionic liquid as electrolyte. Initially, the electrochemical behavior of Ti was studied by potentiodynamic polarization, which revealed the first insights into its electrochemical activity. Subsequently, the galvanostatic discharge experiments were conducted to evaluate the performance of Ti–air batteries in full-cells. The battery could successfully be operated under moderate current densities (up to 0.75 mA/cm2) with an average cell voltage of 1–1.2 V, yielding up to a discharge capacity of 66 mAh/cm2. Post-mortem characterization of the electrode surfaces was performed by SEM in combination with EDS to analyze the potentially deposited discharge products. Furthermore, ICP-OES and FTIR techniques were employed for investigating the electrolytes to gain further insights into the possible mechanisms leading to cell discharge termination over time. Additionally, the possible reaction mechanisms governing within the cell were proposed for the Ti–air battery. Such a metal–air battery holds a unique potential to be the only metal with 4 electrons transfer during its discharge once its full potential is harvested.
Boosting the Initial Coulombic Efficiency of Sustainable Hard Carbon Derived from Polyethylene Terephthalate with Cyclopentyl Methyl Ether As a Co-Solvent for Wide-Temperature Sodium-Ion Batteries
Authors: . Nagmani , Das Dhrubajyoti , Puravankara Sreeraj
Published: February 2024

Upcycling plastic waste into value-added products helps to generate cost-effective and sustainable resources towards a circular materials economy and safer ecosystem. The conversion of polyethylene terephthalate (PET) municipal waste via the carbonization process into hard carbon (HC) delivers a high-reversible capacity, low-cost, sustainable anode material for sodium-ion batteries (SIBs). However, the low initial Coulombic efficiency (ICE) is a significant challenge of the HC anode, which should be optimized by electrolyte and interfacial chemistry.1 In conventional carbonate esters-based electrolytes, ethylene carbonate (EC) forms an organic-rich thick SEI layer, soluble on cycling, limiting the cyclic stability. The low-temperature performance is also a significant concern in achieving high capacity, long cyclability, and ICE.2

Herein, HC derived via single-step carbonization at 1000℃ exhibits larger interlayer spacing of 0.379 nm, low surface area (~205 m2g-1), and unique slit-shaped pores with 84% mesoporosity in the structure. PET-HC exhibits a high reversible capacity of 337 mAh g-1 with ICE of just 66%, using EC-PC-based electrolyte. EC-free cyclopentyl methyl ether (CPME) was used due to its weakly solvating and wide temperature solvent.3 CPME-PC-based electrolytes significantly enhanced the ICE value to 74.5% and reversible capacity to 356 mAh g-1 with superior cycling of 91% after 100 cycles at 0.1C rate. The inorganic-rich SEI layer for CPME-PC-based electrolytes results in a thin SEI that improves the ICE and cyclic stability of the anode. The low-temperature performance (up to -20°C) for CPME-PC-based electrolytes showed ~30% added capacity compared to EC-PC-based electrolytes. This work provided an eco-friendly approach to developing hard carbons from plastic trash and offered an effective strategy to replace EC with CPME for low-temperature sodium storage applications.

References

Shen, L., Shi, S., Roy, S., Yin, X., Liu, W., Zhao, Y., Adv. Funct. Mater.
2021, 31, 2006066.

Ramasamy, H. V., Kim, S., Adams, E. J., Rao, H. & Pol, V. G. Chem. Commun.
2022, 58, 5124–5127.

Zhang, H., Zeng, Z., Ma, F., Wu, Q., Wang, X., Cheng, S., Xie, J., Angew. Chem.
2023, e202300771.

Figure 1
Ni-Fe-S Supported on Mo-Based Mxene (Mo2CTx) As a High-Performance Bifunctional Electrocatalyst for Rechargeable Zinc–Air Batteries
Authors: Yu Wan-Ju , Chen Han-Yi , Doong Ruey-An
Published: February 2024

Rechargeable Zn-air batteries are a promising alternative to lithium-ion batteries due to their high theoretical energy density (1350 Wh kg−1), low cost, and environmental benefits. To meet the growing demand on renewable power for electric vehicles and sustainable goals, inexpensive and efficient bifunctional catalysts with both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities have recently garnered a great interest in energy conversion fields.

MXene, a rising family of two-dimensional (2D) materials, particularly Mo2CTx, has been identified as a promising electrocatalyst supporter. The tunable surface chemistry, atomic thickness, and high surface area of the MXene architecture reduce the reaction barrier by enhancing the conductivity, exposing active sites and increasing the reaction rate in charge transfer and gas/ion diffusion process. Therefore, with coexistence of MXene platform, favorable reaction conditions can be created to facilitate the catalyst's performance.

In this study, a novel bifunctional electrocatalyst of Ni-Fe sulfide uniformly embedded in a Mo-based MXene (Mo2CTx) sheet structure is designed for Zn-air battery applicaiton. Surface characterization shows that 2-D Mo2CTx nanosheets can be successfully fabricated by hydrothermal etching method. The deposition of Ni-Fe sulfide nanocatalysts onto Mo2CTx MXene nanosheets exhibits excellent electrochemical performance, which is attributed to the enhanced intrinsic activity due to rapid electron transfer from MXene, abundant functional groups on the surface to lower the reaction activity energy. In addition, the architecture of MXene support provides a large specific surface area, high porosity, good conductivity and highly exposed active sites. When using MXene supported Ni-Fe-S nanocatalysts as the electrode materials for Zn-air battery application, a high peak power density at 107.24 mW cm−2 with superior cycle stability within 200h is obtained. Moreover, the possible mechanisms on energy storage is also proposed. These results clearly indicates the successfully development of an exciting bifunctional electrocatalyst for electrochemical energy conversion applications.
Investigation of Polarization in Vanadium Redox Flow Batteries with a Fluctuating Supply of Electrolyte Solution
Authors: Sun Pengfei , Matsuo Kaito , Alizadeh Mehrzad , Charoen-amornkitt Patcharawat , Suzuki Takahiro , Tsushima Shohji
Published: February 2024

The rapid development of renewable energy has led to increasing demand for energy storage equipment. The vanadium redox flow battery (VRFB) has attracted more attention due to its advantages such as good safety, long service life, and flexible design [1].

In the VRFB, the electrolyte flow characteristics are important for the concentration overpotential as it significantly affects the supply of vanadium ions [2]. Therefore, many studies are focusing on the influence of flow rates and electrolyte distribution on VRFB performance [3-4]. However, few studies have focused on the effects of fluctuations in electrolyte flow rates on battery polarization and overpotential, which often occurs in practical situations and affects the mass transfer of ions. In this study, we focused on the effect of fluctuations in electrolyte supply induced by the peristaltic pump on the polarization behavior of the VRFB.

The electrodes of the experimental VRFB are Sigracet® GDL 38AA, the membrane is Nafion® 211, and the vanadium ion concentration of the electrolyte is 1.7 mol/L. Before the formal experiment, the cell was charged to 50% state of charge. To determine the fluctuation effect on battery polarization, a peristaltic pump was used on one electrode side and a smooth pump on the other.

Fig. 1 (a) and (b) show the charging and discharging voltage variation with a current of 200 mA/cm2 at different flow rates. The average voltages during charging decrease with increasing flow rates, while the average voltages during discharging increase with increasing flow rates, and all voltages fluctuate up and down.

It can be known that the voltage variation is attributed to the fluctuating supply of electrolyte affecting the mass transfer. At higher flow rates, the vanadium ion transport speed is faster, and the concentration gradient of the reaction surface is smaller, resulting in lower overpotential and polarization. Under fluctuating conditions, the changing electrolyte flow rates also lead to changes in vanadium ion supply speed, resulting in the voltage fluctuation periodically.

Acknowledgement

This work was supported by JSPS KAKENHI Grant Number 21H04540. The first author was supported by the China Scholarship Council.

References

[1] KJ. Kim, MS. Park, YJ. Kim, JH. Kim, SX. Dou, and M. Skyllas-Kazacos, J. Mater. Chem. A, 3 (33), 16913-16933 (2015).

[2] WW. Yang, YL. He, and YS. Li, Electrochim. Acta, 155, 279-287 (2015).

[3] T. Wang, JH. Fu, ML. Zheng, and ZT. Yu, Appl. Energy, 227, 613-623 (2018).

[4] B. Khaki and P. Das, Electrochim. Acta, 405, 139842 (2022).

Figure 1
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
Gel Polymer Electrolytes for Flexible LiXPO4 (X=Mn,Fe,Co)-Fractal-like Fe2O3 Hybrid Supercapacitor Devices
Authors: Jaiswal Rishabh , Chaturvedi Garima , Ilangovan S A , Sujatha S , Ajeesh K S , Tatiparti Sankara Sarma V
Published: February 2024

In the recent years, the development of electrochemical energy storage device has been widely investigated. Supercapacitors are known for their excellent power density and superb cycling stability but restricted by low charge storage capacity, on the other hand batteries provide high energy density, limited by low power density. Here, olivine-structured LiXPO4 (X=Mn,Fe,Co) possessing high energy storage capability is used as a positive electrode. Our recent research demonstrated that Fe2O3-based Fractal-like structures supported on Ni Foam exhibit extremely high specific capacitance of ~2708 F g-1 at 1 A g-1 in 1 M KOH electrolyte, when used as negative electrode [1]. Hence, the Fractal-like Fe2O3 is used as the negative electrode for the envisaged hybrid supercapacitor device. The flexibility is imparted to these devices by employing carbon cloth as the current collector. The choice of suitable electrolyte is crucial for supercapacitor applications as it decides the working potential window, electrode-electrolyte interaction, and ionic conductivity. Here, PVA based gel polymer electrolyte (GPE) is used due to the ease in gel formation and non-toxicity to make flexible hybrid supercapacitor device. Different PVA based GPEs are synthesized using H3PO4, H2SO4 and KOH with Ionic liquids viz. EMIMBF4 and EMIMCl. The role of GPEs in the performance of LiXPO4 (X=Mn,Fe,Co)//GPE//Fe2O3 hybrid supercapacitors is understood through charge storage mechanisms deciphered from galvanostatic charge-discharge (GCD) experiments, Electrochemical Impedance Spectroscopy (EIS).

References

[1] R. Jaiswal, G. Chaturvedi, V. Sharma, S.A. Ilangovan, S. SarojiniAmma, K.S. Ajeesh, S.S. V. Tatiparti, Are Fractal-Like Structures Beneficial for Supercapacitor Applications? A Case Study on Fe2O3 Negative Electrodes, Energy and Fuels. 37 (2023) 1275–1287.
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).
Effect of Fission Products on Molten Salt Corrosion for Nuclear Reactor Applications
Authors: Gakhar Ruchi
Published: February 2024

Molten halide salts are used in various technologically important applications like molten salt reactors and concentrated solar power. A major challenge of molten salts is their corrosivity towards structural materials. However, most of the complex interfacial phenomena related to molten salt corrosion are not well understood, primarily due to the complex impact of salt chemistry on structural material interface. Structural material corrosion is influenced by salt redox potential, fission product buildup, presence of impurities and moisture. Given the huge dependence of operations on salt chemistry, understanding the interactions between soluble fission products and structural alloys is of great importance. EuCl3 is one of the primary fission products and shown EuCl3 to cause accelerated corrosion of structural alloys in molten chloride salts. Given the more positive formal oxidation potential of Eu(III)/Eu(II) compared to nickel, iron, and chromium that are major components of the structural alloys, Eu(III) species act as a strong oxidant to cause the dissolution of these metals. This talk will highlight utilization of novel in situ optical spectroscopy technique to study time-dependent evolution of corrosion damage of metals in presence of EuCl3 as well as the EELS technique to identify changes in oxidation states of dissolved alloying elements.
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) Synthesis and Interfacial Control of Electrode Architectures
Authors: Dai Sheng
Published: February 2024

Enhancement in electrochemical energy storage resides in tailored nanotextures resulting from making electrode materials with controlled compositions and structures. The complex interplay of solvent and solute structures and dynamics at the charged interface, transport of ions into and out of the pores, solvation/desolvation processes occurring in pores approaching bare-ion dimensions, and formation of interfaces via chemical reactions are all important parameters. Herein, several synthesis methods for both inorganic and polymer electrodes tailored for energy storage will be discussed. The objective of this talk is to demonstrate that nanostructured polymers and oxides derived from our synthesis strategies not only entail a high storage capacity but also, most importantly, can be made to have significantly enhanced electronic & ionic conductivities. These enhanced transport properties in electrode architectures are the key to providing high-rate capabilities for the corresponding energy storage systems.
(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