bluuebunny/crossref_metadata_2025_split huggingface dataset:
Optimization of Recycling Process of Layered NCA Material using Li+-H+ Exchange Reaction
Authors: Ariyoshi Kingo , Matsushita Chisa , HIrota Jo 
Published: December 2024

In recent years, recycling of spent batteries is becoming an urgent issue due to the increasing popularity of vehicles. In particular, the sustainable and competitive recovery of rare metals such as Li, Co, and Ni from positive electrode materials is important from the viewpoint of resource depletion and environmental preservation. In this study, we propose a novel recycling method of layered positive electrode materials for separating transition metals and lithium by treating with oxidant solution.
The process proposed in this study utilizes a Li+-H+ exchange reaction (Fig. a), in which Li ions in the layered materials are replaced with H+ in the solution with preserving the structural framework constructing of transition metals and oxygens. Because the recycling process can be classified into one of the direct recycling, there are many advantages compared with hydrometallurgy; small amount of oxidizing agents, only single step for separation of metals, and distinct separation of metals (transition metals as a precipitation and Li ions in the aqueous solution).
Fig. b shows our preliminary results on the recycling of LiNi0.88Co0.09Al0.03O2 (NCA) via the Li+-H+ exchange reaction. By immersing NCA in a 0.1 M of K2S2O8 aqueous solution, the XRD peaks belonging to NCA became weak, and new peaks belonging to NiOOH appeared and grew with increasing the digestion time. This means that Li ions in NCA were exchanged with H+ in the solution during the digestion. Furthermore, heating thus obtained NiOOH with Li source provided virtually the same XRD pattern as the pristine NCA, indicating that recycling of NCA is possible by utilizing Li+-H+ exchange reaction.
To analyze kinetically the exchange reaction for optimization of the recycling process, the immersion experiments were performed with varying temperatures. The degree of exchange reaction was determined from the ICP measurements of the solution after immersion. The exchange reaction was accelerated with increasing the temperature. Plotting the logarithm of the amount of lithium extracted against digestion time showed a linear relationship at all temperatures (Fig. c), indicating that the exchange reaction obeys a first-order reaction.
In this presentation, we will discuss the effects of oxidants on the Li+-H+ exchange reactions and resynthesis of NCA.

Figure 1
Void-Suppression at Low Stack Pressures Using a Microstructurally Engineered Anode
Authors: Veeraraghavan Vijay D. , Lo Chiung-Yuan , Murali Sriram S. , Li Andrew B. , Fincher Cole D. , Viswanathan Venkat , Chiang Yet-Ming 
Published: December 2024

Solid-state batteries (SSBs) with a Li+ working ion promise a step change in specific energy and safety by using less-reactive solid-state electrolytes (SSEs) in contact with Li metal. However, commercialization of SSBs has been hindered by low specific power due to contact loss at solid-solid interfaces. Voids nucleate and grow at the solid-solid interface between Li metal and the SSE, increasing interfacial resistance. It is hypothesized that during charging ionic current intensification at this interface, which magnifies with increased contact loss, can increase the driving force to nucleate Li dendrites which grow until a short circuit causes cell failure.1

A common workaround for these anode/SSE contact loss issues is to use high uniaxial stack pressures (>1 MPa) applied normal to the planar interface; one theory is that mechanical deformation of Li metal via power-law creep suppresses void growth.2,3 This approach negates one of the proposed benefits of SSBs: high stack pressures require additional mechanical fixturing components which reduces the cell specific energy.
We introduce a microstructured Li metal anode which, while operating in contact with Li6.75La3Zr1.75Ta0.25O12 (LLZTO) SSE at low stack pressures (0.15 MPa) and at room temperature, achieves stable Li stripping for areal capacities more than 10 times that of a lithium control group at current densities up to 1 mA cm-2. We will discuss the mechanisms enabling this suppression of contact loss using data from 3-electrode (Li reference) galvanostatic tests allowing contributions from the stripping and plating electrodes to be deconvoluted.
References:
[1] Raj, V.; Venturi, V.; Kankanallu, V. R.; Kuiri, B.; Viswanathan, V.; Aetukuri, N. P. B. Direct Correlation between Void Formation and Lithium Dendrite Growth in Solid-State Electrolytes with Interlayers. Nat. Mater.
2022, 21 (9), 1050–1056.
[2] Wang, M. J.; Choudhury, R.; Sakamoto, J. Characterizing the Li-Solid-Electrolyte Interface Dynamics as a Function of Stack Pressure and Current Density. Joule
2019, 3 (9), 2165–2178.
[3] Fincher, C. D.; Ojeda, D.; Zhang, Y.; Pharr, G. M.; Pharr, M. Mechanical Properties of Metallic Lithium: From Nano to Bulk Scales. Acta Mater.
2020, 186, 215–222.
Acknowledgements:
Funding is gratefully acknowledged from Morphogenic Interfaces, Defense Advanced Research Project Agency, contract HR00112220032. V.D.V. acknowledges funding from the National Science Foundation Graduate Research Fellowship Program. C.Y.L. acknowledges funding from the Chiang-Chen Overseas Fellowship. C.D.F acknowledges funding from the Department of Defense National Defense Science and Engineering Graduate Fellowship.
Corrosion Behavior of Al-Zn Alloys Fabricated By Spark Plasma Sintering
Authors: Chung Euihyuk , Nishimoto Masashi , Tokuda Shimpei , Nishida Yoshikatsu , Muto Izumi 
Published: December 2024

Hot-Dip Al-Zn plated steel sheets are essential materials for societal infrastructure, utilized in construction materials and conveying equipment. To further enhance the durability, a balance between the dissolution resistance of the plating layer and sacrificial corrosion protection for the base steel is crucial. In this study, we fabricated Al-Zn alloys, to analyze the influence of the microstructure refinement on the dissolution behavior.
Using the planetary ball milling, powders of 65at%Al-Zn,75at%Al-Zn and 50at%Al-Zn were prepared. Powders were sintered by plasma sintering. As a comparative reference, a Hot-Dip 55mass%Al-Zn steel was prepared. To investigate corrosion behavior, immersion potential, polarization curves, and galvanic current measurements were conducted using the three-electrode method.
The sintered bodies constitute a complex microstructure consisting of nano-scaled Al-rich and Zn-rich phases. Measurements of the immersion potential revealed that the sintered bodies exhibited dissolution behavior different from the conventionally used Al-Zn plating layer. The base steel was protected after the galvanic current measurements, as observed through surface analysis.
Effect of N on Pit Initiation at MnS in Type 304 Stainless Steel
Authors: Tsuchiko Yusuke , Nishimoto Masashi , Muto Izumi 
Published: December 2024

N is known as an element that improves the pitting corrosion resistance of stainless steels, but its mechanism of action is unknown. Since N is not a resource constraint and the addition of N does not reduce toughness in FCC, it is important to clarify the effect of N on pitting corrosion resistance of austenitic steels and to find a means to utilize N more effectively from the viewpoint of resource conservation in the production of corrosion-resistant steels. In this study, the effect of N on the occurrence of pitting corrosion was analyzed by electrochemical measurements on Type 304 stainless steel containing MnS.
Type 304 stainless steel containing 0.120 mass% N was used as a sample, and Type 304 stainless steel containing 0.005 mass% N was used as a comparison material. Each sample was heat treated at 1100°C for 30 minutes and then water cooled.
After heat treatment, the specimens were polished with 1 µm diamond paste, and inclusions were observed using optical microscopy and SEM-EDS.
Polarization curves were measured under 0.1 M NaCl solution at pH 6.0 and water temperature of 25°C, to compare pitting potentials. After the measurements were made, the areas where pitting corrosion was occurring were observed under an optical microscope.
For each steels, it was confirmed that pitting corrosion occurred starting from MnS inclusions.
The N-doped steels showed a higher pitting corrosion potential than the steels containing little or no N.
Structural and Electronic Modification of Electrocatalyst By Se Doping for Hydrogen Evolution Coupled Selective Electrooxidation of Ethylene Glycol to Glycolic Acid
Authors: Jang Daehee , Park Minseon , Maeng Junbeom , Seo Min Ho , Kim Won Bae 
Published: December 2024

Chemical reforming by electrochemical reaction has attracted great attention due to mild reaction condition and ease of control. As the raw materials for electrochemical reforming, ethylene glycol (EG) is advantageous for its large-scale production and cheap market price. Various organic acids such as glycolic acid (GCA), oxalic acid (OXA) and formic acid (FA) can be produced with simultaneous production of high purity of dihydrogen gas during ethylene glycol oxidation reaction (EGOR). In particular, EG selective oxidation targeted at the production of GCA, which has broad applications in skin care, textile industry and adhesives.
Herein, a noble catalyst material of Pt nanoparticles supported on Se-doped porous carbon (Pt/SePC) is prepared and investigated for the selective EGOR to GCA. The Pt/SePC achieved a maximum EG conversion of 94.6% and GCA selectivity of 84.4%, and maintained this high performance with a negligible degradation during durability tests. The effect of Se doping was investigated through the experimental analyses and theoretical DFT calculations, that lattice deformation and defects introduction caused by Se led to electronic localization in Pt nanoparticle, thus the adsorption energy of intermediate reactants on Pt surface were modified. Furthermore, EGOR required low overpotential compared with oxygen evolution reaction, thus coupling EGOR and hydrogen evolution reaction required potential of 0.60 V while 1.58 V is necessary for water electrolysis. Our study could highlight favorable strategy of catalyst design with heteroatom doping for catalyst stabilization and promoting ethylene glycol conversion to value-added glycolic acid.
Effect of Salt Bridge Formation on Proton Transport in CNTs
Authors: Nakamura Akihiro , Mabuchi Takuya 
Published: December 2024

Various sectors have initiated technology development projects aimed at realizing a hydrogen-based society with low carbon dioxide (CO2) emissions. A proton (H+) transfer system with high permeability and selectivity is essential for the hydrogen infrastructure and fuel cells that support a hydrogen-based society. Therefore, intensive research is underway to design bioinspired artificial proton channels. Natural proteins achieve high proton selectivity by organizing proton-conducting pathways with scattered ionizable side chains and controlling proton transport through Vehicle and Grotthuss mechanisms. The Hv1 channel is a proton-selective protein that contains the amino acids aspartic acid (Asp) and arginine (Arg) in its pathway. As shown in Figure 1, the proton transport mechanism of Hv1 channels is suggested that Asp and Arg can be protonated, allowing them to transport protons via the Grotthuss mechanism. Additionally, Asp and Arg form salt bridges to close the pathway, thereby inhibiting the transport of other ions via the vehicle mechanism. However, the relationship between Asp and Arg and their impact on the transport mechanism remains unclear. It is important to elucidate the relationship between the inhibition of transport and pore size, as well as to understand the correlation between the inhibition of transport and salt bridges, to install proton transport mechanism of Hv1 channels into artificial proton channels. In this study, carbon nanotubes (CNTs) were used as a model pore for artificial ion channels, and we analyzed the effects different sizes of CNTs modifying with Asp and Arg on ion transport properties using molecular dynamics simulations.
We adopted the armchair CNTs model shown in Table 1, using the CNTs chirality (5,5), which is known to spontaneously fill with water at room temperature, as the smallest model. For the molecular models of Asp and Arg, side chain models of Asp(N)–Arg(N) and Asp(-)– Arg(+) pairs, which can form salt bridges, were modified inside CNTs.
The results of the probability of hydrogen bond formation are shown in Figure 2. The results confirm that hydrogen bonds are always maintained at a pore radius R = 4.75 Å (CNTs chirality = 7,7) for both conditions. As the distance between Asp and Arg increases with increasing pore radius R above R = 4.75 Å, it appears that the hydrogen bonds cannot be maintained. Even when the pore radius is smaller than R = 4.75 Å, the probability of hydrogen bonding formation decreases. In the poster, we will present further structural analyses, such as the orientations of Asp and Arg and their relation to the hydronium ion conformation.
[1] Dudev, T., Musset, B., Morgan, D. et al. Selectivity Mechanism of the Voltage-gated Proton Channel, HV1. Sci Rep
5, 10320 (2015).

Figure 1
Fabrication of Tubular Alumina through-Hole Membranes by Anodization of Al Wires
Authors: Yoshinaga Minori , Yanagishita Takashi 
Published: December 2024

Membrane filters with uniformly sized pores have attracted considerable attention because they are useful for filtering a variety of particulates. Among them, anodic porous alumina, obtained by the anodization of Al in an electrolyte, has been studied as a membrane filter for microfiltration because it can form a nanohole array structure with regularly arranged pores of uniform size. We previously reported that a two-layer anodization method using concentrated sulfuric acid can form highly ordered alumina through-hole membranes with high throughput [1]. Using this method, it was possible to form not only flat membrane filters but also tubular membrane filters [2]. Tubular alumina membrane filters have potential applications in filter modules for space savings and efficient microfiltration. To achieve efficient filtration in filter modules consisting of tubular membrane filters, it is necessary to increase the density of the filter packed in the module, which requires the fabrication of tubular filters with small diameters. However, it is difficult to form tubular alumina membrane filters thinner than 1 cm in diameter using a previously reported method. In this report, we describe the results of a new method based on a two-layer anodization process using concentrated sulfuric acid to form tubular membrane filters with millimeter diameters.
Electropolished Al wire was anodized in 0.3 M oxalic acid at 40 V to form anodic porous alumina. The sample was then re-anodized in 12M sulfuric acid at 40V to form a highly soluble alumina layer at the bottom of the previously formed anodic porous alumina. After anodization, the sample was immersed in a mixed solution of chromic acid and phosphoric acid to selectively dissolve the alumina layer formed in concentrated sulfuric acid, thereby exposing the Al substrate at the bottom of the pores. Tubular alumina membrane filters were obtained by selectively dissolving the Al substrate through nanopores in an iodine-methanol solution.
In this study, Al wires with diameters ranging from 2 to 5 mm were used as the starting materials, and in all cases, it was possible to form tubular alumina membrane filters without cracks. SEM observations of the obtained samples showed that the tubular alumina membrane filter was uniformly sized through the holes. The tubular alumina membrane filter obtained in this study is expected to be useful in a variety of applications.
References
[1] T. Yanagisihta and H. Masuda, Electrochim. Acta, 184, 80 (2015).
[2] T. Yanagishita, A. Kato, and H. Masuda, Jpn. J. Appl. Phys., 59, 038002 (2020).
Co-Deposited Hydrogen in Electrodeposited Pd Films: Insights from High-Temperature Thermal Desorption Spectroscopy
Authors: Hashimoto Tomoya , Fukumuro Naoki , Yae Shinji 
Published: December 2024

Palladium (Pd) has been extensively studied for hydrogen absorption and desorption as a fundamental metal of the metal-hydrogen systems. When hydrogen is absorbed into bulk Pd under high pressure or via electrolytic charging, interstitial hydride α and β phases are formed. On the other hand, during Pd electrodeposition, hydrogen atoms are co-deposited in the Pd films, and not only the interstitial hydrides but also vacancy-hydrogen clusters and nanovoids containing molecular hydrogen are formed in the Pd films1). In this study, we will present the findings of Pd film analysis measured using high-temperature thermal desorption spectroscopy.
An alkaline plating bath containing 0.03 M (M = mol dm-3) palladium chloride (Ⅱ), 0.50 M ammonium chloride, and 0.05 M citric acid was used for electrodeposition of the Pd films. The pH of the plating bath was adjusted to 8.3 with an aqueous ammonia solution. A stainless steel (SUS304) plate was used as a substrate from which the Pd films could be peeled off. A platinum plated titanium mesh was used as a counter electrode. The bath temperature was maintained at either 298 or 278 K. The electrodeposition was performed at a constant current density of 50 A m-2. Hydrogen desorption spectra of the Pd films were measured under ultra-high vacuum by increasing the temperature from 300 K to 1300 K and then holding at 1300 K for several hours.
In the thermal desorption spectrum of hydrogen from the Pd film electrodeposited at 298 K, hydrogen desorption corresponding to the desorption of the interstitial hydrogen and break-up of vacancy-hydrogen clusters was observed at temperatures below 900 K1). Above 1100 K, significant hydrogen desorption which may be assigned to the desorption of molecular hydrogen from the nanovoids with grain growth and Pd evaporation was observed. The total amount of desorbed hydrogen from the Pd film was x = 6.5 × 10-2 of which 84% was molecular hydrogen in the nanovoids desorbed at temperatures above 1100 K. In the thermal desorption spectrum of the Pd film electrodeposited at 278 K, a pronounced peak ascribed to the desorption of interstitial hydrogen appeared at around 380 K, and x = 0.15 of which 68% was molecular hydrogen in the nanovoids desorbed at temperatures above 1100 K. These results show that the existing states and concentrations of co-deposited hydrogen depend on the deposition conditions of the Pd films.
This work was supported by JSPS KAKENHI Grant Number JP22K04763.
1) T. Hashimoto, T. Nakamura, N. Fukumuro, S. Yae, Mater. Trans., 64, 2466 (2023). DOI: 10.2320/matertrans.MT-M2023076
High-Entropy Materials As Solid State Electrolytes for Fluoride-Ion Batteries
Authors: Chen Zhihao , Zhong Chengchao , Okazaki Ken-ichi , Shimoda Keiji , Orikasa Yuki 
Published: December 2024

Compared to conventional lithium-ion batteries (LIBs), all-solid-state fluoride-ion batteries (FIBs) offer superior theoretical energy density and enhanced safety features1. The notable advantage of FIBs is their ability to facilitate multi-electron transfer reactions between metals and metal fluorides, potentially unlocking volumetric energy densities of up to 5000 Wh L−
1. Despite these promising properties, the development of FIBs is still at an early stage. A major challenge is their low ionic conductivity at room temperature compared to cation conductors. As a result, FIBs typically require operation at elevated temperatures, in excess of 140 °C, to achieve desirable performance levels.
To overcome this problem, improving the ionic conductivity of electrolytes for FIBs is critical and involves reducing the activation energy for ion migration. High entropy materials have emerged as a potential solution to this challenge, offering a novel way to effectively reduce the activation energy2. Recent advances in this field have led to the development of a lithium superionic conductor, which demonstrates the potential of high-entropy materials to revolutionise ion conductivity3.
In our study, we focused on the synthesis of a high-entropy material, (LaCeNdSmGd)F3, using a solid-state reaction method. Extensive analysis using Rietveld refinement and scanning electron microscopy (SEM) confirmed that the synthesised (LaCeNdSmGd)F3 retains the crystal structure characteristic of LaF3. Using electrochemical impedance spectroscopy, we found that (LaCeNdSmGd)F3 exhibits an ionic conductivity of 1.3×10-7 S cm−
1 at 373 K. Furthermore, Arrhenius plots revealed that (LaCeNdSmGd)F3 has a significantly lower activation energy compared to LaF3, highlighting the effectiveness of high-entropy materials in reducing activation energy.
The introduction of a wide range of cations into the high entropy material (LaCeNdSmGd)F3 leads to structural disorder and site energy overlap. This complexity within the crystal lattice effectively lowers the energy barriers associated with ion migration, thereby enhancing the ionic conductivity of the fluoride solid electrolyte.
Fluoride Ion Conduction of BiSF with Distorted PbFCl-Type Structure
Authors: Ito Yukino , Tachibana Shintaro , Kageyama Hiroshi , Orikasa Yuki , Zhong Chengchao 
Published: December 2024

All-solid-state fluoride ion (F−) rechargeable batteries are expected to have a high energy density due to their wide potential window and the availability of multi-electron reactions at the electrodes. F− conductors used as solid electrolytes have lower conductivity at room temperature than cationic conductors, and the crystal structures studied are limited. We have previously discovered that an anion-ordered structure created by F− and S2− in sulfidefluoride has a F− conduction path that is not found in single anion compounds1), indicating that mixed-anion compound can be used to develop new F− conductors. In this study, we focused on BiSF, a fluorosulfide with distorted PbFCl-type structure. The 6s2 lone pair electrons (LPEs) around Bi3+ are expected to promote F−

conductivity due to their high polarizability. In addition, the ionic conductivity of BiSF was compared with LaSF that has PbFCl-type structure but without LPEs.
BiSF was obtained by mixing Bi2S3 and BiF3 in an Ar atmosphere, forming pellets, placing them in a cell for high-pressure synthesis, and performing high-pressure synthesis at 5 GPa and 650°C for 1 hour. LaSF was obtained by mixing La2S3 and LaF3 under an Ar atmosphere, pellet forming, vacuum sealing, and calcination at 800 °C for 24 hours. Powder X-ray diffraction measurements (XRD) were used to identify the experimental samples, while AC impedance methods were used to measure ionic conductivity.
The XRD results confirmed that the synthesized sample contained few impurities and the target material BiSF was synthesized. AC impedance measurements of BiSF showed a rising behavior at the low frequency side, indicating that BiSF has ionic conduction. The ionic conductivity of BiSF at 30°C was 4.22 × 10−6 S cm−1. LaSF, which has similar PbFCl-type crystal structure as BiSF but without LPEs, did not exhibit F− conduction, suggesting that the F− conduction in BiSF is affected by LPEs present in Bi3+.
【References】
1) S. Tachibana, C. Zhong, K. Ide, H. Yamasaki, T. Tojigamori, H. Miki, T. Saito, T. Kamiyama, K. Shimoda,
Y. Orikasa, Chem. Mater., 35, 4235-4242 (2023).