bluuebunny/crossref_metadata_2025_split huggingface dataset:
Solid Dispersion Flow Battery Particle Synthesis and Electrochemical Characterization
Authors: Koenig Gary 
Published: February 2020

Flow batteries have a number of advantages as an energy storage system, including the ability to decouple the power and energy of the battery. The electroactive material within traditional flow batteries consists of transition metals dissolved in aqueous acidic electrolytes, however, recently there have been reports of using solid particles as the electroactive material. The advantages of solid particles are that by starting with a solid the solubility of the electroactive species is no longer a limiting factor with regards to energy density and the energy density of the flow battery electrolyte can be increased substantially. In addition, by using organic solvents and lithium-ion battery active materials as the solid particles in the flow battery the energy density of the system can be further improved. A challenge in these so-called semisolid flow batteries is that most have carbon additives that form interconnected electrode structures. The carbon addition significantly increases the viscosity of the electrolyte, which results in additional net energy lost to pumping the electrolyte through the system as well as higher power pumps required to achieve equivalent volumetric flow rates through the channels.
Our research group has been investigating flow batteries that rely on solid electroactive materials. However, within our solid dispersion flow battery system the electrochemical reactions are the consequence of collisions with the current collector. The coupling between electrochemical and rheological properties within this flow battery are highly sensitive to both the fluid flow through the channel and the electrochemically active particle morphology and loading within the electrolyte. Thus, this system requires understanding of the electrochemical properties as a function of both particle loading, particle interactions with the current collector, and the flow geometry that the electrolyte traverses through.
In this talk, we will describe recent work within our group to design scalable processes to synthesize particles that form stable dispersions within the solid dispersion flow battery geometry. The synthesis route consists of sacrificial precursor components that results in loosely connected agglomerate structures that are easily separated to form small, dispersible lithium-ion battery active material particles. We will discuss recent efforts to characterize these lithium-ion battery particles within solid-dispersion flow battery systems and experiments to understand the electrochemical and rheological properties and their coupling within flow batteries comprised of dispersed solid particles. Limitations with regards to power capability and the role of the current collectors within this system will also be discussed.
Photo-Potential Property of TiO2 Electrode Prepared By the Screen Printing Method
Authors: Watanabe Fumi , Motoda Shinichi , Morita Motoaki 
Published: February 2020

We have been investigating the marine microbial fuel cell(MFC) composed of biofilm covered stainless steel cathode and TiO2 coated stainless steel anode in seawater. It is necessary to improve the properties of anode electrode for increase the power density of MFC. The purpose of this study is to improve the photo-potential characteristics of TiO2 anode. In the present work, we focused on the film formation method of TiO2 for the improvement of photo-potential properties by introducing screen printing method with the annealing into the coating process of TiO2 film.
The electrode was stainless steel Type 329J4L (40mm in square, 1mm thickness) coated by TiO2 film. Titanium dioxide film was composed of two layers formed by repetition of film forming process with two methods of squeegee printing and screen printing. Sintering condition of first layer took 60 minutes at 150°C and took 30 minutes at 550°C for second layer. The composition of TiO2 paste was as follows, TiO2(anatase):16, alcohols:17 and H2O:67 in mass.%. After film formation, electrodes were annealed with changing heat treatment temperatures. Annealing temperatures were 100°C, 150°C and 200°C, cooling method was air cooling. TiO2 electrodes were immersed in the 1 liter artificial seawater as an electrolyte and photo-potential was measured using the potentiostat with saturated calomel electrode(SCE) as a reference electrode. The light source irradiated was 150W Xenon lamp which was calibrated 250nm to 800nm and quantity of light was 10.5mW/cm2on the electrodes surface.
We measured photo-potentials three times under the light irradiation for each electrode. Steady photo-potentials of electrode manufactured by the squeegee method were -548mV(vs.SCE) at the experiment of first run, -510mV(vs.SCE) at the second and -515mV(vs.SCE) at the third. The increase of photo-potential occurred was considered by the substrate corrosion resulted from small cracks of TiO2 film during the sintering. On the other hand, steady photo-potentials of the electrode manufactured by the screen printing method were -517mV(vs.SCE) at the experiment of first run, -518mV(vs.SCE) at the second and -517mV(vs.SCE) at the third. It was considered that uniformly formed film by the screen printing improved the durability of film. From the results, the durability of electrodes improved reproducibility of repetition by the introducing the screen printing method. It was considered that corrosion which affects the photo-catalytic reaction of TiO2, was suppressed by forming the uniform film due to the screen printing method.
We investigated also the effect of annealing process to the electrode which was coated TiO2 film by the screen printing method. Photo-potentials of electrodes were -557mV(vs.SCE) at annealing temperature of 100°C , -589mV(vs.SCE) at 150°C and -593mV(vs.SCE) at 200°C. It is considered that the increase of the oxygen defect by the annealing process improved the semiconductor intrinsic properties of the TiO2 film.
Electrochemical Intercalation of Bis(trifluoromethanesulfonyl)Imide (TFSI) Anion into Graphitic Carbon from Organic Electrolyte and Application for Dual Carbon Battery
Authors: Kurihara Takuya , Fukuda Taro , Ida Shintaro , Ishihara Tatsumi 
Published: February 2020

Li-ion batteries (LIB) are now widely used in various areas such as electric vehicle (EV) or mobile phone. However, there are some issues of LIB like high-cost, safety, and energy density. Therefore, battery that has higher energy density and high power density is strongly required. Dual carbon battery (DCB), which consists of graphitic carbon for both positive and negative electrodes, is attracting much interest because of superior rate property, low cost, and high discharge potential. In this battery, for charge process, Li ions intercalate into anodic graphite, and counter anions in electrolyte also intercalate into cathodic graphite, and for discharge process, de-intercalation is occurred in both electrodes. Therefore, charge and discharge scheme is similar with that of capacitor, however, by using intercalation reaction, much higher energy storage capacity is expected. In our previous study, we investigated dual carbon battery using LiPF6 and demonstrated that discharge is observed at potential from 4.0 to 5V with 90mAh/g-carbon on the full cell and by using the high concentration electrolyte of 3 M LiPF6 in DMC, energy density is also much increased. Since it is reported that intercalation potential increases with increasing ionic size of anion, we investigated electrochemical intercalation property of bis(trifluoromethanesulfonyl) imide (TFSI) anion in this study. Effects of electrolyte on intercalation of TFSI anion into graphitic carbon was investigated and it was found that intercalation of TFSI anion was observed in propylene carbonate (PC) based electrolyte at room temperature. Among the electrolytes examined, the largest intercalation capacity was achieved in PC-EMC(1:1). By using 3MLiTFSI/PC-EMC (1:1), discharge capacity of 110mAh/g was stably sustained over 50 cycles, however, coulombic efficiency is around 90%. Further detail study was performed on intercalated structure of TFSI anion. Comparing with PF6 anion, intercalation potential is almost the same, however, the capacity is larger (90 mAh/g for PF6, and 110 mAh/g for TFSI). Therefore, it was found that the intercalation of TFSI anion is also usable for cathodic reaction in dual carbon battery. Stage structure of intercalated TFSI- is also studied by using in-situ XRD and it was confirmed that the distance of (002) plane of graphitic carbon was expanded by increasing potential suggesting that electrochemical intercalation of TFSI anion is occurred. From the distance of (002) plane, stage 1 structure seems to be observed at 5.2V with 0.79 nm distance which is little larger than that of PF6- (0.77nm). Although expansion of electrode is little larger, TFSI anion is also promising anion for dual carbon battery from high potential plateau (5V) and large capacity (110mAh/g).
Effects of Additives on the Stability of Positive Electrolytes for All-Vanadium Redox Flow Battery
Authors: Park Se-Kook , Jin Chang-Soo , Yeon Sun-Hwa , Shin Kyoung-Hee , Lee Bum suk 
Published: February 2020

The all- Vanadium redox flow battery (VRFB) is a promising technology for large-scale electrical energy storage systems[1, 2]. VRFB is an electrochemical system using reactions of two redox couples of V2+/V3+ in a negative half-cell and VO2+/VO2
+ in a positive half-cell to perform a reversible conversion between electrical energy and chemical energy. However, poor stability of the electrolytes, especially the positive electrolyte, greatly limits the concentration of redox couples in the electrolyte solution, which significantly affects the performance of VRFBs[3, 4].
In order to achieve high electrolyte performance, a sodium pyrophosphate dibasic (SPD) introduced as an inorganic additive in positive electrolyte VO2
+ for VRFBs. And its effects on long-term stability and electrochemical performances were investigated, through UV-vis spectrophotometry, cyclic voltammetry, and through the performance of a charge/discharge test.
[1] A. Parasuraman, T.M. Lim, C. Menictas, M. Skyllas-Kazacos, Review of material research and development for vanadium redox flow battery applications, Electrochimica Acta, 101 (2013) 27-40.
[2] A.Z. Weber, M.M. Mench, J.P. Meyers, P.N. Ross, J.T. Gostick, Q. Liu, Redox flow batteries: a review, Journal of Applied Electrochemistry, 41 (2011) 1137-1164.
[3] J. Zhang, L. Li, Z. Nie, B. Chen, M. Vijayakumar, S. Kim, W. Wang, B. Schwenzer, J. Liu, Z. Yang, Effects of additives on the stability of electrolytes for all-vanadium redox flow batteries, Journal of Applied Electrochemistry, 41 (2011) 1215-1221.
[4] S.-K. Park, J. Shim, J.H. Yang, C.-S. Jin, B.S. Lee, Y.-S. Lee, K.-H. Shin, J.-D. Jeon, Effect of inorganic additive sodium pyrophosphate tetrabasic on positive electrolytes for a vanadium redox flow battery, Electrochimica Acta, 121 (2014) 321-327.
Indirect Fuel Cell Based on a Redox-Flow Battery Toward the Reduction of Platinum Usage
Authors: Siroma Zyun , Maruyama Jun , Yamazaki Shin-ichi , Ioroi Tsutomu 
Published: February 2020

An indirect fuel cell [1-3], which is composed of a redox-flow battery (RFB) and a chemical reactor to regenerate (oxidize) the catholyte by oxygen and another reactor to regenerate (reduce) the anolyte by a fuel, is constructed as an alternative to a PEFC. We have already proposed a new design for the RFB [4] for our indirect fuel cell, which has a gas phase of hydrogen to separate the catholyte and anolyte to eliminate the crossover of ionic species. In this work, to clarify the possibility to use an indirect fuel cell to reduce the usage of noble-metal catalysts, a non-noble-metal catalyst and a mixture of two molecular catalysts were used in the catholyte and anolyte regenerators, respectively. In the catholyte regenerator, a carbonized hemoglobin powder was used as a solid catalyst. This material has been proved to be effective as an electrocatalyst for oxygen reduction reaction (ORR) in a PEFC [5]. In this work, it was used after immobilization on a polymer sheet support. In the anolyte regenerator, a rhodium complex was used for hydrogen oxidation and another rhodium complex for carbon monoxide oxidation. Although these two complexes contain a noble metal, they are soluble in the electrolyte and used as homogeneous catalysts. Since the active site of such a complex molecular catalyst is a single metal atom, the usage of metal can be reduced compared with a metallic platinum catalyst.
This work demonstrates a steady-state operation of the above-mentioned indirect fuel cell by feeding of oxygen and CO-containing hydrogen to the catholyte and anolyte regenerators, respectively.
This work was supported by JSPS KAKENHI Grant Number 25289363.
[1] A.M. Posner, Fuel, 34 (1955) 330.
[2] S. Ashimura, Y. Miyake, Denki Kagaku, 31 (1963) 598.
[3] D.-G. Oei, J. Appl. Electrochem. 12 (1982) 41.
[4] Z. Siroma, S. Yamazaki, N. Fujiwara, M. Asahi, T. Nagai, T. Ioroi, J. Power Sources, 242 (2013) 106.
[5] J. Maruyama, I. Abe, Chem. Mater., 18 (2006) 1303.
Effect of Metal Cations in Fresh Water on Surface Film Structure and Initial Corrosion of Mild Steel
Authors: Otani Kyohei , Sakairi Masatoshi 
Published: February 2020

Corrosion of steel in fresh water is a serious problem in circulative cooling systems, water supply systems and water storage tanks, therefore many researchers have reported the corrosion of steel in fresh water.1 The initial corrosion behavior of steel has been discussed on the basis of oxide films, and the films are generally destroyed by chloride ions.2 On the other hand, Kato et al. investigated the corrosion behaviour of mild steel by focusing on the effects of metal cations, and they found that some cations show corrosion inhibiting ability.3 However, there have been a few study in which the quantitative effects of metal cations on corrosion of steel in fresh water, and the effect of metal cations in solution to the oxide films has not been clarified.
The authors focused on “hardness of cations, X” to explain the different effect of metal cations on oxide films of mild steel. X is an indicator of the basis of HSAB concept,4 and the value means that tendency of the incorporation between the metal cations and oxygen atoms in the passive films. Therefore, it is expected that the effect of metal cations in solution to the oxide film and the corrosion of mild steel would be explained by using X.
The effects of metal cations on the oxide films and corrosion of mild steel in model fresh water were investigated by immersion tests with surface analysis of X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Five different salt solutions, NaCl (Nasol), MgCl2 (Mgsol), ZnCl2 (Znsol), AlCl3 (Alsol), and ZrCl2O (Zrsol), were used as model fresh water, and the concentration of chloride ions in each solutions was the same. Analysis of XPS showed that metal cations that have large hardness of cations, X, were incorporated with passive films, and then the hydroxides of metal cations were formed on the mild steel. The EIS and immersion results showed that the initial corrosion resistance of mild steel increased with increase in X except for the specimens immersed in Mgsol and Zrsol.
Reference
1. R. E. Melchers, Corros. Sci., 48 ,4174 (2006).
2. H. J. Engell, Eletrochimica Acta, 22, 987 (1977).
3. M. Kato, Boshoku Gijutsu, 31, 27 (1982).
4. M. Misono, E. Ochiai, Y. Saito, Y. Yoneda, J. Inorg. Nucl. Chem., 29, 2658 (1967).
(Invited) Fabrication of Highly Ordered Anodic Porous Alumina and Its Applications to Functional Nanodevices
Authors: Masuda Hideki , Yanagishita Takashi , Kondo Toshiaki 
Published: February 2020

The anodic porous alumina, which is formed by anodization of Al in an acidic electrolyte, has attracted much interest as the starting materials for various types of functional nanodevices due to its unique geometrical structures.1) It has been reported that long-range-ordered anodic porous alumina with an ideally ordered hole arrangement can be obtained under appropriate anodization conditions.2-4) Such ordered structures are useful for the preparation of the functional nanodevices, which require the ordered nano- structures. The control of hole intervals and hole sizes of anodic porous alumina while retaining the long-range ordered hole arrangement is very important for expanding the application fields of the anodic porous alumina. As an example of the expansion of the range of the hole intervals and hole sizes with long-range ordered hole arrangement, we have shown the formation of long-range-ordered anodic porous alumina with reduced hole intervals and hole sizes. In this process, highly ordered anodic porous alumina with reduced hole interval of ~25 nm can be obtained by the appropriate anodizing condition5,6). In the present report, the formation of the highly ordered anodic porous alumina with various hole intervals and hole sizes will be presented. In addition, the template synthesis of the ordered nanostructures with reduced dimensions will be also reported.
1. T. Yanagishita, T. Hidaka, M. Suzuki, and H. Masuda, J. Vac. Sci. Technol. B, 34, 021804 (2016).
2. H. Masuda and K. Fukuda, Science, 268, 1466 (1995).
3. H. Masuda, F. Hasegawa, and S. Ono, J. Electrochem. Soc., 144,L127 (1997).
4. H. Masuda, K. Yada, and A. Osaka, Jpn. J. Appl. Phys., 37, L1340 (1998).
5. H. Masuda, M. Nagae, T. Morikawa, and K. Nishio, Jpn. J. Appl. Phys., 45, L406 (2006).
6. H. Masuda, K. Takenaka, T. Ishi, and K. Nishio, Jpn. J. Appl. Phys., 43, L1165 (2006).
The Effect of Thermal Hydrogenation Processing on the Nano-Size Grain Refinement and Oxide Layer Fomation of Ti-6Al-4V Alloy
Authors: Wang Le-Min , Tsai Chih-Jen 
Published: February 2020

Our earlier works have shown that the better corrosion resistance of Ti-6Al-4V alloy can be achieved by applying a post-THP annealing treatment associated with a controlled oxidation reaction which can produce ﬁner oxide particles and almost seal the oxygen diffusion paths leading to the formation of a much thinner (0.56 μm), but denser oxide layer than has been indicated in the literature [1,2].
This study aims to investigate the effect of common industrial heat treatments on the mechanical properties and corrosion resistance of Ti-6Al-4V alloy following thermal hydrogenation processing (THP) plus related heat treatments under variant hydrogen loadings. The correlation among the microstructural characteristics in matrix, the oxide layer structure on the surface, and the corresponding properties of the samples after related treatments was analyzed. The phase transformation, microstructural evolution, the formation of intermetallic compounds, oxide layer and the possible mechanism of grain refinement into nano-size scale were also discussed by using HRTEM under variant hydrogen loadings.
Keywords：Ti-6Al-4V alloy, Thermal hydrogenation processing, Heat treatment, Microstructure, Oxide layer, , Corrosion resistance, HRTEM.
References
[1]Tsai, C. J. and Wang, L. M., “The Effect of Thermal Hydrogenation Processing on the Oxide Layer Formation of Ti-6Al-4V Alloy,” Journal of the Electrochemical Society, Vol. 160, pp. C560-C568, 2013.
[2] Tsai, C. J., Yu, S. S., Wang, L. M., and Shen, C. C., “The Effect of Thermal Hydrogenation Processing on the Oxide Layer Formation of Ti-6Al-4V Alloy,” ECS Transactions, Vol. 50(30), pp. 79-90, 2013.

Figure 1
Dissociation Oxygen Partial Pressure of CaPd3O4 from 1023 to 1328 K
Authors: Kawamura Kenichi , Yuasa Yasunori 
Published: February 2020

Introduction

The high level radioactive wastes in spent fuels are immobilized in borosilicate glass. The spent fuels is mixed with borosilicate glass and the mixture is heated by joule heat directly supplied by electrical current. The oxides of platinum group metals (Rh, Pd or Ru) exist in the spent fuels. Since the oxides are easily reduced resulting in low resistivity, their thermodynamic properties are indispensable to establish the immobilizing process. The object of this study is to make clear the dissociation oxygen pressure over the Pd-CaO-CaPd3O4 coexistence by using the electrochemical cell.

Experimental

The dissociation of CaPd3O4 is represented by
2CaPd3O4 → 2CaO + 6Pd + 3O2 (1).
Equilibrium oxygen partial pressures of the above reaction were measured by oxygen concentration cells using CaO stabilized ZrO2 solid electrolyte.
The cell is described as
Pt, CaO, CaPd3O4, Pd, O2(sample) |CSZ| O2(air), Pt.
Electromotive force (emf) of the cell from 1023 to 1328 K was measured by a digital volt meter with impedance of 109 Ω.

Results and discussion

The equilibrium value was adopted from an average of emfs for last 30 s when the changes in the emfs were within 1 mV par 30 ks. The least squares fits give the emf's of the cell in the following expression.

E/V = 0.6781 − (5.177x10-4) T

From the obtained emf values, the equilibrium oxygen partial pressures of Pd-CaO-CaPd3O4 coexistence is represented by
log p(O2)/bar = 51.8 - 72.6x103/T.
Therefore, the dissociation oxygen partial pressure is higher than atmospheric oxygen partial pressure above 1310 K.
From the obtained equilibrium oxygen partial pressure, the standard Gibbs energy change of the reaction (1) is represented by
∆G
0(1) / kJ mol-1 = -262.0 + 0.1871 T.
Using the reported values of the standard Gibbs energy of formation of CaO, we obtained the standard Gibbs energy of formation of CaPd3O4 as follows.
Δf
G
0(CaPd3O4) / kJ mol-1 = -1034 + 0.3904T.
Improvement of Oxidation Behavior in Cr(N,O) By Increasing the Oxygen Content
Authors: Suematsu Hisayuki , Suzuki Kazuma , Suzuki Tsuneo , Nakayama Tadachika , Niihara Koichi 
Published: February 2020

Chromium oxynitride(Cr(N,O)) thin films have been developed by controlling the oxygen partial pressure during the deposition 1). The Cr(N,O) thin films show superior properties not only the hardness but also the oxidation behavior than those of CrN, which are suitable for machining tool applications. However, the reason of the oxidation improvement was not known because of the presence of grain boundaries. Recently, we have succeeded in preparation of epitaxially grown Cr(N,O) on MgO and other single crystal substrates to reduce the density of grain boundaries2). In this work, oxidation behavior of the epitaxially grown Cr(N,O) thin films was investigated from crosssectional transmission electron microscope (TEM) observations.
Thin films of Cr(N,O) were epitaxially grown by a pulsed laser deposition method. In the deposition chamber, oxygen gas with a partial pressure of 2x10-5Pa and N radicals from an RF radical source were introduced. A plate of Cr was rotated in the deposition chamber was irradiated by a Nd:YAG pulsed laser with a wavelength of 355 nm. Thin films were deposited on MgO (100) single crystal substrates kept at 973 K in the deposition chamber. After the deposition, oxidation tests were carried out in a furnace at 673-1173 K in air for one hour. After the oxidation tests, powder X-ray diffraction (XRD), crosssectional TEM and electron energy loss spectroscopy (EELS) observations/analyses were conducted for precise phase, microstructure and composition analysis.
From the XRD and TEM analyses, the as-deposited thin films were of epitaxially grown Cr(N,O) on the substrates. After the oxidation tests, from XRD patterns, peaks for Cr2O3were seen from samples heated above 873 K. On the other hand, peaks for Cr(N,O) remained up to 1073 K. From TEM and EELS analyses of the sample heated at 1073K, on the existing Cr(N,O) epitaxially grown thin film, a polycrystalline oxide layer was covering. It was found that the oxide layer works as an oxygen diffusion barrier from the surface.
References

1) T. Suzuki, J. Inoue, H. Saito, M. Hirai, H. Suematsu, W. Jiang, and K. Yatsui, Thin Solid Films 515, 2161 (2006).

2) K. Suzuki, T. Endo, A. Sato, T. Suzuki, T. Nakayama, H. Suematsu, and K. Niihara, Mater. Trans. 54, 1957 (2013).