bluuebunny/crossref_metadata_2025_split huggingface dataset:
Compatibility Studies of New Hückel-Type-Based Electrolytes with Electrode Materials
Authors: Bitner-Michalska Anna , Nolis Gene M , Trzeciak Tomasz , Zukowska Grazyna Zofia , Niedzicki Leszek , Wieczorek Wladyslaw , Marcinek Marek 
Published: February 2020

Sodium has emerged as a major contender to lithium for rechargeable battery applications. Owing to its strengths are its high abundance, low production costs and suitable redox potential (Na/Na+, Eo = -2.71 V, not much less than Li/Li+, E˚=-3.05 V vs. standard hydrogen electrode). However, much like the lithium-ion battery industry, researchers are aware of how critical the electrolyte plays into cell performance. The novel imidazolate sodium salts: sodium 4,5-dicyano-2 (trifluoromethyl)imidazolate (NaTDI), sodium 4,5-dicyano-2-(pentafluoroethyl)imidazolate (NaPDI) and sodium pentacyanopropenide (NaPCPI) are presented [1]. Novel salts present interesting properties for electrolytes with applications in sodium and sodium-ion batteries.
These salts may be synthesized easily and have low cost of production on the industrial scale, but also possess very interesting ionic conductivity in solution containing EC/DMC (Graph 1.). Moreover, the salts studied exhibit electrochemical stability against anode (Graph 2.) and cathode. Electrode materials have been produced by two techniques: tape casting (cathode and anode) and Microwave Plasma Chemical Vapor Deposition (anode) [2]. Presented anodes are based on germanium and antimony.
References:
[1] L. Niedzicki, E. Karpierz, A. Bitner, M. Kasprzyk, G.Z. Zukowska, M. Marcinek, W. Wieczorek, Optimization of the lithium-ion cell electrolyte composition through the use of the LiTDI saltElectrochim. Acta 117C (2014) 224-229
[2] M. Marcinek, L. Hardwick, G. Żukowska, R. Kostecki, Microwave Plasma Chemical Vapor Deposition of Graphitic Carbon Thin Films, Carbon 48 (2010) 1552-1557

Figure 1
Effect of Drying in Electrode Processing for Energy Storage
Authors: Stein Malcolm , Mukherjee Partha P. 
Published: February 2020

Despite the wide range of ideal applications for LIBs, there is still room for improvement in their performance. The effects of varying the composition and chemistry of LIBs are well documented [1-2], however a critical aspect that is often overlooked is the processing steps during fabrication. Typical processing parameters such as film thickness or evaporation have a large impact on critical parameters such as porosity of the electrodes, and thus can affect the electrochemical performance. During the solvent evaporation stage, a non-uniform distribution of electrode constituents can develop in cases where the solvent evaporation rate exceeds that of the diffusion rate of the mobile electrode constituents [3]. An even distribution of carbon black and binder throughout the electrode is crucial to ensuring the minimization of internal cell resistance, and therefore the maximum performance for a given electrode composition.
In this work, we evaluate the impact of evaporation rate on the distribution of binder and carbon black in the electrode microstructure and the subsequent electrochemical performance. Both single-stage and two-stage evaporation was considered, where the two-stage process consisted of a slow rate followed by oven-drying, and the single-stage consisted solely of immediate oven drying, with two different rates. Figure 1 shows the evaporation rate as a function of overall electrode sheet weight percent. Here the first stage for the two-stage sheet occurs over approximately 16 hours, with a loss of roughly 20% by weight.
SEM images of the resulting microstructures indicate the vertical accumulation of carbon and binder on the surface of electrodes, with the increased carbon content in the case of the fast rate cases leading to the formation of a binder/carbon black composite that does not coat the active material particle surface, as shown in Figure 2. This through-plane (along the thickness) accumulation has been shown to decrease the rate performance, as shown in Figure 3.
The experimental results combined with theoretical analysis is expected to shed insight into the optimal drying conditions that may yield an optimum distribution of electrode constituents.

References:

1. M. Armand and J.M. Tarascon, Issues and Challenges facing Rechargable Lithium Batteries. Nature, 414, 359 (2001).

2. Handbook of Battery Materials, Second Edition. Edited by Claus Daniel and Jurgen O. Besenhard. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2011 by Wiley-VCH Verlag GmbH & Co. KGaA.

3. A.F. Routh, Drying of Thin Colloidal Films. Rep. Prog.Phys., 76 (2013)

Figure 1
Fabrication and Characterization of All-Solid-state3D Li-Ion Microbatteries Based on TiO2 Nanotubes
Authors: Vacandio Florence , Knauth Philippe , Djenizian Thierry 
Published: February 2020

The spectacular development of autonomous mobile systems has enhanced the race for the miniaturization of micropower sources. However, the storage performances of devices are seriously compromised when decreasing the size of the components down to the micrometer scale. This is particularly true for the development of all-solid-state microbatteries which are rapidly reaching performance limit in terms of energy and power densities. To overcome these issues, 3D microbatteries have attracted interest while remaining a technological challenge since it requires the marriage between materials science, electrochemistry, and microfabrication processes. In 2009, we proposed to use self-organized TiO2 nanotubes (ntTiO2) as a 3D negative electrode (Figure) for Li-ion microbatteries (Chem. Mater., 2009). This particular geometry is achieved by a simple electrochemical process (anodization) which improves significantly the electrochemical performance of the system. In this study will be proposed an all-solid-state 3D microbattery composed of a polymer electrolyte and a cathode material (LiFePO4) successively deposited at the surface of the nanotubes. While the nanotubes and polymer layers are obtained by electrodeposition process, the cathode material is achieved by cathodic sputtering. We will present in this work, the influence of morphology, structure and chemical composition of the cathode material on the electrochemical performance of the microbatteries in terms of areal capacity, rate capability, and capacity fading.
References :
[1] B. Ellis, P. Knauth, and T. Djenizian, “Three-dimensional Self-supported Metal Oxides for Advanced Energy Storage”, Adv. Mater., DOI 10.1002/adma.201306126(2014). In press (IF : 14,829)
[2] N. Plylahan, M. Letiche, M. Barr, and T. Djenizian, “All-solid-state lithium-ion batteries based on self-supported titania nanotubes”, Electrochem. Commun., 43, 121, 2014 (IF : 4,425)
[3] N. Plylahan, N. A. Kyeremateng, M. Eyraud, F. Dumur, H. Martinez, L. Santinacci, P. Knauth, and T. Djenizian, “Highly conformal electrodeposition of copolymer electrolytes into titania nanotubes for 3D Li-ion batteries”, Nanoscale Res. Lett., 7, 349 (2012). (IF : 2,726)
[4] F. Vacandio, M. Eyraud, P. Knauth, and T. Djenizian, “Tunable electrical properties of self-organized zirconia nanotubes”, Electrochem. Commun., 13, 1060 (2011). (IF : 4,859)
[5] G. Ortiz, I. Hanzu, T. Djenizian, P. Lavela, J. L. Tirado, and P. Knauth, “Alternative Li-ion battery electrode based on self-organized titania nanotubes”, Chem. Mater., 21, 63 (2009).(IF : 7,286)

Figure 1
Improvement of Transport Properties in Li-Conducting Ceramic Oxides
Authors: Aguadero Ainara , Aguesse Frederic , Bernuy-López Carlos , Manalastas William Wang , López del Amo Juan Miguel , Kilner John A. 
Published: February 2020

Li-conducting ceramic electrolytes can be used as ion-selective ceramic membranes adding chemical, thermal and electrochemical stability and preventing capacity fading with time. To date there has been low control of the processing conditions of these materials, however Li-ceramic conductors with high alkaline mobilities, have shown to react with moisture (Li-H exchange) and CO2 even at room temperature1. In recent works we have proven that this corrosion with moisture can promote a huge degradation of the phase purity, microstructure and transport properties and that the control of moisture during processing can improve Li-conductivity in ceramic oxides from 1 to 3 orders of magnitude1
,3.
In this work, we provide a better understanding of the importance of moisture control during the processing of Li-conducting ceramics as it is a limiting factor for their use as solid state electrolytes. For this purpose, we have studied two families of ceramic electrolytes: Li3xLa2/3-xTiO3 (LLTO) and Ga-doped Li7La3Zr2O12. Our approach in the Ga-doped garnet has been to dope in the tetrahedral Li-positions trying to optimize the Li-vacancy content and favour a higher Li-mobility in an octahedral-octahedral path. Impedance spectroscopy combined with 1H and 7Li solid state NMR and neutron power diffraction were used to analyse the cation environments and the effect of moisture on the Li-mobility while electron microscopy was used to evaluate the effect the local structure and microstructure of the dense samples.
We have proven a great effect of moisture on the miscrostructure and transport properties of ceramic oxides. We observed a substantial increase of the densification with densities around 92-95% when sintering under low moisture and CO2 content (< 2ppm). Furthermore, avoiding the corrosion process that leads to the Li-H exchange with the concomitant decrease of Li charge carriers and the formation of secondary phases in the grain surface (Fig. 1), we have increased by 5 times the total conductivity in LLTO2. Moreover, we have achieved a conductivity of 1.3x10-3 S/cm at 24oC for La3Zr2Li6.55Ga0.15□0.3O12which is amongst the highest Li ion conductivities reported for garnet-structured materials to date3.

References

1 a) Boulant, J. F. Bardeau, A. Jouanneaux, J. Emery, J.-Y. Buzare, O. Bohnke, Dalton Transactions 39, 3968, 2010 b) G. Larraz, A. Orera, M.L. Sanjuan, J. Mater.
Chem. A., 1, 11419, 2013.
2 F. Aguesse, J. M. Lopez del Amo, V. Roddatis, A. Aguadero, John Kilner Advance Materials: Interfaces, 1300143, 2014

3 C. Bernuy-Lopez, W. Manalastas, A. Aguadero, J. M. Lopez del Amo, F. Aguesse, J. A. Kilner, Chemistry of Materials, 26, 3610, 2014

Figure 1
Reduced Niobium Oxide in Carbon Matrix As Anode Materials for Lithium Ion Battery
Authors: Yan Litao , Luo Hongmei 
Published: February 2020

Lithium-ion batteries (LIBs) have been extensively investigated as high performance rechargeable batteries for portable electronic devices and electric vehicles (EVs). However, the current LIB technology is handicapped by several critical disadvantages for EV applications including short cycling life and safety hazard resulting from dynamic solid electrolyte interface (SEI) formed at low working potential. Spinel lithium titanate (Li4Ti5O12), anatase titanium dioxide (TiO2) and niobium pentoxide (Nb2O5) have been considered to be as promising anode materials for rechargeable LIBs owing to the considerable safety advantage that their redox potentials match to the lowest unoccupied molecular orbital (LUMO) of the organic liquid-carbonate electrolyte, which prevents the growth of lithium dendrites and the decomposition of electrolyte. Unfortunately, their intrinsic poor electric conductivities, poor lithium ion conductivities, and the capacity decay resulted from pulverization during charge-discharge processes limit their practical use in LIBs, especially for Nb2O5 (σ∼3×10−
6 S·cm−
1).
Herein, we report a one-step facile hydrothermal synthesis of Nb2O5/carbon matrix using glucose as the carbon source. After post-heat treatment under H2 gas, the glucose is carbonized to form carbon matrix and Nb2O5 nanocrystals are homogeneously immersed in carbon matrix. The stoichiometric Nb2O5 insulator becomes to oxygen-deficient niobium oxide semiconductor, and this carbon matrix can efficiently prevent niobium oxide nanocrystals from pulverization during the charge-discharge processes, resulting in improved recyclability. In addition, the carbon matrix and oxygen-deficient niobium oxide can effectively enhance the electronic conductivity and lithium ion conductivity of our electrode material, which results in enhanced rate performance and cycle durability. We believe that such a kind of niobium oxide/carbon matrix structure provides a new design toward high cycle durability niobium oxide based anode materials.
Enhanced Electrochemical Properties of Carbon Coated TiO2 anode for Sodium-Ion Battery
Authors: Lee Joo-Hyeong , Hwang Jang-Yeon , Oh Seung-Min , Yoon Chong seung , Lu Jun , Amine Khalil , Sun Yang-Kook 
Published: February 2020

Many types of commercial batteries use carbonaceous materials materials for the anode, such as meso-carbon microbeads (MCMB) or hard carbon. However, MCMB cannot be used as an anode material for sodium batteries because of the high potential of the Na/Na+(~0.3V higher than Li/Li+) redox reaction and the large ionic radii of the Na+(102 pm).1,2 Therefore, many researchers have been efforts to find a suitable anode material for the sodium – ion battery system. In the case of insertion anodes, various types of non-graphitic carbon materials have been considered and tested.3,4

Here, we confirmed that the carbon coated anatase-type micro-sphere TiO2 anode material has several advantages for the sodium ion battery system, including excellent cycle retention, high efficiency, good rate capability, and high energy density. The carbon coating, introduced by sucrose addition, had an effect of suppressing the growth of the TiO2 primary particles during calcination. The carbon coated TiO2 (sucrose 20 wt.% coated) electrode exhibited excellent cycle retention during 50 cycles (100%) and superior rate capability up to 30 C-rate at room temperature. This cell delivered a high discharge capacity of 155 mAh g-1 at 0.1 C, 149 mAh g-1 at 1 C, and 82.7 mAh g-1 at 10 C-rate, respectively.
(1) Stevens, D. A.; Dahn, J. R. High Capapcity Anode Materials for Rechargeable Sodium-Ion Batteries. J. Electrochem. Soc. 2000, 147, 1271−1273.
(2) Wenzel, S.; Hara, T.; Janek, J.; Adelhelm, P. Room-Temperature Sodium-Ion Batteries: Improving the Rate Capability of Carbon Anode Materials by Templating Strategies. Energy Environ. Sci. 2011, 4, 3342−3345.
(3) Stevens, D. A.; Dahn, J. R. The Mechanisms of Lithium and Sodium Insertion in Carbon Materials. J. Electrochem. Soc. 2001, 148, A803−A811.
(4) Thomas, P.; Ghanbaja, J.; Billaud, D. Electrochemical Insertion of Sodium in Pitch-Based Carbon Fibers in Comparison with Graphite in NaClO4-Ethylene Carbonate Electrolyte. Electrochim. Acta 1999, 45, 423−430.
High Capacity Thick Cathode with a Porous Aluminum Current Collector for Various Rechargeable Lithium Batteries
Authors: Abe Hidetoshi , Kubota Masaaki , Nemoto Miyu , Tanaka Yuichi , Munakata Hirokazu , Kanamura Kiyoshi 
Published: February 2020

As one of the methods to improve the energy density of lithium secondary battery, the use of high capacity anode and cathode materials has been focused. Although metals and alloys are mentioned as anode material candidates with high capacity, on the other hand, the candidates for high capacity cathode are insufficient currently. Therefore, a large amount of active material has to be accumulated and compressed to the cathode to achieve high energy density in consideration of the capacity balance with anode (Fig. 1). However, good performance cannot be obtained in the conventional thick coating electrode with a large amount of active material. The thick coating electrode has many problems. The ohmic resistance increases as the distance between a current collector and active material is made longer. In addition, many cracks, dropouts, and exfoliations are caused by volume changes of the coated layer during charge and discharge. In this study, the high capacity thick cathode has been realized by using a porous aluminum as a current collector as a practical method to improve the energy density of lithium secondary battery (Fig. 2). The combination of the thick cathode with a very high capacity per unit area and a high capacity anode can omit the amount of supporting materials such as a separator in batteries, resulting in the high energy density. The various thick cathodes were prepared using lithium iron phosphate, lithium cobalt oxide, and lithium nickel-cobalt-manganese oxide, respectively, and their electrochemical characteristics were evaluated by half-cell test. Though the cathodes had about several times larger capacity than conventional coating cathodes, they exhibited excellent rate performance. For example, the cell comprised of the thick cathode using lithium iron phosphate with a porous aluminum and two pieces of graphite anodes showed approximately 4-5 times capacity of the cell using conventional coating electrode at the same effective electrode area, and no large difference was observed for a in the polarization of charge-discharge at 1.0CA (Fig. 3). In a cycle-life test, the cell exhibited an excellent charge-discharge cycle performance, and retained approximately 80% of initial capacity even at 2,000th cycle (Fig.4). Such excellent performance is expected to be due to the easy electrolyte permeation from one side to the other side of the thick cathode, which is achieved by a porous aluminum current collector in addition to three-dimensional current collection. Of course, the lithium-ion diffusion in the cathode is expected to be insufficient for charge and discharge reactions when the cathode and C rate become thicker and larger, respectively. Thus, further optimization is needed for the cathode as well as for the electrolyte solution and separator to improve the ion supply in the cell. Such battery design will be also mentioned in this study.

Figure 1
A Novel Anion Exchange Membrane Enabling Generation of Syngas from Water and Carbon Dioxide at Industrially Important Rates
Authors: Liu Zengcai , Masel Richard I , Chen Qingmei , Kutz Robert , Yang Hongzhou , Lewinski Krzysztof A. , Matthews Tyler Scott , Kaplun Marina 
Published: February 2020

The electrochemical production of syngas would enable production of transportation fuels from carbon dioxide (CO2), water and renewable energy, but a suitable process does not exist. CO2 reduction to carbon monoxide (CO) has been a particular problem, in that high overpotentials are often needed to drive the CO2 reduction process, so the cost of the process was too high to be economic. Recently, we discovered a helper catalyst, an imidazolium-based ionic liquid (IL), by which CO2 can be reduced to CO at an overpotential as low as 0.17 V on silver (Ag) particle catalysts [1]. The IL suppresses hydrogen evolution on the Ag electrode to a degree tunable by modifying, for instance, the pH and water content of the IL electrolyte.
In previous work, the currents were too low to be practical. In the present paper, we present results using a newly developed DX4-13 membrane. We find that the new membranes allow us to obtain 300 mA/cm2 of CO current at room temperature and atmospheric pressure.
We also find that by changing the membrane composition, or varying the pH, we can produce syngas from a single electrolyzer. We have observed syngas production from a single cell running at room temperature at 100 mA/cm2 total current, however H2production is reduced at higher currents due to CO poisoning of the hydrogen production process. These and other results will be discussed.
[1] Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. A.; Zhu, W.; Whipple, D. T.; Kenis, P. J. A.; Masel, R. I. Science, 2011
, 334, 643.
Sensivity Analysis of a PEM Electrolyser Cathode with Respect to the Platinum and Nafion Loading
Authors: Paciok Paul , Rakousky Christoph , Carmo Marcelo , Maier Wiebke , Stolten Detlef 
Published: February 2020

The energy excess of intermittent power sources can be stored as hydrogen. Polymer electrolyte membrane (PEM) electrolysis is an efficient way to produce electrolytic hydrogen.[1] Due to the acidic environment only scarce and expensive noble metals like platinum and iridium are used as cathode and anode catalysts respectively.
To cut down the investment cost of a PEM electrolyzer, one of the main tasks is the reduction of the noble metal amount while retaining or increasing the performance of the electrolyser.[2] Thereby the influence of the decrease of the noble metal loading and possible degradation of the active material on the durability of the HER catalyst are both essential.
In this study we investigated the degradation of catalyst coated membranes (CCM) under constant and intermittent PEM electrolysis conditions. For this purpose we conducted long term test (1000h) with 4 different commercial CCMs each having different cathode loadings. To date, the durability of CCMs is examined under moderate current densities (0.9 to 1.4 A cm-2).[3] However, in this study the long-term test were performed at a current density of 2 A cm-2 to simulate real electrolysis conditions. As a next step we manufactured CCMs with a low platinum loading and different Nafion amounts at the cathode to examine the influence of the ionomer content on the long-term durability. TEM, XRD and EIS were applied to monitor physical and electrochemical changes during the durability test. The cathode and anode potentials were measured with the help of a reference electrode to determine the cause of degradation.[4]

CCMs with a platinum loading of 0.8 mgPt cm-2 showed a small degradation rate at a constant and dynamic operation mode. We observed that the reduction of the cathode loading to 0.05 mgPt cm-2 lead to a 5 fold increase of the degradation rate at the constant and the dynamic operation mode. The increase of the cathode potential during the durability test indicates a degradation of the cathode catalyst, which was verified by TEM and XRD analyses: Agglomeration of the platinum particles on the carbon support was observed.
Our study clearly identifies the mechanisms responsible for the degradation of the cathode. This information opens up new possibilities to implement counter measures against the deterioration of the Pt/C catalyst, and to produce cost effective CCMs with low loadings and high durability.
1) M. Carmo, D. L. Fritz, J. Mergel, D. Stolten, Int. J. Hyd. Energ., 2013, 38(12),4901 - 34.
2) K. Ayers, Annual Merit Review DOE Hydrogen and Fuel Cells and Vehicle Technologies Programs, Washington, DC, 2014. Http://www.hydrogen.energy.gov/pdfs/review14/pd098_ayers_2014_o.pdf
3) M. Debe, J. Electrochem. Soc., 2012, 159(6), K165-K176.
4) S.A. Grigoriev, P. Millet, V.N. Fateev, J. Power Sources,
2008, 177(2), 281 - 285.

Figure 1
Alkaline Hydrogen-Iodine Fuel Cell
Authors: Konwar Dhrubajit , Nguyen Trung Van 
Published: February 2020

We have considered the acid-based Hydrogen-Iodine (H2-I2) fuel cell along with the acid-based Hydrogen-Bromine (H2-Br2) fuel cell as potential systems for electrical energy storage but decided to drop the H2-I2 system because of its low cell open circuit potential (0.54V), even though the H2-I2 system offers a major advantage of being a much more benign system than the H2-Br2 system because of the high corrosivity and toxicity of bromine. Recently, we found that by operating the hydrogen reactions in an alkaline medium we could shift the electrode standard reduction potential from 0V to -0.83V which combined with the bromine electrode standard reduction potential of 1.09V increases the cell potential of an alkaline H2-Br2 fuel cell from 1.09V to 1.92V [1]. See Figure 1.
This 0.83V shift in the hydrogen electrode potential motivated us to take another look at the alkaline H2-I2 system because of the higher cell potential (1.37V). See Figure 2. This presentation will discuss the alkaline H2-I2 system, its advantages and disadvantages, and recent results obtained by our group at the University of Kansas.

Figure 1