bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cu-Ni-Mo-P/C Electrocatalyst for the Co-Generation of Energy and Fine Chemicals from Glycerol Electrooxidation
Authors: Elendu Oyidia , Kalu Egwu Eric , Yeboah Yaw D. 
Published: February 2020

CuNiMoP/C synthesized using a mixture of sodium hypophosphite and formaldehyde as reducing agents in a single electroless bath has been used as anode side catalysts for the oxidation of glycerol. The copper to nickel ratio in the electroless deposits was 9. The ratio of NaOH/glycerol charged to the anode side of an unstirred divided electrochemical reactor at the beginning of the electro-oxidation was 4. The cathode (platinum) was depolarized with oxygen during each oxidation. The anode and cathode compartments were separated by an anion exchange membrane.
Using voltammetry and high pressure liquid chromatography, we show that changing the potential applied at a CuNiMoP/C anode affects both glycerol conversion and product yield/selectivity. The applied anode potentials studied ranged from 0.5 V - 1.3 V (versus Ag/AgCl in satd KCl). The major liquid products obtained were glyceraldehyde, dihydroxyacetone, oxalic acid, lactic acid and tartronic acid at room temperature. Glycerol conversions ranged from 20% to 30% for six to eight hour operations.
Electrochemical characterization of the CuNiMoP/C gave a Tafel slope of 130 mV/decade, and an exchange current density of 1.8 mA/cm2. Electrochemical impedance spectroscopy was carried out between 25 0C and 80 0C to study the effect of temperature on impedances, since the higher temperature approximate actual liquid fuel cell conditions. Some preliminary results on the CuNiMoP/C stability while in use, determined from 72 hours uninterrupted use of the electro-catalysts for glycerol electro-oxidation, will also be presented.
These results have important implications for portable applications with a direct alkaline glycerol fuel cell.

Figure 1
A Molten Salt Electrolysis Procedure to Form Al-Sc Alloys
Authors: Polat Çağlar , Erdogan Metehan , Karakaya Ishak 
Published: February 2020

Recently, alloys such as Al-Sc and Al-Mg-Sc came to the forefront due to the reinforcement effect of scandium on the properties of aluminum such as mechanical strength, thermal stability, resistance to recrystallization, resistance to intergranular fracture and corrosion

[1]. The main scandium source for these aluminum alloys is the Sc2O3 by-product obtained during uranium (U), tungsten (W) or tantalum (Ta) production. It has been shown that it is possible to produce Sc by the molten salt electrolysis method with dissolution of Sc2O3 in Na3ScF6 as in the Hall-Héroult process [2]. This scandium can be used to produce Al-Sc alloy in-situ, provided that required amount of aluminum was already present in the reactor. Furthermore, the production of Al-Sc alloy by the dissolution of Sc2O3 in a molten salt containing CaCl2, in which the solubility of oxide ions is very large has been reported [3]. The Al-Sc alloy formation by the reduction of other Sc containing compounds in a molten salt containing CaCl2 was investigated in this study. The preliminary tests revealed that Al3Sc intermetallic was successfully formed and distributed homogeneously throughout the Al matrix as confirmed by the XRD, SEM-EDS and optical microscopy analyses. As can be seen in the optical micrograph shown in Figure (a), due to the long electrolysis and the high voltage applied, calcium contamination was observed by the presence of black Al4Ca eutectics in between the white faceted Al3Sc intermetallics. On the other hand, in the optical micrograph shown in Figure (b), it can be seen that the calcium contamination was inhibited by changing the electrolysis duration and the voltage while keeping the homogeneous distribution of Al3Sc.
References
[1]Ahmad, Z. (2003). The properties and application of scandium-reinforced aluminum. JOM, 55(2), 35-39.
[2] Vickery,R.C. Production of scandium and yttrium. U.S. Patent No 3,111,467, 1963
[3] Harata, M., Yasuda, K., Yakushiji, H., & Okabe, T. H. (2009). Electrochemical production of Al–Sc alloy in CaCl2–Sc2O3 molten salt. Journal of Alloys and Compounds, 474(1), 124-130.

Figure 1
Electrochemical Reduction of Solid Silica to Form Silicon in Molten Salts
Authors: Akpinar Bengisu , Erdogan Metehan , Ergul Emre , Akduman Baris , Karakaya Ishak 
Published: February 2020

Nowadays, Silicon is the most critical element in solar cells and/or solar chips. Silicon having 98 to 99% Si as being metallurgical grade, requires further refinement/purification processes such as zone refining [1,2] and/or Siemens process [3] to upgrade it for solar applications. A promising method, based on straightforward electrochemical reduction of oxides by FFC Cambridge Process [4], was adopted to form silicon from porous SiO2 pellets in molten CaCl2 and CaCl2-NaCl salt mixture [5]. It was reported that silicon powder contaminated by iron and nickel emanated from stainless steel cathode, consequently disqualified the product from solar applications. SiO2 pellets sintered at 1300oC for 4 hours, were placed in between pure silicon wafer plates to defeat the contamination problem. Encouraging results indicated a reliable alternative method of direct solar grade silicon production for expanding solar energy field.
[1] P.R. Mei, S.P.Moreira, E.Cardoso, A.D.S.Cortes, F.C.Marques, “Purification of metallurgical silicon by horizontal zone melting”, Sol. Energ. Mat. Sol., 98 (2012), 233-239.
[2] P. Siffert, E.F. Krimmel, eds. Silicon: Evolution and future of a technology. Berlin,Springer (2004).

[3] Siemens & Halske: BRD Patents 1.102.117 and 1.140.1594 filed 1954, issued 1956
[4] G.Z. Chen, D. J. Fray, T. W. Farthing, “Direct Electrochemical Reduction of Titanium Dioxide to Titanium in Molten Calcium Chloride”, Nature, 407 (2000), 361-364.
[5] E. Ergül, İ. Karakaya, M. Erdoğan, “Electrochemical decomposition of SiO2 pellets to form silicon in molten salts” Journal of Alloys and Compounds, 509 (2011), 899-903.
Bimetallic Electrocatalysts in Li-O2 Battery: How the Componential Proportion Influences the Battery Performance
Authors: Luo Xiangyi , Ge Le , Ma Lu , Kropf Jeremy , Wen Jianguo , Zuo Xiaobin , Ren Yang , Miller Dean , Wu Tianpin , Lu Jun , Amine Khalil 
Published: February 2020

In comparison with conventional Li-ion batteries, the superior theoretical energy density makes the lithium-air battery one of the most promising technologies for next-generation energy storage. However, its commercialization is still hindered by several challenges, such as poor cycleability and large overpotential. Particularly, the high charge overpotential not only induces a low Coulombic efficiency and low round-trip efficiency, but also aggravates the whole battery system by increasing the possibility of electrolyte decomposition and byproducts. It is well known that, due to the multiple electron transfer nature, the sluggish kinetics of the OER usually leads to charge overpotential. Hence, various electrocatalysts have been explored to lower the overpotential and to improve the battery performance. However, most of the charge potentials are still too high for practical use of the rechargeable Li-O2 battery.
Over the last few decades, nanostructured bimetallic catalysts have shown extraordinary electronic and chemical catalytic properties for many applications, such as fuel cells, nitrogen production, and biomass-fuel conversion. The greatly enhanced catalytic performance can be ascribed to the formation of the heteroatom bonds on the metal surface and the variation of the local bonding geometry. The former modifies the electronic environment of the surface atoms and their reactivity, while the latter affects the electronic structure of the metal. Therefore, it is possible to tailor the composition and structure of nanostructured bimetallic catalysts to meet requirement for certain applications.
Here, by choosing a right component proportion in Pt-Cu bimetallic electrocatalysts which optimize the electrocatalytic activity on the electrochemical reactions, especially on oxygen evolution reactions, we demonstrated a superior electrochemical behavior with the low charge overpotential of 0.2 V and the cycleability of 50 discharge/charge cycles before the capacity fading. Synchrotron high-energy X-ray diffraction (HE-XRD), X-ray absorption spectroscopy (XAS), and electron microscopy (EM) were employed to study the morphology and component of the electrochemical reaction products. The results of this study have shown that the optimized Pt-Cu bimetallic electrocatalysts significantly reduce the charge overpotential, and furthermore enhance the efficiency, stability, and cycleability of an aprotic Li-O2 battery. It would also serve as a general guide for nanostructured bimetallic catalysts design and optimization.
Transition Metal Sulfides As Cathode Materials for Rechargeable Aluminum Ion Battery
Authors: Geng Linxiao , Guo Juchen 
Published: February 2020

Rechargeable aluminum battery system is very intriguing due to the following reasons: First of all, aluminum has high capacity due to its trivalency. And aluminum is very cheap since it is the most abundant metal element in earth’s crust.1 As a result, rechargeable aluminum battery can be very promising in large scale energy storage application. One of the main reasons that hinders the development of rechargeable aluminum battery is the lacking of electrolyte that can enable facile deposition and dissolution of aluminum in the anode side. On the other hand, facile electrochemical deposition and dissolution of aluminum can be achieved in room temperature ionic liquid (molten salt) synthesized by mixing aluminum chloride (AlCl3) with organic salts such as 1-butylpyridinium chloride, 1-ethyl-3-methylimidazolium chloride, etc. at a certain ratio.2,3 In a previous research, our group proposed Chevrel phase Mo6S8 as the first conventional intercalation type cathode material.4 The logic of choosing transition metal sulfide instead of transition metal oxide as cathode material for aluminum ion battery is very important. Due to the strong coulombic effect, the energy barrier of multivalent ions transportation in the crystal structure is very high.5 Thus, a softer anionic framework is needed. Sulfide has a much lower electronegativity than oxide, which makes transition metal sulfide a very promising cathode candidate for rechargeable aluminum ion battery. To further validate this assumption, we synthesized nano sized layered TiS2 and cubic Ti2S4 as well as investigated their electrochemical properties as cathode materials for ionic liquid electrolyte based rechargeable aluminum ion battery at both room temperature and 50 °C. We further confirmed the aluminum intercalation in the TiS2 and Ti2S4 crystal structure using ex-situ XRD and XPS. The proposed titanium sulfide cathode materials showed decent reversible capacity and a higher working potential. In order to further understand the mechanism of Al intercalation into Chevrel Phase Mo6S8, high resolution TEM is used to directly visualize the crystal structure of AlxMo6S8 from different discharged and charged stages. Powder XRD Rietveld refinement is also undertaken to provide support from a theoretical simulation perspective.
1. Li, Q.; Bjerrum, N. J. J. Power Sources 2002, 110, 1.
2. Endres, F. ChemPhysChem 2002, 3, 144.
3. Jiang, T.; Chollier Brym, M. J.; Dube, G.; Lasia, A.; Brisard, G. M. Surf. Coat. Technol. 2006, 201, 1.
4. Geng, L.; Lv, G.; Xing, X. Guo, J. 2015, 27, 4926−4929.
5. Rong, Z.; Malik, R.; Canepa, P.; Sai Gautam, G.; Liu, M.; Jain, A. Persson, K.; Ceder, G. Chem. Mater., 2015, 27 (17), pp 6016–6021.
Optimizing Battery Design for Fast Charging through a Genetic Algorithm Based Multi-Objective Optimization Framework
Authors: Liu Changhong , Liu Lin 
Published: February 2020

As the innovation of battery technology, batteries have higher power density than before and electric vehicles can travel longer distance per charge. However, the long charging time of electric vehicles is still one of its limitations. Electric car takes much longer time to fully charge its batteries. Fast charging and super charging are the available solutions but they have a potential of damaging battery with accelerated degradation. It is critical to reduce the charge time without compromise long-term performance. New materials, nanoscale structures, charging strategy have been studies to decrease the charging time. All of these approaches can further benefit from an optimal design of the batter structure for fast charging. We investigate the effect of design variables such as porosity, particle size, and thickness for both anode and cathode electrodes on battery charging and degradation by using a physics-based side-reaction coupled electrochemical model. We develop a computational optimization framework with the Elitist Non-Dominated Sorting Genetic Algorithm (NSGA-II) to find the optimal design variables to improve battery charging and long-term performance. The computational optimization work is computationally efficient of providing a guidance for battery design.
Design Principles of Non-Graphitic Carbon Electrodes for Energy Storage
Authors: Li Zhifei , Bommier Clement , Jian Zelang , Ji Xiulei 
Published: February 2020

Energy storage is the missing enabler to facilitate the widespread installation of renewable-but-intermittent solar and wind energy. There are two primary metrics for stationary energy storage: cost and cycling life, where the latter is also about the cost, indeed. It is thus a must to rely on Earth-abundant elements, which rules out lithium-based devices for the stationary purposes, as lithium is rare and its supply is geopolitically challenged. This warrants attention for Na-ion batteries (NIBs) and K-ion batteries (KIBs). For metal-ion batteries, the choice of anode often determines the fate of the battery commercialization, as anode typically determines battery’s cycling life as well as safety features. Considering the cost and performance, non-graphitic carbon anodes are the leading candidates for NIBs and KIBs. To date, much effort has been devoted to preparing such carbons from various unique organic precursors. However, there has been a dearth of knowledge on the basic correlation between the local structures of carbon anodes and their Na (K)-ion storage behavior, where the alkali-metal-cation storage mechanism in hard carbon and soft carbon is still a debated topic. In this talk, I will introduce new insights on storage mechanisms and design principles of hard carbon anodes for NIBs based on the structure-capacity correlation revealed by experimental and theoretical studies. I will also discuss K-ion storage properties of major carbons, including graphite, which proves incorrect an old assumption between graphite and potassium.
An Experimental Analysis on the Impacts of Current Pulsing with Varying Current Amplitudes on Lithium Ion Cells
Authors: Rajagopalan Kannan Dhevathi Rajan , Moss Pedro L. , Weatherspoon Mark H 
Published: February 2020

Lithium ion batteries can be charged by different techniques. CCCV (constant current, constant voltage) charging is the conventional method that is predominantly employed for charging the lithium ion batteries. A theoretical analysis of pulse charging using varying current amplitudes with the relaxation periods has shown reduction in the charging time without reaching lithium saturation over the period [1]. It is based on the concept of increasing surface concentration of lithium at initial stages and maintaining the concentration value close to the saturation.
The objective of this work is to experimentally investigate the impacts of varying current pulse amplitudes on the lithium ion battery materials. This method consists of constant width charging, rest period and the applied current is decreased as the charging progress. Implementing the pulsed currents of different amplitudes on cathodic (Lithium Iron Phosphate) and anodic (Graphite and Li 4Ti5O12) half cells separately creates varied impacts on the electrode materials. The results of charging time and overall cycle life are then compared with conventional charging method.
Figures 1 and 2 show the constant current and a portion of pulsed current profile that are used in the analysis. In this experiment, pulsed current profile is controlled by varying the duty cycle, relaxation periods are included in between pulses and current amplitudes are reduced as the charging progress. EIS, SEM and XRD are used in analyzing the impacts of both the charging protocols on the lithium ion cells.

References:

[1] B. K. Purushothaman and U. Landau, “Rapid Charging of Lithium-Ion Batteries Using Pulsed Currents A Theoretical Analysis,” J. Electrochem. Soc., vol. 153, no. 3, pp. A533–A542, Mar. 2006.

Figure 1
Increase in Cycling Stability of Doped Lithium Nickel Manganese Oxide Spinels during Charging Between 2.0 and 5.0 V
Authors: Höweling Andres , Stoll Andreas , Geßwein Holger , Binder Joachim R. 
Published: February 2020

The increase in batteries energy is one of the main issues in current battery research and mandatory for the development of electric vehicles with long ranges. The energy of a battery is determined by the capacity and the potential difference of the active materials. Thus, both parameters offer the ability for an increase in energy.
In many studies high capacity cathode materials are analyzed. One of the most promising materials is a Li-rich layered oxide. Other studies use high voltage cathode materials (e.g. LiMxMn2-xO4, with M = e.g. Ni, Co) in order to increase the operational voltage of the cell. Cells with high voltage cathodes suffer from unwanted side reactions with the electrolyte. This is because the operational voltage is higher than the stability window (ca. 1.0 – 4.3 V vs. Li+/Li0 in the presence of transition metal ions like Ni4+ and Mn4+) of current organic electrolytes. The reactions consume active lithium and a severe capacity fade occurs. On the other side, the increase of energy of high capacity cathode materials is limited due to the relatively low voltages of ca. 3.5 V vs. Li+/Li0 of these materials and the need for balancing of anode capacity.
In principle the high voltage spinel (LiNi0.5Mn1.5O4) offers the ability to increase the voltage and the capacity compared with other cathode materials. This can be reached when a metallic lithium anode is used. The spinel lattice can host a second lithium and therefore the theoretical capacity is increased from 147 to 294 mAh g-1. The increase in capacity during cycling between 2.0 and 5.0 V and the high operational voltage lead to a theoretical specific energy of more than 1000 Wh kg-1 based on the active materials. During intercalation of the second lithium, the spinel undergoes a phase transition from cubic to tetragonal because of a cooperative Jahn-Teller-distortion of Mn3+in the low voltage area. This is associated with material degradation and capacity loss.
Here we use different LiNi0.5Mn1.5O4-spinels doped with transition metals and treated with different temperature programs in order to increase the cycling stability. It is found that the stability and the initial capacities are directly dependent on the treatment and doping elements. At a rate of C/2 a capacity of 190 mAh g-1 is achieved with 92 % of the initial capacity retained after 100 cycles. The difference in the discharge behavior of the materials is analyzed based on electrochemical data, particle morphology and in-situ XRD analysis. A model, which can explain the different behaviors is introduced and will be discussed.
Stability of Ni-Rich NMC Cathode Materials in Water and Electrolyte Solutions during Aqueous Electrode Processing
Authors: Wood Marissa , Sheng Yangping , Keever Tamara J. , Li Jianlin , Wood David L 
Published: February 2020

Despite recent advances in lithium-ion battery technology, further energy density improvements and cost reductions are necessary to achieve widespread adoption of electric vehicles. Nickel-rich formulations of lithium nickel manganese cobalt oxide (NMC) have been developed as promising high-energy, high-voltage cathode materials capable of significantly increasing the energy density of lithium-ion batteries. Aqueous processing of these cathodes offers significant environmental benefits and lower production expenses compared to traditional processing using N-methylpyrrolidone (NMP). However, Ni-rich NMC materials can react with water during electrode preparation, and with electrolyte during battery assembly and cycling, resulting in metal leaching that can cause structural changes and performance degradation. We investigated the effect of aqueous processing on the structure and electrochemical behavior of these cathode materials by exposing four NMC powders with varying nickel contents (NMC 333, NMC 532, NMC 622, NMC 811) to water and electrolyte for different time durations meant to simulate electrode processing and battery assembly conditions. The resulting metal dissolution was then measured using inductively coupled plasma mass spectrometry (ICP-MS). Since the pH of aqueous slurries can differ depending on composition, and pH variation may lead to additional reactions, the effect of pH was also explored.
We found that lithium dissolution increases with increasing nickel content at all pH values, and slurries made with all four powders become basic during typical processing times. Dissolution of Ni, Mn, and Co in water was minimal for all formulations. In order to gain a better fundamental understanding of the structural changes taking place during these reactions, a subset of the NMC powders was characterized by SEM and X-ray photoelectron spectroscopy (XPS) before and after exposure to water and electrolyte. In addition, the effect of aqueous processing on battery performance was evaluated by comparing the rate performance of pouch cells made using cathodes processed with different water exposure durations. Correlating processing conditions with performance could lead to the design of new approaches to mitigate metal leaching from Ni-rich NMC materials and enable the use of these cathodes for high energy density lithium-ion batteries.
Acknowledgment
This research at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) under contract DE-AC05-00OR22725, was sponsored by the Office of Energy Efficiency and Renewable Energy (EERE) Vehicle Technologies Office (VTO) (Deputy Director: David Howell) Applied Battery Research subprogram (Program Manager: Peter Faguy).

Figure 1
Advanced Sodium-Ion Battery Anode Constructed Via Chemical Bonding Between Phosphorus, Conducting Polymer and Crosslinked Polymer Binder
Authors: Song Jiangxuan , Zhang Li 
Published: February 2020

Maintaining structural stability is a great challenge for high-capacity conversion electrodes with large volume change, but is necessary for the development of high-energy-density, long-cycling batteries.[1-3]Here, we report a stable phosphorus anode for sodium-ion batteries by the synergistic use of chemically bonded phosphorus-conducting polymer hybrid and cross-linked polymer binder. The phosphorus-conducting polymer hybrid was synthesized through ball-milling of red phosphorus and functionalized polyacrylonitrile. The P-O(S)-C bonds formed in this process help maintain contact between phosphorus and CNTs, leading to a durable hybrid. As a result, this anode delivers a high initial capacity and excellent cycling stability, along with a high Coulombic efficiency of ~99%. The unique electrode framework through chemical bonding strategy reported here is potentially inspirable for other electrode materials with large volume change in use.
References
[1] W. Luo, F. Shen, C. Bommier, H. Zhu, X. Ji, L. Hu, Acc. Chem. Res.
2016, 49, 231.
[2] J. Song, Z. Yu, M. L. Gordin, S. Hu, R. Yi, D. Tang, T. Walter, M. Regula, D. Choi, X. Li, A. Manivannan, D. Wang, Nano Lett.
2014, 14, 6329.
[3] J. Song, Z. Yu, M. L. Gordin, X. Li, H. Peng, D. Wang, ACS Nano
2015.