bluuebunny/crossref_metadata_2025 huggingface dataset:
Supercapacitor Calendar Ageing and Post Mortem Analysis
Authors: Gualous Hamid , Omar Noshin , Samba Ahmadou , Van den Bossche Peter , Van Mierlo Joeri
Published: February 2020

Abstract not Available.
Electrochemical Impedance Spectra of Hybrid Electrolyte for Energy Conversion
Authors: Zhang Guoqing , Jiang Yong , Xiong Zhu
Published: February 2020

Abstract not Available.
Nuclear Magnetic Resonance Studies of Ion Adsorption On Titanium Carbide-Derived Carbons
Authors: Forse Alexander C. , Griffin John M. , Wang Hao , Trease Nicole M. , Presser Voker , Gogotsi Yury , Simon Patrice , Grey Clare P.
Published: February 2020

Abstract not Available.
Advanced MnO2/CNT Ultracapacitors- Transition From Planar to Micropatterned Array Electrodes
Authors: Raina Supil , Hsu Shao Hua , Akbulut Serkan , Yilmaz Mesut , Kang Weng Poo , Huang Jin Hua
Published: February 2020

Abstract not Available.
Effect of Pore Size Distribution in Carbon/Carbon Supercapacitors Operating in Phosphododecatungstic Acid
Authors: Skunik-Nuckowska Magdalena
Published: February 2020

Abstract not Available.
Single Particle Measurement of Single Crystal LiCoO2 and Wire-Shaped LiCoO2
Authors: Nishikawa Kei , Munakata Hirokazu , Kanamura Kiyoshi , Zettsu Nobuyuki , Teshima Katsuya
Published: February 2020

Lithium-ion batteries (LIBs) with high gravimetric and volumetric energy density are very important key devices to encourage the popularization of an environmental friendly energy system, which is consisted of solar cells, wind power generations, smart grid, and batteries. LiCoO2 is widely used as the active material for the positive electrode. Many researchers have reported the dynamics of crystal structure change accompanied with the lithium insertion and extraction1. In commercial Li-ion battery, the positive electrode is composite electrode which is composed of polycrystalline LiCoO2 powder, binders and conductive agents. It is difficult to obtain the intrinsic property of LiCoO2 from the composite electrode. LiCoO2 thin film electrode is widely used as the model electrode in order to discuss the mechanism of charge and discharge reaction. However, the thin film electrode is not appropriate for commercial batteries. In this study, the single crystal LiCoO2 powders and wire-shape LiCoO2 particles which are accumulated one-dimensionally by single crystal LiCoO2 are synthesized by a flux method in order to discuss the Li transfer phenomenon in LiCoO2 crystal by using a single particle measurement technique. Figure 1 shows the SEM images of single crystal and wire-shaped LiCoO2. The single particle measurement technique is very powerful to measure the intrinsic electrochemical properties of the active material with 5~30 μm size, because it can eliminate the effect of binders and conductive agents. The schematic diagram of the single particle measurement system is demonstrated in Fig.2. This technique has revealed that LiCoO2, LiMn2O4 and LiFePO4 particles have very good rate characteristics2-4. This study focuses on the effect of morphological and crystalline variations of LiCoO2 to the electrochemical characteristics.

References

1) T. Ohzuku, and A. Ueda, J. Electrochem. Soc., 141, 2972 (1994)

2) K. Dokko, N. Nakata, K. Kanamura, J. Power Sources 189, 783 (2009)

3) T. Saito, H. Munakata, K. Kanamura, J. Soc. Inorg. Mater., Jpn., 18, 201 (2011)

4) H. Munakata, B. Takemura, T. Saito, K. Kanamura, J. Power Sources 217, 444 (2012)
Alternative Binder for Silicon Based Anodes in Lithium-Ion Batteries Towards Elevated Temperatures
Authors: Klamor Sebastian , Schappacher Falko , Brunklaus Gunther , Winter Martin
Published: February 2020

Li-ion batteries are one of the most promising systems for mobile energy storage. While carbon based anodes have been well explored and applied in most of commercially available Li-ion batteries, the investigation of silicon based anode materials is still in progress. Silicon as active material has the capability to exceed and replace all other anode materials in future lithium-ion batteries due to the highest specific capacity among all other anode materials. For ambient temperature lithiation of bulk silicon, the lithium richest phase Li15Si4 achieves a specific capacity of 3579 mAh g-1.[1]

One major drawback of silicon is its volume change (up to 300%) during the lithiation, which leads to mechanical stress of the anode and a poor cycling stability.

Although many efforts have been made in changing the binder, different active material combinations and adapting a composition of carbonate based electrolytes, these cell systems suffer from a breakdown in functionality at ambient as well as elevated temperatures up to 60°C.[2
,3
]Besides the volume expansion, it is expected that the decomposition of the electrolyte is the main reason for the fast end of life at elevated temperatures.

With respect to the increasing demand of environmentally-friendly electrode manufacturing, we focused on water solvable binders and compared an alternative new binder to carboxy methyl cellulose (CMC), which is well known as a standard binder for silicon and silicon composite based electrodes.[4,5
]In this work we propose an alternative binder which shows a stable cycling at room temperature as well as at 60°C with the usage of organic carbonate based electrolytes.

Moreover, we present different spectroscopic analysis to understand the binding mechanisms of the different binder systems of silicon based and silicon / graphite composite electrodes accompanied by electrochemical measurements.

We kindly thank the Deutsche Forschungsgemeinschaft (DFG) for the funding of the project SPP 1473 - WeNDeLIB (WI 2727/4-1).

[1] M.N. Obrovac, L. Christensen, Electrochem. Solid-State Lett. 7 (2004), A93-A96.

[2] C.L. Campion et al., J. Electrochem. Soc. 152 (2005), A2327-A2334.

[3] N.S. Hochgatterer et al., Electrochem. Solid-State Lett. 11 (5) (2008), A76-A80.

[4] Li, Jing, R. B. Lewis, and J. R. Dahn. Electrochem. Solid-State Lett. 10.2 (2007), A17-A20.

[5] S. Lux et al., J. Electrochem. Soc. 157(3) (2010), A320.
Coating of Vanadium Nitride Onto Carbon Nanotubes: A Binder-Free Supercapacitor Electrodes
Authors: Liao Yu-Xiang , Lin Yao-Nan , Hsu Wen-Kuan
Published: February 2020

Supercapacitors are one of the most promising energy storage devices, which could be used in hybrid vehicles, portable electronics and other pulse-power applications. Electrodes however play a crucial role in determining the performance of supercapacitors and current study mainly focused on transition metal oxides/nitrides and conducting polymers that show a large pseudo-capacitance in repeated charging-discharging profiles. Among these materials, the vanadium nitride (VN) possesses a high specific capacitance and chemical stability and is metallic in nature. VN, however, is often made in powder form and must combine with polymer to form electrode. In this case, conductivity and ionic accessibility, due to polymer addition, are reduced and capacitance also decreases at high voltage scan rates. In this work, the carbon nanotubes (CNTs) are electrochemically coated onto nickel mesh and sol-gel technique is then used to deposit V2O5 onto tube coatings, followed by calcining composite under anhydrous ammonia atmosphere. The morphology and structural properties of electrode are characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Raman measurement, and X-ray photoelectron spectrometer (XPS). A three-electrode system is employed to study the electrochemical behavior, including cyclic voltammetry (CV), galvanostatic charge–discharge cycling (CD). The experimental results suggest that CNTs provide an open mesoporous texture for access of electrolytes and conductive path for electron transfer to Ni collector.
The Application of Anodizing for Hybrid Capacitor
Authors: Park Soo-gil , Yang Jeong-Jin , Kim Hanjoo , Kim Hongil , Habazaki Hiroki
Published: February 2020

Introduction

Anodizing is widely studied because of its good advantages such as low cost and tractability in over a wide industrial area as one of the surface treatment processing technologies. Thus the anodized metal electrode is used as anode electrode of an electrical circuit. Consequently this process is named anodizing. Recently this process has the limelight to fabricate nano-scale structure with aluminum and titanium metals, etc. For these reasons anodizing have been used for fabrication of nano-scale linear materials and this linear type materials are applied to functionality inorganic membrane, photonic crystals, bio sensor, and electrode in energy storage devices

Experimental

The template was prepared by anodizing of 99.99% pure aluminum template of 0.2 mm thickness at 40V in 0.3 mol dm-3 sulfuric acid electrolyte at 20 ̊C. It was used as working electrode, and an aluminum sheet was also used as a counter electrode. After anodizing, pore-widening treatments were conducted by immersing the anodic alumina template obtained in 5wt% phosphoric acid at room temperature for 2 hours.

Then, the mixture of anodic porous templates and carbon resource was heated in argon at 300 ̊C and kept at this temperature for 30min. After that, the temperature increased up to 600 °C and kept for 1 hour. In this heat treatment, the carbon resource was decomposed to liquefy into porous structure of template. And templates were dissolved in 10% NaOH solution and the CNFs formed were filtered. The morphologies and structures were examined using SEM, Tem, Impedance analysis, Cyclic-voltammetry and Charge-discharge analysis.

Result & Discussion

Figure shows SEM images of the AAO templates after pore-expansion treatment with 2nd anodized AAO templates. The effects of the two-step anodizing process can be seen clearly, and we can confirm that the AAO template shows a well-ordered pore distribution and increase of pore diameter according to pore-expansion time after the second anodizing step.

References

[1] M. Kiriu, M. Hayashi, H. Konno, H. Habazaki, Materials Chemistry and Physics, 105, (2007) 367-372.

[2] M. Kiriu, H. Konno, H. Habazaki, Electrochemistry Communications, 8, (2006) 1275-1279.

[3] M. Saito, M. Ishiguro, H. Asoh, S. Ono, Journal of the Electrochemical Society, 151(8), (2004) B473-B478.
Simple, Low-Cost Synthesis of an Iron Oxide and Carbon Foam Composite for Supercapacitor Electrodes
Authors: Khani Hadi , Wipf David O
Published: February 2020

Iron oxide-carbon foam (IOCF) materials with a high specific surface area and conductivity have been synthesized via a facile, cost-effective, and one-step template-free method. The structure and morphology of the IOCF composite have been investigated by electron microscopy, cyclic voltammetry, and Raman spectroscopy. The as-prepared IOCF was coated on a nickel metal foam electrode as an active material for constructing supercapacitor electrodes. The electrochemical performance of IOCF composite electrodes was tested by cyclic voltammetry and galvanostatic charge/discharge in a Na2SO4 electrolyte. The as-assembled symmetric supercapacitor with optimal mass ratio can be operated reversibly over a wide voltage range of 0 to -1.0 V, and presents a high capacitance of 170 F g-1 in Na2SO4 aqueous electrolyte. Moreover, the supercapacitor exhibits excellent rate capability and retains a high capacity with extended cycling. These attractive results make this material promising as a component of an aqueous electrolyte-based supercapacitor having high energy and power densities.
Improvement in the Electrochemical Performances of Spinel LiMn2O4 cathodes By MnO2 coating for Lithium Ion Battery Application
Authors: Choi Wonchang , Kang Bongjo , Joo Jaebaek , Lee Joonkee , Park Minsik
Published: February 2020

Lithium ion batteries (LIBs) are considered as attractive power sources for electric vehicles (EV) and aenergy storage systems (ESS) as well as portable electronic devices due to their high energy density and long cycle life. Importantly, EV and ESS applications require high power density and thermal stability as well as low cost. In this regard, spinel LiMn2O4 is a promising cathode material because of its low cost, good safety, high abundance and environmental harmlessness. However, LiMn2O4 generally exhibits poor capacity retention especially at elevated temperatures mostly owing to the Mn dissolution. Moreover, Jahn Teller effect also causes the structural instability, which can be seen on the surface of LiMn2O4 at high current application. Previous literatures verify that surface-modification by coating plays an important role in electrochemical performances of LiMn2O4. The surface treatment of LiMn2O4 is known to prohibit Mn dissolution from LiMn2O4 electrode. In this study, the MnO2 were prepared on the surface of LiMn2O4 powders. The synthesis procedure includes mixing KMnO4 solution with ethylene glycol through oxidation-reduction reaction under ambient conditions. Electrochemical evaluation as well as storage test at elevated temperatures reveal that the surface-modification with MnO2 enhance the rate capability and improve the storage characteristics at 60oC of spinel LiMn2O4 cathode materials. In-depth analyses such as X-ray Photoelectron Spectroscopy and Electrochemical Impedance Spectroscopy are also performed to elucidate the effect of surface-modification using MnO2.
Post-Test Analysis of Battery Materials: Another Part of the Question
Authors: Bloom Ira , Dietz Nancy , Bareno Javier
Published: February 2020

Battery testing is an on-going program at Argonne. Here, battery deliverables from DOE[1] and USABC[2]projects are evaluated in terms of initial performance and how that performance changes using standard sets of test protocols under a given set of conditions. These test data provide a lot of information regarding how the battery performs and how performance changes. The data are often used to infer what physical and/or chemical changes occurred in the battery, but they cannot definitively determine the exact cause of performance decline. Post-test diagnostics can provide this missing information by using physical, spectroscopic, metallographic, and electrochemical tests. Like battery testing, these methods are used in a standardized manner to make comparisons of failure modes within a given technology, and, perhaps, across technologies, easier.

As an example, small cells containing 5-V spinel cathodes and graphite anodes were cycled. Upon disassembly, an unexpected “zebra” staining pattern was seen on the separator facing the anode and on the anode itself (see Fig. 1). Further characterization of the separator by energy-dispersive spectroscopy (EDS) showed that lighter-colored areas had significantly more fluorine than did the dark-colored areas, as shown in Fig. 2.

This talk will describe Argonne’s Post-Test Facility, with an emphasis on capabilities and opportunities for collaboration. Cell disassembly, sample harvesting procedures and recent results will be discussed. In particular, SEM and XPS characterization of Li- and Mn-rich NMC and Li-Ni-Mn spinel cathodes, both pristine and aged in graphite-anode cells, reveal changes in chemical composition of evolved surface films.

This work was performed under the auspices of the U.S. Department of Energy, Office of Vehicle Technologies, Hybrid and Electric Systems, under Contract No. DE-AC02-06CH11357.

[1] US Department of Energy

[2] US Advanced Battery Consortium. The USABC consists of representatives from the US DOE and from the three major automakers in the US, GM, Ford and Chyrsler.
Systematic Characterization of Ionic Liquid Electrolyte Systems for Lithium Ion Batteries
Authors: DiLeo Roberta A. , Takeuchi Kenneth J , Marschilok Amy C , Takeuchi Esther S
Published: February 2020

Introduction

Conventional lithium ion batteries are multi-component systems with the anode and cathode active materials determining the voltage and theoretical energy content. In addition, current electrolyte systems of lithium ion batteries comprise a lithium salt and a mixture of carbonate solvents which to date, have allowed for the use of cathodes with 4V operating windows. These electrolyte systems are relatively conductive at 5-10 mS/cm, and many of them form stable solid-electrolyte interphase layers to promote effective battery operation. However, carbonate-based electrolytes suffer from poor thermal stability and an upper limit of electrochemical stability of 4.5V vs. Li/Li+. Expansion of the voltage window is needed in order to allow use of higher voltage cathodes, above 4.5 V.

Results and Discussion

The study of ionic liquids for use in energy storage applications is a relatively recent occurrence; however, they are prospective candidates because of their potential for increased electrochemical stability and thermal safety. Many ionic liquids have been investigated in neat and mixed solutions to find an optimal balance of viscosity, conductivity, electrochemical stability, and thermal safety. Mixtures with carbonate based organic solvents have also proved promising for incrementally changing electrolyte systems toward more favorable performance using currently studied ionic liquids.

In recent work physical and electrochemical properties of ionic liquids were systematically investigated.[1, 2] Cation type, anion type, and substituent chain length effects on conductivity, viscosity, electrochemical stability, and wettability as determined by cyclic voltammetry, impedance, and contact angle were explored. In addition, mixtures of ionic liquids with organic carbonate solvents similar to those used in conventional liquid electrolytes were prepared and similar characterization was completed. Further characterization via calorimetry and contact angle measurements can support the understanding of ionic liquid behavior and give insight into continued optimization of electrolyte systems using these materials.

References

1. Di Leo, R.A.; Marschilok, A.C.; Takeuchi, K.J. and Takeuchi, E.S., "Battery electrolytes based on saturated ring ionic liquids: Physical and electrochemical properties,"
Electrochimica Acta,
2013,
109(0),27-32.

2. Di Leo, R.A.; Marschilok, A.C.; Takeuchi, K.J. and Takeuchi, E.S., "Battery Electrolytes Based on Unsaturated Ring Ionic Liquids: Conductivity and Electrochemical Stability,"
Journal of The Electrochemical Society,
2013,
160(9), A1399-A1405.
Behind Extended Cycling of Li-O2 Battery
Authors: Nasybulin Eduard N , Xu Wu , Mehdi B. Layla , Thomsen Ed , Engelhard Mark H , Masse Robert , Meng Gu , Bennett Wendy , Nie Zimin , Wang Chongmin , Browning Nigel , Zhang Ji-Guang
Published: February 2020

New battery technologies are demanded for a growing market of electric and hybrid vehicles. Rechargeable Li-O2 batteries are promising candidates for this application because of their high theoretical energy density. Although high capacity values are achievable for Li-O2batteries, their cycling stability is typically limited by only a few full discharge-charge cycles. On the other hand, good cycling behavior under limited capacity conditions has been reported by several groups.

Rechargeability of Li-O2 batteries is based on the reversible formation/oxidation of Li2O2. Unfortunately, the electrochemical processes of oxygen reduction and evolution are harmful for commonly used carbon-based electrodes and organic electrolytes causing severe decompositions. Generation and continuous accumulation of insulating side products on the electrode/electrolyte interface results in increasing polarization and fast capacity fading with cycling.

In the present report we demonstrate that long cycle life of Li-O2 batteries is in principle achievable upon selection of appropriate carbon material and catalyst for air cathode fabrication in addition to a proper cycling protocol (Fig. 1a). The origin of the extended cycling is in efficient decomposition of both Li2O2 and side products during the charging step of the battery operation. Extended cycling of a Li-O2 battery was investigated by quantification of Li2O2 yield during discharge and O2 release during charging. There is a drastic shift from the predominant formation of Li2O2 to the predominant formation of carbonate- and carboxylate-containing side products within first few cycles followed by a stabilization of Li2O2 yield. Mass spectroscopy of gasses evolved during the corresponding charging steps demonstrate drop in oxygen release and increase in CO2release in the very beginning of battery cycling (Fig. 1b).

Drastic switch to the formation of side products in the beginning of battery cycling originates from certain changes on the electrode/electrolyte interface as was analyzed with X-ray photoelectron spectroscopy. In addition, morphological considerations and cycling conditions to achieve unrestricted cycling of Li-O2battery will be discussed in the presentation.

Acknowledgement

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U. S. Department of Energy (DOE). The microscopic analysis in this work was supported by the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences.

Figure 1. a) Voltage profiles and b) in situ MS analysis of O2 and CO2 evolved during charging of the battery with CNTs/Ru electrodes cycled in TEGDME-LiTf electrolyte.
Understanding the Performance of Lithium-Sulfur Batteries through Analysis of Shuttle Currents
Authors: Moy Derek , Manivannan A. , Narayanan S. R.
Published: February 2020

The development of a rechargeable lithium-sulfur battery has been of considerable interest due to its high theoretical specific capacity of 1675 mAh/g and high energy density of 2600 Wh/kg. These properties coupled with the low cost and non-toxicity of sulfur makes lithium-sulfur batteries very attractive for multiple battery applications. One of the major problems of lithium-sulfur batteries, however, is their poor cycle life. Typically 20-50% of the capacity is lost in around 100 cycles. This poor cycleability results from the parasitic reaction known as the polysulfide shuttle.

The polysulfide shuttle exists because the polysulfide discharge products of the sulfur electrode, S8
2- and S4
2-, are soluble in the electrolyte. These soluble polysulfide species diffuse towards the lithium anode where they are reduced. Afterwards, the reduced polysulfides shuttle back towards the sulfur cathode where they have to be re-oxidized.1-2During cycling, this phenomenon causes incomplete charging. When the cell is idle, this phenomenon results in self-discharge.

The polysulfide shuttle also impacts the cycle life because some of the reduced polysulfide discharge products formed at the anode, S2
2- and S2-, are insoluble. Normally during cycling, these insoluble discharge products are produced at the sulfur cathode where they can later be re-oxidized. However, when these insoluble discharge products are produced at the lithium anode, they will precipitate out and cause an irreversible capacity loss. We herein present a technique of directly measuring the currents associated with the polysulfide shuttle and an analysis of how these shuttle currents impact the performance of the cell.

The technique of measuring shuttle currents is based on reversing the inherent self-discharge caused by the shuttle process. The current measured by holding the cell voltage constant results from the shuttle process. In this case, as soon as the soluble polysulfide species diffuse from the cathode, the concentration gradient of sulfur species at the cathode will change, affecting the potential of the cell. In order for the cell to maintain its potential, the cell must oxidize polysulfide species at the cathode as they shuttle back.

The shuttle currents measured at various cell voltages are shown in Figure 1. We present analysis of these shuttle currents as a function of state-of-charge, cell design, and additives. We provide insight into how the magnitude of the shuttle currents relate to the reduced cycle life and discharge capacity of the cell.
Nano-Membranes for Lithium/Sulfur Batteries
Authors: Bucur Claudiu B , Muldoon John
Published: February 2020

Membranes are of interest for a wide variety of applications such as gas separation, water desalination, fuel cells and batteries.1-6 Because the flux across a membrane scales inversely with the membrane thickness, a thick membrane is required to achieve high selectivity, at the expense of permeability. New ultrathin membranes which promise to offer high selectivity and high permeability are highly desirable. Elemental sulfur can provide five times higher capacity than existing Li-ion cathode materials based on transition metal oxides or phosphates. Various problems have hindered the practical use of the highly attractive sulfur cathode such as the facile diffusion of polysulfides from cathode to anode which results in an irreversible loss in capacity.7 An ultrathin ion exchange nano-membrane would impede the polysulfide diffusion while maintaining a low overall resistance.

Here we show the proof of concept for a 5 nm membrane self-assembled from commercial polymers to encapsulate a carbon/sulfur composite and maintain the performance even at discharge rates five times more rapid than its non-encapsulated counterpart. The cycling stability of a three layer encapsulating membrane is shown in Fig. 1a, along with the non-encapsulated sulfur composite. At a discharge rate of 1C and consistent with previously reported mesoporous carbon supports, the non-encapsulated cathode cannot constrain the soluble polysulfides more than 200 cycles. The encapsulating nano-membrane can constrain these polysulfides more efficiently and allows the encapsulated cathode to be cycled 300 times with a slight capacity fade. Surprisingly, the ultrathin membrane does not impede higher discharge rates presumably due to its thickness only being 5 nm; the cycling performance of the encapsulated cathode at a 5C discharge/charge rate mirrors the performance of the non-encapsulated cathode at a substantially lower rate of 1C (Fig. 1b).

Figure 1. a. The cycling stability of encapsulated (blue circles) and non-encapsulated (black circles) cathodes at a 1C charge/discharge rate b. The cycling stability of non-encapsulated (black circles at a 1C discharge rate) and encapsulated cathodes (red circles at a 5C discharge rate).

References

Bucur, C. et al., Energy Environ. Sci.
6, 3286-3290 (2013).

Tsuchiya, M. et al., Nat. Nanotech.
6, 282-286 (2011).

Peng, X. et al., Nat. Nanotech.
4, 353-357 (2009).

Bouchet, R. et al., Nat. Mater. (2013). doi: 10.1038/nmat3602.

Hassoun, J. & Scrosati, B., Angew. Chem. Int. Ed.
49, 2371–2374 (2010).

Carta, M. et al., Science
339, 303-307 (2013).

Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M., Nat. Mater.
11, 172–172 (2012).
Latest Research Trends and Prospects Among the Various Materials and Designs Used in Lithium-Based Batteries
Authors: Wagner Ralf , Preschitschek Nina , Passerini Stefano , Leker Jens , Winter Martin
Published: February 2020

Increasing energy consumption, shortages of fossil fuels, and concerns about the environmental impact of energy use, especially emissions of carbon dioxide, give fresh impetus to the development of renewable energy sources. However, many renewable energy sources, such as solar photovoltaic and wind are unavailable during extended periods of time. The generated power from these sources is always fluctuating due to the environmental status. Hence, with the advent of renewable energy, it is now indispensable that efficient energy storage systems are developed. One of the most promising storage systems to be employed in stationary energy storage applications are lithium-based batteries (LIB), mainly due to their high energy density, high power, and nearly 100% efficiency. The speed and scope of research and development of LIB make it critical for researchers to be aware of the progress in this field across different laboratories. Thus, in a first step, we aim at giving a general overview on the research activities in the field of LIB. To this end, we conduct a patent search on LIB and their main components. We identify the main fields of patent activity in LIB and give an overview on the state-of-the-art in LIB technology. In a second step and based on our first findings, we aim at forecasting possible future research trends among the various battery components, main materials, and dominant designs used in LIB.
A Multi-Physics Model for Solid Oxide Iron-Air Redox Flow Battery
Authors: Guo Meng , Zhao Xuan , White Ralph E. , Huang Kevin
Published: February 2020

A rigorous physics-based mathematical model for a solid oxide iron-air redox flow battery system is presented in this paper. The modeled flow battery system combines a Fe-FeO redox couple as the energy storage unit and a regenerative solid oxide fuel cell as the electrical functioning unit in a 2D axial symmetric geometry. This model was developed from fundamental theories of reaction engineering in which basic transport phenomena and chemical/electrochemical kinetics are included. The model shows good agreement with the experimental data. Simulation results for the chemical, electrochemical and transport behavior of the battery are discussed.
Electrodeposition in Ionic Liquids for Fission Product Recovery
Authors: Biddinger Elizabeth J. , Shrestha Sujan , Gjoka Eriugen , Shillingford Tyrone Kirk
Published: February 2020

There is more than 57,000 tons of spent fuel being stored at U.S. nuclear power plants today(1). The spent fuel rods contain a mixture of unreacted fuel and, radioactive and non-radioactive fission products. This is both an environmental and security concern long-term. Additionally, the unreacted fuel could be recycled back to the reactor, making it more sustainable. A goal for long-term handling of the power plant waste is to separate the fission products by half-life and then only sequester the much smaller volume, long-half life products.

To address this challenge, we are examining controlled electrodeposition of the fission products in ionic liquids. Ionic liquids, salts with melting points below 100°C, can be used as non-flammable, minimally volatile, selective extractants for the separation of fission products from the aqueous system resulting from the acid digestion of spent fuel rods(2). Ionic liquids are also favorable electrolytes. They have wide electrochemical potential windows, moderate-to-high conductivities, and can be tuned to control the solubility of the reactants by changing the anion-cation pair(3). They are also considered recyclable. The wide electrochemical window is especially appealing for the electrodeposition of metals with redox potentials frequently outside of the water electrochemical window.

Noble metals are present in the fission product waste and have relatively low degrees of radioactivity(4), making them interesting for both separation for the product stream but also for further use. Additionally, they can be used as model systems for other radioactive fission product streams.

We have investigated the electrodeposition of noble metals in ionic liquids. Ionic liquid selection is very important for both the electrochemical properties and solubility properties. Figure 1 shows the solubility of PdCl2 in four ionic liquids. It can be seen that the ionic liquids with stronger ligands ([DCA]-) solvate the palladium salt, while those with weaker ligands ([NTf2]-) do not. Table 1 shows structures of the ionic liquid used. Palladium (II) chloride electroreduction is easily obtained using ionic liquids. Figure 2 shows a two-wave reduction of PdCl2in [Bmim][DCA].

Impact of ionic liquid selection and electrochemical conditions on the electrodeposition efficiency, deposition composition and morphology, as well as the phenomena associated with the electrodeposition will be presented.

References

1. Fact sheet on licensing Yucca Mountain, U.S. NRC, 2012, http://www.nrc.gov/reading-rm/doc-collections/fact-sheets/fs-yucca-license-review.html. Date accessed 11/26/12.

2. J. F. Wishart, Energy & Environmental Science, 2, 956 (2009).

3. H. Ohno, Electrochemical Aspects of Ionic Liquids, John Wiley & Sons, Inc., Hoboken, New Jersey (2005).

4. M. Benedict and T. H. Pigford, Nuclear Chemical Engineering, McGraw-Hill Book Company, Inc., New York (1957).
Gravitational Effects on the Initial Stage of Cu Electrodeposition
Authors: Inari Hirofumi , Konishi Yoko , Alkire Richard , Homma Takayuki , Fukunaka Yasuhiro
Published: February 2020

The electrochemical processing has been favorably reviewed in the microelectronics industry. It is essential to control the nucleation and crystal growth in the initial stages of electrodeposition process. For this purpose many effects of additive have been examined. However, few quantitative examinations has been reported on the coupling phenomena of ionic mass transfer rate and microstructural/morphological variations through nucleation and crystal growth.

This work discusses various gravitational levels as new parameters into the nonequilibrium electrochemical processing in order to create or tailor the unique physical properties in micrometer space field. It is fruitful in terms of not only physical chemistry but also industrial applications to comprehensively understand the coupling phenomena. In fact, it has been confirmed that the gravitational levels as well as the magnetic field introduce the intensive effects to the coupling behavior different from that under 1 G normal environment.

Here is a report to analyze the effect of gravitational level on the initial stages of Cu electrodeposition on TaN or TiN substrate installed in a cavity-type electrolytic cell. In case of Cu on TaN substrate, cathode, anode and reference electrode are TaN substrate, copper sheet and copper wire, respectively. Electrolyte solution is 0.05 M CuSO4 – 0.05 M H2SO4. Two kinds of electrolytic cell configuration are used; one is a cathode facing downward over anode horizontally (C/A), and another is an anode over a cathode (A/C). A centrifugal field is applied to introduce a high gravitational field.

Time dependence of nucleus number density shows that the nucleation of Cu on TaN is “progressive” nucleation. Under 1 G, saturated nucleus number density (N0) increases and mean diameter (dmean) becomes smaller as the electrode potential decreases. At any potential, N0 in A/C configuration is higher and dmean is smaller than C/A. The current transient shows the difference caused by two cell configurations and macroscopic natural convection due to the concentration difference should be inevitably induced with time progressed in a cavity in the A/C configuration. The image analysis indicates the nucleus distribution is considerably deviate from the Poisson distribution as long as the nearest-neighbor distance concerns. The existence of “exclusion zone” around the growing nuclei in nucleation phenomena has been found. Under high G level field, N0 becomes slightly increased and is saturated as G level increases. The effect of G level on the current transient is quite large. It is almost saturated under G level over 100 G. It is moreover found that the nucleation is saturated under high G level earlier than under low G level. The effect of ionic mass transfer rate due to the concentration difference becomes significant to enhance the nucleation rate knN0.
Corrosion Study of Fe-C Porous Materials in Coking Wastewater
Authors: Hao Suju , Jiang Wufeng , Zhang Yuzhu , Ling Yunhan
Published: February 2020

Based on the electrochemical redox reaction principle, Fe-C micro-electrolysis had developed gradually with the application of iron to wastewater treatment. Except for the electrochemical redox reaction, during the process many reactions also contribute to the degradation of pollutants, such as electrical enrichment, coagulation adsorption and filtration reaction. There are lots of other advantages, such as, the reactor has a simple structure and is easily manufactured and operated. The process also keeps low processing cost, long service life and good effects. Coking wastewater is a typical organic wastewater with high toxicity and difficult bio-degradation, so it is hard to treat. So much effort has been done to study the treatment of coking wastewater using Fe-C micro electrolysis method. But during treating wastewater, oxide iron will be generated on the surface of iron, this will hinder the further reaction. In this work, Fe-C porous materials were prepared by calcining iron-bearing dust and pulverized coal. The as-prepared Fe-C porous materials were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), X-ray energy-dispersive spectrometry (EDS), N2 adsorption and mercury intrusion measurements. Tafel polarization curves of the Fe-C porous materials and scrap iron in coking wastewater were studied using the IM6e electrochemical workstation. The results show that the Fe-C porous materials have large specific surface areas and more micro pores than scrap iron, this leads to increasing corrosion rate of the Fe-C porous materials in coking wastewater. Coking wastewater degradation results show that the effects of the Fe-C porous materials are better than the scrap iron.
Demonstration of a Reactive Hydrogen Pump Using Methanol
Authors: Fane Brian , Zawodzinski Thomas A. , Goenaga Gabriel A.
Published: February 2020

Polymer electrolyte membrane (PEM) fuel cells are an attractive energy conversion device because of the potential for extremely high efficiency and low emissions. Hydrogen is an ideal fuel for PEM fuel cells but it is energy intensive to produce.

Currently the main method of producing hydrogen is steam reforming of natural gas. This is a break from the renewable energy future promised by hydrogen fuel cells. The most obvious method of producing hydrogen is water electrolysis but that is highly energy intensive since the electrolysis requires greater than the theoretical voltage of 1.23 V and thus is somewhat inefficient. To fulfill the promise of fuel cells, less energy intensive methods of producing hydrogen must be found.

Here we describe some initial exploration of the concept of replacing water in the anode electrolyzer feed with a feedstock from which hydrogen can be stripped and purified in a combined electrochemical reactor. As a first step in testing this concept, we use methanol as the feed. Oxidation of methanol to hydrogen takes place at a theoretical voltage of .03 V. This is a significantly lower over-potential than water electrolysis and since most of the operating cost is energy, it has the potential to be significantly cheaper. Of course, the methanol oxidation reaction requires substantial overpotential because of sluggish kinetics but this is only an initial study.

We constructed a methanol water electrolyzer based the conventional direct methanol fuel cell architecture as shown in Figure 1. The electrolysis cell uses a Pt-Ru black catalyst in the anode and a Pt cathode with a Nafion 117 membrane. We examined the effects of several different catalyst loadings, back-pressures, temperatures, and humidity levels. Finally, we utilized electrochemical impedance spectroscopy (EIS) and a dynamic hydrogen electrode (DHE) to more accurately determine the effectiveness of the catalysis and sources of voltage loss.

Figure 2 shows an initial polarization curve obtained with this cell. Hydrogen was chosen for the working electrode and methanol for the counter electrode. The counter electrode potential stays fairly steady as does the ASR, while the working and cell potentials depend somewhat on the current being drawn. Increasing polarization of the working electrode begins to have a negative effect on cell current after .6V vs DHE.

Acknowledgements

We gratefully acknowledge the support of the Office of Naval Research for this activity.

References

C. Cloutier and D. Wilkinson, International Journal of Hydrogen Energy., 35,9,(2010)

S. Thomas, X. Ren, S. Gottesfeld and P. Zelenay, Electrochimica Acta., 47 (2002)
Electrically Driven Molecule Transport within a Series of Ionomers and Improvement of Electrodialysis Process
Authors: Wang Donghui
Published: February 2020

Electrodialysis (ED) is a separation technique for ionic solutions through an electrochemical membrane that has been used in industry for several decades. ED process can significantly change the features of conventional processes and have great advantage in the recovery of resources, the control of pollutants, and the chemical processing because of the simple process, high efficiency, and low disposal of wastes. It can be used in the separation and concentration of salts, acids and bases from aqueous solutions, the separation of monovalent ions from multivalent ions and the separation of ionic compounds from uncharged molecules. It can be used for either electrolyte reduction in feed streams or recovery of ions from dilute streams. Industrial applications encompass several industries and include the desalination, amino acids from protein hydrolysates, salts, acids, and alkali from industrial rinse waters, fruit juice deacidification, sugar and molasses desalting and blood plasma protein recovery. In our study, we analyze the process of ion flow through the anion exchange membrane, AEM (PC-SA) and cation exchange membrane, CEM (PC-SK) (provided by PCCell Corp.) and poly[t-butyl styrene-b-hydrogenated isoprene-b-sulfonated styrene-b-hydrogenated isoprene- b-t-butyl styrene) (tBS-HI-S-HI-tBS), Penta Block Copolymer, (PBC)(provided by Kraton Polymers LLC, Houston, TX and used to replace PC-SA). Comparing the power consumption of commercial polymers and PBC, it is significantly accepted that PBC is a kind of novel, low energy consuming, and less time requiring ionomer in the process of ED with great chemical and physical properties.
Laboratory-Scale Apparatus for Semi-Continuous Electrokinetic Dewatering of Phosphatic Clay Suspensions
Authors: Huang Yuelong , Orazem Mark E. , Kong Rui , Yu Dazhi , Lai Han , Moghaddam Saeed , Bloomquist David , Cleveland Christopher
Published: February 2020

The by-products of phosphatic clay suspensions are a major waste product of the phosphate mining industry. The phosphate clay suspensions produced from beneficiation are about 130,000 gallons per minute (GPM) at about a solids content of 2 wt%. After flocculation the settled clay suspensions at 10% solids content are pumped into the clay settling areas (CSAs) for natural settling. This natural clay settling process takes as much as 25 years to reach the demanded value of 40 wt% solids content. Therefore, the CSAs are frequently constructed on the unmined land and currently cover an area of over 100,000 acres in Florida. Disposal of the phosphatic clay suspensions has become the phosphate mining industry’s major challenge. Thus, it is necessary to develop a technique to increase the solids content of the effluent of phosphate clay suspensions from a phosphate mining beneficiation plant and thereby can save the land used for CSAs and recycling water.

A semi-continuous electrokinetic dewatering apparatus for phosphatic clay suspensions has been designed and its performance has been evaluated. A 23 factorial design was applied to determine the optimum process parameters. The results show that the electric field was found to have the greatest positive influence on the solids content. The maximum change in solids content reached a plateau as a function of operating time at a given electric field. Moreover, the plateau occurred earlier at larger electric fields, indicating that for the maximum solids content the optimum parameters of the electric field and the operating time can be determined. The CEDA had lower energy consumption and continuously produced the thickened clay which had the highest solid content of about 33 wt%. The CEDA can be operated to cope with dilute initial solids content (3-10%) from a phosphate mining beneficiation plant. The CEDA has potential to replace existing thickening equipment.
Graphene Supported Platinum-Cobalt Nanocomposites As Electrocatalysts for Borohydride Oxidation
Authors: Tamasauskaite-Tamasiunaite Loreta , Radomskis Algimantas , Antanaviciute Kornelija , Jablonskiene Jolita , Balciunaite Aldona , Zieliene Albina , Naruskevicius Leonas , Vaiciuniene Jurate , Kondrotas Rokas , Norkus Eugenijus , Jagminiene Aldona
Published: February 2020

In relation to other types of fuel cells direct borohydride fuel cells (DBFCs) are of particular value for their high theoretical capacity and specific energy density, i.e. 5.6 Ah/g and 9.3 Wh/g for NaBH4, respectively. For reducing the amount of Pt, transition metals such as Ni, Co, Fe, Cu have been added as alloy metals to the Pt-based catalysts. Recently, graphene as catalyst support has incurred intense interest in fuel cell applications due to its unique, outstanding physicochemical properties, such as an extremely high specific surface area (2600 m2g–1).

A rapid microwave heating method was used to prepare the graphene supported PtCo catalysts with the Pt:Co molar ratio 1:7, 1:22 and 1:44. TEM and ICP-OES were employed to characterize the morphology and composition of catalysts. The electrocatalytic activity of the synthesized catalysts towards the oxidation of borohydride was investigated by means of the cyclic voltammetry and chronoamperometry. The kinetics of the catalytic hydrolysis of NaBH4 in the presence of the synthesized catalysts was also investigated.

It was found that Pt nanoparticles of about 1-3 nm in size were successively deposited onto the surface of graphene nanosheets. Pt nanoparticles were uniform and well dispersed on the surface of graphene. The EDX spectra confirm the presence of Pt and Co nanoparticles in the investigated PtCo/GR catalysts.

The Pt loadings were 0.125 mg Pt cm–2 in the Pt/GR and 0.165, 0.144 and 0.125 mg Pt cm–2 in the synthesized PtCo/GR having the Pt:Co molar ratio 1:7, 1:22 and 1:44, respectively. It has been determined that the synthesized graphene supported PtCo catalysts show an enhanced electrocatalytic activity towards the oxidation of H2 generated by catalytic hydrolysis of BH4
– and direct oxidation of BH4
– ions comparing with the graphene supported bare Pt and Co catalysts. The graphene supported PtCo catalyst having the Pt:Co molar ratio 1:44 exhibits the highest electrocatalytic activity for the both oxidation reactions of H2 and BH4
– ions.

Acknowledgement

This research was funded by a Grant (No. ATE-08/2012) from the Research Council of Lithuania.