bluuebunny/crossref_metadata_2025_split huggingface dataset:
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.
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.
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).
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).