bluuebunny/crossref_metadata_2025_split huggingface dataset:
Layered and Tunneled Manganese Oxides As Battery Cathode Materials - the Role of Electrochemically Active and Inert Metal Cations
Authors: Marschilok Amy C , Takeuchi Esther S , Takeuchi Kenneth J 
Published: February 2020

Fundamental studies involving the impact of physical and chemical properties of materials on their electrochemical properties are critical to the rational development of battery materials which may address the present and future requirements for stationary and portable power. For large scale batteries, the use of environmentally benign and low cost energy storage materials is desired. Manganese-based materials are desirable in this regard as they are environmentally friendly, inexpensive, and can be prepared using scalable, aqueous based synthesis methods. Preparation, characterization, and battery electrochemistry of two promising structural motifs of manganese oxides will be described, specifically tunneled (hollandite) and layered (birnessite) crystallographic structures. The use of complimentary bulk (synchrotron based diffraction, thermogravimetric analysis, optical emission spectroscopy) and local (transmission electron microscopy based atomic imaging, nanodiffraction and electron energy loss spectroscopy) to elucidate structures of as-prepared, electrochemically reduced and oxidized materials will be highlighted. The impact of crystallite size will also be discussed.
Hollandites (Mx’Mn8O16) are one-dimensionally (1D) structured materials consisting of octahedral units of edge-sharing manganese oxide octahedra which interlink to form tunnels of 2 x 2 dimensions. Bimetallic hollandite type materials have been prepared where cations with 1+ or 2+ charge partially occupy locations within the manganese oxide tunnels, and the Mn cations possess mixed 3+ and 4+ oxidation states. Typically, the ion located within the tunnel (M’) is electrochemically inert (i.e. K+); however, silver hollandite is an interesting case as the Ag+ cationic center is potentially electrochemically active. The electrochemistry of potassium and silver based hollandites in lithium-ion and beyond lithium-ion battery systems will be described. The impact of the structural M’ cation and the role of oxygen vacancies on ion transport will be discussed. A novel recyclable battery electrode will also be described, which provides full restoration of initial capacity after a facile regeneration process.
Birnessite (Mx’MnO2), a layered manganese oxide, exists as a monoclinic crystal comprised of layers of edge-sharing manganese-oxygen octahedra (MnO6) with cations positioned between the layers. Although birnessite can be formed without any interlayer cations, monovalent (i.e. Na+, K+, Li+, Cs+) or divalent (Mg2+ or Cu2+) cations can also be incorporated between the layers. The impact of an electrochemically active interlayer cation, copper (Cu2+), on capacity and structural integrity of the birnessite structure upon discharge-charge cycling will be described, including a detailed view of the Mn and Cu oxidation state changes along with variations of the local neighboring atom environments around the Mn and Cu centers.
Turning Lead into Gold: Systematic Electrocatalytic Water Oxidation Current Enhancement at Nanostructured Fe2O3 Electrode Surface
Authors: Bachmann Julien , Haschke Sandra , Manshina Alina 
Published: February 2020

We coat the pore walls of an anodic nanoporous template with atomic layer deposition (ALD) to obtain structured electrode surfaces that provide the experimentalist with a well-defined, tunable geometry. Indeed, the platform consists of a hexagonally ordered array of metallic or oxidic nanotubes of cylindrical shape, embedded in an inert matrix. The diameter of the tubes can be defined between 20 and 300 nm and their length between 0.5 and 100 μm, approximately. We utilize them as a model system in which the electrode's specific surface area can be increased and its effect on the electrocatalytic current characterized systematically.
Diffusion-limited electrochemical transformations remain unaffected by changes in the length of the electrode's pores, whereas the steady-state galvanic current density observed for slow multielectron transformations increases linearly with the pore length. In particular, this approach enables us to increase the electrochemical water oxidation turnover at iron oxide surfaces by two to three orders of magnitude at the optimal point. An additional roughening effect occurring upon annealing and steady-state electrolysis is further evidenced by a combination of spectroscopic, microscopic, and electrochemical methods.
These results highlight a strategy for optimizing electrochemical energy transformation devices which could be generalized: the geometric tuning of catalytically mediocre but abundant and cost-effective material systems.

We acknowledge the Center for Optical and Laser Materials Research and the Interdisciplinary Resource Center for Nanotechnology at Saint Petersburg State University for their participation.

Figure 1
(Invited) Tribute to Prof. Zempachi Ogumi : In Operando Studies and in Situ Techniques for Li-Ion and Lithium Metal Polymer Batteries
Authors: Zaghib Karim , Marceau H , Hovington P , Wen Z , Kim C , Trudeau M , Veillette R , Laul D , Paolella A , Lagace M , Chaker M , Vijh A , Guerfi A , Mauger A , Julien C.M , Armand M 
Published: February 2020

Prof. Ogumi is one the leading pioneers of lithium-ion technology in Japan and worldwide. His research studies on battery materials include LiCoO2, graphite, and highly oriented pyrolytic graphite (HOPG), Much of his research involved in situ techniques that utilized X-ray, Raman spectroscopy and atomic force spectroscopy (AFM) to investigate the SEI (passivation layer) and lithium intercalation in graphite and HOPG in propylene carbonate (PC)- and ethylene carbonate (EC)-based electrolytes.
In this presentation, we will show data and video movies that were obtained during studies of lithium-ion and solid-state batteries using various In operando studies and in situ techniques involving scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction and ultraviolet-visible absorption spectroscopy (UV-vis). These in situ studies are helpful to understand the mechanisms for volume expansion of anodes consisting of lithium metal (20 %), graphite (10 %) and LTO (0 %). Another example that will be discussed is the dimensional changes of the anode, cathode and electrolyte that occur during charge/discharge. The mechanism of lithium dendrite formation was also studied, and details will be discussed in this presentation.
[Don’t know what is meant by Bleand and deleted because I‘m not sure it is needed.] Lithium/solid polymer electrolyte (SPE)/sulfur cells were studied by two in situ techniques: SEM and UV-vis. During the operation of the cell, extensive polysulfide dissolution in the solid polymer electrolyte (cross-linked polyethylene oxide) leads to the formation of a catholyte.
A clear micrograph was obtained of the thick passivation layer on the sulfur-rich anode and the decreased SPE thickness during cycling confirmed the failure mechanism; the capacity decays by reducing the amount of active material, which contributes to a charge inhibiting mechanism called polysulfide shuttle. The formation of elemental sulfur is clearly visible in real time during the charge process beyond 2.3 V. The non-destructive UV-vis also shows the characteristic absorption peaks that evolve with cycling, demonstrating the accumulation of various polysulfide species, and the predominant formation of S4
2- and of S6
2- during discharge and charge, respectively. This finding implies that the charge and discharge reactions are not completely reversible and proceed along different pathways.
Electrocatalytic Reduction of Selenate on Gold Electrodes Alongside Copper Deposition
Authors: Strobl Jonathan , Scherson Daniel 
Published: February 2020

Reduction of aqueous selenate (SeO4
2-) to lower oxidation states of selenium is regarded as a very difficult reaction and thus far, only very few methods have yielded positive results [1-6]. One such previous study asserts that gold electrodes can catalyze reduction of commercial selenate at potentials below 0.6 V vs SHE [1], forming an elemental selenium deposit that can be anodically stripped above 0.9 V vs SHE, (see peaks A and B, black curve in Fig. 1 recorded in 1 mM Na2SeO4 in 0.1 M HClO4). However, commercially supplied selenate usually contains some selenite (SeO3
2-), a far more electroactive selenium oxyanion believed to yield elemental selenium and/or selenides as the product(s) of reduction. In fact, as shown by experiments performed in our laboratories, such voltammetric features vanished upon removal of selenite from the selenate solutions by adsorption on TiO2(see red curve in Fig. 1).
This contribution will present strong evidence that the reduction of selenate under the same conditions can proceed on a layer of underpotentially deposited copper on Au, yielding a corresponding layer of CuxSe. To be discussed are various aspects of the formation mechanism of this CuxSe using potentiostatic deposition and linear sweep stripping voltammetry (LSSV) experiments. During LSSV experiments, Cu can be anodically stripped, leaving behind a layer of adsorbed elemental Se (peak C, Fig. 2). At higher potentials, this layer is oxidized to selenite (peak B, Fig. 2) [7-9]. Repetitive formation and oxidation of the CuxSe product on gold electrodes via an AC deposition / stripping waveform may allow for continuous turnover of selenate into selenite.

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Acknowledgements:

This work was supported by a grant from the NSF, # CHE-1412060.
Figure 1. Cyclic voltammograms recorded with a Au wire in a solution of 1 mM Na2SeO4 before (black curve) and after purification (red curve, see text) in 0.1 M HClO4at a scan rate ν = 0.2 V/s.
Figure 2. Linear scans recorded at ν = 0.1 V/s obtained for a Au RDE after holding the potential at Ehold = 0.375 with the electrode rotating at ω = 1500 rpm in 0.1 M HClO4, 1 mM Na2SeO4 (purified) and 1.2 mM Cu(ClO4)2 solutions for thold = 10 (red), 100 (blue) and 1000 s (green).

Figure 1
High Activity Oxygen Evolution Reaction Catalysts from Additive-Controlled Electrodeposited Ni and Nife Films
Authors: Gewirth Andrew A. , Hoang Thao Thi Huong , Schmitt Kevin Gary 
Published: February 2020

We use electrodeposition for energy and microelectronics purposes. Electrodeposition of Ni or NiFe films exhibiting fractal-like behavior from plating baths containing an inhibitor, such as 3,5-Diamino-1,2,4-triazole (DAT), is found to yield oxygen evolution reaction (OER) catalysts for alkaline solutions exhibiting high current densities (100 mA/cm2), high mass activity (~ 1200 A/g of catalyst), high stability (> 72 hours) and low overpotentials (~ 300 mV). By changing electrodeposition time, the activity of the catalyst can be tuned, with longer times yielding higher activities. The electrodeposition method works with any conductive substrate yielding unprecedented performance and providing an easy route to high activity catalysts.
We also investigate the mechanism of 3-mercapto-1-propanesulfonate (MPS) acceleration of Cu electrodeposition in the presence of Cl- through comparison with the inactive but related model compounds 1-butanesulfonate and 1-butanethiol (BuSH). In situ Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy (SHINERS) was used to evaluate these additives as a function of potential. MPS adsorbs to the Cu electrode in the presence of Cl- through the thiol functional group. DFT calculations reveal that the adsorption of thiol has a depolarizing effect on the strength of the interaction between adsorbed Cl- and the electrode surface, the consequences of which are observed spectroscopically. The sulfonate moiety does not interact directly with the electrode. However, cyclic voltammetry used to assess the permeability of adsorbed MPS and BuSH adlayers indicates that the sulfonate group has a more direct role in Cu deposition beyond simple disruption of the surface layer.
(Invited) Electrochemical Deposition of Thick and Adherent MnO2 Films for Thin-Film Batteries
Authors: Labyedh Nouha , Arman Meryem Ozge , Timmermans Marina , Deheryan Stella , Vereecken Philippe M. 
Published: February 2020

Electrolytic manganese dioxide (EMD) is fabricated by anodic electrodeposition typically from acid manganese sulfate baths. After electrodeposition it is peeled from the electrode and ground into powder, hence poor adhesion is required. EMD powder is mainly used for primary alkaline-Zn and Li-ion batteries. EMD allows Li-ion intercalation in the open channels in the γ-MnO2 lattice. In our research group we are interested in adapting the EMD process for bulk batteries to be used for fabrication of thin-film Li-ion batteries.
EMD thin films deposition was developed on different substrates. Scanning electron microscopy (SEM) and Rutherford Backscattering Spectrometry (RBS) measurements were performed to extract the film porosity. It was found that all the deposited films have similar porosity values around 50 %.
Anodic electrodeposition of EMD films from conventional acid manganese sulfate baths is not possible on easy to oxidize substrates like TiN (passivation) or Ni (dissolution). For this reason a neutral and complexing acetate bath was used. Using this deposition bath thick and adhesive EMD film were deposited on Ni and even on TiN substrates. Up to 1 μm thick film on planar substrate and 600 nm on 50 μm high Si pillar array with 2 μm pillar diameter and 2 μm interpillar spacing. A study of the EMD film deposition in a temperatures range from 5 °C to 50 °C using the neutral acetate deposition bath was performed. The relationship between the morphology and the electrochemical performance of the EMD films deposited at different temperatures were investigated.
Anodized Porous Oxide Thin Films for Energy Application
Authors: Cheng Hua , Zhang Dehui , Wu Dong , Lu Zhouguang 
Published: February 2020

Highly ordered porous oxide thin films including Fe3O4, NiO, ZnO, CuO, Co3O4 have been prepared by a facile multi-pulse electrochemical anodization method. The as-obtained oxide films are directly grown on the corresponding metallic substrate, featuring nano-channels with periodically rugated channel walls running throughout the film thickness direction and can also be peeled off from the substrate to become free-standing. The geometry and size of the films can be finely tuned by the electrochemical anodization parameters. The fabricated oxide films have been intensively applied as electrode materials for lithium ion batteries and micro-combustion. Very promising performance has been achieved due to the very special periodic rugated nanostructures of these anodized thin films.

Acknowledgments

This work was financially supported by the Shenzhen Peacock Plan (KQCX20140522150815065), the Natural Science Foundation of Shenzhen (JCYJ20150630145302231) and the Science and Technology Innovation Foundation for the Undergraduates of SUSTC (2015x19 and 2015x12).

References

[1] H Cheng, R Xiao, HD Bian, et al. Mater. Chem. Phys.
2014, 144, 25.
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2012, 22, 22692.
[3] H Cheng, SW Shu, ZG Lu, et al. J. Appl. Phys.
2014, 116, 153511.

Figure 1
Bimetallic Pt-Based Electrocatalysts Supported on Carbon Fiber for Coal Electrooxidation to Produce Hydrogen
Authors: Yu Ping 
Published: February 2020

The electrolysis of coal slurries to produce hydrogen is a new approach to utilize coal in a clean and efficient manner [1, 2]. However, various results show that the process is less favorable kinetically [3-7]. Therefore, it is important to explore the design of new electrocatalysts with emphasis towards high activity, low cost, and long life.
It is well known that Pt-based bimetallic catalysts containing a transition metal, such as Pd, Co, Fe, Ti, Ru and Sn, often demonstrate improved catalytic performance compared to pure Pt catalysts [8-12]. Significant effort has been made to employ bimetallic catalysts that can decrease the content of noble metals and improve performance based on bi-functional properties.
In this work, Pt-based bimetallic electrode supported on carbon fibers (CFs) was prepared by the impregnation and reduction and evaluated for the electrolysis of coal to produce hydrogen. The characterization of the electrocatalyst of Pt-based bimetallic electrocatalysts using XRD, TEM, and SEM/EDS is performed. The activity and stability of the electrodes prepared are simultaneously investigated.

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(Invited) An Impedance Study of the Factors Affecting the Passivity of Steel in Concrete
Authors: Deus J.M. , Díaz B. , Nóvoa X.R. , Pérez M. C. 
Published: February 2020

Reinforced concrete is one of the materials used most often in civil construction thanks to its unique low ratio of cost to mechanical performance. Although reinforced concrete elements and structures are expected to last for several generations, everyday experience shows that this is not true and repairing measures are often necessary after only few years of being in service.
The chemical stability of the steel reinforcements lies in the formation of the passivation layer whose stability is the key for durability. The passive layer degrades in low pH environments, that occurs in carbonated concrete, and in the presence of chlorides that are typical of marine environments.
Although carbonation and chlorides are the main factors that affect the durability of reinforced concrete structures, the exposure conditions have also to be considered for reliable lifetime predictions. Wetting/drying cycles and temperature can be cited among the most relevant environmental factors involved.
The present communication aims at reviewing the recent literature on the effect of temperature in both the concrete cover and the passive layer, to introduce new data on EIS measurements performed on samples exposed up to 15 years outdoors.
(Invited) Electrochemical Impedance Analysis of Printable Porous Carbon Electrode for Realization of High-Power Biofuel Cell and Wearable Self-Powered Biosensor
Authors: Shitanda Isao , Hoshi Yoshinao , Itagaki Masayuki 
Published: February 2020

A paper-based biofuel cell (PBFC) have been attracted as a potential application as energy harvesting power sources in the Internet of Things (IoT) field [1-3]. To use the PBFC for practical application, the cell power density of PBFC, generally limited by the biocathode performance, should be improved. The distance between the redox site of the enzyme and the electrode material surface is one of the key factors for biocathode development. By entrapping enzymes in a mesopore of a porous carbon material, the redox center can approach the electrode material surface with high probability. In addition, the stability of the enzyme may be improved. A branch structure (double pore structure) porous carbon material is a suitable porous material for biosensors and biofuel cell electrodes, because the branch structure porous carbon material such as MgO-templated mesoporous carbon (MgOC) has large specific surface areas and mesopores whose size can be easily controlled. In the present study, we formed the branch structure porous carbon electrodes for biofuel cathode by screen-printing technique, and the electrode performance was evaluated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) to improve the electrode structure for biofuel cell cathode. In the present paper, we discuss the experimental result in detail and introduce our wearable PBFC performance using the printed porous carbon electrodes.
[1] I. Shitanda et al., Chem. Commun. 49 (2013) 11110.
[2] Claudia W. Narváez Villarrubia et al., Electrochem. Commun, 45 (2014) 44.
[3] Carolin Lau et al., Int. J. Hydrogen. Energy, 42 (2015) 14661.
The Joint Center for Energy Storage Research: Integration of Research, Development, and Demonstration
Authors: Brushett Fikile R. , Trahey Lynn , Hodge Devin 
Published: February 2020

The Joint Center for Energy Storage Research (JCESR) seeks transformational change in transportation and the electric grid driven by next generation high performance, low cost electrochemical energy storage. To pursue this transformative vision JCESR introduces a new paradigm for battery research: integrating discovery science, battery design, research prototyping, and manufacturing collaboration in a single highly interactive organization. This new paradigm aims to accelerate the pace of discovery and innovation and to reduce the time from conceptualization to commercialization, thereby crossing the famed “valley of death” between research and industry. While JCESR exclusively focuses on beyond lithium-ion batteries, this paradigm is portable and can be applied to a wide range of challenging problems facing today’s scientists and engineers. To this end, this talk will present JCESR’s motivation, vision, mission, strategy, and intended outcomes or legacies. Lessons learned in the development, execution, and refinement of this Hub will be discussed and key accomplishments enabled by this new mode of operation will be highlighted.