bluuebunny/crossref_metadata_2025_split huggingface dataset:
Investigation of Solid Electrolyte Interface Formation in Li3as Electrode Material in a Solid-State Battery Configuration
Authors: Samuthira Pandian Amaresh , Hood Zachary D. , Wang Hui , Liang Chengdu , Dudney Nancy J 
Published: February 2020

Solid state batteries have gained attention due to the promise of safe operation of battery at high voltage and for longer duration. Solid electrolytes may also help to stabilize conversion electrodes for higher energy density. Arsenic alloys are rarely studied, but several may be interesting as the negative electrode, for example, FeAs, As/C, and InAs.1 The fact that the cost per pound of Arsenic is less than the counterpart negative electrode candidates like Si, Ge, In, Pb, Ti, and V is advantageous.2

In this context, we chose Li3As as a negative electrode material in a solid-state battery configuration. The intrinsic high electronic conductivity of Li3As and conversion reaction mechanism providing a high energy density are the reasons behind selecting Li3As for studying the cycling and interface stability with a Li-P-S based solid electrolyte. The solid-state battery was cycled at different temperatures and the resultant pellet was dissected for analyzing the interface layer formed. The battery that has the iodide doped solid electrolyte performed well in terms of electrochemical cycling properties compared to the undoped electrolyte. An iodide rich layer between the solid electrolyte and Li3As electrode formed within few cycles. This thin iodide rich layer is responsible for the stable performance of the solid-state battery for over 100 cycles.
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 under the Advanced Battery Materials Research Program. Synthesis of the electrolyte was conducted as part of user proposal at ORNL’s Center for Nanophase Materials Sciences (CNMS), which is an Office of Science User Facility.
References:

(a) J. Chen, H. Zhao, N. Chen, X. Wang, J. Wang, R. Zhang, and C. Jin, J. Power Sources, 200, 98 (2012); (b) X. Lia, D. Xiao, H. Zheng, X. Wei, X. Wang, L. Gu, Y.-S. Hu, T. Yang, and Q. Chen, Nano Energy, 20, 194(2016); (c) C.-M. Park, J. Solid State Electrochem., 20, 517 (2016).

N. Nitta and G. Yushin, Part. Part. Syst. Charact., 31, 317 (2014).

*Corresponding author email: dudneynj@ornl.gov
Titanium Dioxide As a High Capacity Anode for High Voltage Aqueous Lithium-Ion Batteries
Authors: Ramanujapuram Anirudh , Gordon Daniel , Coffman Keith , A. Sosa Ramón , Zhang Shuchen , Yushin Gleb 
Published: February 2020

Aqueous lithium-ion batteries are gaining increasing interest as a potential candidate for the next generation batteries. These batteries provide much higher safety and reduced cost of manufacturing as the prime advantages. Aqueous electrolytes also offer higher ionic motilities for lithium ions which could pave the way for faster charging batteries.
Despite the advantages, a huge drawback in aqueous batteries is the lower electrochemical stability window for water-based electrolytes. Titanium dioxide (TiO2) is one candidate electrode material that can offer a high capacity, but the redox potential for TiO2 is much lower than the hydrogen evolution potential for water.
Here we report on our efforts to increase the over-potential for hydrogen evolution on the anode in order to achieve good cycle stability of TiO2 in aqueous electrolytes. By using a combination of in-situ and ex-situ surface coatings on the anode and tuning the composition and molarity of aqueous electrolytes, we demonstrate that the over-potential for hydrogen evolution can be suppressed to sufficiently low potentials to allow reversible Li insertion and extraction to/from TiO2. These achieved results are critically important for the development of high voltage aqueous batteries.
Materials characterization of TiO2 electrodes using scanning and transmission electron microscopy (SEM and TEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction and vibrational spectroscopy studies (Raman and FTIR) before and after electrochemical cycling will be reported. Results of electrochemical characterization tests, such as cyclic voltammetry (CV) conducted at different sweep rates, charge-discharge (C-D) conducted at different current densities and different temperatures and electrochemical impedance spectroscopy (EIS) studies, show the relationships between the composition of cell components and cell electrochemical performance.
Characteristics of Double Layerd TiO2 Cathode Assembling to Marine Microbial Fuel Cell
Authors: Motoda Shinichi , Morita Motoaki , Tamura Sho 
Published: February 2020

For these recent several years, biomass, geothermal, wind power, and the solar power becomes the urgent issues from a development demand that arise from global environment such as the running out crisis of the fossil fuel. However, there are not so many electric power generation systems in conjunction with the ocean accounting for 70% of the surface area of the earth. In the present work, we tried it using marine environment and solar for the purpose of improving a performance of the biofilm battery which was one of the microbial fuel cells (MFC).
The biofilm formed to a cathode electrode ennoble the electrode potential and the photocatalytic effect of the TiO2 film coated metal surface of an anode electrode makes it possible to be an renewable energy source.
However, we are not yet put it to a practical use by a reason such the lack of stability in the photocatalytic effect of the titanium dioxide coated on to the stainless steel anode by a plasma spraying technique. Therefore, in this study, we aimed to improve the photocatalytic activity of the anode electrode by developing the electrode which layered titanium dioxide by two phases using the the squeegee method and a plasma gas arc spraying method by improving those properties in the biofilm battery.
As a result of measured electrode potential of the TiO2 electrode, following results were obtained;
1) The photocatalytic potential of the TiO2 single-layered electrode showed -0.63V (SCE). This made the electrode potential lower 0.13V than that of an electrode conventionally, and improvement of the photocatalytic activity. In addition, reproducibility and stability were observed in the time variations of photo potential. When this electrode assembled in a biofilm battery, the open circuit voltage rose 0.09V in comparison with a battery conventionally, and the maximum power increase 1.33 times enabled.

2) The output of the biofilm battery which assembling double layer TiO2 anode electrode rose 1.81 times electric power in comparison with previous one. It is thought that the electron which moves from the anatase outer layer to substrate stainless steel through the rutile intermediate layer accelerated by the heterojunction effect at the anatase / rutile interface.
Development of a Lower Temperature Operating Sodium Beta-Alumina Battery (LT-NBB): Strategies and Technical Challenges
Authors: Jung Keeyoung , Park Yoon-Cheol , Cho Namung , Son Sori , Lee Younki , Kim Chang-Soo , Kim Goun , Jin Dana , Shim Wooyoung , Li Guosheng , Sprenkle Vincent 
Published: February 2020

The sodium nickel chloride (Na/NiCl2) battery is one of the most promising candidates for a large scale electrochemical energy storage device. The battery comprises NiCl2 and molten Na as positive and negative electrodes in its charged state, and uses a Na+ ion conducting β"-Al2O3 solid electrolyte (BASE) to separate the cathode and anode. In order to facilitate fast sodium ion transport in the cathode compartment, molten NaAlCl4, as a secondary electrolyte (or catholyte), is infiltrated into the powdered cathode material. The battery typically operates at 250~300°C to maximize the ionic flux in the NaAlCl4 and through the solid electrolyte, and to minimize the dissolution of NiCl2into the melt. However, this efficient battery has yet to be widely used in grid scale energy storage applications, since it is still expensive; it is difficult to dramatically reduce the cell price in its present form mainly due to its use of expensive sealing technologies.
The presentation introduces U.S.-Korea collaborative efforts to develop a sodium beta-alumina battery with a Na/NiCl2 chemistry that operates at a lower temperature. Since the novel battery runs below 200°C, it can be fabricated at an ultralow manufacturing cost by (1) introducing a new planar cell design with a greatly reduced number of cell components, and (2) eliminating expensive sealing technologies. Enhanced degradation resistance of cathode materials is another important advantage of this technology. This presentation will start by stating problems found in traditional sodium beta-alumina batteries, and our strategies to resolve the issues will be described. Technical challenges and progress in materializing prototype LT-NBB cells and related core technologies will be briefly discussed, which include cell design, a highly toughened BASE, an enhanced wetting agent, and an inexpensive sealing method.
The Re-Discovery of Scandium-Substituted Na3Zr2(SiO4)2(PO4)
Authors: Ma Qianli , Guin Marie , Naqash Sahir , Tsai Chih Long , Tietz Frank , Guillon Olivier 
Published: February 2020

In recent years, the requirement of energy storage for renewable clean energy, like solar and wind energy, has attracted more and more interest of the relevant research globally. As one of the choices, room-temperature Na-ion batteries (NIBs) show advantages of unlimited sources, low price of starting materials and easy recycling,[1] which promise them high potential for energy storage applications. NIBs in all-solid-state design are regarded as the batteries of the next generation because of their non-leakage, non-volatilization, non-flamma­bility, separator-free design and adaptability to temperature changes.[2] Trivalent-cation-substituted Na3Zr2(SiO4)2(PO4)3 in NASICON structure are regarded as promising electrolyte materials for all-solid-state NIBs because of their high Na-ion conductivity and reliable chemical and physical stability. In this study, scandium is chosen as the substitution element for Na3Zr2(SiO4)2(PO4) (Sc substituted Na3Zr2(SiO4)2(PO4)3, NSZSP), because among all the trivalent cations, the ionic radius of Sc3+ (74.5 pm) is the closest to that of Zr4+ (72.0 pm), indicating that the substitution only generates a deficiency in positive charge, but does not cause distortions in the crystal structure. NSZSP has received hardly any attention so far. Only one reference reported this kind of materials.[3] However, the reference mainly targeted the performance of NSZSP at high temperatures (~300°C). Only a few conductivities at room temperatures were mentioned, and they are rather moderate (maximum 5.0 × 10-4 S cm-1). In this study, a solution-assisted solid-state reaction method was invented by which a series of NSZSP nano-powders with favorable microstructures were prepared. With increasing of scandium substitution, the conductivity of sintered NSZSP samples also increases. Na3.4Sc0.4Zr1.6(SiO4)2(PO4) shows the highest conductivity of the system so far, more scandium substitution decreases the conductivity because there exists a most suitable ratio between occupied and vacant Na sites. The total-ionic conductivity of Na3.4Sc0.4Zr1.6(SiO4)2(PO4) reaches 4.0 × 10-3 S cm-1 at 25 °C. To our knowledge, it is not only the best value for all materials with NASICON type structure, but also the best reported value for all polycrystalline oxidic Na-ion conductors. It is even comparable with common liquid electrolytes of NIBs. The possible reason for such high conductivity is discussed in specific.
[1] D. Larcher, J. M. Tarascon, “Towards greener and more sustainable batteries for electrical energy storage”, Nat Chem
2015, 7, 19-29.
[2] A. Hayashi, K. Noi, A. Sakuda and M. Tatsumisago, “Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries”, Nat. Commun. 2012, 3, 856-861.
[3] M. A. Subramanian, P. R. Rudolf and A. Clearfieled, “The Preparation, Structure, and Conductivity of Scandium-Substituted NASlCONs”, J. Solid State Chem. 1985, 60, 172-181.
Simultaneous Analysis of Thin-Film Manganese Dioxide Deposits Using Eqcm, Cyclic Voltammetry, Step Potential Electrochemical Spectroscopy and Electrochemical Impedance Spectroscopy
Authors: Donne Scott W , Cameron Hayden 
Published: February 2020

As a population the reliance on portable electronics and rapid development in electric vehicles in order to combat global warming has caused researchers to search for materials that exhibit excellent energy storage properties. Thin film MnO2 deposits have been observed to exhibit these properties and has become a popular research material for capacitors and batteries.
In this project a method was developed in which the mass change for a thin film of MnO2 during electrochemical experiments could be observed. It was conducted by depositing MnO2 onto a platinum quartz crystal, by doing this it allowed for the mass change throughout the deposition process to be recorded providing a better understanding of the deposition mechanism. Once the MnO2 was deposited the EQCM was used as a working electrode throughout further electrochemical testing which included cyclic voltammetry (CV), step potential electrochemical spectroscopy (SPECS), and electrochemical impedance spectroscopy (EIS) while recording the mass change throughout each test.
Cyclic voltammetry was conducted with a 25mV sweep from 0 - 0.8V for 250 cycles. By doing this the capacitive performance of the material was determined, however, by recording the mass change throughout the experiment it was possible to determine if there were faradaic, non-faradaic process occurring on the surface of the electrode affecting the charge storage mechanism and to observe sample stability throughout cycling.
SPECS and EIS immediately followed the cycling which allowed for the observation of the maximum charge storage capability of the material and the mechanism in which the material stores energy. The impedance data allows for the analysis of the charge transfer mechanism and the various interfacial resistance and capacitance at the electrode-electrolyte interface.
This technique has allowed for significantly greater understanding of the processes that the electrode materials are undergoing throughout the experiments and can be used as a powerful tool in various aspects of electrochemical analysis.

Figure 1
A Novel Rapid Processing Route to Sintered Plaque Aqueous Nickel Electrodes for Low Cost Building Scale Energy Storage
Authors: Marinaccio Jordan Domonic , Glover Carol Frances , Subramanian Raman , Barnes Alistair David , Williams Geraint , Elvins Jonathon 
Published: February 2020

Electrification of heating systems and transportation as well as decarbonisation of electrical energy production will continue to place more and more stress and strain on current electrical grid infrastructures. Renewable energy generation technologies such as photovoltaics and wind power generation are seen by many as the future for energy production and security. With high dependence on such intermittent and ‘highly distributed micro-generation’ energy production technologies, ‘highly distributed micro-storage’ solutions such as secondary batteries could prove to be the answer. An appropriate technology would ideally possess a lifetime in-line with current photovoltaic technologies (20 years), be inherently safe and be able to cope with the unpredictable cycling conditions posed by intermittent generation and user demand.
One such technology, namely nickel-iron aqueous batteries (pioneered by Thomas Alva Edison in 1901) boasts cycle life in excess of 5000 cycles, as well as tolerance of both physical and electrical abuse. Low energy density (both gravimetrically and volumetrically) are long standing issues with the chemistry, however given the nature of the application, such issues are not of the greatest concern.
The greatest issue posed by the nickel cathode material is the poor high rate charge/discharge capability, due to the insulating nature of nickel hydroxide active materials. This can be addressed by configuring the cathode active material within a conductive scaffold (sintered nickel plaque on nickel-plated steel current collector). This does however hinder manufacturability of the cathode, requiring a highly energy intensive heat treatment (900oC, 30 minutes). Herein we evaluate electrodes produced via 2 process routes: - A traditional process route consisting of a slurry deposition and subsequent convection sintering process and a continuous current active material deposition process, versus a novel rapid process route, utilising high volume throughput screen printing of both nickel and titanium dioxide scaffolds and Near Infrared rapid curing technology, as well as a pulsed current active material deposition. The latter results in a substantial reduction in manufacture time, opening the door to semi-continuous processing for sintered nickel battery technologies and therefore low-cost energy storage.
Electrochemical Modeling, Optimization and Control of Lithium Metal Batteries
Authors: Lee Seong Beom , Kolluri Suryanarayana , Xu Wu , Zhang Ji-Guang , Subramanian Venkat R. 
Published: February 2020

Li metal is receiving great attention in recent years as an anode material. It has the lowest negative electrochemical potential (-3.040V vs. SHE), a low gravimetric density (0.534 g∙cm-3), and an extremely high theoretical specific capacity (3860 mAh∙g-1) compared to graphite (372 mAh∙g-1) used in Li-ion batteries1. Most available battery models, however, focus on the performances of Li-ion batteries, which are not good enough to predict the behavior of Li metal batteries and even Li metal battery models that are used today do not account for the internal states of the battery system2.Therefore, development of a simulation model to explain the unique feature of Li metal batteries will be critical in this field and will largely accelerate the development of rechargeable Li metal batteries.

The control of the charge/discharge rate which is very critical for the long-term stability of Li metal batteries has been recently developed by Zheng et al3. The key aims in this presentation include: (1) development of multiscale models that will provide optimal charge/discharge controls to enhance the lifetime of Li metal batteries, (2) electrochemical characterization to validate the predicted improvement in life/performance.

Acknowledgements

The authors acknowledge financial support from the University of Washington’s Clean Energy Institute and Washington Research Foundation.

References

1. J. Qian, W. A. Henderson, W. Xu, P. Bhattacharya, M. Engelhard, O. Borodin and J.-G. Zhang, Nature communications, 6 (2015).

2. Z. Li, J. Huang, B. Y. Liaw, V. Metzler and J. Zhang, Journal of power sources, 254, 168 (2014).

3. P. Y. Jianming Zheng, Donghai Mei, Mark H. Engelhard, Samuel S. Cartmell,Bryant J. Polzin, Chongmin Wang, Ji-Guang Zhang, and Wu Xu, Advanced Energy Materials, 1502151 (2016).
Rde Kinetic Study of V(IV)/V(V) and V(II)/V(III) Reactions on Thermally Activated and Non-Activated Carbon Felts
Authors: Li Yue , Parrondo Javier , Ramani Vijay K 
Published: February 2020

Graphite felt is the most common electrode material used at both the cathode and the anode in vanadium redox flow batteries (VRFBs). Graphite felt exhibits good activity towards the redox reactions, has a wide operational potential range, and exhibits stability in acidic environments. A variety of studies have been conducted to investigate the effects of different felt pre-treatment methods for on VRFB performance (1, 2). Basically the pre-treatment methods can be categorized into oxidation and reduction of the graphite felts. Even though this field has been extensively studied by using different techniques, there is still some controversy. It is commonly accepted that chemical/electrochemical oxidation of graphite felts increases their activity towards V(IV)/V(V) reactions (3, 4). However, there are few studies reporting the opposite result (5, 6). It is therefore necessary to perform a fundamental study of the kinetics of vanadium species redox reactions on activated and non-activated graphite felts.
The felt material (non-activated or activated) was ground using a mortar and mixed with epoxy resin to form a paste (33wt% of epoxy). The paste was pressed (8000 kg/cm2) in a stainless steel mold until it hardened, and the resultant electrode was employed as the disk in the rotating disk electrode experiments (RDE). To our best knowledge, this is the first RDE study of vanadium reactions on non-activated and activated graphite felts. The results and trends obtained in the RDE studies were verified by performing vanadium flow battery experiments. The presentation will discuss how the RDE disk was made, present the kinetic data of non-activated graphite felt and thermally activated (7) graphite felt for both V(IV)/V(V) and V(II)/V(III) redox reactions. The kinetic analysis will be accompanied with the analysis of the carbon felts by scanning electron microscopy, X-ray photoelectron spectroscopy, and charge/discharge curves in an all-vanadium redox flow battery.

References
1. W. G. Zhang, J. Y. Xi, Zhaohua Li, H. P. Zhou, L. Liu, Z. H. Wu, and X. P. Qiu, Int. J. Electrochem. Sci., 4700 (2013).
2. X. G. Li, K. L. Huang, S. Q. Liu, N. Tan, and L. Q. Li, Trans. Nonferrous Met. Soc. China, 17, 195 (2007).
3. Y. Men and T. Sun, Int. J. Electrochem. Sci., 3482 (2012).
4. L. Yue, W. S. Li, F. Q. Sun, L. Z. Zhao, and L. D. Xing, Carbon, 3079 (2010).
5. A. Bourke, M. A. Miller, R. P. Lynch, J. S. Wainright, R. F. Savinell, and D. N. Buckley, J. Electrochem. Soc., 162, A1547 (2015).
6. A. Bourke, M. A. Miller, R. P. Lynch, X. Gao, J. Landon, J. S. Wainright, R. F. Savinell, and D. N. Buckley, J. Electrochem. Soc., 163, A5097 (2016).
7. B. Sun and M. Skyllas-Kazacos, Electrochim. Acta, 37, 1253 (1992).