bluuebunny/crossref_metadata_2025_split huggingface dataset:
Additively Manufactured Solid-State Ion Conductors for Resistive Switching Devices
Authors: Tsui Lok-kun , Plumley John Bryan , Peng Thomas , Garzon Fernando H 
Published: February 2020

Additive manufacturing of solid-state ion conductors opens the possibility to fabricate at low-cost novel electrochemical devices as an alternative to clean room techniques. This would promote their use for small-scale production or rapid prototyping. Memristive devices based on conductive bridging are a promising technology for next generation memories, neuromorphic computing, and reconfigurable electronic switches.1,2 Electrochemically driven growth of a metal filament from the cathode to the anode through a solid-state ionic conductor is used to switch the device from a low conductivity state to a high conductivity state. They are of particular interest in satellite electronics due to their innate radiation hardness compared to traditional transistor-based devices.
We have printed Pt/AgI/Ag electrochemical cells (Figure 1(a), inset) as a proof of concept that such devices can be produced by additive manufacturing. The AgI electrolyte is deposited by computer controlled extrusion of a paste and the electrodes are formed by initially by vapor deposition and subsequently by inkjet printing. The latter demonstrates a completely additively manufactured device. During filament formation AgI acts as an Ag+ ion conductor, Pt is the cathode, and Ag is the anode. The current of the device at a fixed applied voltage is found to increase by three orders of magnitude (Figure 1(a)) as the conductive bridging is completed. Cyclic voltammetry was also able to demonstrate reversible switching between the high and low conductivity states (Figure 1(b)). Finally, impedance measurements were performed to evaluate the conductivity of the printed AgI electrolyte as a function of temperature.

References

I. Valov and M. N. Kozicki, J. Phys. D. Appl. Phys., 46, 74005 (2013).

A. H. Edwards, H. J. Barnaby, K. A. Campbell, M. N. Kozicki, W. Liu, M. J. Marinella, Proc. IEEE, 103, 1004–1033 (2015).

Figure 1 (a) Resistance decreases three orders of magnitude during filament formation when bridging is complete at point X. A schematic of the cell is provided in the inset. and (b) Reversible switching between a high resistance state and a low resistance state by cyclic voltammetry with a Pt/AgI/Ag cell.

Figure 1
Redox Stability of La0.6Sr0.4Fe0.9Sc0.1O3-Δ for a Solid Oxide Cell Interconnector
Authors: Kim Sun-Dong , Kwak Minjoon , Choi Hyun-Jong , Kim Tae Woo , Seo Doo-Won , Woo Sang-Kuk 
Published: February 2020

A ceramic interconnector of a solid oxide cell (SOC) should require high phase stability and conductivity in a redox environment. Due to these limitations, only a few materials were found to meet the usage requirement as SOC interconnector. Under various synthetic conditions, La0.6Sr0.4Fe1-xScxO3-δ (LSFSc) was synthesized for the purpose of introducing a redox stable and electrically conductive ceramic interconnector. The crystalline phases of LSFSc are stable when the solution pH is low (pH=2), and the calcination temperature is sufficiently high (T=1200ºC). From the XPS analysis, it is accepted that incorporation of Sc in the B site of La0.6Sr0.4FeScO3-δ lattice further stabilizes its structural stability under reducing conditions. When the Sc concentration exceeds 10 mol%, phase stability of La0.6Sr0.4Fe1-xScxO3-δ was obtained. Figure 1 shows the ASR variations of ceramic interconnectors based on LaFeO3 doped at A-site with Sr and B-site with Sc in various redox environments. The electrical conductivity of La0.8Sr0.2FeO3-δ is remarkably low at both oxidation and reduction atmospheres due to the high area specific resistance. However, the ASR of La0.6Sr0.4FeO3-δ is less than half of La0.8Sr0.2FeO3-δ when exposed to air at one side and is exposed to H2 on the opposite side. This is one of the main reasons why we selected the composition as the basic crystal structure. However, La0.6Sr0.4FeO3-δ shows big augment due to the decomposition at reduction atmosphere. Moreover, the instability against high relative humidity (RH) is the main downside of La0.6Sr0.4FeO3-δ. For these reasons, it is difficult to employ La0.6Sr0.4FeO3-δ
as an interconnector material. Among the proposed materials, La0.6Sr0.4Fe0.9Sc0.1O3-δ exhibited the most desirable performances at the various gas conditions for 1000 h. Therefore, La0.6Sr0.4Fe0.9Sc0.1O3-δ is considered to be the most stable composition for redox stable and electrically conductive ceramic interconnectors for solid oxide cells.
Figure 1. The ASR variations of the La0.6Sr0.4Fe1-xScxO3-δ specimen depending on gas atmosphere and operation time.

Figure 1
Development of High Performance Metal-Supported Solid Oxide Electrolysis Cells
Authors: Wang Ruofan , Dogdibegovic Emir , Lau Grace , Tucker Michael C 
Published: February 2020

Hydrogen as an energy carrier has the highest energy/weight ratio, and therefore it has been advocated as the desired fuel for automotive power, auxiliary power, stationary power generation, and also as an energy storage medium. Among various hydrogen generating methods, high temperature electrolysis (HTE) of water using solid oxide electrolysis cells (SOECs) has attracted substantial attention over the last decade due to its high efficiency of conversion and low energy consumption.
To date, extensive effort has been devoted to the development of SOECs and promising results have been shown.1,2 However, while most of SOECs are based on an anode-supported cell (ASC) structure, only limited research on metal-supported SOECs is reported.3,4 Compared with conventional ASC type SOECs, metal-supported solid oxide electrolysis cells (MS-SOECs) have unique advantages due to low cost of fabrication, high mechanical strength, good redox stability, and excellent thermal cycling resistance.5,6 Because of these characteristics, MS-SOECs are considered as a promising solution for intermittent and mobile electrolysis applications.
In this work, symmetric-structure MS-SOECs with stabilized zirconia electrolyte are developed at LBNL. Nanostructured cathode and anode are fabricated by infiltrating catalysts on both steam and oxygen electrodes. The cells are tested in the temperature range of 650 to 800 ◦C, with steam content between 3-75 vol%. Our MS-SOECs show the highest performance for the cells with zirconia-based electrolyte (Figure 1), to the best of our knowledge. At 1.3 V (thermoneutral voltage) and 50 vol% steam content, the measured current densities were 4.8 A/cm2 at 800 ◦C, 3.1 A/cm2 at 750 ◦C, 2.0 A/cm2 at 700 ◦C, and 1.2 A/cm2 at 650 ◦C. This performance was achieved by optimizing the catalyst chemistry, catalyst arrangement, and infiltration process. In order to study the effects of the cell fabrication process, the electrochemical performance at various steam contents and overpotentials is analyzed, and the corresponding microstructures are examined. The high cell performance shows a great potential of MS-SOEC technology, and the insight from these experiments will provide guidance for further research and development.

1S.D. Ebbesen, S. H. Jensen, A. Hauch, and M. B. Mogensen, Chem. Rev., 114(21), 10697-10734 (2014).

2M. A. Laguna-Bercero, J. Power Sources, 203, 4-16 (2012).

3T. Chen, Y. Zhou, M. Liu, C. Yuan, X. Ye, Z. Zhan, and S. Wang, Electrochem. Commun., 54, 23-27 (2015).

4G. Schiller, A. Ansar, M. Lang, and O. Patz, J. Appl. Electrochem., 39(2), 293-301 (2009).

5M. C. Tucker, J. Power Sources, 195(15), 4570-4582 (2010).

6M. C. Tucker, Energy Technol., 5(12), 2175-2181 (2017).

Figure 1. Performance of a metal-supported solid oxide electrolysis cell (a) at 700 ◦C with 3%, 25%, 50% and 75% steam contents in the cathode, and (b) with 50% steam content in the cathode at 650, 700, 750 and 800 ◦C.

Figure 1
Anode Configuration of Li Metal for Lithium Sulfide Full Cell for High Energy Li-S Battery
Authors: Jung Yongjo , Kang Byoungwoo 
Published: February 2020

Since Li-ion batteries (LIBs) have been commercialized in the early 1990s, LIBs have become popular power sources for portable electronics due to their high gravimetric and volumetric energy density. Recently, the use of Li-ion batteries has been extended to large scale applications such as electric vehicles (EVs) and energy storage systems. For powering electrical vehicles, LIBs require high gravimetric and volumetric energy density, superior safety, and low cost. To meet these requirements in LIBs, there are several approaches. Among them, the use of S as a cathode material can be a very promising approach because sulfur can achieve 4 ~ 5 times higher energy density than conventional cathode materials such as LiCoO2 and is abundant and then cheap. However, the use of S needs the source of Li in a cell such as Li-metal or lithiated materials as an anode material. For example, the use of Li metal in Li-S cell is not trivial because of not only serieous safety issues origianted from the dendritic growth of Li but also poor couloumbic efficiency that can require excess amount of Li metal. The excess amount of Li metal under a limited cell volume needs additional sapce for Li metal leading to poor volumetric energy density. This requirement can make a limited utilization of Li-S.
As an alternative approach, Li2S can be considered as a cathode material for Li-S cell. Li2S as a cathode can achieve a little lower energy density than S but still higher than the conventional electrode materials. Moreover, the use of Li2S can extend the choice of anode materials from a graphite to a silicon to Li metal without any limitations because large amount of available lithium ions can be provided from Li2S. When Li metal as a anode material in the same volume of the Li2S cell can be used, the required space for Li metal in the Li2S cell will be decreased compared to Li-S cell because of additional Li can be provided from Li2S. Less required space for Li metal in the Li2S cell implies that additional Li2S in the saved space can be loaded and then volumetric energy density can be increased.
In this talk, we will discuss the use of Li metal as an anode material in Li2S cell and the factors affecting the nucleation and growth of Li metal on the electrode. Furthermore, we will talk about electrochemical performances of Li2S full cell at different conditions of Li metal.
A Strategy to Solve the Problem of Initial Charge Irreversibility in P2-Type Layered Cathode Materials for Sodium-Ion Battery
Authors: Kim Seong In , Park Geun-gyung , Lee Da-Yeon , Eom Ji-Yong 
Published: February 2020

Na-ion batteries are currently the focus of significant research activity due to the relative abundance of sodium and its consequent cost advantages. Thus, enormous efforts have been made to improve the electrochemical performance of SIBs through the development of novel cathode materials.
According to the previous literatures, P2-type layered cathode materials for SIBs have suffered from their low initial coulombic efficiency, which inevitably requires the pre-sodiation of carbon anode materials under full cell systems. In this regard, we focused on how to increase their initial charge capacity with sacrificial salts in the level of electrode fabrication. Thus, in the present study, we suggest new electrode fabrication process with sacrificial salts to reduce the high initial irreversible.
Layered Li-Rich Oxide Cathode with High Rate Capability By Reductive Treatment
Authors: Jung Dae Soo 
Published: February 2020

Layered Li-rich oxide cathode materials (denoted as OLO), such as Li1+xMn1-x-y-zNiyCozO2 (x > 0), have attracted recent research interest because these OLO materials offer high capacity performance (> 250 mAh g–1). However, it is still difficult to use these materials in commercial cathodes because their rate capability and capacity decrease with repetitive cycle life as a result of low electrical conductivity and phase transformations. Accordingly, there have been many studies focusing on structure stabilization and enhancement of their electrical conductivity, such as through substitution with Mg, Zn, Mo and Cr ions and surface coating with Al2O3, TiO2 and Li4Ti5O12. We previously reported on the stabilization of these structures and enhancing the electrochemical performance of Li-rich cathode materials via substitution and coating. There have also been recent attempts to find new approaches for surface modification such as through the use of heterostructures. S. Lee et al. reported spinel cathode material coating on layered cathode materials, which enhanced their electrochemical performance due to the spinel structure which functions as a conductive agent and prevents side reactions. J. Cho et al. also reported heterostructured cathode materials such as spinel-layered core-shell materials and Ni-rich/Li-rich core-shell materials. Y-K. Sun et al. demonstrated a concentration-gradient shell (CGS) cathode material, featuring different concentrations of transition metals (Ni, Co and Mn) at different layers in the material. While these studies showed outstanding enhancement for stabilization of structure and electrical conductivity with good electrochemical performances, they all required complex syntheses to realize their heterostructured cathode materials.
Here, we report a facile approach to realize surface modification of the OLO cathode materials with heterostructures; our approach only includes gas change for conventional synthesis without additional surface modification steps. We obtained Li1.167Ni0.18Mn0.548Co0.105O2, layered Li-rich oxide cathode material with enhanced electrochemical performance by reductive treatment with Ar gas.

Figure 1
Multi-Redox Molecule for High-Energy Redox Flow Batteries
Authors: Kwon Giyun , Lee Sechan , Hwang Jinyeon , Shim Hyun-Soo , Lee Buyngju , Lee Myeong Hwan , Ko Youngmin , Jung Sung-Kyun , Ku Kyojin , Hong Jihyun , Kang Kisuk 
Published: February 2020

RFBs, which use soluble redox species dissolved in electrolytes, show great promise for large-scale energy storage systems (ESSs) because of their scalability, cost-effectiveness, and design flexibility that can decouple power and energy for diverse purposes; however, their low energy density has limited their widespread application. Most conventional ways to increase the energy density to date have relied on either exploiting high-concentration electrolytes that contain large amounts of redox materials per volume or developing redox materials with higher solubility. Although this approach of exploiting high-concentration electrolytes is simple and effective, it results in unfavorable trade-offs, including increased electrolyte viscosity and high cell resistance, and often leads to the precipitation of salts, which causes the failure of the system. Furthermore, non-aqueous RFBs can be more vulnerable to these trade-offs because of the intrinsically lower ionic conductivity of non-aqueous electrolytes compared with that of their aqueous counterparts, which typically results in inferior power capability of the system. Here, we demonstrate that the use of multi-electron molecules as redox materials can offer an alternative route to overcome these issues and achieve high-energy-density RFBs. Unlike doubling the electrolyte concentration, for instance, which would easily result in the solubility limit being exceeded or significant reduction of the kinetics, the utilization of the double-redox activity from a single-redox material would approximately double the energy density without negatively affecting the electrolyte properties. Nevertheless, the use of a second-electron redox reaction in most redox-active materials in RFBs has often been shown to be irreversible or to promote severe degradation because of the poor chemical stability of the redox materials at highly oxidized states in the solution.
In this study, we demonstrate, for the first time, an all organic flow system using a multi-electron redox-active organic material with the superior chemical stability, which is a phenazine derivative. In addition, an analysis of the electrochemical kinetic properties of redox couple on both diffusion- and charge transfer-controlled kinetic is conducted through rotating disk electrode test; The redox couple displays outstanding kinetic characteristics. Moreover, the redox couple presents the highest theoretical and practical energy density among reported redox couples for both aqueous and non-aqueous RFB at the same concentration. The redox mechanism and the chemical stability of redox couple are investigated through raman spectroscopy and density functional theory calculations. These findings on this multi-electron redox material provide a potential new pathway for the design of high-energy-density RFBs and practically feasible ESSs.
Development of High Capacity Metal-Ligand Electrolytes for Grid-Scale Non-Aqueous Redox Flow Battery
Authors: Maurya Sandip , Chu Terry , Park Eun Joo , Kim Yu Seung , Smythe Nathan , Gordon John , Davis Benjamin L , Mukundan Rangachary 
Published: February 2020

Redox flow batteries (RFBs) are emerging as the preferred choice for Mega-watt scale energy storage for the future grids in large part to the decoupled energy/power outputs from the storage system [1]. However, narrow electrochemical stability window of water limits the operating voltage of aqueous flow batteries to < 1.6 V and poses an obstacle to achieving high capacity aqueous RFBs. A higher capacity (energy density) can be obtained if water is replaced with organic solvents such as acetonitrile processing a broader electrochemical stability window (>5 V). While organic solvents increase the cost per kilowatt-hour of the electrolyte this can be offset by the greater energy storage capacity of the RFBs [2]. This tradeoff can be beneficial if less-expensive metal-ligand redox couples are used in non-aqueous RFBs, especially those based on Fe on both the anolyte and catholyte [3]. The other significant cost factor of RFBs is expensive perfluorinated Nafion® membranes. Therefore, the combination of less-expensive redox couples and hydrocarbon membranes could lead to the DOE long term target of 100 USD per kWh for RFBs.
To achieve these strict economic targets, we have combined the expertise of inorganic synthesis and fuel cell capabilities at the Los Alamos National Laboratory’s towards non-aqueous flow battery development. We are systematically studying the structure-property relationship of Iron and Nickel-containing inorganic redox-active couples as anolyte and catholyte in RFBs. Design aspects of these redox couples and electrochemical characterization will be discussed in this presentation. Besides, results will be presented on specifically tailored anion exchange membrane with high compatibility with organic solvents and the active redox couples. In addition to the component work, results of flow battery testing using these novel membranes and electrolytes will be presented. A voltage window >3 V has been achieved in preliminary results using the Ni and Fe systems. The reversibility of these redox couples and their potential for long-term operation in RFBs will be discussed.

Acknowledgement

This work is supported by Laboratory Directed Research & Development, Los Alamos National Laboratory.

References:

[1] S.H. Shin, S.H. Yun, S.H. Moon, RSC Advances, 3 (2013) 9095-9116.
[2] R.M. Darling, K.G. Gallagher, J.A. Kowalski, S. Ha, F.R. Brushett, Energy & Environmental Science, 7 (2014) 3459-3477.
[3] J. Friedl, M.A. Lebedeva, K. Porfyrakis, U. Stimming, T.W. Chamberlain, Journal of the American Chemical Society, 140 (2018) 401-405.
Design of Stoichiometric Layered Potassium Transition Metal Oxide for K-Ion Batteries
Authors: Kim Haegyeom , Seo Dong-Hwa , Urban Alexander , Lee Jinhyuk , Kwon Deok-Hwang , Bo Shou-Hang , Shi Tan , Papp Joseph K , McCloskey Bryan D. , Ceder Gerbrand 
Published: February 2020

The layered transition metal oxides (TMOs) which have been investigated as cathode materials for K-ion batteries (KIBs) have so far exhibited moderate specific capacity and rate capability. [1-6] However, all the layered K-TMOs reported to date are K-deficient phases (x ≤ 0.7 in K
x
TMO2),[1-6] which limits their use in practical rocking-chair batteries because a pre-potassiation process of the electrodes would be required to insert enough K in the cells. In this respect, it is important to understand the factors that destabilize (or stabilize) the layered structure of K
x
TMO2 (x = 1) and then design a stoichiometric K
x
TMO2 (x = 1) cathode material.
In this work, we find that the strong electrostatic repulsion between K ions due to the short K+-K+ distance destabilizes the layered structure in a stoichiometric composition of KTMO2. However, a stoichiometric KCrO2 is thermodynamically stable in the layered structure despite short K+-K+ distance unlike other KTMO2 compounds that form non-layered structures. The unique stability of layered KCrO2 is attributable to the unusual ligand field preference of Cr3+ in octahedral sites that can compensate for the energy penalty from the short K+-K+ distance. Therefore, we develop the stoichiometric layered KCrO2 cathode material for KIBs and investigate its K-storage properties. In K-half cells, the KCrO2 cathode delivers a reversible specific capacity of ~90 mAh/g with an average voltage of ~2.73 V (vs. K/K+). In-situ diffraction and electrochemical characterization further demonstrate multiple phase transitions via reversible topotatic reactions occurring as the K content changes.

References

Vaalma, C., et al. Non-aqueous K-ion battery based on layered K0.3MnO2 and hard carbon/carbon black. J. Electrochem. Soc. 163, A1295 (2016)

Kim, H. et al. K-ion batteries based on a P2-type K0.6CoO2 cathode. Adv. Energy Mater. 7, 1700098 (2017)

Hironaka Y. et al. P2- and P3-KxCoO2 as an electrochemical potassium intercalation host. Chem. Commun. 53, 3693 (2017)

Kim, H. et al. Investigation of potassium storage in layered P3-type K0.5MnO2 cathode. Adv. Mater. 29, 1702480 (2017)

Wang, X. et al. Earth Abundant Fe/Mn-based layered oxide interconnected nanowires for advanced K-ion full batteries. Nano Lett. 17, 544 (2017)

Liu, C. et al. K0.67Ni0.17C0.17Mn0.66O2: A cathode material for potassium-ion battery. Electrochem. Commun. 82, 150 (2017)