bluuebunny/crossref_metadata_2025 huggingface dataset:
Compositional Dependence of Mössbauer Spectra for Mechanically Milled (Fe1-xAlx)2O3
Authors: Nakaishi Hayato , Takai Shigeomi , Yabutsuka Takeshi , Yao Takeshi , Kitao Shinji , Seto Makoto
Published: February 2020

Introduction

Although α-Fe2O3 is promising anode material of LIB for excellent theoretical capacity as 1007 mAhg-1, it shows the severe cycle deterioration due to conversion reaction during the charge-discharge process. We have considered that the formation of Fe2O3-Al2O3 solid solution allows the Fe ions to react reversibly around the original site in the corundum-type structure. Although both α-Fe2O3 and α-Al2O3 have the corundum-type structure, solid solution ranges are restricted within 10% from the both end components [1]. In recent years, we have successfully obtained the Fe2O3-Al2O3 solid solution for all the compositional range through the mechanochemical synthesis method. It was also found that the obtained solid solution shows good cycle characteristics as an anode material of LIB [2]. Nevertheless, this solid solution has just been newly found and any magnetic property has not been clarified yet. In this study, we have carried out the Mössbauer measurement to discuss the magnetic properties of Fe2O3-Al2O3 solid solution.

Experimental

The solid solutions of (Fe2O3)1-x(Al2O3)x (x = 0, 0.1, 0.25, 0.33, 0.50 and 0.67) were prepared by mechanical alloying method. About 0.5 g of the stoichiometric mixtures of γ-Fe2O3 and γ-Al2O3 were put into a silicon nitride milling vessel with 20 ml in volume accompanied by 10 silicon nitride balls with 10 mm in diameter without any solvent. A planetary ball milling machine has been operated with the rotation speed of 800 rpm for 240 min. Mössbauer measurement was performed on the obtained samples of (Fe1-xAlx)2O3 (x = 0, 0.1, 0.25, 0.33 ,0.50 and 0.67) at room temperature. 57Co was used as a gamma ray source for Mössbauer measurement.

Results and Discussions

Fig. 1 shows the Mössbauer spectra of (Fe1-xAlx)2O3 measured at room temperature for x = 0, 0.1, 0.25, 0.33, 0.5 and 0.67. For the Fe2O3 (x = 0) obtained by milling, the sextet spectrum was observed. This would correspond to weak ferromagnetism appearing from a cant structure, in which the spin of Fe is slightly inclined from 90° to the c-axis direction. This spectrum is essentially similar to the α-Fe2O3 reagent without milling. The Mössbauer spectra gradually changed into doublet with increasing the concentration of aluminum x and the change is almost completed to the x = 0.5. Fourier transform of the EXAFS signal shows that |χ| peak value around 1.5 Å corresponding to Fe-O distance did not vary significantly, while that around 2.5 Å for Fe-Fe distance decrease with x. Dilution of Fe3+ with Al3+ would result in the change in spin interaction, or (Fe1-xAlx)2O3 changes from weak ferromagnetism to the paramagnetic state by reducing spin interaction.

References

[1] A. Muan, C.L. Gee, J. Am. Ceram. Soc., 39 207-214 (1956).

[2] S. Takai, E. Sawada, J. Harada, S. Park, M. Oda, S. Esaki, M. Nishijima, T. Yoshie, T. Yabutsuka, T. Yao, Solid State Ionics, 313 1-6 (2017).

Figure 1
Removal Mechanism of Concrete Deterioration Factor Using Expanded-Cafe Layered Double Hydroxides
Authors: Choa Yong-Ho , Park Ji Young , Yoo Su-been , Cho Hong-Baek
Published: February 2020

The main deterioration factor ions cause corrosion and expansion of concrete with chloride, sulfate and carbonate ions. It is a major problem in field of construction resulting in a huge economic loss, also inducing serious safety disasters frequently. Layered double hydroxides (LDHs) has been successfully used for various purposes owing to its anion-exchange property. Among them, the calcium-based LDHs can improve immobilizing the migration of chloride, sulfate and carbonate ions in cement-based materials. In this study, we will focus on the description of the structural transformation of CaFe LDHs and anion exchange mechanism of immobilizing deterioration factors. The formation of expanded-CaFe LDHs occurred under the calcination conditions (400℃, 550℃ and 700℃, respectively). The characterizations of the expanded-CaFe-LDH after the adsorption was investigated using ion chromatography, x-ray fluorescence, fourier transform infrared spectroscopy, x-ray diffraction, field emission scanning electron microscopy and transmission electron microscope. The adsorption mechanism of ions by the CaFe LDHs related with structure property variation that happens during calcination process.
Investigation of Chemical Corrosion and Electrochemical Charge/Discharge Behavior of Preferentially Faceted Zinc Particles for Battery Applications
Authors: Faegh Ehsan , Ng Benjamin , Hayman Dillon , Cook Kaitlyn , Mustain William E.
Published: February 2020

Zinc-based batteries have been reliable energy storage device in primary batteries for decades due to their intrinsic safety, resulting from the use of aqueous and non-flammable electrolytes, low cost and high natural abundance of Zinc. For many years, Zinc-based electrodes have been sought as a promising option for secondary batteries, though the cycling performance of Zinc electrodes is still limited by shape change and dendrite formation – especially in alkaline electrolytes.

To address this issue, shape-controlled electrolytic Zinc particles were synthesized. Using scanning electron microscopy (SEM), it was observed that these micron-sized Zinc particles possess preferentially-faceted, hexagonal shape, which allowed us to explore the morphological variation of synthesized well-faceted Zinc particles during corrosion and charge/discharge in alkaline media. It was found that both chemical corrosion and electrochemical discharge of single Zinc particle happens from the basal plane in alkaline media and step-edge planes were more corrosion resistant for an individual Zinc particle. X-ray diffraction patterns showed that by heat-treatment of electrodeposited Zinc particles the degree of crystallinity, and thus, the number step-edge planes were increased which resulted in creation of “terraced” Zinc structures. Higher capacities were achieved during discharge using “terraced” Zinc particles. Such highly faceted particles also led to significantly improved cyclability compared to traditional Zinc structures.
Commercial 18650 Lithium-Ion Cells for High-Energy, High-Power, and Radiation Applications
Authors: Krause Frederick C. , Bugga Ratnakumar V , Billings Keith J. , Ruiz John Paul , Brandon Erik J.
Published: February 2020

Interest in commercial off-the-shelf (COTS) cylindrical lithium-ion cells for NASA missions has increased in recent years due to their increasing performance and demonstrated reliability. There is particular interest in cells in the 18650 format, due to their wide availability from well-established vendors. Multiple commercial products are available, offering greater than 250 Wh∙kg-1 and/or 3 kW∙kg-1 at the cell level. High specific energy has made small cells competitive with heritage large-format prismatic lithium-ion cells for spacecraft power systems; high power capability could offer an alternative to thermal batteries in some applications.

The descent stage of the Europa Lander mission concept was baselined with a combination of a high specific energy lithium primary battery and thermal batteries to provide the required energy content and high-power pulse capability during deorbiting and landing. High specific energy and power lithium-ion cells could fulfill the functions of both of these, while also allowing for cell pre-screening and testing, unlike primary or thermal batteries. In support of this concept and future NASA missions, we have performed extensive evaluation of the components and performance characteristics of a number of COTS 18650 Li-ion cells, including destructive physical analysis, cycle life, rate capability, and ionizing radiation tolerance.

ACKNOWLEDGEMENT

The work described herein was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under contract with the National Aeronautics and Space Administration. Support from the Europa Lander Mission concept and the NASA Engineering Safety Commission is gratefully acknowledged. Pre-Decisional Information – For Planning and Discussion Purposes Only.
Tailoring of Liquid Electrolytes for Room-Temperature Fluoride Shuttle Batteries
Authors: Kawasaki Mitsuo , Morigaki Ken-ichi , Kano Gentaro , Minato Taketoshi , Abe Takeshi , Ogumi Zempachi
Published: February 2020

Fluoride ion shuttle batteries (FSBs), alternatively referred to as fluoride ion batteries (FIBs), are anion-based rechargeable batteries with fluoride (F-) ions as charge transporting and redox active species, and potentially offer a high electrochemical energy storage capability that overwhelms those of the state-of-the-art lithium ion batteries. The theoretical gravitational capacities for some typical metal/fluoride combinations, e.g., Ag/AgF, Cu/CuF2, Bi/BiF3, and Al/AlF3, amount to 249, 844, 385, and 2980 mAh/g, respectively.

Nevertheless, despite some considerable efforts in the past decade or so, FSBs are still far from practical, because of a number of technical limitations to overcome no matter which type of FSB, all-solid type or liquid type, is of major interest. In particular, liquid-electrolyte based FSBs suitable for room-temperature cell operation require high-quality fluoride ion transporting electrolytes ensuring both high enough reactivity of the fluoride ions with the active material of interest and sufficient electrochemical stability of the electrolyte as a whole. Unfortunately, normally none of alkali fluorides are soluble in whatever high boiling battery-oriented organic solvents. One way to solve this problem has been to use organic fluoride salts. Another sophisticated way out has been to utilize a so-called anion acceptor (AA) that makes alkali fluorides substantially soluble even in low polarity solvents such as the glyme series. AA can also play another important role to facilitate the dissolution and re-deposition of the active materials into and from the electrolyte, which are unique pathways available in liquid-electrolyte based FSBs. However, the overall cell performances so far reported in the literature are still limited in capacity and cyclability.

In this paper, we introduce lactone-based liquid electrolytes tailored for room-temperature FSBs, where either CsF or KF is dissociated without the help of any special addenda to offer strong electrolytes. Although the maximum fluoride ion concentration achieved by this method is around 0.05 M, it affords the ionic conductivity more than 0.5 mS/cm and the fluoride ions transported between the cathode and anode exhibit high reactivity with various metals to sustain reversible redox reactions to and from their fluoride counterparts. We have also achieved some successful battery operations using practical polymer-composite electrodes. Together with a superior cyclability, the thus tailored liquid fluoride electrolytes offer the opportunity to make a big step forward to establish the room-temperature rechargeable FSBs.

Acknowledgement.

This work was supported by the Research and Development Initiative for Scientific Innovation of New Generation Battery 2 (RISING2), financially supported by New Energy and Industrial Technology Development Organization (NEDO).
Crosslinked Quaternized Poly(arylene ether benzonitrile) Membranes for Vanadium Redox Flow Batteries
Authors: Park Eun Joo , Maurya Sandip , Kim Yu Seung , Mukundan Rangachary
Published: February 2020

Development of membrane separators is important to decrease cross-over and enhance efficiency and durability of non-aqueous redox flow batteries. Desired properties of the membranes for the application include (a) selective ion permeability, (b) high conductivity and (c) good chemical and mechanical stability in operating conditions of redox flow batteries. Our approach to satisfy these criteria is synthesizing cation-functionalized nitrile-containing polyaromatics, poly(arylene ether benzonitrile)s, for membrane separators. While these membranes exhibited good performances in an aqueous vanadium redox flow battery (VRFB) system, in non-aqueous systems where acetonitrile is used as electrolytes, the membranes could not be utilized due to their limited mechanical strength. To endure the harsh operating condition of non-aqueous VRFB, we developed crosslinked quaternized poly(arylene ether benzonitrile)s. A series of high molecular weight polymers with tertiary amine groups were synthesized via aromatic nucleophilic substitution polycondensation followed by the simultaneous quaternization and crosslinking reactions. In this presentation we will discuss the membrane properties and the electrochemical performance of these membranes in terms of cycling efficiencies, vanadium permeation and membrane durability. The applicability of crosslinked quaternized poly(arylene ether benzonitrile) membranes in non-aqueous VRFB systems will be summarized.

Acknowledgement

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

The submission of the manuscript is approved by LANL (LA-UR-19-23557)
Controlling Electrochemical Lithium Deposition and Sulfur Reduction Mechanism through Liquid Electrolytes
Authors: Lin Tzu-Yun , Wang Chun-Yao , Wu Heng-Liang
Published: February 2020

Lithium metal anode has been regarded as the "Holy Grail" of next-generation battery technologies. In order to stabilize the electrodeposited Li metal for safe and high energy batteries, highly concentrated electrolytes (solvate electrolytes) have been proposed to suppress the formation of Li dendritic structure and polysulfide dissolution in lithium-sulfur (Li-S) batteries. (1-5) In this talk, we use in situ transmission X-ray microscopy (TXM) to study the effect of solvate electrolyte on Li plating/stripping process. In situ TXM images show that electrodeposited Li particles with uniform density are formed in solvate electrolyte during initial plating process. The effect of solvate electrolyte on the mechanism of Li growth is studied in detail. Additionally, in situ spectroscopy including Raman and X-ray spectroscopy (X-ray diffraction and X-ray absorption spectroscopy) are used to investigate sulfur reaction mechanism and the interaction between polysulfide and solvate electrolyte. We found that the sulfur species formed in the solvate electrolyte are different from the sulfur species formed in conventional DOL/DME electrolyte. These results suggest that solvate electrolyte changes both polysulfide solubility and sulfur reaction mechanism. We next propose different solvate electrolytes with low polysulfide solubility and high stability toward Li metal to enhance the capacity retention of Li-S batteries.

References:

[1] L. Suo et al., Nat. Commun. 2013, 4, 1481.

[2] K. Dokko et al., J. Electrochem. Soc. 2013, 160, A1304.

[3] M. Cuisinier et al., Energy Environ. Sci., 2014, 7, 2697.

[4] Y. Yamada et al., J. Electrochem. Soc. 2015, 162 (14), A2406.

[5] L. Cheng et al., ACS Energy Lett. 2016, 1, 503.
Faster High Throughput Electrochemical Testing for Batteries
Authors: Breedon Michael , Collis Gavin , Best Adam Samuel
Published: February 2020

The Fast Autonomous Screening Test for Electrochemical Response (FASTERTM), is a high throughput electrochemical screening technique developed at CSIRO for rapid assessment of electrochemically active materials (see Figures 1 &2). This system leverages robotic actuation, dispensing and mixing of materials into individually addressable electrochemical test cells, which are chemically and physically isolated from each other. In this manner, we seek to screen and identify unique battery electrolyte formulations with superior electrochemical and physical properties. Further, conventional battery electrode materials can be utilized as the working electrode, with electrolyte additives introduced into test cells to elucidate their effect on the electrochemical system being tested. We will report upon the development of the latest iteration of this technology as embodied in Figure 1, which facilitates the rapid preparation and screening of a multitude of electrolyte combinations for the development of next generation battery systems.

Figure 1
Lithium Air Batteries; Challenges and Opportunities
Authors: Salehi-Khojin Amin
Published: February 2020

Metal-air batteries are greatly considered as an advanced solution for future energy requirements due to their remarkably high-energy density. For instance, the theoretical energy density of Li-air batteries (3500 Wh/kg) is about one order of magnitude higher than that of commonly used Li-ion batteries (~400 Wh/kg). In terms of cruising-speed range on passenger cars, the performance of Li-air batteries is comparable to that of internal combustion engines. Thus far, the research on the Li-air battery has been limited to the short life study of lithium oxygen (Li-O2) batteries where the O2, as the oxidant in Li–air cells, needs to be extracted from air to eliminate the side reactions of N2, CO2 and water with lithium or cell components. Hence although oxygen is an abundant and freely available element, its use will require on-site purification, which is energetically expensive and reduce the energy density of practical cells.

In this presentation, I will overview our recently developed Li-air battery system that operates with the actual air components (N2, O2, CO2 and H2O) with a superior cycle life and energy efficiency that can operate up to 700 continuous cycles with the capacity of 500 mAh/g [1]. This Li-air battery benefits from a novel protected Li-anode, an air cathode based on MoS2 catalyst and a mixture electrolyte including DMSO and EMIM-BF4 ionic liquid. Various characterizations including differential electrochemical mass spectroscopy (DEMS), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy on the cathode reveal that the only discharge product in our system is lithium peroxide (Li2O2) with no evidence of side products such as lithium hydroxide (LiOH) and lithium carbonate (Li2CO3). Nuclear magnetic resonance (NMR) results also show the stability of the electrolyte. Density functional theory calculations suggest that the combination of MoS2 cathode and ionic liquid in the electrolyte provides a kinetically favorable system for Li2O2 formation. The study of this Li-air system is a key step toward the development of next generation lithium batteries with higher energy density and cycle life for transportation and grid scale applications.

[1] A. Salehi-Khojin et al., A lithium–oxygen battery with a long cycle life in an air-like atmosphere, Nature, 555 (7697), 502, 2018.
A Novel Eutectic Aluminum-Silicon Alloy Doped Li7La3Zr2O12 Garnet-Type Solid Electrolytes for Solid State Lithium Ion Batteries
Authors: Anand Rohit , Pathak Anil Daliprasad , Sahu Kisor Kumar
Published: February 2020

Lithium ion batteries are considered as a promising candidate for electric vehicles and other similar demanding applications. Electrolyte is one of the main components of a rechargeable battery and safety of a battery largely depends on it. Various types of liquid electrolytes were developed over time to enhance the performance of the battery. However, liquid electrolytes promote the growth and formation of lithium dendrites, which cause short circuit in the battery which eventually leads to fire hazard. Solid state electrolyte was found to be a better alternative, because it suppresses the growth and formation of the lithium dendrites between the electrodes. Garnet-type Li7La3Zr2O12 (LLZO) has been considered as a promising candidate for next-generation solid-state electrolyte in lithium batteries because it possesses high ionic conductivity, wider electrochemical and thermal stability window.

This is the first report of doping LLZO by eutectic Al-Si alloy. Al-Si alloy is added because Al is considered as a cubic phase stabilizer and Si helps in modifying the path of lithium ions in LLZO. Further, lithium based solid state batteries are fabricated by using lithium foil anode, LLZO based electrolyte and LiFePO4 cathode material. The doped Ai-Si LLZO solid electrolyte showed better electrochemical performance over the bare LLZO solid electrolyte. Thus, the Al-Si doped LLZO could be a candidate material for solid electrolyte for next generation all solid state lithium batteries.
Effect of Pressure on Sulfide Based All Solid-State Batteries
Authors: Doux Jean-Marie , Banerjee Abhik , Wang Xuefeng , Tan Darren Huan Shen , Wu Erik , Nguyen Han , Meng Shirley
Published: February 2020

All solid-state batteries (ASSBs) are predicted to be the next generation of lithium ion batteries with their wider operating temperature range, higher energy density, and improved safety compared to conventional liquid electrolyte-based batteries. For sulfide-based solid-state batteries, the most common form factor is the stacked pellet type cells consisting of the following layers: a cathode composite, a thick solid-electrolyte, and an anode, all of which are kept under pressure to ensure proper contact. Although this pressure is mandatory for battery operation, there have been no detailed studies of the actual effect of the stack pressure on battery performance nor any indication of an ideal applied load.

In this work, we have studied in detail the effect of varying the applied pressure at two stages: during cell fabrication and cell testing. Our results explain discrepancies for ionic conductivity values found in literature for sulfide-based solid-state electrolytes. This study suggests that the pressure used to fabricate the cell is a critical factor for cell performance and also that controlling the stack pressure is necessary to ensure reliable operation of sulfide-based solid-state batteries.
Electrochemical Oxidation Characteristics of Boron Doped Diamond Electrodes
Authors: Kim Tae-Gyu
Published: February 2020

BDD is a substance which is generated by doping Diborane (B2H6) in CH4 and H2, and then synthesized with thin diamond film. It has good corrosion resistance, is physically and chemically stable, has a wide potential window, low electrical conductivity, good heat impact resistance and optimal hardness, so it is highlighted among electrodes. PbO2, an electrode previously used for generating ozone water, presents environmental problems since the structure of the electrodes is changed and aged due to the strong acidity of the ozone generated when these electrodes are employed for a long time, so it is considered to have short longevity. Moreover, Pb a heavy metal component, is eluted, etc. In contrast, BDD has recently been highlighted as an electrode that can be used for next-generation ozone water generation to solve these problems. Boron-doped diamond electrodes have excellent hardness, excellent physical properties. Chemical stability, and durability. In addition, BDD has a wide potential window and low current density characteristics, so application attention is focused. This study evaluated the ozone-generating characteristics of BDD electrodes generated in accordance with the doping concentration of boron. The BDD generated was examined by field emission scanning electron microscopy and Raman spectroscopy, and its electric characteristics were determined by Hall measurements. The amount of ozone generated at the boron doping concentration was compared using an ozone generating kit.

Figure 1
Fundamental Understanding of Redox Characteristics of Defect-Rich Holey Graphene for Lithium Ion Energy Storage Devices
Authors: Jin Shikai , Lee Seung Woo
Published: February 2020

Graphene has received intensive research interest as a promising electrode material for energy storage applications because of its unique combination of properties including high intrinsic electrical conductivity, good mechanical flexibility, exceptional theoretical surface area and capacitance. The approaches to engineer graphene-based materials mostly involve functionalization, structural modification for the porous structure with abundant defective sites or incorporating other redox-active substances as the composite. Among various oxygen functional groups on graphene oxide, carbonyl group is regarded as the most active group to provide reversible redox reactions with Li ions.[1] The conservation of the redox-active carbonyl group during conventional chemical and thermal reduction processes of graphene oxide has so far shown only limited effect. Thus, the selective reduction process of oxygen functional groups on graphene oxide is a particularly promising strategy to enhance the charge storage performance on highly porous nanostructures. In this study, we prepared reduced holey graphene oxide with a combination of chemical etching and selective reduction processes, proposing a high performance cathode material for rechargeable lithium ion batteries. In addition, in order to further enhance the charge storage performance, a redox-active organic compound is introduced onto the holey graphene oxide structure.

References

T. Y. Liu, K. C. Kim, R. Kavian, S. S. Jang, S. W. Lee, Chem. Mater. 27, 3291-3298 (2015).
In-Situ Hydrogen-Induced Defects on the Single Layer CVD Growth Graphene
Authors: Ion-Ebrasu Daniela , Enache Adrian , Enache Stanica , Parvulescu Viorica , Carcadea Elena , Varlam Mihai
Published: February 2020

In this paper we present in-situ hydrogen-induced defects on the single layer CVD growth graphene sheets with reactive terminated edges and holes within the graphene matrix. The samples are obtained by low-pressure CVD graphene growth in hydrogendiluted methane [1]. In order to obtain graphene membranes with macroscopic selectivity towards proton transport, the hydrogen flow rate is adjusted so that it has an etching effect during the growth process [2,3]. Graphene sheets growth by CVD on copper is carried out at high temperature (~1025°C), in the large glass resistant furnace of the chemical vapor deposition system. Several parameters (gases and flows, temperature, pressure, reaction time) are adjusted. The defects and holes allow graphene layer further doping and functionalization in order to obtain protonic conductivity layers for hydrogen isotopes separation and applications. The quality and thickness uniformity of graphene is ascertained directly on the metal substrate, immediately after CVD growth, using optical microscopy. To get a good overview of the morphology of a graphene layers, such as pores distribution and defects, reactive terminated edges, and elements within the graphene matrix, the samples are studied by Field Emission Scanning Electron Microscopy (FESEM). Raman studies of the graphene is carried out in order to obtain precise information on the features of the graphene layers and the number of layers.

References:

Birong Luo, Enlai Gao, Dechao Geng, Huaping Wang, Zhiping Xu, and Gui Yu, Etching-Controlled Growth of Graphene by Chemical Vapor Deposition, Chem. Mater. 2017, 29, 1022−1027

Saheed Bukola, Ying Liang, Carol Korzeniewski, Joel Harris, and Stephen Creager, Selective Proton/Deuteron Transport through Nafion/Graphene/Nafion Sandwich Structures at High Current Density, J. Am. Chem. Soc. 2018, 140, 1743−1752.

Qiuju Zhang, Minggang Ju, Liang Chen, and Xiao Cheng Zeng, Differential Permeability of Proton Isotopes through Graphene and Graphene Analogue Monolayer, Phys. Chem. Lett. 2016, 7, 3395−3400.
Carbon Nanotube-Based Non-Precious Metal Electrocatalysts with High Performance and Durability
Authors: Nishida Jin , Yang Jun , Uchimura Shunsuke , Matsuda Junko , Nakashima Naotoshi
Published: February 2020

Development of non-precious metal electrocatalyst for fuel cells, water splitting and batteries with high performance, durablity,and scalability is a strong social demand for the next-generation eco-friendly energy society[1].

In this meeting, we summarize our recent studies on i) seven different nanocarbons /iron phthalocyanine (II) hybrids with well-defined nanostructures that show excellent efficiency and durability for oxygen reduction reaction[2,3], iii)decorating unoxidized-carbon nanotubes with homogeneous spinel nanocrystals that show superior performance for oxygen evolution/reduction reactions[4].

References

[1] N. Nakashima (Editor), "Nanocarbons for Energy Conversion-Supramolecular Approach", Springer, 2018, pp. 1-564.

[2] J. Yang, J. Tao, T. Isomura, H. Yanagi, I. Moriguchi, N. Nakashima, Carbon, 2019, 145, 565-571.

[3] J. Yang, F. Toshimitsu, T. Fujigaya, N. Nakashima, J. Mater. Chem. A, 2017,5, 1184-1191

[4] J. Yang, T. Fujigaya, N. Nakashima,Sci. Rep., 2017, 7, art.no.45384.
(Invited) Evolution of Redox Couples in Li- and Mn-Rich Cathode Materials and Mitigation of Voltage Fade by Reducing Oxygen Release
Authors: Hu Enyuan , Yu Xiqian , Bi Xuanxuan , Lin Ruoqian , Lu Jun , Bak Seong-Min , Nam Kyung-Wan , Xin Huolin L. , Jaye Cherno , Fischer Daniel , Amine Khalil , Yang Xiao-Qing
Published: February 2020

Voltage fading is a major problem in battery applications for high-energy Lithium- and Manganese-rich (LMR) layered materials. Because of the complexity in the LMR structure, the voltage fade mechanism is not well understood. Here we conduct both in situ and ex situ studies on a typical LMR material (Li1.2Ni0.15Co0.1Mn0.55O2) during charge-discharge cycling, using multi-length-scale X-ray spectroscopic and 3D electron microscopic imaging techniques. Through probing from surface to bulk, from individual to the whole ensembles of particles, we show that the average valence states of each type of transition metal cations are continuously reduced, which is attributed to the oxygen release from LMR. Such reductions activate the new lower voltage Mn3+/Mn4+ and Co2+/Co3+ redox couples in addition to the original ones like Ni2+/Ni3+, Ni3+/Ni4+, and O2-/O-, directly leading to the voltage fade. We also show that the oxygen release causes microstructural defects such as the formation of large pores within particles which also contributes to the voltage fading. The surface coating and modifications are suggested to be effective in suppressing the voltage fade through reducing the oxygen release.
(Invited) Advanced Material Development for the Next Generation EV Batteries
Authors: Bang Sungrok
Published: February 2020

As battery technology advanced, batteries have had more price competitiveness, driving distances of over 300 miles, and fast charging speed. Therefore, Major research institutions predict that the market share of EV will reach to 25% of the sales volume of existing internal combustion engines in 2030. In this presentation, we will introduce R&D status and direction in LG Chem. on developing the advanced next generation batteries as an alternative to Li-ion battery for EV application.
(Keynote) Important and Less Important Challenges of Metal Sulfur Batteries
Authors: Dominko Robert
Published: February 2020

Metal (Li, Mg) sulfur batteries can be considered as important energy storage devices in the future due to abundance of sulfur and high theoretical gravimetric energy density. In the last decade different groups showed progress in the electrochemical stability during cycling and in the understanding of complicated conversion reactions connected with unpredictable equilibrium states of sulfur in different solvents. Vast of reports was connected with application of different types of host matrices for sulfur impregnation and recently also with additives which can adsorb polysulfides. Much less work has been performed on development of novel electrolytes, ion selective separators and on protection of the negative electrode.

Sulfur and polysulfides are soluble in the classical electrolytes based on glyme solvents and this future enables reduction of sulfur to metal sulfide and its reoxidation. But on the same time, in the liquid cells with high excess of electrolyte, soluble sulfur species diffuse/migrate to the negative electrode where can be further reduced and even deposited on the surface of the negative electrode.

Although sulfur conversion in Li-S and Mg-S batteries is very similar, their electrochemical stability is completely different what can be connected with passivation of the negative electrode. Recent progress in understanding of both systems and their electrochemical stability will be discussed in this presentation.

Acknowledgement: This work is supported by the HELiS project which receives funding from the European Union‘s Horizon 2020 research and innovation program under Grant Agreement No 666221. The financial support from the Slovenian Research Agency (research core funding No. P2-0393) is fully acknowledged.

Reference
s
:

[1] R. Dominko, A. Vizintin, G. Aquilanti, L. Stievano, M.J. Helen, A.R. Munnangi, M. Fichtner, I. Arcong, J. Electrochem. Soc., 2018,165, A5014-A5019.

[2] S. Drvarič Talian, S. Jeschke, A. Vizintin, K. Pirnat, I. Arčon, G. Aquilanti, P. Johansson, R. Dominko, Chem. Mater., 2017, 29, 10037–10044.

[3] A. Vizintin, M. Lozinšek, R. K. Chellappan, D. Foix, A. Krajnc, G. Mali, G. Drazic, B. Genorio, R. Dedryvère and R. Dominko, Chem. Mater., 2015, 27, 7070–7081.

[4] A. Robba, A. Vizintin, J. Bitenc, G. Mali, I. Arčon, M. Kavčič, M. Žitnik, K. Bučar, G. Aquilanti, C. Martineau-Corcos, A. Randon-Vitanova, R. Dominko, Chem. Mater.,2015, 29, 9555-9564.

[5] R. Dominko, M. U. M. Patel, V. Lapornik, A. Vizintin, M. Koželj, N. Novak Tušar, I. Arcon, L. Stievano, and G. Aquilanti, J. Phys. Chem. C, 2015, 119, 19001–19010.
(Keynote) Structural Factors for Designing High Performance Ni-Rich Layered Cathode Materials
Authors: Yoon Won-Sub
Published: February 2020

Higher-energy-density batteries require higher capacity in the electrode, which motivates the increase of Ni in the NCM system. Nevertheless, fundamental effects of Ni element in the three-component layered system have not been systematically studied. Therefore, to unravel the role of Ni as a major contributor to the structural and electrochemical properties of Ni-rich materials, Co-fixed LiNi0.5+xCo0.2Mn0.3-xO2 (x = 0, 0.1, and 0.2) layered materials were investigated. The results, on the basis of synchrotron-based characterization techniques, present a decreasing trend of Ni2+ content in Li layer with increasing total Ni contents. Moreover, it is discovered that the c
hex.-lattice parameter of layered system is not in close connection with the inter-slab thickness related to actual Li ion pathway. The inter-slab thickness increases with increasing Ni concentration even though the c
hex.-lattice parameter decreases. Furthermore, the lithium ion pathway is preserved in spite of the fact that the c-axis is collapsed at highly de-intercalated states. Also, a higher Ni content material shows better structural properties such as larger inter-slab thickness, lower cation disorder, and smoother phase transition, resulting in better electrochemical properties including higher Li diffusivity and lower overpotential when comparing materials with lower Ni content. More details will be discussed in the meeting.
(Plenary) High Energy Density Lithium Batteries Via in Situ solidification
Authors: Huang Jie , Li Wenjun , Yang Qi , Geng Zheng , Lu Jiaze , Qiu Jiliang , Xu Jieru , Zheng Jieyun , Yu Xiqian , Li Hong , Chen Liquan
Published: February 2020

One of the challenges for all solid lithium batteries is to keep low area specific resistance during cycling without external pressure. Many efforts have been paid. In this report, our strategy to develop high energy density lithium ion batteries and metallic lithium batteries with hybrid solid/liquid electrolyte or all solid electrolyte via in situsolidification is introduced. The problems of the hybrid system and possible solutions are discussed. By tuning the type of solvents, salts and additives, controlling the formation conditions, introducing prelithiation, coating inorganic solid electrolyte very thin layer on cathode, the cell can operate at wide temperature range with reasonable rate performance. Energy densities of the pouch cells are in the range of 210-500Wh/kg, mainly depending on the weight ratio of lithium in anode and the selection of the cathode. Some basic scientific problems in this design will be also addressed.
(Invited) Circular Economy and Sustainability of Battery Segment with Recycling of Strategic Metals
Authors: Farouk Tedjar
Published: February 2020

Energy issues and climate changes are now asking urgent solution and one of the solutions is large growing of renewable energy part in the consumption models. However, major part of renewable energy equipment’s contains strategic metals while they could be potential sources of negative environment impact when recycled with non-appropriate processes. Within this problematic we will present 2 segments related to Lithium ion and Ni-MH batteries.

Since its introduction 15 years before, lithium ion battery (LIB) become today the most largely adopted for portable electronic devices. Recently the new chemistry of both cathodes and anodes allow the LIB system to be among the best system candidate for in EV and HEV segment. However the composition of those batteries imposes a particular consideration of their end of life management due to the environment impact and valuable resource conservation for materials. Several processes were proposed for recycling LIB while in the meantime composition of li-ion batteries is strongly moving from lithium cobalt oxides / carbon portable segment to several kinds of cathodes materials, electrolytes and anodes materials. This means that we are in the need of new flexible processes. The sustainable way to recycle LIB must take account on next challenges:

Lowest energy consumption

CO2 emission (from organic solvents and carbon)

Fluorine control (from anion of lithium salts and PVDF).

Loss of valuable resources such as graphite lost as CO2, Mn and Li trapped into slag.

Nickel metal hydride batteries are also now more and more substituting the Ni-Cad system. Until now at industrial level the main efforts were devoted to recycling Nickel and the rare earths (RE) were generally lost in slag if metallurgical way is used.

The position of RE in critical metals classification imposes to consider the Ni-MH as high source of RE.

Geopolitical aspect as well as sustainability and availability for the main strategic metals of LIB and Ni-MH batteries will be presented and commented.

To achieve high recycling rate and low environment impact new approach will be presented.

The new process allows having precursors for producing new battery materials such as LCO, NMC, LFP and Graphite.

Acceptable capacity (mA/g) were obtained allowing Close The Loop.
(Invited) All Solid State Lithium Metal Batteries: Status, Prospects and Future
Authors: Zaghib Karim , Chisu Kim , Cho M , Guerfi A , Bouchard P , Mauger A , Julien C , Goodenough J , Armand M
Published: February 2020

Novel lithium metal polymer solid state batteries with nano CLiFePO4 , nano Li1.2V3O8 counter-electrodes (average particle size 200 nm) and NMC were studied for the first time by in situ SEM and impedance during cycling. The kinetics of Li-motion during cycling is analyzed self-consistently together with the electrochemical properties. We show that the cycling life of the nano Li1.2V3O8 is limited by the dissolution of the vanadium in the electrolyte, which explains the choice of nano C-LiFePO4 (1300 cycles at 100% DOD): with this olivine, no dissolution is observed. In combination with lithium metal, at high loading and with a stable SEI an ultrahigh energy density battery was thus newly developed in our laboratory. The electrochemical of new polymer with high voltage with NMC cathode material will show during this presentation.

The commercial use of lithium metal batteries was delayed because of dendrite formation on the surface of the lithium electrode, and the difficulty finding a suitable electrolyte that has both the mechanical strength and ionic conductivity required for solid electrolytes. Recently, strategies have developed to overcome these difficulties, so that these batteries are currently an option for different applications, including electric cars. In this work, we review these strategies, and discuss the different routes that are promising for progress in the near future. We will explain the Gen 2 solid state lithium metal battery technology: from the laboratory to commercialization.
(Keynote) The Solvation Structure and Rational Design of Liquid Organic Electrolytes
Authors: Persson Kristin A.
Published: February 2020

Electrolytes with improved stability and transport properties have the potential to transform the current state-of-the-art Li-ion architectures and enable future technologies such as multivalent systems (e.g., Mg2+, Ca2+ and Zn2+), as well as Li-S and Li-O2 conversion systems. To address the need for novel and optimized electrolytes, in this work, we apply our high-throughput computational infrastructure1
to a range of systems – spanning both multivalent as well as monovalent charge carriers- and present our insights, highlighting the role of careful speciation for rational design of future, improved energy storage concepts.

To improve our understanding of structural and dynamical properties of highly concentrated LIB electrolytes, we use classical molecular dynamics simulations with enhanced sampling techniques to allow for correct statistics in these more viscous systems. We describe the modes of charge transport in LiPF6 /propylene carbonate electrolyte in concentrated to superconcentrated regimes and elucidate the minority as well as majority species solvation structures and corresponding atomistic transport motifs. For multivalent systems, we find that the existence of multimeric species, such as contact-ion pairs are vitally important to account for the anodic stability of the electrolyte.2
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4 The plating process inherently requires the solvated divalent ion to undergo a transient, partially charged valence state; e.g. Mg+ or Ca+, which is identified as the fundamental descriptor for electrolyte stability. We find most solvent molecules as well as ion-paired anion molecules to be highly susceptible to rapid decomposition when in close contact with the reactive partially charged cation, thereby precluding stable, reversible plating behavior. This insight provides a ready explanation why so few classes of solvents and salts have demonstrated reversible Mg and Ca metal plating as well as enabling a path forward for rapid, in silico rational design and testing of novel, highly functional electrolyte molecules. 5

References:

1 X. Qu, A. Jain, N.N. Rajput, L. Cheng, Y. Zhang, S.P. Ong, M. Brafman, E. Maginn, L. a. Curtiss, and K. a. Persson, Comput. Mater. Sci. 103, 56–67 (2015).

2 N.N. Rajput, X. Qu, N. Sa, A.K. Burrell, and K.A. Persson, J. Am. Chem. Soc. (2015).

3 S.-D. Han, N.N. Rajput, X. Qu, B. Pan, M. He, M.S. Ferrandon, C. Liao, K.A. Persson, and A.K. Burrell, ACS Appl. Mater. Interfaces 8, (2016).

4 N.N. Rajput, T.J. Seguin, B.M. Wood, X. Qu, and K.A. Persson, Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes—A Review (Springer International Publishing, 2018).

5 N.T. Hahn, T.J. Seguin, K.C. Lau, C. Liao, B.J. Ingram, K.A. Persson, and K.R. Zavadil, J. Am. Chem. Soc. 140, 11076–11084 (2018).
(Keynote) Architectural Re-Design of Zinc Anodes Physically Thwarts Dendrite Formation—with Zinc Batteries Now Rechargeable, What’s Next?
Authors: Rolison Debra R. , Parker Joseph F. , Ko Jesse S. , Hopkins Brandon J. , Chervin Christopher N. , Geltmacher Andrew B. , Long Jeffrey W.
Published: February 2020

We recently demonstrated that redesigning dendrite-prone zinc anodes as 3D monolithic Zn architectures solves the limited rechargeability of alkaline batteries. Three structural features of these emulsion–derived “sponges” physically ensure dendrite suppression: (i) long-range electronic conductivity within the electrode volume throughout charge–discharge; (ii) more uniform current distribution; and (iii) confined internal void volume that controls Zn/Zn2+ precipitation/dissolution dynamics and product redistribution.

With Li-ion competitive cyclability to deep depths-of-discharge (theoretical DODZn), primary utilization to >90% DODZn (with >90% recovery), and tens of thousands of cycles at low-DODZn creates new performance curves for the entire family of alkaline Zn batteries (Ni–Zn, Ag–Zn, MnO₂–Zn, Zn–air) plus neutral pH zinc-ion batteries. Our second-generation emulsion protocol increases volumetric density of the sponge, which improves the energy density of the cell, and adds mechanical ruggedness to the anode. Development paths for this safer energy-storage breakthrough will be discussed.
(Invited) Advancing Fast Charge Capability and Challenges
Authors: Snyder Kent , Liu Minghong , Zhou Qian
Published: February 2020

From consumer electronics to automotive applications, the advancement and deployment of fast charge capable energy storage supports a combination of absolute customer need in some cases, with product differentiation and real or perceived customer desire in others. At the same time, potential near- and far-term advancements toward achieving higher energy density, greater sustainability, and lower cost simultaneously present a direct technical counter-challenge to fast charge advancement in many cases. Between energy storage for consumer electronics and energy storage for automotive, there is both common ground and differences in terms of the seeming counterbalance of the challenges of fast charge advancement with those of energy density increase and other desired energy storage improvements.

This presentation will discuss fast charge issues and progress among applications and will describe future energy density advancement and other trends which may add significant challenge along the way. Methods which may potentially provide partial relief from these challenges, and which may transcend the counterbalancing effect, will be described.
The Rechargeable Aprotic Lithium-Oxygen Batteries
Authors: Gao Xiangwen , Chen Yuhui , Johnson Lee R , Bruce Peter G.
Published: February 2020

Rechargeable battery such as Li-ion battery will be the main focus worldwide for decades to come. However, energy storage beyond the capabilities of Li-ion technologies are becoming increasingly important to satisfy society’s future energy storage needs. One such alternative is aprotic Li-air (O2) battery with its theoretical specific energy several times higher than that of Li-ion. However, many challenges including early cell death, high overpotential and poor cycle life need to be addressed before its commercialisation. Fundamental studies of the processes at the positive electrode have shown that this is a result of passivating Li2O2 film at the electrode surface.

It is generally accepted that solution growth of discharge product Li2O2 is required to achieve high rates and capacities. One way to achieve solution mechanism is use of high donor or acceptor number electrolytes, however, such electrolytes are less stable towards the reactive oxygen species in aprotic Li-O2 cell. Here, we discuss our new strategies to use redox mediators as soluble catalysts, to reduce O2 to Li2O2 by halving the overpotential on discharge, without forming passivating films and with less side reactions in ether solvents, while on charge Li2O2 can be oxidized rapidly to O2 even when the former is not in contact with the electrode surface, Fig. 1. As a result, cycling of an aprotic Li-O2 cell has been demonstrated with rates and capacities of several mA and mAh cm-2 respectively. The advantages and disadvantages of redox mediators during cycling and decomposition of carbon electrode will be discussed.

Figure 1: Schematics of positive electrode reactions on discharge and charge in the presence of dual mediators.

Figure 1