bluuebunny/crossref_metadata_2025_split huggingface dataset:
Organic Cathode Based on Quinone-Sulfide Polymer for Both Li and Mg Batteries
Authors: Tran Ngoc Anh , Leprêtre Jean-Claude , Berthelot Romain , Alloin Fannie 
Published: May 2020

The undeniable benefit of lithium-ion (LIB) batteries for the development of a more environmentally friendly economy was recognized by the 2019 Nobel Prize in Chemistry. However, relying only on LIBs to energy storage will put considerable strain on lithium and cobalt resources used in these batteries. Therefore, alternative battery technologies other than LIBs are desirable to satisfy our growing demand for energy. Magnesium-ion batteries offer many distinct advantages over LIBs, including the high earth-abundance of magnesium, its high energy density and reversible dendrite-free Mg deposition1. In parallel, organic materials are receiving an increasing amount of attention as electrode materials for future post lithium-ion batteries due to their versatility and sustainability2. In order to propose organic cathode with both high potential and specific capacity, new polymer based on hydroquinone sulfide, poly(benzoquinone disulfide) (PBQDS), were prepared in view to be applied in both lithium and magnesium batteries. Diglyme and sulfolane solvents associated with both LiTFSI (lithium bistrifluomethane sulfonimide) and Mg(TFSI)2 salts were selected, as electrolytes, in order to evaluate the potentiality of the active material3. First of all, the electrochemical responses of PBQDS in lithium and magnesium based electrolytes was performed in a cavity micro-electrode. Whereas in both case the cyclic voltammetry exhibit a close to reversible redox stem (Fig. 1a), The electrochemical characteristics of the material are very similar in term of potential and ΔEpeak in both lithium and magnesium systems at a relative high scan rate i.e. 1 mV s-1. An improvement of the redox couple reversibility seems to be observed in Mg form, with a ΔEpeak= 400 mV at E° of 0.3 V vs Fc+/Fc (3.5 vs Li+/Li). Given this interesting behavior, PBQDS in a coin cell configuration using glyme + LiTFSI electrolyte, was analyzed. . A stable capacity of 160 mAh g-1 was obtained at C/10 after 70 cycles, whereas a value of 120 mAh g-1 was maintained at C rate (Fig. 1b). In order to improve, the electrochemical performances, especially at high C-rate, the impact of the particle sizes (controlled grinding) of the cathodic material is in progress in view to approach its theoretical capacity value. In addition, the electrochemical investigations in both Mg and Li based electrolytes will be presented in regard to the electrolyte nature and the PBQDS morphology.

1. H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour, D. Aurbach, Energy Environ. Sci., 2013, 6, 2265–2279.
2. P. Poizot, F. Dolhem, Energy Environ. Sci., 2011, 4, 2003
3. H. Dong, Y. Liang, O. Tutusaus, R. Mohtadi, Y. Zhang, F. Hao, Y. Yao, Joule 2019, 3, 1–12

Figure 1
Preparation and Electrochemical Studies of Metal Fluorides for Lithium Batteries
Authors: VenkatashamyReddy MogalahalliVenkatesh , Abdulrahman Shahul Hameed , Karim Zaghib 
Published: May 2020

Conventional positive (cathodes) electrode materials for lithium batteries, use mixed-conducting lithium containing transition metal oxides, metal phosphates etc. which are able to store both lithium and electrons by changing their oxidation state. In this presentation, we discuss the facile synthesis of materials suitable for alternative electrode concepts including Transition metal fluorides MF2 (M=Fe, Mn, Zn) were obtained by reacting Fe, Mn, Zn-Metal salts with fumaric acid as a one-dimensional metal organic framework, and a polymer (PVDF) as Fluorine source, final products are obtained by heating at 600°C, 6h in Ar gas. The MOF were initially prepared by a simple chimie douce method. Incorporation of the MOF with a fluorinated polymer and the eventual decomposition lead to carbon coated metal fluoride nanoparticles of high surface area of >200 m2/g for FeF2. The obtained materials will be characterized in detail by X-ray diffraction, Scanning and Transmission electron microscope (SEM/TEM) are used to evaluate the structure and morphology, X-ray photoelectron spectroscopy are used understand structure, vibrational bands and oxidation state of the materials and BET surface area method. Electrochemical studies were carried out in the voltage, range 4 to 1.0 vs. Li, at current rate of 50 mA/g (0.1 C) using 1MLiPF6 (EC;DEC) as liquid electrolyte and tested with Li-metal as a counter and reference electrodes. The cyclic voltammetry at scan rate of 0.075 mV/sec at room temperature (24°C). Galvanostatic cycling of FeF2 demonstrates that the material exhibit stable and good reversible capacity of 580 mAh/g during the first cycle and slight capacity fading has been observed after 20 cycles. Further studies on rate performance is being carried up to 2.5 C rate. Whereas MnF2 and ZnF2 showed reversible capacity of 220 and 200 mAh/g and retained a capacity around 100 mAh/g after 20 cycles and showed lower capacity than FeF2. Discuss the structural, reaction mechanism of FeF2 during charge-discharge cycling by in situ/operando X-ray diffraction and electrochemical impedance spectroscopy studies discuss in detail.
Keywords: Metal fluorides (MF2 M=Fe, Zn, Mn); Electrochemical properties; Insitu studies; Electrochemical impedance spectroscopy; energy storage
Solid State Ion Conductors to Enable Low Temperature Molten Sodium Batteries
Authors: Spoerke Erik D. , Peretti Amanda , Gross Martha M. , Percival Stephen , Small Leo J. , Hill Ryan , Cheng Yang-Tse 
Published: May 2020

Molten sodium batteries show clear promise for safe, long-lifetime grid-scale energy storage, and there is growing expectation that they may be able to impact a host of energy storage areas, ranging from vehicle electrification to industrial applications. Key to the successful development and implementation of these technologies, though, are 1) reducing the traditionally high operating temperature of these batteries and 2) identifying robust, zero-crossover solid state separators that will perform effectively at these reduced temperatures. Traditional molten sodium batteries, such as sodium-sulfur and sodium-nickel chloride (ZEBRA), operate near 300°C, where ceramic separators, such as β”-Al2O3 have high ionic conductivity, but these high temperature systems can be cost-prohibitive. Here, we discuss a significant deviation from these chemistries and materials in a sodium-iodide (NaI) battery that utilizes a molten sodium anode and a sodium iodide-based molten salt catholyte, operating at drastically reduced temperatures near 100°C. NaSICON (Na Super Ion CONducting) separators show promise as effective ceramic separators in lab-scale demonstrations of this battery chemistry, but challenges to cost, widespread availability of the material, electrochemical compatibility, and mechanical stability of the ceramic have motivated the search for new sodium ion conducting separator materials and designs. We will describe not only critical synthetic considerations, but also important benefits and shortcomings of NaSICON separators for use in this specific battery chemistry. Importantly, we will describe recent efforts build on the promise of NaSICON materials, exploring new composite materials and hybrid structures that meet strenuous demands of ionic conductivity, chemical compatibility, and mechanical robustness for separators in low temperature sodium batteries. Innovative designs that take advantage of controlled particle morphology and organization in polymer-ceramic composites, for example, promise improved mechanical durability and effective ionic conductance in low cost, highly processable systems. Understanding the critical relationships between material composition, microstructure, and electrochemical performance of these emerging materials will be central to the successful development of a new generation of solid-state ion conductors and the realization of effective low temperature molten sodium batteries.
Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
(Invited) Understanding Chemical, Mechanical and Thermal Stability of NCA in Polymer Solid-State Batteries
Authors: Besli Muenir Mustafa , Metzger Michael , Hellstrom Sondra , Usubelli Camille , Liu Yijin , Nordlund Dennis , Doeff Marca M , Christensen Jake , Kuppan Saravanan 
Published: May 2020

The structural integrity and chemical stability of layered Ni-rich oxide cathode materials are influential factors that critically affect the performance and reliability of lithium batteries. Prolonged battery operation often involves repeated phase transitions, buildup of mechanical stresses, which could result in chemical and mechanical changes in cathodes. Chemo-thermo-mechanical interplay can cause performance degradation through various processes. Here we systematically investigate such complex chemomechanical and chemothermal interplays over a wide range of length scales within the hierarchically structured polymer solid-state batteries. This presentation will discuss our understanding of 1) The formation of mesoscale cracks and corresponding state of charge (SOC) inhomogeneity within secondary NCA particle cycled in solid polymer batteries1 2) Thermal decomposition, fracture (intergranular and intragranular), and mesopores formation due to oxygen evolution in delithiated Li0.30NCA particles upon heating2 3) long-term chemothermal stability of delithiated Li0.30NCA at relevant operating conditions of polymer solid-state batteries.3

Our investigation provides a fundamental understanding of chemo-thermo-mechanical breakdown of the NCA in solid-state polymer batteries.
Reference :
1. Besli, M. M. et al. Mesoscale Chemomechanical Interplay of the LiNi0.8Co0.15Al0.05O2 Cathode in Solid-State Polymer Batteries. Chem. Mater.
31, 491–501 (2019).
2. Besli, M. M. et al. Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles. J. Mater. Chem. A
7, 12593–12603 (2019).
3. Besli, M. M. et al. Long-Term Chemothermal Stability of Delithiated NCA in Polymer Solid-State Batteries. J. Mater. Chem. A 11–13 (2019) doi:10.1039/c9ta11103d.
Gel Polymer Electrolyte Made of an Amorphous Polyacrylonitrile-Based Elastomer
Authors: Verdier Nina , Lepage David , Zidani Ramzi , Prébé Arnaud , Ayme-Perrot David , Pellerin Christian , Dollé Mickael , Rochefort Dominic 
Published: May 2020

Lithium-ion batteries (LiBs) are a mature technology which has attracted much attention over the last three decades with the development of portable devices. With the increasing number of LiBs and their use in electric vehicles, there are persistent efforts to enhance their safety by identifying suitable substitutes for liquid non-aqueous electrolytes, which are highly flammable, volatile, and can cause leakage. To this end, gel polymer electrolytes (GPEs) represent a promising alternative. To be suitable in applications and maximize ionic conductivity, polymers must meet specific requirements, the most important ones being a low glass transition temperature (Tg) and a low crystallinity, as ions move faster in amorphous phase. Moreover, these polymers need to be electrochemically stable and provide mechanical resistance as well as flexibility to the GPE. To increase the conductivity, polymers with polar functional groups that can dissolve salts are required. Several polymers, like PEO or PAN have already been studied but one limitation is their high Tg (above ambient temperature) as well as a high crystallinity which make them brittle and limit the ionic conductivity.
To circumvent this limitation, we studied an amorphous polymer based on acrylonitrile monomers. This elastomer, HNBR (Hydrogenated Nitrile Butadiene Rubber), was previously studied by our group and was shown to be thermally cross-linkable, leading to a polymer chemically resistant to electrolytes and electrochemically stable over a wide potential range. Hence, we propose to investigate thermally cross-linked HNBRs to gain a better understanding on the effect of interactions between polar nitrile functions and lithium ions and finally use this system as a GPE for Li-ion battery. To do so, a three-component system comprising HNBR:solvent:LiTFSI was studied to pinpoint the correct ratio to provide the GPE with competitive conductivity. Infrared spectroscopy was used to shed light on the interactions between nitriles and lithium ions while PFG-NMR was utilized to obtain spin-lattice relaxation times (T1) and diffusion coefficients of 7Li and 19F for various HNBR-based GPEs. These results were correlated to EIS measurements and among the GPEs tested, those composed of 2M LiTFSI in propylene carbonate and HNBR with an acrylonitrile content of 50% are the most promising. This study highlights the benefits of high acrylonitrile content in the polymer and the use of a solvent with moderate donor number to promote interactions between nitriles and Li+.
Indigo As Single Additive in Liquid Electrolyte for Lithium Metal Batteries
Authors: Mallet Charlotte , Rochon Sylviane , Zaghib Karim 
Published: May 2020

Rechargeable lithium ion batteries (LIBs) have been successfully developed and widely used to power today’s portable electronic devices. The long term success in electric vehicles and energy storage system relies on rising the energy density, low temperature efficiency, safety and increased cycle life.
In parallel, lithium metal batteries (LMBs), described as a system with Li0 as anode and metal oxide as cathode (NMC, LFP, LMO) are arising as aim of research for a plethora of groups. Lithium metal anode is considered as ideal anode due to high theoretical capacity (3860 mAhg-1), lower negative electrochemical potential and lower density (0.534 g.cm-3).1 Researchers used complex liquid electrolyte (ionic liquid, etc.) systems in order to avoid lithium dendrite and degradation, conventional liquid electrolyte (LiPF6, carbonate solvants) degraded faster than expected, and consequently, generated cells fading. Therefore conventional liquid electrolyte in such cell was not used.
Use organic additive in electrolyte and/or electrodes is considered as one of the most economical and effective’s approaches for solved many problems as cited previously. The additive can interact with electrolyte or anode to prevent degradation or enhanced cell performances.
This presentation will outline commercial organic compounds: Indigo and his derivatives use as single additive in NMC/Li batteries with conventional liquid electrolyte, which considerably increased the cycle life of Li metal batteries. Dyes such Indigoïd contain electron density donor (-NH-) and acceptor (-C=O) groups linked by conjugated bonds, which participate to their versatile electrochemical properties.
Used as additive in cathode materials or electrolyte, indigo modified the electrode structure and changed the composition of the Li-ions battery electrolyte and solid electrolyte interface (SEI) on lithium metal.

1.Zhang, H., Eshetu, G.G.,Judez, X., Li, C., Armand, M., Angew. Chem. Int. Ed. 2018, 57, 15002-15027

Figure 1
Interface Modification between Li3PS4 Electrolyte and Li Metal Using Molten Salt Electrolyte Based on Alkali Bis(fluorosulfonyl)Imides
Authors: Li Qin , Cao Yi , Gao Yunzhi 
Published: May 2020

All-solid-state lithium batteries employing sulfide solid electrolyte hold high promise to replace traditional liquid-electrolyte lithium ion batteries due to their high safety[1]. However, the formation of Li dendrites which would lead to short-circuiting of batteries is a serious issue that hinders its successful practical application[2]. Introduction of an interlayer by ex-situ or in-situ formation between a Li metal and sulfide solid electrolyte is a well-known method intended to reduce the interfacial resistance and suppress the dendrite growth inside all-solid-state batteries. Here, we applied molten salts which possess excellent electrolyte properties[3] to modify the electrolyte/anode interface. Symmetric cells of Li3PS4 electrolytes with the binary eutectic mixture of LiFSI-KFSI exhibited better Li dissolution-deposition performance and enabled operation at high current density (2.98 mA cm−2, 100 ℃) without short-circuiting. The higher interface energy of in-situ formed LiF derived from the reaction of LiFSI/KFSI and Li metal as well as the excellent electrolyte properties of the LiFSI-KFSI eutectic mixture lead to the enhanced electrochemical performance. These results indicate that interface modiﬁcation is promising strategy to achieve all-solid-state batteries with high energy densities.
[1]Xu R, Han F, Ji X, et al. Interface engineering of sulfide electrolytes for all-solid-state lithium batteries[J]. Nano energy, 2018, 53: 958-966.
[2]Han F, Yue J, Zhu X, et al. Suppressing Li dendrite formation in Li2S‐P2S5 solid electrolyte by LiI incorporation[J]. Advanced Energy Materials, 2018, 8(18): 1703644.
[3]Xu F, Liu C, Feng W, et al. Molten salt of lithium bis (fluorosulfonyl) imide (LiFSI)-potassium bis (fluorosulfonyl) imide (KFSI) as electrolyte for the natural graphite/LiFePO4 lithium-ion cell[J]. Electrochimica Acta, 2014, 135: 217-223.

Figure 1
A Simple Way to Stabilize Li and Na Metallic Electrodes Surfaces
Authors: Roch Marlene , Davoisne Carine , Fleutot Benoit , Dedryvère Rémi , Morcrette Mathieu 
Published: May 2020

Post Li-ion technologies such as Li-air, lithium sulphur or all-solid-state batteries have in common the use of lithium metal as negative electrode. Known from decades, dissolution and deposition of lithium induce the growth of inactive lithium moss or more critically the dendritic growth that can lead to short circuit phenomenon. Therefore, researchers try to tackle this problem by adding functional layers at the Li surface that may generate an improvement in capacity, lifetime and performances at high current rates.
There are different ways to protect lithium such as ALD inorganic coating1,2, grafting of organic materials3,4,5, polymers6 or deposition of inorganic alloys7,8. In this work, by dip coating (a simple and cheap process) a lithium foil into a solution of glyme with phosphorus trichloride (DME-PCl3), we succeeded in obtaining a thin and protective phosphorus-based layer.
Through electrochemical characterization techniques (EIS, GITT in 2 or 3 electrodes) and surface characterization techniques (SEM, and more importantly XPS), we were able to determine its morphology and chemical composition, its influence on the lithium plating and stripping processes and the mechanism of lithium diffusion through the protective layer. Cycling results in lithium symmetric cells but also full cells (Li-ion, Li-S) will be presented.
Finally, since our results were very promising with lithium, we extended this type of protection to sodium since the reactivity of this metal with electrolyte is ever more pronounced. With the same methodology, we will demonstrate that our protection nicely improves the use of Na metal in liquid cells.

1 A. C. Kozen and al., Next-generation lithium metal anode engineering via Atomic Layer Deposition, acsnano, 2015, 9, 6, 5884-5892

2 C-F Lin, and al., ALD protection of Li-metal anode surfaces – Quantifying and preventing chemical and electrochemical corrosion in organic solvent, Adv. Mater. Interfaces, 2016, 3, 1600426

3 F. Marchioni and al., Protection of lithium metal surfaces using chlorosilanes, Langmuir, 2007, 23, 11598 - 11602

4 S. Neuhold and al., Effect of surface preparation and R-group size on the stabilization of lithium metal anode with silanes, Journal of Power Sources, 2012, 206, 295 -300

5 S. Neuhold and al., Enhancement in cycle life of metallic lithium electrodes protected with Fp-silanes, Journal of Power Sources, 2014, 254, 241-248

6 Y. Liu and al., Lithium-coated polymeric matrix as a minimum volume-change and dentrite-free lithium metal anode, Nature communications, 2016, 7, 10992

7 X. Liang and al., A facile surface chemistry route to a stabilized lithium metal anode, Nature Energy, 2017, 2, 17119

8 L-L. Kong and al., Lithium-Magnesium alloy as a stable anode for Lithium-sulfur battery, Adv. Funct. Mater., 2019, 29, 1808756

9 L. Lin and al., Lithium phosphide/lithium chloride coating on lithium for advanced lithium metal anode, J. Mater. Chem. A, 2018, 6, 15859
(Invited) Advancement of Low Temperature Ceramic Synthesis for Solid State Battery Components and Cells – a Personal Love Story
Authors: Rupp Jennifer L.M. 
Published: May 2020

Next generation of energy storage devices may largely benefit from fast and solid Li+ ceramic electrolyte conductors to allow for safe and efficient batteries and fast data calculation. For those applications, the ability of Li-oxides to be processed as thin film structures and with high control over Lithiation and phases at low temperature is of essence to control conductivity. Through this presentation we review the field from a new angle, not only focused on the classics such as Li-ionic transport and electrochemical stability window for Li-solid state battery electrolytes, but focusing on opportunities and challenges routes in thermal and ceramic processing of the components and their assemblies with electrodes. Also, we will carefully review and give perspectives on the role of solid state battery ceramic strategies for the electrolyte on the electrode interfaces and towards charge transfer and vs. current densities. In other words, it will be a little ceramicist (own) love story on the good and the evil we can design by smart ceramic design at the interfaces originating by the very first choices made in the electrolyte ceramic structure and material design. In the second part of the talk we will discuss new opportunities on low temperature processing of solid state electrolyte ceramics that do not technically require “classic sintering” and avoid prior particle calcination; instead demonstrating opportunities to use liquid based direct densification routes and vacuum techniques to design solid electrolytes and grafting interfaces to new hybrid and solid state battery prototypes targeted at processing below 700C for all parts. Collectively, the insights on solid state energy storage provide evidence for the functionalities that those Li-solid state material designs can have for cost and mass manufacturable solid state and hybrid battery prototypes.

References:

1. A Low Ride on Processing Temperature for a Fast Li Conduction in Garnet Solid State Battery Films
R Pfenninger, M. Struzik, I Garbayo, E Stilp , JLM Rupp, Nature Energy, 4, 475–4832019, 2019
2. Lithium-Containing Thin Films
JLM Rupp, R Pfenninger, M. Struzik, A Nenning, I Garbayo, US 62/718,838 (2018)
3. Methods of Fabricating Thin Films Comprising Lithium-Containing Materials
JLM Rupp, R Pfenninger, M. Struzik, A Nenning, I Garbayo, US 62/718,842 (2018)
4. Glass-Type Polyamorphism in Li-Garnet Thin Film Solid State Battery Conductors
I Garbayo, M Struzik, WJ Bowman, R Pfenninger, JLM Rupp, Advanced Energy Materials, 1702265 (2018)
5. Solid-state Electrolyte and Method of Manufacture Thereof.
ZD Hood, Y Zhu, L Miara, JLM Rupp. US 62/713,366 (2018)
6. Solution-Processed Solid-state Electrolyte and Method of Manufacture Thereof.
Y Zhu, ZD Hood, L Miara, JLM Rupp US 62/713,428 (2018)