bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Sodium-Ion Battery: Effect of Electrolyte Additives on the SEI Layer of Hard Carbon Anodes
Authors: Dimogiannis Konstantinos , Bhaskar Akkisetty , Johnson Lee R 
Published: December 2020

Since their discovery, lithium-ion batteries (LIBs) have dominated the energy storage and power market due to their attractive attributes. However, LIBs cannot cope with the ever-growing energy demand and new alternatives must be explored. The low cost, and abundance of sodium, as well as its similar chemical properties to lithium, make the sodium-ion battery (SIB) a promising alternative for the future.1-5

SIBs often suffer from a short cycle lifespan, which is mainly attributed to the formation of an unstable solid electrolyte interphase (SEI) layer on the hard carbon anode surface. During the first cycle, the electrolyte solution is reduced, and its decomposition products form a passivation film (SEI) on the anode. Ideally, the SEI should protect the electrolyte from further decomposition during subsequent cycling, while being permeable to sodium ions. To reach this ideal situation, the employment of film-forming electrolyte additives in small amounts is necessary.6-11

In this study, in-operando electrochemical quartz crystal microbalance is used to monitor how additives affect the mass variation during the sodium intercalation/de-intercalation process. Mass spectrometry is further employed to identify and quantify the generated gaseous species during the initial SEI formation. After cycling, scanning electron microscopy and X-ray photoelectron spectroscopy are used to explore the additives effect on the SEI thickness and composition. A range of additives are considered including 1,3-propane sultone, succinonitrile and sodium-difluoro(oxalato)borate. The results of this study will be presented, along with suggestions for future research.

Reference
s
:

[1] P. K. Nayak, L. Yang, W. Brehm, P. Adelhelm, Angew. Chem. Int. Ed. 57 (2018) 102–120.
[2] S. Roberts, E. Kendrick, Nanotechnol. Sci. Appl.11 (2018) 23-33.
[3] H. Li, X. Zhang, Z. Zhao, Z. Hu, X. Liu, G. Yu, Energy Storage Mater. 26 (2020) 83–104.
[4] J. Deng, W. B. Luo, S. L. Chou, H. K. Liu, S. X. Dou, Adv. Energy Mater. 8 (2018) 1–17.
[5] L. Li, Y. Zheng, S. Zhang, J. Yang, Z. Shao, Z. Guo, Energy Environ. Sci., 11 (2018) 2310–2340.
[6] G. Eshetu, M. Martinez-Ibañez, E. Sánchez-Diez, I. Gracia, L. Chunmei, L. M. Rodriguez-Martinez, T. Rojo, H. Zhang, M. Armand, Chem. Asian J. 13 (2018) 2770-2780.
[7] M. Dahbi, T. Nakano, N. Yabuuchi, S. Fujimura, K. Chihara, K. Kubota, J.Y. Son, Y.T. Cui, H. Oji, S. Komaba, ChemElectroChem, 3 (2016) 1856–1867.
[8] G. Yan, K. Reeves, D. Foix, Z. Li, C. Cometto, S. Mariyappan, M. Salanne, J.M. Tarascon, Adv. Energy Mater. 4 (2019) 36244–36251.
[9] S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki, T. Nakayama, O. Atsushi, G. Kazuma, K. Fujiwara, Adv. Funct. Mater. 21 (2011) 3859-3867.
[10] A. Bouibes, N. Takenaka, T. Fujie, K. Kubota, S. Komaba, M. Nagaoka, Appl. Mater. Interfaces. 10 (2018) 28525-28532.
[11] M.A. Muñoz-Márquez, D. Saurel, J.L. Gómez-Cámer, M. Casas-Cabanas, E. Castillo-Martínez, T. Rojo, Adv. Energy Mater. 7 (2017) 1-31.
Investigating Abuse Tolerance and Improved Cycle Life in Si Anode Systems with Novel Electrolyte Design
Authors: Torres Gabriel , Brown Kevin , Raghunathan Aditya , Vaidya Rutvik , Moganty Surya 
Published: December 2020

Si has emerged as the most promising successor to graphite as an anode material in Lithium-ion batteries. Known to have nearly ten times the capacity of graphite, Si is increasingly being used to partially replace traditional graphite to raise the overall energy density of a cell. High nickel cathode chemistries such as NMC811 are also of particular interest due to its high specific capacity and low cobalt content, which drives down cost. Pairing these active materials is an obvious design choice, however it results in combining their respective drawbacks. Relative to lower nickel NMCs, NMC811 has been shown to be more reactive with carbonate electrolyte components and is known to be more violently reactive upon thermal decomposition. Si based materials swell dramatically upon lithiation, causing the SEI layer to break and reform with repeated cycling, consuming the electrolyte in the process. In combination, high energy density also implies increased safety concerns. To overcome these problems new electrolyte additives are needed.
We report a new family of electrolyte additives designed to improve the robustness of the SEI and overall stability of the electrolyte system, which carries significance in improving cycle life and abuse tolerance in higher energy density cells. This is a tunable, drop-in solution to addressing the need for improving battery performance as well as safety. We demonstrate the effect of these additives on the SEI via analytical characterizations (SEM, XPS) and how it relates to improved long-term cycle life. The effect of additives on thermal decomposition at the material level is investigated via DSC and on the cell level via ARC, presenting a relationship between electrolyte design and inhibited electrode-electrolyte decomposition reactions. Novel electrolyte additives are thus shown to be a promising approach to resolving future high energy demand without compromising safety.
A Numerical Framework for Concentrated-Solution Theory
Authors: Van-Brunt Alexander John , Farrell Patrick E. , Monroe Charles W. 
Published: December 2020

Effective and stable electrolytes will be crucial to the implementation of next-generation battery chemistries. In particular, the engineering of novel electrolytes that suppress dendrites and facilitate stable SEI formation, whilst maintaining high conductivity and other desirable transport properties, will be necessary to enable lithium-metal anodes. Beyond this, electrolyte models that account for multiple dissolved components would be useful to analyze metal-oxygen batteries and lithium-sulfur batteries, and could shed light on the numerous transport processes potentially associated with the known side reactions that degrade today's lithium-ion cells.
The Onsager--Stefan--Maxwell (OSM) equations from irreversible thermodynamics, which underpin concentrated solution theory, provide a natural framework for multicomponent-electrolyte multiphysics. OSM flux laws are force-explicit, however, which has led to difficulties in numerical implementation, and in turn posed a barrier for electrolyte designers to apply the transport equations in their most natural form. Leaving the implementation issues aside, the OSM formalism can be useful because it more readily includes additional physics such as elasticity and pressure, which could be important for developing accurate models of intercalation materials and solid electrolytes.
This presentation will focus on numerical methods applicable to complex geometries. We will develop a general methodology to compute solutions of OSM transport problems, with a particular focus on how robust, rapidly converging results can be achieved when simulating materials that span multiple spatial dimensions. This methodology can be applied in both ideal and non-ideal settings, and will be illustrated with a variety of three-dimensional simulations. Particular emphasis is placed on devising a numerical algorithm which preserves and exploits the thermodynamic structure of the problem. The role of physical effects such as pressure and momentum, which tend to be neglected in most continuum simulations, will be highlighted. Insight into electrolyte design from these simulations will be discussed, and comparisons will be made to experimental data.
New Solid-State Electrolytes Based on Organic Ionic Plastic Crystals
Authors: Pringle Jenny , Yunis Ruhamah , Al-Masri Danah , Howlett Patrick C , Forsyth Maria , Hollenkamp Anthony F. 
Published: December 2020

The development of new solid-state electrolytes for energy storage devices is important for increasing their stability, reliability and safety. Organic ionic plastic crystals (OIPCs) are a relatively new class of material that show increasing promise as solid state electrolytes for devices such as lithium or sodium batteries.[1]

OIPCs are crystalline phases found in many of the same organic salt families as ionic liquids but these materials have elevated melting points and exhibit various forms of disorder, which is the origin of their plastic mechanical properties. One of the keys to the development of OIPCs as solid state electrolytes is expanding the range of cations and anions available, and understanding the structure and dynamics of the resultant material.
For application in a device, OIPCs are combined with salts of the target ion (e.g. Li+ or Na+), after which detailed analysis of the electrochemical and device parameters is performed. OIPC-based electrolytes can also be combined with polymer nanofibers to further improve their mechanical and transport properties.
This presentation will provide an overview of the new OIPC families that we have recently designed and synthesized, and progress of these materials towards their use in practical solid-state lithium and sodium based batteries. We have also investigated the use of nanoscale polymer composites and the combination of OIPCs with very high concentrations of lithium or sodium salts,2 and the recent work on developing these composite materials will be discussed.
References:
[1] H. Zhu, D. R. MacFarlane, J. M. Pringle, M. Forsyth Trends in Chemistry, 2019, 1 (1), 126
[2] D. Al-Masri, R. Yunis, H. Zhu, L. Jin, P. Bruce, A. F. Hollenkamp, J. M. Pringle Journal of Materials Chemistry A, 2019, 7, 25389-25398
Designing Solid Electrolyte Interface for Stabilized Silicon Anode for Lithium-Ion Battery
Authors: Jiang Sisi , Zhang Zhengcheng 
Published: December 2020

The exploration for the next generation of anode materials in the lithium-ion batteries is a vital subject in energy storage field. Silicon (Si) stands out among all the candidate materials due to its high theoretical specific capacity (4200 mAh/g for Li4.4Si), high safety and low cost. However, one of the biggest issues causing rapid capacity fade of Si anode is the continuous breakage and reformation of SEI due to unstable electrode/electrolyte interphase. One effective way to address it is to use electrolyte additives as represented by vinylene carbonate (VC) and fluoroethylene carbonate (FEC). It is believed that the decomposition of FEC generates electrochemical stable LiF and elastomeric polymerizable vinylene carbonate radical. These decomposition products form a passive layer on Si surface, leading to improved electrochemical performance. However, it is hard to control the composition and structure of the SEI.
We take a different approach attempting to solve the above issue. Organic functional groups are introduced on the surface of Si nanoparticles (SiNPs) via Pt-catalyzed hydrosilylation reaction. The surface group helps form more robust SEI thus boosts the electrochemical performance of silicon anode evidenced in both half- and full-cells. This method provides an efficient approach confronting the issues associated with SEI.

Figure 1
Characterization of Solid Electrolyte Interphase on Some Electrodes in the Bis(fluorosulfonyl)Amide Anion-Based Ionic Liquids with Different Li Salt Concentrations
Authors: Furuya Ryota , Hara Tomitaro , Fukunaga Takao , Kawakami Kiyomoto , Serizawa Nobuyuki , Katayama Yasushi 
Published: December 2020

Aprotic ionic liquids are investigated as the next generation electrolytes for lithium ion battery (LIB) because non-flammability of ionic liquids is expected to improve the safety of the LIB. Bis(fluorosulfonyl)amide (FSA) anion-based ionic liquids have been attracting attention because of the formation of stable solid-electrolyte interphase (SEI) on the electrode surface during charge-discharge reactions. The SEI is known to form as a result of reductive decomposition of electrolytes and considered as a lithium ion conductor, though its nature like composition has not been clarified yet especially in ionic liquid electrolytes. In the present study, the SEIs on some different electrodes in 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)amide (MPPFSA) containing LiFSA at different concentrations were characterized by electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS).
The formation and growth of the SEI were confirmed by the EIS spectra of a Cu electrode kept at 0 V vs. Li|Li(I) and Li deposited on a Cu electrode in MPPFSA containing different concentrations of LiFSA with the elapse of time.
The SEIs prepared on the Cu electrode and the deposited Li in the electrolytes for 1 week were characterized by XPS washing with monoglyme (G1) without exposure to air. The XPS peaks corresponding to C, N, O, F, S atoms were observed on the Cu electrode, suggesting the ionic liquids are adsorbed on the electrode surfaces even after washing by G1. Such decomposition products of the electrolytes as LiF and LiOH were detected on the Cu electrode and the deposited Li. In case of the deposited Li, the peak assignable to alkyl lithium (R-Li) in the C1s spectra was observed probably due to the reaction of Li with the organic cation of the ionic liquids. The ratio of the peak intensity for LiF to that for SO2-F on the Cu electrode and the deposited Li increased with an increase in the LiFSA concentration in the electrolyte. On the other hand, the relative intensity for R-Li on the deposited Li decreased with an increase in the LiFSA concentration, suggesting an increase in the LiFSA concentration suppressed the decomposition of MPP+ and promoted the decomposition of FSA-.
Improvement on Electrochemical Performance and Safety Using Mixtures of Ionic Liquid and Conventional Organic Electrolyte for Sodium-Ion Batteries
Authors: Hwang Jinkwang , Huan Yang , Matsumoto Kazuhiko , Hagiwara Rika 
Published: December 2020

The success of commercializing sodium-ion batteries is inhibited by the implementation of suitable electrolytes that have economic feasibility and stable electrochemical performance. Organic electrolytes such as Na[ClO4]- or Na[PF6]-including organic solvents, EC, PC, DMC, and DEC, are most widely used to investigate the performance of sodium-ion batteries. These electrolytes are widely accepted because of the analogous studies in LIBs, but their flammability can cause reliability issues. Moreover, the SEI layer composed of sodium cations is known to be inhomogeneous and fragile, giving a higher solubility than that based on lithium cations.(1) In this regard, ionic liquid electrolytes are a drawing huge attention to constructing safe electrochemical devices owing to their unique properties such as low volatility and low flammability. Furthermore, recent studies report ionic liquids show similar electrochemical performance at room temperature to organic electrolytes and better interfacial properties.(2-4) Despite this bright improvement, the cost of ionic liquids drags down the advantage of economical sodium-ion batteries.
In this study, ionic liquid and organic liquid electrolytes are mixed to adjust the balance of cost, performance, and safety. The [C3C1pyrr][FSA] (C3C1pyrr+ = N-methyl-N-propylpyrrolidinium) ionic liquid and PC organic solvent are used as mother electrolytes with Na[FSA] (FSA = bis(fluorosulfonyl)amide) and Na[ClO4] salts. The physical and electrochemical properties of the various mixing ratio of those mixture electrolytes are investigated for sodium-ion batteries. These mixture electrolytes improve not only flammability but also show better rate and cycling performance. The detailed electrochemical properties are evaluated by comparing reference electrolytes to clarify the dual salts effect and dual solvents (ionic liquids and organic solvent) effect. This performance will be discussed based on half cell tests using a Na2FeP2O7 positive electrode and full cell tests using a hard carbon negative electrode and a NaCrO2 positive electrode.
References
1. G. Yan, D. Alves-Dalla-Corte, W. Yin, N. Madern, G. Gachot, J.-M. Tarascon, J. Electrochem. Soc.,
165, A1222 (2018).
2. K. Matsumoto, J. Hwang, S. Kaushik, C.-Y. Chen, R. Hagiwara, Energy Environ. Sci.,
12, 3247. (2019).
3. J. Hwang, K. Matsumoto, Y. Orikasa, M. Katayama, Y. Inada, T. Nohira, R. Hagiwara, J. Power Sources, 377, 80 (2018).
4. J. Hwang, K. Takeuchi, K. .Matsumoto, R. Hagiwara, J. Mater. Chem. A,
7, 27057 (2019)
Data Driven Approach for Predicting Thermal Runaway in Li Ion Battery
Authors: Ragone Marco , Yurkiv Vitaliy , Ramasubramanian Ajaykrishna , Anahideh Hadis , Kashir Babak , Shahbazian-Yassar Reza , Mashayek Farzad 
Published: December 2020

Safety problems of high energy density and high-power Li-ion batteries (LIBs) associated with thermal runaway (TRA) have become a serious problem resulting in massive recalls by manufacturers, and at times even endangering the lives of the consumers. In general, the TRA consists of a battery’s rapid self-heating sourced from exothermic (electro-)chemical reactions and/or mechanical abuse. It is impossible to directly monitor the occurring events during the TRA in practical operating conditions (e.g., in cell phones or electric vehicles). However, the change in electrical parameters (pattern) during the TRA-like events could potentially indicate the existence of a failure, thus allowing to foresee the LIBs malfunction.
In this contribution, we employ multi-physics modeling and machine learning (ML) to address this important TRA problem in LIBs. Specifically, we use ML techniques to learn and predict the likelihood of the TRA, using the data acquired from the multi-physics modeling of LIBs. The multi-physics modeling approach is comprised of a coupled thermal, electrochemical (P2D model) and degradation sub-models. In this work, a degradation phenomenon leading to the TRA is the solid electrolyte interface (SEI) formation/decomposition in the negative electrode. Subsequently, due to the time-varying characteristic of the variables affecting TRA (i.e, voltage, C-rate, state-of-charge, temperature, etc.), we propose three ML techniques, namely, Support Vector Machine, Deep Neural Network, and Recurrent Neural Network to be customized and applied for determining the TRA likelihood. For deep learning methods, we propose a new activation function, TK-MARS, based upon a partitioning based multivariate adaptive regression spline (MARS). Finally, to mitigate the uncertainty of the prediction results under different degradation conditions, we built an ensemble framework (i.e., a committee of single prediction models) incorporating the trained individual models, in order to maximize the robustness and generalization power of the prediction for a new unseen observation without prior knowledge on the degradation. Thus, the developed combined multi-physics and ML modeling approach establish a basis for accelerated or ‘on-the-fly’ prediction of the TRA as well as a framework for extending machine learning methodologies to broad applications in electrochemistry.
Hierarchical Porous Structure of Niobium Prepared By an Electrochemical Method
Authors: Joe Gi hwan , Shin Heon-Cheol 
Published: December 2020

Fabrication of meso-/macro-porous electrode materials is known to be one of the effective ways to improve the performance of functional electrochemical devices since the porous structure would provide large surface area and allow rapid transport of atoms and ions. Recently, niobium (Nb) or Nb-based porous material has drawn much attention because of its highly versatile chemical and physical properties. There are various ways to form the porous Nb structure, such as hydrothermal, sol-gel, anodic oxidation and electrochemical etching methods. Among them, an electrochemical etching method is noteworthy because it is cost-effective, and the porous structure of the surface is easily tunable by adjusting etching conditions. Nevertheless, the general use of a noxious chemical (e.g. HF) for Nb porous structure formation needs to be avoided and then the creation of highly-porous Nb structure using F--free, more environmentally-benign chemical is still a challenge.
In this work, the novel hierarchical Nb porous structure is created by an electrochemical method by using F--free etching solution. In particular, it is confirmed that the pulse etching is far more effective to form a hierarchical or self-similar fractal porous structure of Nb than conventional continuous etching, most likely due to the repetitive and incessant supply of aggressive anion. It is further proved experimentally that the initial concentration of aggressive anion is one of the essential factors in forming well-defined, high-order hierarchical Nb porous structure. Under the optimal etching condition, the porous Nb structure with more than 3 hierarchical order can be successfully created by single etching process.
On the basis of the experimental observation of pore shape, the formula for the surface area of porous Nb is derived as a function of the hierarchical order of pore. From the comparison of the theoretically calculated surface area with the experimentally estimated one, the actual pore shape along with the hierarchical order of pores can be reasonably analyzed. In this presentation, the governing factors to construct a hierarchical Nb porous structure are suggested. Moreover, the utility of the formula between surface area and hierarchical pore order is discussed in terms of the non-uniformity of porous structure and hypotheses used to derive it.
Enhancement of Electrochemical Performance of All-Solid-State Lithium‐Ion Thin-Film Batteries By Interface Modification with Al2O3 Interlayer
Authors: Kim Jong Heon , Xiao Cheng-Fan , Kim Hyun-Suk 
Published: December 2020

Introduction
All-solid-state lithium-ion thin-film battery is one of the promising candidates for next-generation battery systems. However, the low Li-ion conductivity of solid electrolytes and the considerable electrolyte/electrode interface resistance greatly hamper the commercialization of all-solid-state thin-film Li-ion batteries. In this study, we fabricate the all-solid-state lithium-ion thin-film battery using V2O5 electrode and LiPON solid electrolyte. And we introduce Al2O3 interlayer between the Li metal and LiPON solid electrolyte to decrease the interfacial resistance.
Experimental
The Cathode (V2O5), the solid electrolyte (LiPON) and the interlayer (Al2O3) were prepared on Ti/Pt-coated Si substrates by RF sputtering system. In addition, The Li anode and the Cu current collector were deposited by thermal evaporation. The thicknesses of the V2O5 and LiPON thin films were approximately 100 and 500 nm, respectively. To evaluate the electrochemical properties, 2032-type coin cells were assembled in an argon-filled glove box. Charge/Discharge tests were carried out at various C rates from 0.5 to 100 C with cutoff voltages of 2 and 4 V. Electrochemical impedance spectroscopy was conducted in the frequency range of 100 KHz – 1 Hz with a sinus amplitude voltage of 10 mV.
Results and Discussion
The XRD results of the V2O5 and LiPON thin film shows the amorphous structure. The Charge/Discharge profiles shows typical curves of amorphous V2O5 electrode. The rate capability results show that the insertion of Al2O3 interlayer between the Li metal and the LiPON solid electrolyte sample enhanced the rate performance. Also, The TEM cross-section image results demonstrate that Al2O3 interlayer improves the adhesion to Li metal on LiPON solid electrolyte. These results indicate that as the adhesion between Li metal and LiPON solid electrolyte is improved, electrochemical performance is improved in all-solid-state lithium-ion thin-film batteries.
Conclusions
We successfully fabricated the all-solid-state lithium-ion thin-film battery using the amorphous V2O5 electrode and LiPON solid electrolyte. In addition, through the insertion of Al2O3, the interface between LiPON and Li became uniform and the electrochemical properties were improved. In other words, the interfacial control between solid electrolyte and Li metal is a key factor for the improvement of the electrochemical properties of all-solid-state lithium-ion thin-film batteries.