bluuebunny/crossref_metadata_2025_split huggingface dataset:
Li/Mn-Rich Layered Transition-Metal Oxides As High-Energy Cathode Materials for Lithium Ion Batteries
Authors: Helbig Jonathan , Schmuch Richard , Naber Verena , Winter Martin , Placke Tobias 
Published: February 2020

The class of Li-Mn-rich layered transition metal oxides (LMR-NCM) is one of the most promising candidates for cathode materials in advanced lithium ion batteries (LIBs) due to their high specific discharge capacity of up to 300 mAh/g and specific energy up to 1000 Wh/kg at material level.[1-4] Furthermore, those materials contain a high content of low-cost manganese due to the addition of a Li2MnO3 component compared to standard layered transition metal oxides, which at the same time enables the access of additional capacity. Nevertheless, a strong capacity and voltage fade as well as a poor rate capability plagues the class of LMR-NCM materials. The pronounced reversible oxygen redox activity (causing the voltage hysteresis), the transition metal migration and a phase transition to a spinel-like phase (causing the voltage fade) add to an even stronger fade of the specific energy and inhibit the commercialisation of these cathode materials so far.
To closely study the underlying phenomena, LMR-NCM oxides with different morphologies are synthesized. Therefore, the syntheses via coprecipitation in a Couette-Taylor flow reactor and in a conventional flask are compared. The constant monitoring of critical parameters during the synthesis by means of the reactor leads to dense spherical particles with a narrow particle size distribution. These characteristics offer a spherical cathode material with enhanced capacity retention due to a more compact structure with a lower surface area. Also, taking the voltage fade into consideration allows a more objective evaluation of LMR-NCM oxides materials especially in direct comparison with state-of-the-art NCM-based cathodes.
[1] E. M. Erickson, F. Schipper, T. R. Penki, J.-Y. Shin, C. Erk, F.-F. Chesneau, B. Markovsky, D. Aurbach J. Electrochem. Soc. 2017, 164, A6341 – A6348.
[2] B. Qiu, M. Zhang, L. Wu, J. Wang, Y. Xia, D. Qian, H. Liu, S. Hy, Y. Chen, K. An, Y. Zhu, Z. Liu, Y. S. Meng Nat. Commun. 2016, 7, 12108.
[3] D. Andre, S.-J. Kim, P. Lamp, S. F. Lux, F. Maglia, O. Paschos, B. Stiaszny J. Mater. Chem. A 2015, 3, 6709 – 6732.
[4] T. Placke, R. Kloepsch, S. Dühnen, M. Winter J. Solid State Electrochem. 2017, 21, 1939 – 1964.
A Versatile Polyol Synthesis for Layered, Spinel, and Olivine-Type Cathode Material
Authors: Meng Ying Shirley , Chung Hyeseung , Zhang Minghao 
Published: February 2020

One of the most pressing challenges modern society faces is how to provide an energy source for a variety of applications, ranging from small portable devices to electric vehicles (EVs) and a large grid-scale system to store energy from intermittent solar or wind-driven devices. Recently, enough technological advancement has been made that Li-ion batteries (LIBs) are considered as the most promising solution to solve this problem. Over the years, diverse synthetic methods have been developed to synthesize battery cathode materials, such as: solid-state, co-precipitation, sol-gel, hydrothermal, and molten salt syntheses. Each of the synthesis process used to make the cathode oxide material proved to be useful, but simultaneously accompanies some major drawbacks. In the traditional solid-state method, the mixing of multiple metal sources is done by grinding or ball milling. This results in a microcrystalline product with long Li diffusion pathways as well as inhomogeneous morphology and metal distribution. Co-precipitation compensates for some of these shortcomings, but it also requires a careful control of pH in the carbonate method or an inert atmosphere to minimize the undesired impurities in the hydroxide method. Previous studies show that the hydrothermal method is an effective way to synthesize cathode material with high crystallinity, but it requires a complex experimental set up which utilizes a stainless steel autoclave to withstand high vapor pressure during its lengthy reaction time. Furthermore, all the methods require a long post annealing process, typically lasting more than 12 hours at high temperature (>800ºC).
Herein, we developed a novel polyol synthetic process to prepare the most promising cathode materials in layered, spinel, and olivine structure. Developed by Fievet group in 1985, polyol-mediated synthesis has been widely used for the past decades, but its scope has been mostly limited to the synthesis of metals and metal oxides. In this work, our group has extended this synthesis method to develop more complex metal oxide used for battery cathode materials. All three of the synthesized materials are monodispersed nanoparticles with dispersive morphology and competitive electrochemical performance. Using a combination of powder x-ray diffraction (XRD), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and energy dispersive spectroscopy (EDS), we also confirmed its high crystallinity and uniform elemental distribution for all three polyol-synthesized cathode materials. Finally, HAADF-STEM image and electron energy loss spectroscopy (EELS) for cycled NMC material was analyzed to confirm its structural stability even after charge-discharge process. We anticipate that these findings lead to the plethora of new cathode materials that can be explored using this synthetic method.

Figure 1
Mastering the Anode/Electrolyte Interphase Reactivity with Slight Surface Fluorination
Authors: Charles-Blin Youn , Flahaut Delphine , Monconduit Laure , Louvain Nicolas , Guerin Katia , Dubois Marc , Ledeuil Jean-Bernard , Martinez Hervé 
Published: February 2020

In secondary batteries, the anode/electrolyte interphase plays a key role in the electrochemical performances. As the liquid organic electrolyte undergoes degradation in the electrochemical potential window of a cycling battery, a Solid Electrolyte Interphase (SEI) is formed upon cycling. This interphase layer leads to a double-edged problematic: the formation of the SEI lowers the coulombic efficiency and causes irreversible capacity loss, but it also passivates the electrode from the electrolyte and prevents further aging processes. Knowing this, any modification of the SEI should be performed with parsimony as it could break the balance between the positive and negative aspect of the SEI. By synthetizing a chemisorbed thin fluorinated layer upon anode material, we managed to improve the passivating power of the SEI leading to enhanced electrochemical performances. We also determine that very low quantities of fluorine on the active electrode material surface leads to several beneficial effects.

The chemical nature of the surface layer was describe by the mean of the XPS (figure 1), as well as the fluorine distribution on the surface with both AES and SAM. The fluorine has been quantified around 10 at. % of the extreme surface of the Li4Ti5O12 (LTO) material, without diffusion in particles bulks. The bulk and sub-surface properties of fluorinated LTO (LTO-F) were also investigated by coupling XRD, Raman Spectroscopy and NMR 19F, showing no modifications of the crystallographic structure. The influence of the surface fluorination on the electrochemical performance was investigate by galvanostatic cycling and by coupling XPS and SAM on cycled electrodes. We had a specific attention to the impact of the fluorination on the SEI thickness and stability in charge and discharge. Indeed, LTO-F exhibit a new reactivity toward the electrolyte, leading to a thinner and stabilized SEI. Finally, the gas generation of the LTO-F electrodes has been investigate by Gas Chromatography – Mass Spectrometry (GC-MS), as gassing is known to be a roadblock to the commercialization of LTO1,2. We demonstrate that the CO2 outgassing is reduced by the surface fluorination. The strategy implemented in this work, from synthesis to thorough characterization, allow to propose new solutions to improve SEI for Lithium ion batteries.
(1) He, Y.-B.; Li, B.; Liu, M.; Zhang, C.; Lv, W.; Yang, C.; Li, J.; Du, H.; Zhang, B.; Yang, Q.-H.; et al. Gassing in Li(4)Ti(5)O(12)-Based Batteries and Its Remedy. Sci. Rep.
2012, 2, 913.

(2) Zhang, L.; Zhang, S.; Zhou, Q.; Snyder, K.; Miller, T. Electrolytic Solvent Effects on the Gassing Behavior in LCO||LTO Batteries. Electrochimica Acta 2018, 274, 170–176.

Figure 1
Fluoride Shuttle Batteries by Liquid Electrolytes
Authors: Kawasaki Mitsuo , Morigaki Ken-ichi , Kano Gentaro , Abe Takeshi , Ogumi Zempachi 
Published: February 2020

Rechargeable batteries with fluorides as charge transporting ions, which we refer to as fluoride shuttle butteries (FSBs, see Fig. 1), potentially offer a high electrochemical energy storage capability that overwhelms those of the state-of-the-art lithium-ion batteries (LIBs). This is due to the unique properties of monovalent fluoride ions, which are lightest of halides, hardly oxidized, and yet capable of reacting with various metals to form mono- and multi-valent fluoride salts. They thus allow anion-based, multi-electron transfer, redox reactions under wide potential window. Besides, FSBs as such no longer require host lattices (prerequisite in LIBs), which further adds to the high energy density.
The fundamental concepts and some successful examples of FSB systems that had been developed in the RISING battery project were addressed by one of the present co-authors (Z. Ogumi) in IBM2017 and IBA2018. We here focus on the recent advance in liquid-type FSBs that came out through the continued RISING2 battery project. It should be noted that none of alkali fluorides are soluble in common buttery-oriented organic solvents no matter how large static dielectric constants they have. Used as alternative electrolytes have thus typically been organic fluoride salts (such as alkylammonium or substituted alkylammonium fluorides) in combination with preferably ionic liquids. Another, more-or-less sophisticated, way out is to utilize so-called anion receptors that make even alkali fluorides substantially soluble in common organic solvents.
We here show nonaqueous plain liquid fluoride electrolytes, which, according to our comprehensive and careful analyses, are apparently free from any addenda but somehow solvated Cs+ (or K+) cations and F- anions at a molar concentration of ~50 mM to give total ionic conductivity of typically ~0.8 mS/cm. The simple electrolytes exhibit versatile performance to make a variety of combinations of electrodes (ranging from Au/AuF3 to at least Zn/ZnF2) work reversibly in terms of the expected conversion reaction between the respective metal and its fluoride counterpart.
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).

Figure 1
Diagnostic Tools and Safety Aspects of Aged Commercial Li-Ion Batteries
Authors: Vie Preben J. S. , Maehlen Jan Petter , Lian Torleif , Forseth Sissel , Andersen Hanne Flåten 
Published: February 2020

The degradation and ageing of Li-ion batteries will in many cases contribute to reduced thermal stability which potentially affects the safety performance of the batteries. The fact that aging of lithium-ion cells leads to a reduced capacity and cell life, is extensively covered in the literature by several research groups, e.g. Vetter[1]. The safety effects of ageing are far less studied, with only a handful of empirical studies published, e.g. [2-4].
This poster presents ageing data and safety aspects of large commercial Li-ion cells. The cells have been aged and cycled at 5, 25 and 45 °C. Several diagnostic tools have been applied to characterise the ageing mechanisms. These tools include high power pulse characterisation, entropy spectroscopy, incremental capacity analysis and impedance spectroscopy.
The ageing mechanisms are however different at low and high temperatures and this will affect the thermal stability of the aged cells. The thermal stability of cells which have been aged with different ageing mechanisms was characterized with an Accelerated Rate Calorimeter (ARC). It was e.g. observed that a cell cycled at 5 °C for 3000 cycles reaching 70% State-of-Health showed a reduced thermal runaway limit from 240 to 150 °C compared to the uncycled cell. This was also lower than the exotherm onset temperature for the uncycled cell.

References

Vetter, J., et al., Ageing mechanisms in lithium-ion batteries. Journal of Power Sources, 2005. 147(1-2): p. 269-281.

Fleischhammer, M., et al., Interaction of cyclic ageing at high-rate and low temperatures and safety in lithium-ion batteries. Journal of Power Sources, 2015. 274: p. 432-439.

Gilljam, M., et al., 7E. Effect of electrical energy and aging on cell safety, in Safety of Lithium Batteries, J. Garche and K. Brandt, Editors. 2017, Elsevier.

Friesen, A., et al., Influence of temperature on the aging behavior of 18650-type lithium ion cells: A comprehensive approach combining electrochemical characterization and post-mortem analysis. Journal of Power Sources, 2017. 342: p. 88-97.
Temperature Influence on Silicon-Based Anodes for Li-Ion Batteries
Authors: Piernas-Muñoz María José , Trask Stephen E. , Dunlop Alison R , Bloom Ira 
Published: February 2020

Environmentally friendly hybrid, plug-in hybrid and full-electric vehicles (EVs) are gaining importance [1]. However, to gain further acceptance by the consumer, it is essential to extend the autonomy range of EVs to be similar to that of a gasoline-fueled car. There is a need for finding next-generation lithium-ion batteries (LIBs) with larger specific capacity and, therefore, higher energy density.
Undoubtedly, one of the most direct strategies to boost the specific capacity of LIBs is to replace the widely used graphite anode with other materials capable of delivering much larger capacities.[2] Among potential candidates, silicon is one of the most promising anode materials, since it offers a theoretical capacity (~3579 mAh/g) approximately 10 times higher than that of graphite (~370 mAh/g) [3], [4]. Besides, silicon is the second most abundant element in the earth’s crust, which positions it as a commercial-friendly substitute of carbon materials for anodes of LIBs[5]. Nevertheless, silicon anodes display pronounced capacity fade upon cycling and, thus, presents a great challenge to battery design 3
,
4
,
5.
Another aspect that so far has not been considered nor explored is the influence that temperature would have over the cyclability of silicon anodes in LIBs. To understand its effect, we performed galvanostatic experiments at different temperatures with silicon-based anodes in half-cells. In addition, the effect of using fluoroethylene carbonate (FEC) as an additive was also investigated. The different capacity fading observed and the possible kinetic mechanisms behind that distinct behavior will be discussed here.

We gratefully acknowledge support from the U. S. Department of Energy (DOE), Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357.
The U.S. government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the government.

[1] M. Armand and J-M. Tarascon. Nature 2008, 451, 652-657. Building better batteries.
[2] V. Etacheri, R. Marom, R. Elazari, G. Salitra and D. Aurbach. Energy Environm. Sci. 2011, 4, 3243-3262. Challenges in the development of advanced Li-ion batteries: a review.
[3] X. Su, Q. Wu, J. Li, X. Xiao, A. Lott, W. Lu, B. W. Sheldon and J. Wu. Adv. Energy Mater. 2014, 4, 1300882. Silicon-Based Nanomaterials for Lithium-Ion Batteries: A Review.
[4] H. Wu and Y. Cui. Nanotoday 2012, 7(5), 414-429. Designing nanostructured silicon anodes for high energy lithium ion batteries.
[5] U. Kasavajjula, C. Wang and A. J. Appleby. Journal of Power Sources 2007, 163, 1003. Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells.
Dilution Effects of Highly Concentrated Carbonate Ester-Based Electrolyte Solutions for LiNi0.8Co0.1Mn0.1O2 Positive-Electrode
Authors: Cao Ziyang , Hashinokuchi Michihiro , Doi Takayuki , Inaba Minoru 
Published: February 2020

A LiNi0.8Co0.1Mn0.1O2 positive-electrode exhibits a high initial discharge capacity of ca. 200 mAh g-1 by charging up to 4.3 V
vs
. Li/Li+
[1]. However, the cycle performance is poor in conventional electrolyte solutions due to the oxidative decomposition of the electrolyte at such a high potential. In our previous work, the charge/discharge cycle performance of LiNi0.8Co0.1Mn0.1O2 was greatly improved in the nearly saturated 8.67 mol kg-1 LiBF4/dimethyl carbonate (DMC) electrolyte solution, which has low DMC/Li molar ratio of 1.28. Unfortunately, the high viscosity and low ionic conductivity restrict its practical use. In this work, we applied fluorinated ester, i.e. methyl 3,3,3,-trifluoropropionate (FMP), as a diluent to decrease the viscosity. Then, we replaced a part of DMC in LiBF4/DMC+FMP with propylene carbonate (PC) to improve its stability against oxidation. LiNi0.8Co0.1Mn0.1O2 showed excellent cycle durability in the resultant ternary system of LiBF4/PC+DMC+FMP electrolyte solution.
The slurry consisted of 80 wt% LiNi0.8Co0.1Mn0.1O2 powder, 10 wt % carbon conductive agents (Ketjenblack) as a conductive additive, and 10 wt % polyvinylidene fluoride (PVdF) as a binder in an N-methyl-2-pyrrolidone (NMP) was coated onto Al foil. The sheet was dried at 80 ℃ for 18 h under vacuum, and punched into 13 mm diameter discs. Then, the disc electrodes were used to assemble two-electrode coin-type cells with Li foil as a counter electrode. The electrolyte solutions used in this study were 2.5 mol kg-1 LiBF4/DMC+FMP (1:2 by volume, DMC/Li=1.28, 11.4 mPa s) and 2.5 mol kg-1 LiBF4/PC+DMC+FMP (1:3:8 by volume, PC+DMC/Li=1.28, 14.5 mPa s). Li|LiNi0.8Co0.1Mn0.1O2 half-cells were prepared by using these electrolyte solutions and cycled galvanostatically at 0.1 C (1 C=275 mAh g-1) between 3.0 and 4.3 V at 30oC.
In 2.5 mol kg-1 LiBF4/DMC+FMP, the discharge capacity decreased to 88.0 % of the initial one in 50 charge/discharge cycles. On the other hand, 96.5% of the initial discharge capacity (195 mAh g-1) was maintained even at the 50th cycle in 2.5 mol kg-1 LiBF4/PC+DMC+FMP. The average coulombic efficiency (99.6 %) in the 50 cycles was higher than that obtained for 2.5 mol kg-1 LiBF4/DMC+FMP (99.5%). The Raman spectra suggests that adding FMP to dilute the saturated LiBF4/DMC has damage to the solvate structure and leads to the increase of free solvate. However, the PC+DMC+FMP-based electrolyte solution is stabilized against oxidation by forming aggregates (AGGs) [2], which should result in improvement of charge/discharge cycle performance of LiNi0.8Co0.1Mn0.1O2 positive-electrode.

References
:

[1] Y. Bi
et al
.,
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Power Sourc

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[2] T. Doi
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Carbon Nanotubes-Silica Nano Composite Synthesis By CVD Method: A Promising Composite Material Development for Lithium Ion Battery Application
Authors: Ali Zulfiqar 
Published: February 2020

Carbon-silicon material for lithium ion battery has recently been realized is promising material due to excellent lithiation property of silicon coupled with good carbon nanotube electrical conductivity in nanocomposite. In this work such material synthesis technique is described by first employing nickel silica alcogel as catalyst followed by direct chemical vapor deposition of prepared catalyst to result into nickel silicon carbon nanotubes nanocomposite. later, nickel metal which formed in-situ during CVD is successfully removed by treatment with concentrated hydrochloric acid. Thus, we have just synthesized this unique material which is promising and may be used as suitable anode material for lithium ion battery and lithium ion battery tests such as charge discharge, energy density, power density etc. will be performed and results will be presented by the time of conference.
The graphitic carbon deposition was confirmed by X-ray diffraction (XRD) studies and field emission secondary electron microscopic (FE-SEM) images reveled the tube-like and nest type morphologies which are characteristics of MWCNTs in silica matrix. The effect of nickel content and temperature on carbon nanotubes contents in silica matrix were also studied. The carbon content in the samples was estimated with CHNS elemental analyzer. The average tube diameter of material synthesized was in the range of 30-60 nm. Moreover, it was found that 12M hydrochloric acid concentration was required to completely remove nickel content from synthesized carbon nanotubes nanocomposite which was confirmed by XRD studies.

Figure 1
(Invited) Atomic-Scale Insights into Solid Electrolyte Materials: Defects, Conduction & Interfaces
Authors: Islam M. Saiful 
Published: February 2020

Major advances in solid-state lithium batteries require the discovery and characterization of solid electrolyte materials. It is clear that a complete understanding of such materials requires greater fundamental knowledge of their underlying structural, ion transport and interface properties on the atomic- and nano-scales. For example, grain boundary effects on Li-ion transport are not fully understood. This talk will highlight recent studies [1-3] in two related areas: the influence of grain boundaries on Li-ion conduction in the Li-rich anti-perovskite Li3OCl and the particle morphologies and lithium segregation to surfaces of the garnet Li7La3Zr2O12. A combination of advanced materials modelling techniques has helped us gain new insights into these complex materials, which are valuable in developing strategies to optimize their electrolyte properties.
[1] J.A.Dawson et al., J. Am. Chem. Soc., 140, 362 (2018).
[2] P. Canepa et al, Chem. Mater., 30, 3019 (2018)
[3] Y. Deng et al., ACS Appl. Mater. Interfaces
, 9, 7050 (2017); Y. Deng et al, Chem. Mater., 30 (2018)
Ni Ions Catalyzation Effects on Cathode Electrolyte Interphase for High Performance and High Safety Lithium Ion Battery
Authors: Wang Fu-Ming 
Published: February 2020

In January 2017, Samsung announced the reason why the Note 7 explodes and losses of more than 5 billion US dollar. According to their explanations, it was caused by the internal short circuit problem in the lithium ion battery. Currently, there is no effectively solution for eliminating the internal short circuit problem owing to the sudden accident.
In this research, a new technology has been developed, which can be used to terminate the thermal runaway and promise the safety performance of lithium ion battery. High voltage Li-excess and Ni-rich layer-type cathode material is employed and combined with this safety electrode additive for investigation. In terms of the results, the new technology LIVING@additive significantly enhances the cycle performance at 60oC and high voltage. In addition, the following figures illustrated that the battery containing LIVING@technology is stable and passed the nail penetration test. On the other hand, the battery without LIVING@ cannot be used when the short problem is taking place. The LIVING@contains self-polymerized hyper branch structure in order to insulate the directly contact between anode and cathode. This electrode additive not only provides high thermal stability on electrochemical reaction, but the columbic efficiency of charge-discharge is also enhanced.