bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fast Operando GCMS Gas Analysis for Monitoring Electrolyte Decomposition in Lithium Ion Batteries
Authors: Kahr Jürgen , Rezqita Arlavinda , Antoniadou Maria , Rosenberg Erwin , Fontana Daniela , Jahn Marcus 
Published: May 2020

Lithium Ion Batteries (LIB) find not only wide use in portable devices and consumer electronics, but also attract increasing attention in stationary energy storage and the automotive sector. In this regard, LIBs play a significant role as intermediate energy storage due to their high volumetric and gravimetric energy, high power density, and long cycle life.
To achieve the required performance, the interaction of novel anode and cathode materials is of paramount interest. Particularly, the safety of cell operation must be assessed with respect to the formation of volatile and reactive species during cycling which can negatively alter cell components. Gas chromatography mass spectroscopy (GCMS) has proven to be a reliable tool for species detection. Unfortunately, conventional GC systems lack time resolution for in-situ gas analysis regarding fast processes, for example battery failure. Therefore, developing operando testing methods with improved time resolution is key to giving insight into electrolyte alterations during battery operation.
Here one of them, a novel multiplex injection method is presented as a monitoring technique for gas species arising from the decomposition of conventional LIB electrolytes. The combination of the multiplexing technique and GCMS allows the analysis of fast decomposition processes by 15 fold increase of time resolution compared to conventional gas chromatography. In addition, FTIR allows online monitoring of selected vibration bands. Commercially produced pouch cells were monitored with respect to evolving gas species during battery operation under overcharge conditions. For the decomposition of LiPF6 / organic carbonate- based electrolytes alkanes, alcohols, ethers, esters, aldehydes and also derivatives that appear in the presence of hydrofluoric acid such as fluorinated alkane species, have been evaluated.
The author gratefully acknowledges the FFG (Austrian Research Promotion Agency) for funding this research within project No. 858298.
3D Printable Ionogels with High Ionic Conductivity
Authors: Lange Alyna , Zehbe Kerstin 
Published: May 2020

Hybrid materials based on ionic or polymer components are very useful in electrochemical devices like battery systems or fuel cells due to their unique properties like thermal and electrochemical stability and polarity. For all advances over the past, lithium ion based materials are still costly, limited and not very stable. Currently, solid-state polymer electrolytes (SPEs) and gel polymer electrolytes (GPEs) [1] have ion conductivities below 10-4 S/cm at room temperature.
Polymer electrolytes can be established by ionic liquids (ILs) which combine beneficial properties like high ionic conductivity, wide electrochemical potential window and high viscosity. These kinds of electrolytes can be very beneficial in solid-state batteries for example. This technology has garnered immense excitement from investors and large corporations. The main advantage of all-solid-state to liquid electrolyte-based batteries is that the size can be easily made smaller e.g. solid‐state electrolytes have a typical thickness of approximately 1.0 μm, whereas the separator in liquid electrolyte‐based cells typically has a thickness of 20 μm. Several investigators are exploring 3D architectures for thin-film rechargeable battery electrodes. Nevertheless additive manufacturing, also known as 3D printing, could revolutionize the structural properties of batteries. In addition, this technology could improve the adaptability of the electrolyte to the electrodes.
This scientific approach introduces the possibility to combine ionic liquids with a commercial photoreactive resin to realise a well-defined structure by using stereolithography (SLA). This provides, for the first time, access to ionogels (IGs) with complex 3D shapes (figure 1a) with potential application in battery or fuel cell technology. For first experiments new IGs were prepared by adding a series of sulfonate-based ionic liquids (ILs), 1-methyl-3-(4-sulfobutyl)imidazolium para-toluenesulfonate [BmimSO3H][pTS], 1-methyl-1-butylpiperidiniumsulfonate para-toluenesulfonate [BmpipSO3][pTS], and 1-methyl-3-(4-sulfobutyl) imidazolium methylsulfonate [BmimSO3H][MeSO3] with a clear photoreactive resin which were used in a Form 2 3D printer [2]. Moreover, the IGs are thermally stable up to about 200 °C and mechanically robust. In addition to this synthesized protic conductive IGs, sulfobataine, metal and lanthanides containing IGs were prepared and analysed. These IGs exhibit higher conductivities compared to the sulfonated based IGs in the range from 10-4 to 10-2 S/cm at room temperature. 3D Printable metal-lanthanide IGs could possibly be an adequate replacement for lithium-ion electrolytes.

Figure 1: a) Well-defined structures of IGs by SLA, b) Rhd battery cell for electrochemical measurements.

Literature:

[1] Stephan, A.M., Review on gel polymer electrolytes for lithium batteries. European polymer journal, 2006. 42(1): p. 21-42.

[2] Zehbe, K.; Lange,A.; Taubert, A., Stereolithography provides access to 3D printed ionogels with high ionic conductivity, Energy and Fuels, accepted.

Figure 1
Effects of Discharge Products on Zinc-Air Flow Cells
Authors: Fuchs David , Müller Christoph , Mahlendorf Falko , Heinzel Angelika 
Published: May 2020

As one of the proposed post lithium-ion technologies, zinc-air batteries have received revived interest in the recent years, which is driven by the increased demand of high-performance, efficient, safe and environment-friendly energy storage solutions. These energy storage systems need to address variable power, capacity and profitability requests. Zinc-air flow batteries with higher specific energy density than lithium-ion and low-cost, highly available, eco-friendly active materials are suitable to fulfill these requirements. The energy density of most zinc-air flow batteries is limited by the low solubility of ZnO in the electrolyte. The use of a flow battery type with zinc-particles suspended in alkaline solution (zinc-slurry) in addition with high performance oxygen-reduction electrodes enables the development of high-power zinc-air batteries. This setup also enables the independent scaling of capacity and power.
The cooperative project, ZnMobil, funded by the Federal Ministry of Economic Affairs and Energy in Germany, combines the experience of industrial and academic partners (Covestro Deutschland AG; Grillo-Werke AG; VARTA Microbattery GmbH; Accurec Recycling GmbH; Technical University Freiberg, Gottfried Wilhelm Leibniz University Hannover; University of Duisburg-Essen; the fuel cell research center ZBT GmbH) to develop a high-performance and low-cost zinc-air flow battery.
The battery system consists of a 100 cm² copper plate as current collector for the zinc-suspension electrode and an oxygen reduction electrode with gas-diffusion layer (supplied by Covestro Deutschland AG). The zinc-slurry contains zinc particles (supplied by Grillo-Werke AG) suspended in alkaline solution (30 wt-% KOH) and stabilized with polyacrylic acid.
Here we present a systematic study regarding the effects of the discharge products on the cell performance. Depending on the state of discharge and operation parameters the discharge product ZnO causes several important effects. The solid ZnO limits the discharge capacity in several ways. At high current densities, passivation is the main topic. If passivation is avoided, e.g. with the help of additives, the solid ZnO causes a viscosity increase until the cell is blocked. For this study we evaluated parameters like cell voltage, cell resistance, slurry viscosity, ZnO concentration in the electrolyte and other parameters in correspondence to the state of discharge. The understanding of these effects is essential to build a hydraulically rechargeable battery with high zinc usage and therefore high energy densities.
Depending on parameters like current density and additive selection, it is possible to reach more than 70 % DOD, which corresponds to 287 mAh/gslurry or 574 mAh/gzinc. A demonstrator-cell was operated for more than 140 h. During this time it was successfully hydraulically recharged several times.
3D Thermal Gradient of Li-Ion Prismatic Cell during High Current Discharge: A Numerical and Experimental Study
Authors: Raccurt Olivier , Geniès Sylvie , Bachir-Elezaar Kamel , Pham Quynh Trang , Coste Pierre , Daniel Lise , Montaru Maxime , Fiette Sébastien , Hergott Julien , Antunes Benoit 
Published: May 2020

Thermal management of the Li-ion batteries is one of major challenges to manage the performances and safety of the cell [1][2]. In battery pack, cooling systems are required to manage the heat generation of the cells during the charge and discharge cycles. The heat generated by the electrochemical processes inside the cell depends on the materials properties, the internal electrical resistance of the cell and the applied current rate [3][4].
In this study, the thermal behaviour of a 25 Ah prismatic cell has been modelled by a 3D approach. From an ante mortem analysis, the structure and configuration of the cells were determined. From such analysis, a 3D model of the cell was constructed by ANSYS and STARCCM software. A thermal source has been imposed in the jelly roll to simulate the heat generation during electrochemical reactions. Different cooling strategies were simulated to determine the temperature profile inside the cell volume and on the external surface.
To validate the developed thermal model, electrochemical tests in charge and discharge at different C-rates (up to 5C) into a thermal chamber were used to study the evolution of the surface temperature of the cell over 35 measuring points. The experimental results show the presence of a temperature gradient on the surface of the cell during the discharge step. This gradient increase according to the discharge rate. This thermal behaviour observed by experiment was in agreement with the simulation results. In addition, the current work will discuss on the methodology to improve the sensitivity of the 3D thermal model. The comparison of different cooling strategies explored by simulation will be also presented and discussed.
References
[1] A. Mauger and C. M. Julien, “Critical review on lithium-ion batteries: are they safe? Sustainable?,” Ionics, vol. 23, no. 8, pp. 1933–1947, Aug. 2017.
[2] D. Lisbona and T. Snee, “A review of hazards associated with primary lithium and lithium-ion batteries,” Process Safety and Environmental Protection, vol. 89, no. 6, pp. 434–442, 2011.
[3] P. Wu, J. Romberg, X. Cheng, W. Hao, H. Si, H. Li, and X. Qiu, “A study on thermal runaway of commercial lithium-ion cells: influence of soc, cell chemistry and ageing status on safety performance,” Lecture Notes in Electrical Engineering, vol. 486, pp. 619–627, 2019.
[4] Y.-S. Duh, K. H. Lin, and C.-S. Kao, “Experimental investigation and visualization on thermal runaway of hard prismatic lithium-ion batteries used in smart phones,” Journal of Thermal Analysis and Calorimetry, vol. 132, no. 3, pp. 1677–1692, Jun. 2018.

Acknowledgement

The present work has been launched by FAURECIA Group and supported by CEA Liten
Development of Porous Electrode Theory to Accommodate Voltage Gradients and Nonlinearity
Authors: Turney Damon 
Published: May 2020

Simulations of ionic and solvent mass transfer in electrolytes are typically based upon either i) the Poisson-Nernst-Plank equations with Fickian diffusion (Poisson-Fickian), or ii) the Newman-type porous electrode equations with Stefan-Maxwell transport (Newman-Stefan-Maxwell). Computational expense usually limits the Poisson-Fickian-type simulations to simple systems with only one or two phases, and one or two dimensions. Meanwhile the Newman-Stefan-Maxwell-type equations are explicitly only one-dimensional but are much easier to execute and can crudely handle more phases. This ease and flexibility made the Newman-Stefan-Maxwell approach popular over the past thirty years, and the Newman-type model continues to be popular with modern usage at current date.
The work presented here shows a further development of the Newman-Stefan-Maxwell equations that extend the Newman theory to i) simulate voltage and pressure gradients in the electrolyte that are significant when ionic concentrations are below ~2 Molar, and ii) include more accurate thermodynamics when describing the chemical potential of the species. The new equations are shown and justified. No significant increase in computational expense or model complexity is necessary for these improvements.
An additional predictor-corrector modelling scheme is shown for calculating the chemical composition at the particle-liquid interface, which allows for the overall model to be solved with explicit time-differencing without requiring extremely small time steps. The explicit time-differencing is advantageous because it discards the requirement to linearize all equations, and therefore allows for fully nonlinear charge-transfer equations to be tested with an arbitrary complexity desired.
The new model is capable of simulating one-dimensional full battery operation (anode, cathode, separator, electrolyte) with improved accuracy over the classical Newman-Stefan-Mawell model regarding spatio-temporal patterns of electrochemical potential, concentrations, and reaction rate. Some example applications are shown for CV cycling and galvanostatic cycling of: i) a 1 Molar Zn-MnO2 battery, ii) a EMImCl:AlCl3 aluminum-graphite battery. Additional systems are proposed for study where the voltage and pressure gradients are important to simulate.
NiFe2O4 Nanoparticles Anchored on Porous Graphene Sheets Offered Robust Electrochemical Performance for Supercapacitor Applications
Authors: Sethi Meenaketan , Shenoy U Sandhya , Bhat D Krishna 
Published: May 2020

A Facile solvothermal method is used for the synthesis of porous graphene − NiFe2O4 (PGNF) nanocomposite. Thorough elemental, diffraction, microscopic and spectroscopic studies confirmed the formation of PGNF composite in which, the NiFe2O4 nanoparticles are covered over the porous graphene (PG) surface strongly depicting the formation of composite structure. Among the obtained composites, the 10 PGNF composite showed a high surface area of 107 m2 g-1, with large pore volume which will be favorable for the charge storage property. Utilizing the material as an electrode for supercapacitors in a 2 M KOH aqueous electrolyte, the electrode displayed a high capacity value of 1465.0 F g-1 at a scan rate of 5 mV s-1, and 1320.0 F g-1 (594 C g-1) at a current density of 1 A g-1, along with high capacitance retention rate of 94 % after 10000 discharge cycles. The fabricated symmetrical supercapacitor device by using the best performed electrode (10 PGNF), displayed a high capacitance value of 303 F g-1 at a scan rate of 5 mV s-1, with 96 % initial capacitance retention value after a long 10000 discharge cycles along with a good energy density of 5.5 Wh kg-1 while maintaining a high power density of 1008.0 W kg-1 at a current density of 4 A g-1, and still produces an energy density of 4.0 Wh kg-1 at a high power density of 3600.0 W kg-1 at the applied current density of 14 A g-1. The superior results showed by the material is mainly due to the inclusion of PG having high surface area and pore volume, in addition to that NiFe2O4 nanoparticles presence also increased the electronic conductivity by acting as spacer to keep the neighboring sheets apart along with it has maintained the mechanical strength during continuous electrochemical redox process. Thus, we believe that the increased electrochemical performance is mainly due to the synergetic effect of the materials which not only provided enough electroactive channels for the smooth passage of electrolyte ions but also maintained the hybrid structure intact in the ongoing electrochemical process. The obtained result supports the promising utility of this material for future electrochemical energy storage devices.
Keywords: Porous graphene, NiFe2O4 nanoparticles, composite, specific capacitance, cyclic stability.
(Invited) A New Family of Lithium-Rich Layered Sulfides (Li[LitTi1-t]S2, 0 < t ≤ 0.33) Belonging to the LiTiS2 – Li2TiS3 System
Authors: Delmas Claude , Flamary Florian , Boulineau Adrien , Martinez Hervé , Suchomel Matthew , Pecquenard Brigitte , Le Cras Frederic 
Published: May 2020

Li-rich layered oxide (Li[LixM1-x]O2, (M = Mn, Ni, Co,...) positive electrode materials are considered as a key component for next generation lithium ion batteries, as they display outstanding specific energy originating from a combination of additional lithium de-intercalation and the unusual oxidation of oxygen anions.
Recently we have extended these studies to the homologous titanium sulfides belonging to the LiTiS2 – Li2TiS3 system. Layered Li2TiS3 was obtained for the first time by direct reaction of Li2S on TiS2. Its structure is similar to the Li2MnO3 one, with a small amount of stacking faults. Overlithiated compositions (Li[LitTi1-t]S2, (0 < t ≤ 0.33)) were synthesized by direct synthesis from Li2TiS3 and LiTiS2 and structurally characterized. While LiTiS2 exhibits the O1 type sulfur packing, all compositions with ~0.08 < t ≤ 0.33 exhibit the O3 type sulfur packing like the homologous oxides.
High resolution HAADF images recorded for the Li2TiS3 end-member reveal that lithium and titanium are fully ordered within the [Li1/3Ti2/3]S2 slabs of the typical honeycomb lattice usually observed for Li-rich layered oxides. Nevertheless, stacking faults are observed along the hexagonal C axis. In the Li[LitTi1-t]S2, (0.08 < t ≤ 0.33) solid solution the honeycomb ordering is observed only in some domains thank to the departure from the ideal ratio required for the ordering.
The electrochemical studies shows that up to 1.1 Li per Li[LitTi1-t]S2 can be reversibly cycled with a negligible irreversibility. The high capacity (≈240 mAh/g) and the shape of the charge curves suggest that Ti3+ ions are oxidized in a first step and the S2- ions in a second step to form S2
2- ions. The very small irreversibility results from the easy oxidation of S2- ions, which does not induce any sulfur release from the particle surface and subsequent structural densification. The XPS study of the deintercalated material confirms the formation of S2
2- species.
Contrary to oxides, there is a very small fading and voltage decay upon cycling. This behavior suggests that there is no significant structure modification as it is observed in lithium-rich oxides. In a particular composition range, they exhibit high electrochemical performance with a reversible capacity and an energy density exceeding respectively 265 mAh·g-1 and 600 Wh·kg-1, a very low irreversible capacity in the first cycle, fast activation and a limited voltage decay.
Their operation potential within the electrochemical stability window of sulfide-based fast ionic conductors makes them promising cathode materials for all-solid-state lithium and Li-ion batteries.
Improving the Efficient of Porphyrin-Based Organic Solar Cell
Authors: Cuesta Virginia , de la Cruz Pilar , Sharma Ganesh , Langa Fernando 
Published: May 2020

The optical and electrochemical properties of porphyrins can be tailored by changing the central metal and functionalization of the periphery, being excellent candidates as donors for Organic Solar Cells (OSCs). In the early years, the PCE values of OSCs based on porphyrins were very low, but by structural modifications, we achieve efficiencies in the range of 9-10%. In this presentation, I´ll show our recent work in design, synthesis and application of A−π−D−π−A and D−π−A−π−D porphyrin-based small molecules for efficient OSCs (»10%).

Figure 1. A−π−D−π−A and D−π−A−π−D porphyrin-based small molecules
References
1. 1. V. Cuesta, M. Vartanian, P. d. l. Cruz, R. Singhal, G. D. Sharma and F. Langa, J. Mater. Chem. A, 2017,
5, 1057-1065.
2. S. Arrechea, A. Aljarilla, P. de la Cruz, M. K. Singh, G. D. Sharma, F. Langa. J. Mater. Chem. C,
2017, 5, 4742.
3. 5. M. Vartanian, R. Singhal, P. de la Cruz, S. Biswas, G. D. Sharma and F. Langa, ACS Appl. Energy Mater.
2018, 1, 1304.
4. 6. M. Vartanian, P. de la Cruz, F. Langa, S. Biswas, G. D. Sharma. Nanoscale,
2018, 10, 12100-12018.
5. M. Vartanian, R. Singhal, P. de la Cruz, G. D. Sharma, F. Langa, Chem. Commun, 2018, 54,14144-14147.
6. V. Cuesta, R. Singhal, P. de la Cruz, G. D. Sharma, F. Langa, ACS Mater. Interfaces, 2019, 11, 7216-7225.

Figure 1
Acroleylcorroles
Authors: Paolesse Roberto , Caroleo Fabrizio , Di Zazzo Lorena , Nardis Sara , Petrella Greta , Cicero Daniel Oscar 
Published: May 2020

Corrole continues to attract the interest of different research groups, since this macrocycle shows peculiar and intriguing characteristics, which open its application in different fields.
For this reason, the functionalization of the corrole is a fundamental step for the optimization of the macrocycle features for the target application.
We have been interested in the introduction at the peripheral positions of the corrole ring of acroleyl groups by Vilsmeier reaction, because they can allow the preparation of hybrid materials by grafting the corrole derivative onto poly-acrolein microballs. These hybrid materials have been successfully exploited to develop chemical sensors.
The regioselectivity of the Vilsmeier reaction strongly depends on the corrole structure and in the case of the free base the macrocyclic inner core showed an unexpected reactivity.
The characterization of these species, together the applications of the functionalized corroles will be presented and discussed.
Host-Guest Chemistry of Porphyrins in Liquid Crystalline Macrocycles
Authors: Tanaka Kentaro 
Published: May 2020

Structurally well-defined macrocyclic molecules have great potential to accommodate specific guest molecules in the hollow. Recently, we have reported a series of macrocycles which are composed of four carbazoles connected with four salphen ligands1, four dibenzothiophenes connected with four salen ligands2, or four diindrocarbazoles connected with four salphen ligands3 (MC1, MC2 and MC3, respectively). The macrocycles with appropriate peripheral alkyl chains and their tetranuclear metal complexes with square planar metal ions showed thermotropic columnar liquid crystalline properties1,2. These macrocycles stacked to form columns inside the fluid materials. Especially, the giant macrocycle MC3 contained a square hollow with a diagonal of 2.5 nm. This giant macrocycle has the largest inner cavity among known discrete shape-persistent macrocycles that exhibit thermotropic LC properties. The size and shape of the hollow structure make it interesting for molecular inclusion applications. For example, MC3 molecule can accommodate a tetrapyridylporphyrin inside the hollow to afford a planar conjugate, and the conjugate showed liquid crystalline behavior.

Reference:

[1] S. Kawano, Y. Ishida, and K. Tanaka, J. Am. Chem. Soc.
2015, 137, 2295.
[2] Kawano, S.; Hamazaki, T.; Suzuki, A.; Kurahashi, K.; Tanaka, K. Chem. Eur. J.
2016, 22, 15674-15683.
[3] Kawano, S.; Kato, M.; Somiya, S.; Nakayama, M.; Onoe, J.; Tanaka, K. Angew. Chem. Int. Ed.
2018, 57, 167–171.

Figure 1