bluuebunny/crossref_metadata_2025_split huggingface dataset:
Correlating Solid-Electrolyte Interface Composition to Charge Transfer Resistance for Improved Low-Temperature Performance of Lithium-Ion Batteries
Authors: Singh Triesha , McCloskey Bryan D. 
Published: February 2024

The adverse impact of low temperatures on Li-ion batteries (LIBs) is a well known challenge. Currently, at subfreezing temperatures, the efficiency of conventional LIBs greatly decreases compared to their room temperature performance, which of course severely limits the performance of applications using LIBs in the colder regions on the planet. From a fundamental perspective, the causes of such performance decreases are yet to be fully understood, but are believed to be related to the ability of ions to move through the various phases (as well as move across phase interfaces) that exist in the battery.
Several studies have been conducted to improve the low-temperature performance of LIBs, most of them focusing on using solvents with lower viscosity and higher dielectric constant to promote transport through the electrolyte at the lower temperatures so as to achieve lower bulk resistance (Rbulk) of the cell. However, our Electrochemical Impedance Spectroscopy (EIS) studies at low temperatures have indicated that it is the charge transfer resistance (Rct) that grows exponentially as we go to sub-zero Celsius temperatures and is responsible for the increase in the total resistance of the cell. EIS on 3-electrode cells have shown that the anode side (Gr) is predominantly responsible for the poor cell performance, necessitating our focus on the charge transfer process in the Gr-electrolyte interface. We observe that the Rct is not only related to the Li-solvation shell but also to the composition of the Solid Electrolyte Interface (SEI). By modifying the electrolyte, such as by changing the salt concentration, adding additives, and changing the solvent, significant changes in the interface and hence in the RSEI and Rct of the cell have been observed. By combining EIS with various techniques like mass spectrometry, differential capacity analysis and SEM, we have been able to better understand the SEI composition and its impact on interfacial resistances. We specifically focus on the influence of SEI composition on the charge-transfer resistance of the cell, correlating the effect of amounts of LiF and carbonates in the SEI with the interfacial performance of the cell. Through these relations, we aim to facilitate the development of electrolytes by having a better understanding of the solvation shells and the SEI composition for low temperature performance.
Transition-Metal Interdiffusion in Solid-State Batteries Revealed By Cryo-TEM
Authors: Zhang Ruizhuo , Strauss Florian , Jiang Lin , Casalena Lee , Li Letian , Janek Jürgen , Kondrakov Aleksandr , Brezesinski Torsten 
Published: February 2024

Solid-state lithium-ion batteries are being considered as a future energy-storage technology, with superior energy/power density and improved safety over conventional lithium-ion batteries. However, their commercial implementation is hampered by side reactions and electro-chemo-mechanical degradation occurring during cycling (mostly at the positive electrode side). Many efforts have been made to reveal the underlying mechanisms in order to alleviate such problems.
In the current study, the Thermo Scientific IGST workflow solution was used to enable a DualBeam to TEM workflow by protecting both bulk sample and prepared lamella under argon atmosphere with a CleanConnect transfer module. Because of the beam and temperature sensitivity of the superionic lithium thiophosphate solid electrolyte and the cathode interphases formed during cycling, the lamella preparation process (incl. bulk milling, lift out, attachment to the TEM grid, and final thinning) was carried out at cryogenic temperature (−178 °C). The lamella was then transferred to a Talos F200X CFEG for TEM analysis using an inert gas sample transfer workflow.
STEM and EELS investigations revealed Ni, Co, and Mn dissolution from a Ni-rich cathode and subsequent solid electrolyte poisoning. Transition-metal dissolution/migration during cycling operation has previously only been reported for conventional (liquid-electrolyte-based) batteries.
Screening of First-Row Transition Metal Complexes for Aqueous Redox Flow Batteries: Experimental and Density Functional Theory Approaches
Authors: Rahbani Noura , de Silva Piotr , Bellay Corentin , Guihéneuf Solène , Godet-Bar Thibault , Baudrin Emmanuel 
Published: February 2024

The development of redox flow batteries took new directions in the last decades. From initial metal-based systems, it evolved towards organic and hybrid approaches in aqueous media. Furthermore, redox targeting flow batteries are an emerging alternative to the traditional redox flow battery architecture which offer improved energy density via an added electroactive solid ‘booster’. Whatever the system, there is a need of soluble electroactive species with potentials allowing large cell potentials within the water stability window or imperative redox potentials matching between soluble redox mediator and the solid for redox targeting. Transition metal complexes are a promising class of redox electroactive centers due to the tunability of their solubility and electrochemical potential, and the ability to take into account sustainability1. Recent reports underlined for instance that either the modification of the ligand2 or using heteroleptic complexes3, can lead to iron complexes with solubilities higher than 1 M and potentials higher than 1 V vs SHE. Furthermore, reliable and time-efficient prediction tools for the redox potentials of transition metal complexes are needed to help the search for new potential systems. While density functional theory usually provides a good trade-off between computational cost and accuracy, calculations on transition metal complexes often result in large errors. We thus developed a procedure and compared different solvation methods and levels of theory using an initial experimental data set based on aqueous iron complexes with bidentate ligands (Figure 1).
In the present contribution, we will illustrate this coordination approach through a screening of new complexes based on non-toxic and affordable transition metal complexes. In this perspective, electrochemical characterization at different pH, coupled with NMR and UV-Visible studies will be presented, to screen for new candidates as electrolyte in redox flow batteries. Finally, we will show how the calculations corrected using a simple linear regression using training data yields a good prediction of redox potentials (mean average error =0.09 V).

References:

(1) Robb B.H.; Waters S.E.; Marshak M.P., Evaluating aqueous flow battery electrolytes: a coordinated approach, Dalton Trans., 2020; 49: 16047.
(2) Gao J, Amini K, George TY, et al. A High Potential, Low Capacity Fade Rate Iron Complex Posolyte for Aqueous Organic Flow Batteries. Adv Energy Mater. 2022; 12: 2202444.
(3) Li X, Gao P, Lai YY, et al. Symmetry-breaking design of an organic iron complex catholyte for a long cyclability aqueous organic redox flow battery. Nat Energy. 2021;6(9):873

Figure 1
Designing Metal Complexes for Redox Flow Batteries By High-Throughput Synthesis
Authors: Li Qiujun , Peljo Pekka 
Published: February 2024

Redox flow batteries (RFBs) are an attractive device for high-capacity energy storage systems. Due to the disadvantages of vanadium RFBs such as high cost and limited temperature operability [1], researchers have been developing new redox couples to replace vanadium. The use of relatively inexpensive transition metals (Fe, Cr, Co, etc.) in combination with ligands to form metal-ligand complexes has received considerable attention [2]. The redox potential of a metal ion of a metal-ligand complex can be tuned by forming a complex with a ligand, and the metal-ligand complex form helps alleviate the crossover problem [3].
A major challenge in the discovery and development of functional materials is to find and select the most optimized candidates from millions of possible materials [4]. High-throughput Synthesis (HTSy) enables simultaneous screening, synthesis and characterization of a large number of different material classes, providing unprecedented throughput and reproducibility. Therefore, HTSy can save energy, time, and cost for more efficient discovery of advanced functional materials [5]. In this study, based on HTSy methods, we used an automatic synthesis device (OT-2 liquid pipetting robot) to mix and heat metals (Ni, Cr, Cu, etc.) and ligand liquids to automatically design metal complexes. At the same time, a robot platform is developed to perform high-throughput electrochemical tests to quickly select suitable metal complexes for RFBs, and then conduct further related RFBs performance tests.

References

[1] C. Zhang et al., “Progress and prospects of next-generation redox flow batteries,” Energy Storage Mater, vol. 15, pp. 324–350, Nov. 2018, doi: 10.1016/J.ENSM.2018.06.008.
[2] C. Noh, M. Shin, and Y. Kwon, “A strategy for lowering cross-contamination of aqueous redox flow batteries using metal-ligand complexes as redox couple,” J Power Sources, vol. 520, p. 230810, Feb. 2022, doi: 10.1016/J.JPOWSOUR.2021.230810.
[3] C. Noh, Y. Chung, and Y. Kwon, “Highly stable aqueous organometallic redox flow batteries using cobalt triisopropanolamine and iron triisopropanolamine complexes,” Chemical Engineering Journal, vol. 405, p. 126966, Feb. 2021, doi: 10.1016/J.CEJ.2020.126966.
[4] Q. Zhang, A. Khetan, E. Sorkun, and S. Er, “Discovery of aza-aromatic anolytes for aqueous redox flow batteries via high-throughput screening,” J Mater Chem A Mater, vol. 10, no. 41, pp. 22214–22227, 2022, doi: 10.1039/D2TA05674G.
[5] J. Rodriguez, M. Politi, S. Adler, D. Beck, and L. Pozzo, “High-throughput and data driven strategies for the design of deep-eutectic solvent electrolytes,” Mol Syst Des Eng, vol. 7, no. 8, pp. 933–949, 2022, doi: 10.1039/D2ME00050D.

Figure 1
Modification of Carbon Electrodes with Mxene (Ti3C2Tx) for Vanadium Redox Flow Batteries
Authors: Teenakul Kavin , Alem Sayed Ali Ahmad Ali Ahmad , Thakur Anupma , Anasori Babak , Khataee Amirreza 
Published: February 2024

MXenes, a group of two-dimensional materials, have gained considerable attention in the field of electrochemistry due to their outstanding electrical conductivity, high surface area, and hydrophilicity resulting from their rich surface chemistry. In this study, Ti3C2Tx MXene-coated carbon paper electrodes were prepared through drop-casting and tested for vanadium redox flow batteries (VRFBs). The resulting MXene-coated electrodes demonstrated a significant improvement in the electrochemical activity of the negative electrode of VRFBs (V(II)/V(III)) compared to heat-treated and untreated carbon paper.
The electrochemical activity of the V(II)/V(III) reaction on MXene-coated electrodes was characterized using cyclic voltammetry and electrochemical impedance spectroscopy techniques. The cyclic voltammetry results indicated that the MXene-coated electrodes displayed a peak current ratio (ipa/ipc) closer to 1 than heat-treated and untreated carbon paper. Electrochemical impedance spectroscopy shows that ohmic and charge transfer resistance are significantly reduced, rivaling a heat-treated carbon paper electrode. VRFB tests were conducted using MXene-coated electrodes on the negative side at a current density of 130 mA/cm2. Carbon paper anodes with MXene loading of 0.1 mg/cm2 maintained voltage efficiency and coulombic efficiency above 70% and 95% for 50 cycles, respectively, which is comparable to that of heat-treated carbon paper, whereas using untreated carbon paper, the voltage efficiency dropped below 60%.
Untreated carbon paper electrode has maximum discharge capacities of 77.4 mAh with a capacity loss of 36%. MXene-coated electrodes, on the other hand, showed impressive maximum discharge capacities of 178.8 mAh and a capacity loss of 19%.
Towards Operando Secondary Ion Mass Spectrometry Imaging of Lithium Redistribution in Solid-State Lithium-Ion Batteries: Correlation of Structural, Chemical and Electrochemical Characteristics
Authors: Eswara Santhana , Cressa Luca , Wirtz Tom 
Published: February 2024

Innovations in lithium-ion batteries rely crucially on the availability of advanced characterization techniques. High-resolution chemical imaging of low-Z elements e.g., lithium (Li) is often difficult in many conventional chemical analysis techniques such as Energy-Dispersive X-ray Spectroscopy. High-resolution Secondary Ion Mass Spectrometry (SIMS) imaging is a well-known technique for the analysis of all elements including isotopes. For this reason, SIMS imaging is used in numerous studies related to Li-ion battery research. While direct imaging of Li in post-mortem battery components is helpful to understand parts of the degradation mechanisms, a complete dynamic view of the evolution of the Li distribution at high resolution during operation (‘operando’) of batteries is required to fully understand the local interfacial processes, charge transport characteristics and the degradation mechanisms. A few reports presenting operando Time-of-Flight SIMS imaging of batteries have recently been published [1], but the lateral resolution demonstrated in these reports is not adequate to study local processes that occur at nanoscale.
In order to demonstrate operando SIMS chemical imaging with sub-20 nm lateral resolution, we developed a novel operando methodology suitable for Focused Ion Beam (FIB)-SIMS imaging and analysis (see Fig. 1). An in-house designed magnetic-sector mass spectrometer [2] attached to a ThermoFisher SCIOS Ga+ FIB is used for SIMS chemical imaging. A special operando sample holder was designed to enable electrochemical cycling of batteries within the FIB-SIMS instrument. The micromanipulator inside the FIB (typically used for preparing thin lamellae for Transmission Electron Microscopy) is used to contact one of the battery electrodes through the operando sample holder and complete the electrical circuit. An external potentiostat is then connected to the instrument to drive the charging/discharging of batteries. The proof-of-concept experiments were performed using Li|Li7La3Zr2O12|Li symmetric half-cells. Galvanostatic cycling was performed in-situ inside the FIB-SIMS instrument until the sample failed. SIMS chemical mapping revealed a redistribution of Li during cycling. Lithium rich phases appeared during cycling which likely percolated through grain-boundaries and pores of the solid electrolyte causing a short-circuit failure. These results validate our methodology for operando analysis of Li-ion batteries with the possibility to obtain SIMS chemical images with sub-20 nm lateral resolution [3].
This work was funded by the Luxembourg National Research Fund (FNR) through the grant INTER/MERA/20/13992061 (INTERBATT).
[1] Y. Yamagishi, et al., J. Phys.
Chem. Lett. 2021, 12, 19, 4623–4627
[2] O. De Castro, et al., Analytical Chemistry, 2022, 94, 30, 10754–10763.
[3] L. Cressa, et al., Analytical Chemistry, 2023, under review.

Figure 1
(Digital Presentation) Electrochemical Study of Mxene-Metal Oxide Composites for the Degradation of PVC-Based Microplastics
Authors: Alom Nur , Yeasmin Habiba , Han Tan Kim , Saidur R , Jamal Mamun 
Published: February 2024

Microplastics (MPs) are fragments of any type of plastic less than 5mm in length, and it is harmful to our ocean and aquatic life. In recent years, the prevalence of MPs in aquatic environments has grown to be a serious environmental problem that has recently gained lots of attention [1, 2]. However, there is still a lack of studies on electrocatalytic treatment for an effective breakdown of MPs [3]. Here, Mxene-Metaloxide composites modified graphite electrode-based electro-fenton (EF) technology has been proposed to break down polyvinyl chloride (PVC) MPs. Advanced oxidation processes are widely studied and applied for the decomposition of MPs. Hydroxyl radicals (•OH) were generated by the electro-oxidation (EO) and electro-peroxidation (EO- ) process which has exhibited great capability for catalytic degradation of MPs and converted into H2O and CO2.
In this work, electro-oxidation was carried out in a three-electrode system with an oxygen-saturated environment where Mxene-Metaloxide composites modified graphite electrode, graphite electrode, and Ag/AgCl electrode were used as a working electrode, counter electrode, and reference electrode respectively. Different operating parameters such as electrolyte type, electrolyte concentration, temperature, and reaction time were maintained for EO. Cyclic voltammetry was employed to analyze the catalytic performance of the MXene-TiO2/C modified graphite electrode in the context of the Oxygen Reduction Reaction. The obtained results revealed that the EO process can degrade 54.5% of MPs after potentiostatic electrolysis at -0.7V Ag/AgCl at 80 °C for 6 hours. Fig 1 presents the removal efficiency of PVC MPs in 0.05M Na2SO4 solution. The results from scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), UV-Vis spectroscopy, and Energy dispersive X-ray spectroscopy (EDX) revealed that the MPs degraded directly into CO2 and H2O. The results of this research showed that such a heterogeneous EF-like technology using Mxene-metal oxide composites modified graphite electrode was hoped to give an eco-friendly technique for treating MPs in wastewater.
References:
1. K. Dey, E. Uddin & M. Jamal, Environ. Sci. Pollut. Res., 2021, 28, 16925-16947
2. K. Dey, M. Rasel, T. Roy, E. Uddin, B. K. Pramanik & M. Jamal, Sci.Total Environ., 2023, 867, 161390
3. K. Dey, M. Jamal &E. Uddin, J. Water Process. Eng., 2023, 52, 103554
Fig. 1. Removal efficiency of MPs in 0.05M Na2SO4 solution.

Figure 1
Electrochemical Framework for Dynamic Tracking of Soil Organic Matter (SOM)
Authors: Dhamu Vikram Narayanan , Paul Anirban , Muthukumar Sriram , Prasad Shalini 
Published: February 2024

Soil Health parameters serve as excellent surrogate measures towards assessing environmental quality and understanding effects of climate change mitigation via carbon sequestration. Soil health monitoring in the near past has been highly qualitative and speculative with more recent advancements still trying to fill the void of determining a holistic soil profile through phantom based measurements. In fields and crop-circles, testing methods to perform in-situ profiling however from one lab is likely to vary with another and hence results are not universally compatible. Additionally, these normalized techniques ideally involve empirical approaches, extensive sample preparation which adds on to a temporal factor along with equipment for extraction and subsequently-analysis. Even with the upcoming research breakthroughs in non-destructive approaches like spectroscopy and tomography-based models, there is a barrier in-terms of equipment complexity and availability as well as high costs and high logistical overhead.
There are a wide number of redox systems present in soil that exist in reduced state under ideal conditions (submerged). While Carbon monitoring would be highly beneficial in the field, an overall sense of the organic matter nutrients present in soil denoted as soil organic matter understanding would offer a wholistic manner of surveying soil and environmental health. In this work, faradaic and non-faradaic measurements are utilized to determine threshold changes in soil electrochemical activity due to presence of various electroactive substances present in the matrix. First, a galvanostatic approach using the chronopotentiometry modality was applied to a soil slurry system- ‘test’ sample to which different levels (w/v %) of the following amendments were added to see how the effective charge modulation can be visualized. Utilizing this experimental framework as preliminary information- A hypothesized mechanism of interaction between the RTIL (Room Temperature Ionic-Liquid) modified electrode and the OM functional moieties based on hydrogen bonding and pi-pi interactions captured using charge-based (chronocoulometry) and interfacial mapping-based (electrochemical impedance spectroscopy) method is utilized to design and test a first-of-a-kind electrochemical soil organic matter (SOM) sensor.

Figure 1. Chronopotentiometric characterization of soil organic matter using an RTIL modified electrode.

Figure 1
Lithium-Ion Capacitor Characterization Using Optical Fiber Sensors
Authors: Wahl Markus Solberg , Guo Xiaoyang , Lamb Jacob , Boles Steven T , Burheim Odne Stokke 
Published: February 2024

With the high power density and long cycle life, lithium-ion capacitors (LICs) are anticipated to fill the performance gap with lithium-ion batteries. As LICs generally has one battery-type electrode with slow kinetics, and one capacitor-type electrode with fast kinetics, the bulk concentration of lithium ions is believed to change significantly. To capture the rapidly changing concentration and analyzing it with regards to the charge and discharge rates will reveal important information about the system.
The lithium-ion concentration is measured with an in-house built fiber-optic sensor setup, see Fig. 1. The fiber is placed between the electrodes (Fig. 1a) and the concentration-dependent reflectivity is measured (Fig. 1b). Calibration of the sensor using known concentrations enables the calculation of the electrolyte concentration with rapid acquisition and high accuracy (Fig. 1c).

Figure 1