Surface Analysis of Pristine and Cycled NMC/Graphite Lithium-Ion Battery Electrodes: Addressing the Measurement Challenges.

Lithium-ion batteries are the most ubiquitous energy storage devices in our everyday lives. However, their energy storage capacity fades over time due to chemical and structural changes in their components, via different degradation mechanisms. Understanding and mitigating these degradation mechanisms is key to reducing capacity fade, thereby enabling improvement in the performance and lifetime of Li-ion batteries, supporting the energy transition to renewables and electrification. In this endeavor, surface analysis techniques are commonly employed to characterize the chemistry and structure at reactive interfaces, where most changes are observed as batteries age. However, battery electrodes are complex systems containing unstable compounds, with large heterogeneities in material properties. Moreover, different degradation mechanisms can affect multiple material properties and occur simultaneously, meaning that a range of complementary techniques must be utilized to obtain a complete picture of electrode degradation. The combination of these issues and the lack of standard measurement protocols and guidelines for data interpretation can lead to a lack of trust in data. Herein, we discuss measurement challenges that affect several key surface analysis techniques being used for Li-ion battery degradation studies: focused ion beam scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and time-of-flight secondary ion mass spectrometry. We provide recommendations for each technique to improve reproducibility and reduce uncertainty in the analysis of NMC/graphite Li-ion battery electrodes. We also highlight some key measurement issues that should be addressed in future investigations.

A Critical Evaluation of the Effect of Electrode Thickness and Side Reactions on Electrolytes for Aluminum-Sulfur Batteries.

The high abundance and low cost of aluminum and sulfur make the Al-S battery an attractive combination. However, significant improvements in performance are required, and increasing the thickness and sulfur content of the sulfur electrodes is critical for the development of batteries with competitive specific energies. This work concerns the development of sulfur electrodes with the highest sulfur content (60 wt %) reported to date for an Al-S battery system and a systematic study of the effect of the sulfur electrode thickness on battery performance. If low-cost electrolytes made from acetamide or urea are used, slow mass transport of the electrolyte species is identified as the main cause of the poor sulfur utilization when the electrode thickness is decreased, whereas complete sulfur utilization is achieved with a less viscous ionic liquid. In addition, the analysis of very thin electrodes reveals the occurrence of degradation reactions in the low-cost electrolytes. The new analysis method is ideal for evaluating the stability and mass transport limitations of novel electrolytes for Al-S batteries.

Ion Speciation and Transport Properties of LiTFSI in 1,3-Dioxolane Solutions: A Case Study for Li-S Battery Applications.

Lithium-sulfur battery is considered to be one of the main candidates for "post-lithium-ion" battery generation because of its high theoretical specific capacity and inherently low cost. The role of electrolyte is particularly important in this system, and remarkable battery performances have been reported by tuning the amount of salt in the electrolyte. To further understand the reasons for such improvements, we chose the lithium bis(trifluoromethanesulfonyl)imide in 1,3-dioxolane electrolyte as a model salt-solvent system for a systematic study of conductivity and viscosity over a wide range of concentration from 10-5 up to 5 m. The experimental results, discussed and interpreted with reference to the theory of electrolyte conductance, lead to the conclusion that triple ion formation is responsible for the highest molal conductivity values before reaching the maximum at 1.25 m. At higher concentrations, the molal conductivity drops quickly because of a rapid increase in viscosity and the salt-solvent system can be treated as a diluted form of molten salt.

Ultrafast Ionic Liquid-Assisted Microwave Synthesis of SnO Microflowers and Their Superior Sodium-Ion Storage Performance.

Tin oxide (SnO) is considered one of the most promising metal oxides for utilization as anode material in sodium ion batteries (SIBs), because of its ease of synthesis, high specific gravimetric capacity, and satisfactory cycling performance. However, to aim at practical applications, the Coulombic efficiency during cycling needs to be further improved, which requires a deeper knowledge of its working mechanism. Here, a microflower-shaped SnO material is synthesized by means of an ultrafast ionic liquid-assisted microwave method. The as-prepared SnO anode active material exhibits excellent cycling performance, good Coulombic efficiency as well as a large capacity delivered at low potential, which is fundamental to maximize the energy output of SIBs. These overall merits were never reported before for pure SnO anodes (i.e., not in a composite with, for example, graphene). Additionally, by combining ex situ XRD and XPS, it is clearly demonstrated for the first time that the Sn-Na alloy, which is formed during the initial sodium sodiation, desodiates in two successive but fully separated steps. Totally different from the previous report, the pristine SnO phase is not regenerated upon desodiation up to 3 V vs Na/Na+. The newly disclosed reaction route provides an alternative view of the complex reaction mechanism of these families of metal oxides for sodium ion batteries.

Critical Insight into the Relentless Progression Toward Graphene and Graphene-Containing Materials for Lithium-Ion Battery Anodes.

Used as a bare active material or component in hybrids, graphene has been the subject of numerous studies in recent years. Indeed, from the first report that appeared in late July 2008, almost 1600 papers were published as of the end 2015 that investigated the properties of graphene as an anode material for lithium-ion batteries. Although an impressive amount of data has been collected, a real advance in the field still seems to be missing. In this framework, attention is focused on the most prominent research efforts in this field with the aim of identifying the causes of such relentless progression through an insightful and critical evaluation of the lithium-ion storage performances (i.e., 1st cycle irreversible capacity, specific gravimetric and volumetric capacities, average delithiation voltage profile, rate capability and stability upon cycling). The "graphene fever" has certainly provided a number of fundamental studies unveiling the electrochemical properties of this "wonder" material. However, analysis of the published literature also highlights a loss of focus from the final application. Hype-driven claims, not fully appropriate metrics, and negligence of key parameters are probably some of the factors still hindering the application of graphene in commercial batteries.

Boosting the power performance of multilayer graphene as lithium-ion battery anode via unconventional doping with in-situ formed Fe nanoparticles.

Graphene is extensively investigated and promoted as a viable replacement for graphite, the state-of-the-art material for lithium-ion battery (LIB) anodes, although no clear evidence is available about improvements in terms of cycling stability, delithiation voltage and volumetric capacity. Here we report the microwave-assisted synthesis of a novel graphene-based material in ionic liquid (i.e., carved multilayer graphene with nested Fe3O4 nanoparticles), together with its extensive characterization via several physical and chemical techniques. When such a composite material is used as LIB anode, the carved paths traced by the Fe3O4 nanoparticles, and the unconverted metallic iron formed in-situ upon the 1(st) lithiation, result in enhanced rate capability and, especially at high specific currents (i.e., 5 A g(-1)), remarkable cycling stability (99% of specific capacity retention after 180 cycles), low average delithiation voltage (0.244 V) and a substantially increased volumetric capacity with respect to commercial graphite (58.8 Ah L(-1) vs. 9.6 Ah L(-1)).

The role of graphene for electrochemical energy storage.

Since its first isolation in 2004, graphene has become one of the hottest topics in the field of materials science, and its highly appealing properties have led to a plethora of scientific papers. Among the many affected areas of materials science, this 'graphene fever' has influenced particularly the world of electrochemical energy-storage devices. Despite widespread enthusiasm, it is not yet clear whether graphene could really lead to progress in the field. Here we discuss the most recent applications of graphene - both as an active material and as an inactive component - from lithium-ion batteries and electrochemical capacitors to emerging technologies such as metal-air and magnesium-ion batteries. By critically analysing state-of-the-art technologies, we aim to address the benefits and issues of graphene-based materials, as well as outline the most promising results and applications so far.