Aprotic sulfur-metal batteries: lithium and beyond

Metal-sulfur batteries constitute an extraordinary research playground that ranges from fundamental science to applied technologies. However, besides the widely explored Li-S system, a remarkable lack of understanding hinders advancements and performance in all other metal-sulfur systems. In fact, similarities and differences make all generalizations highly inconsistent, thus unavoidably suggesting the need for extensive research explorations for each formulation. Here we review critically the most remarkable open challenges that still hinder the full development of metal-S battery formulations, starting from the lithium benchmark and addressing Na, K, Mg, and Ca metal systems. Our aim is to draw an updated picture of the recent efforts in the field and to shed light on the most promising innovation paths that can pave the way to breakthroughs in the fundamental comprehension of these systems or in battery performance

Dynamics of Mn3+ in off-stoichiometric LiMn1.5Ni0.5O4

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Super hygroscopic non-stoichiometric cerium oxide particles as electrode component for PEM fuel cells

The design of highly efficient promoters for the oxygen reduction reaction (ORR) is an important challenge in the large-scale distribution of proton exchange membrane (PEM) fuel cells. Hygroscopic cerium oxide (CeO2) is here proposed as co-catalyst in combination with Pt. Physical chemical characterizations, by means of X-ray diffraction, vibrational spectroscopy, morphological and thermal analyses, were carried out, demonstrating high water affinity of the synthesized CeO2 nanoparticles. Composite catalysts (i. e., Pt : CeO2 1 : 0.5 and 1 : 1 wt:wt), were studied by either rotating disk electrode (RDE) and fuel cell tests performed at 80 °C and 110 °C. Interestingly, the cell adopting the Pt : CeO2 1 : 0.5 catalyst enabled the achievement of high power densities reaching ∼80 and ∼35 mW cm−2 under low relative humidity and high temperatures. This result demonstrates that tuning material surface properties (e. g. oxygen vacancies) could significantly boost the electrochemical performance of cathodes as a combined result of optimized water retention and improved ORR kinetic

Deciphering the Interplay between Binders and Electrolytes on the Performance of Li4Ti5O12 Electrodes for Li-Ion Batteries

Lithium titanium oxide (Li4Ti5O12, LTO) is an attractive negative electrode for the development of safe-next-generation-lithium-ion batteries (LIBs). LTO can find specific applications complementary to existing alternatives for LIBs thanks to its good rate capability at high C-rates, fast lithium intercalation, and high cycling stability. Furthermore, LIBs featuring LTO electrodes are inherently safer owing to the LTO's operating potential of 1.55 V vs. Li+/Li where the commonly used organic-based electrolytes are thermodynamically stable. Herein, we report the combined use of water-soluble sodium alginate (SA) binder and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-tetraglyme (1m-T) electrolyte and we demonstrate the improvement of the electrochemical performance of LTO-based electrodes with respect to those operating in conventional electrolyte 1M LiPF6-ethylene carbonate: dimethyl carbonate (LP30). We also tackle the analysis of the impact of combining the binder/electrolyte on the long-term cycling performance of LTO electrodes featuring SA or conventional polyvinylidene fluoride (PVdF) as binders. Therefore, to assess the impact of the combination of binder/electrolyte on performance, we performed post-mortem characterization by ex situ synchrotron diffraction experiments of LTO electrodes after cycling in LP30 and 1m-T electrolytes

Highly stable Fe3O4/C composite: a candidate material for all solid-state lithium-ion batteries

Fe3O4 nanoparticles synthesized by a base catalyzed method are tested in an All-Solid-State (ASLB) battery using a sulfide electrolyte. The pristine nanoparticles were morphologically characterized showing an average size of 12 nm. The evaluation of the electrochemical properties shows high specific capacity values of 506 mAhg−1 after 350 cycles at a specific current of 250 mAg−1, with very high stability and coulombic efficiency

Singlet oxygen from cation driven superoxide disproportionation and consequences for aprotic metal-O2 batteries

Aprotic alkali metal-oxygen batteries require reversible formation of metal superoxide or peroxide on cycling. Severe parasitic reactions cause poor rechargeability, efficiency, and cycle life and have been shown to be caused by singlet oxygen (1O2) that forms at all stages of cycling. However, its formation mechanism remains unclear. We show that disproportionation of superoxide, the product or intermediate on discharge and charge, to peroxide and oxygen is responsible for 1O2 formation. While the overall reaction is driven by the stability of peroxide and thus favored by stronger Lewis acidic cations such as Li+, the 1O2 fraction is enhanced by weak Lewis acids such as organic cations. Concurrently, the metal peroxide yield drops with increasing 1O2. The results explain a major parasitic pathway during cell cycling and the growing severity in K-, Na-, and Li-O2 cells based on the growing propensity for disproportionation. High capacities and rates with peroxides are now realized to require solution processes, which form peroxide or release O2via disproportionation. The results therefore establish the central dilemma that disproportionation is required for high capacity but also responsible for irreversible reactions. Highly reversible cell operation requires hence finding reaction routes that avoid disproportionation

An electrochemical compatibility investigation of RTIL-based electrolytes with Si-based anodes for advanced Li-ion batteries

Silicon is amongst the most attractive anode materials for Li-ion batteries because of its high gravimetric and volumetric capacity; importantly, it is also abundant and cheap, thus sustainable. For a widespread practical deployment of Si-based electrodes, research efforts must focus on significant breakthroughs to addressing the major challenges related to their poor cycling stability. In this work, we focus on the electrolyte-electrode relationships to support the scientific community with a systematic overview of Si-based cell design strategies reporting a thorough electrochemical study of different room temperature ionic liquid (RTIL)-based electrolytes, which contain either lithium bis(fluorosulfonyl)imide (LiFSI) or lithium bis(trifluoromethylsulfonyl)imide (LiTFSI). Their galvanostatic cycling performance with mixed silicon/graphite/few-layer graphene electrodes are evaluated, with first cycle coulombic efficiency approaching 90% and areal capacity ≈2 mAh/cm2 in the limited cut-off range of 0.1–2 V vs. Li+/Li0. The investigation evidences the superior characteristics of the FSI-based RTILs with respect to the TFSI-based one, which is mostly associated with the superior SEI forming ability of FSI-based systems, even without the use of specific additives. In particular, the LiFSI-EMIFSI electrolyte composition shows the best performance in both Li-half cells and Li-ion cells in which the Si-based electrodes are coupled with 4V-class composite NMC-based cathodes

SnO2-Nafion\uae nanocomposite polymer electrolytes for fuel cell applications

Fuel cells are capable to exploit the combustion of hydrogen to convert chemical energy into electricity. Polymer electrolyte fuel cells based on Nafion membranes are able to work in a relatively low temperature range (70\u201390\ubaC) but require operating relative humidity (RH) close to 100%. To develop proton-exchange membranes with adequate performances at low RH, an attractive strategy consists of the incorporation of inorganic fillers into the host Nafion polymer. Here, we report on the incorporation of SnO2 nanopowders with high acidic properties as fillers in Nafion-based polymer electrolytes. Nanometre-sized sulphated SnO2 particles have been synthesised and incorporated in Nafion polymer membranes. Morphological and vibrational properties of the oxides and membranes, as well as their electrochemical behaviour, have been investigated by atomic force microscopy (AFM), micro-Raman and infra-red (IR) spectroscopies and electrochemical impedance spectroscopy (EIS). The nanocomposite electrolytes have been used to form a membrane-electrodes assembly with commercial Pt-based catalysts and tested in hydrogen fuel cells

High fidelity numerical fracture mechanics assisted by RBF mesh morphing

The study and design of cyclically loaded structures cannot neglect the evaluation of their fatigue behavior. Today numerical prediction tools allow adopting, in various industrial fields, refined and consolidated procedures for the assessment of cracked parts through analyses based on fracture mechanics. An high level of detail can be obtained through the use of well consolidated FEM methods, allowing an accurate and reliable calculation of the flaw Stress Intensity Factor (SIF) and its resulting prediction in terms of crack propagation. A challenging step for this computational workflow remains, however, the generation and update of the computational grid during crack evolution. It is in this context that radial basis functions (RBF) mesh morphing is emerging as a viable solution to replace the complex and time-consuming remeshing operation. The flaw front is updated, according to its propagation, by automatically deforming the numerical grid obtaining an evolutionary workflow suitable to be used for industrially-sized numerical meshes (many millions of nodes). A review of applications, obtained by exploiting FEA (Ansys Mechanical) and mesh morphing (RBF Morph) state of-the-art tools, is presented in this work. At first the proposed workflow is applied on a circular notched bar with a defect controlled by a two-parameters evolution. The same approach is then refined and demonstrated for a Multi Degree of Freedom (MDoF) case on the same geometry and on the vacuum vessel port stub from the fusion nuclear reactor Iter