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At least 1,585 records · Page 88

Concentration dependent properties and plastic deformation facilitate instability of the solid-electrolyte interphase in Li-ion batteries

Lithium-ion batteries (LIBs) often suffer from capacity fading and poor cyclic performance due to mechanical degradation of the solid-electrolyte interphase (SEI). Here we perform numerical simulations and theoretical analysis to elucidate the role of plasticity in wrinkling and ratcheting behaviors of an SEI/electrode system. A coupled diffusion and finite deformation framework is formulated and numerically implemented as a user-element subroutine (UEL) to describe transient lithium diffusion and accompanying elastic–viscoplastic deformation of the electrode. It is found that concentration dependent properties and plastic deformation facilitate wrinkling in such a system. A wrinkled morphology may further lead to ratcheting and related failure under cycling. A phase diagram of four types of cyclic behaviorsis identified in terms of the charging rate and time. Our analysis suggests several potential strategies to avoid wrinkling and ratcheting instabilities, such as charging/discharging the electrode at a sufficiently slow rate, and/or introducing a thick artificial SEI with a pre-tension.

25 ENERGY STORAGE↗

Interaction of beryllium with 316H stainless steel in molten Li 2 BeF 4 (FLiBe)

The increased demand in renewable energy resources has led to a renewed interest in nuclear reactors including a new generation of molten salt reactors. One of the issues encountered in handling of molten chloride or fluoride salts is the inability of metals to form and retain a protective oxide surface layer, generally chromium oxide. The low chromium content, nickel-based alloy INOR-8, later marketed as Hastelloy N, was specifically developed to contain molten fluorides. This alloy had some deficiencies, but its composition resulted in it incurring far less chromium depletion by the molten fluoride salts than alloys like 316 stainless steel. For the next generation of molten salt reactors, an alloy with pressure vessel code approval and higher temperature capability than Hastelloy N is required. Consequently, several reactor designers have reportedly chosen to build the reactor containment vessel from 316H stainless steel. In order to minimize corrosion of the stainless steel by the molten fluoride salt (2LiF-BeF 2 ), it is proposed to add beryllium metal to the salt to react with impurities and provide a means to lower the oxidation potential thus making the salt less corrosive. Even so, there is a concern whether the beryllium would react with components of the stainless steel. To address this concern, static capsule tests were conducted in which selected amounts of beryllium were added to capsules containing 2LiF-BeF 2 (FLiBe) salt and 316H stainless steel and Hastelloy N samples. Following exposure, the samples were cleaned and examined using a variety of analysis techniques including, optical microscopy, SEM-EDS, XPS, LIBS, XRD and EPMA. Tensile samples were also exposed in capsules, and those were subjected to tensile testing. Notably, It was found that for the level of beryllium additions used in this study, intermetallic compounds were formed which could be detrimental to the long-term performance of the 316H stainless steel.

36 MATERIALS SCIENCE↗

Research advances on cobalt-free cathodes for Li-ion batteries - The high voltage LiMn 1.5 Ni 0.5 O 4 as an example

LiMn 1.5 Ni 0.5 O 4 is one of the most promising cathode materials for use in either next generation lithium-ion batteries or all solid-state batteries. However, despite the significant Research and Development (R&D) carried out throughout the last two decades the material has not made serious inroads into market. One of the major reasons is the lack of consistency in the reported intrinsic properties and electrochemical performance owing to major controversies in synthesis, crystal structure and bulk and interfacial properties of LiMn 1.5 Ni 0.5 O 4 , notably in contact with electrolytes. This paper is a compelling review providing an assessment on the mainstream R&D dealing with the various crystal structures of LiMn 1.5 Ni 0.5 O 4 and their evolutions observed during synthesis and cycling in correlation with their electrochemical performance. Influence of electrolytes and additives along with modifications through doping and surface treatments are interrelated, and the electronic and ionic transport properties of the ordered and disordered LiMn 1.5 Ni 0.5 O 4 phases are discussed. Overall, this review provides a detailed assessment on LiMn1.5Ni0.5O4 and the underlying mechanisms governing its electrochemical performance broadly providing a focused framework for further advancement towards commercialization.

25 ENERGY STORAGE↗

The influence of temperature on area-specific impedance and capacity of Li-ion cells with nickel-containing positive electrodes

The temperature-dependent behaviors of five nickel-containing positive electrodes (NCA, NMC811, NMC622, NMC532, and NMC111) in lithium-ion batteries are investigated using an electrochemical protocol involving rate studies, mild aging (~100 cycles), and hybrid pulse power characterization (HPPC). Tests are conducted using coin-cells with graphite negative electrodes at -20 °C, 0 °C, 20 °C, and 40 °C. Three techniques are compared for determining the area-specific impedance (ASI): i) fits to the rate study average voltages, ii) fitting to the entire voltage curves using a regularization scheme, and iii) HPPC. When fit to an Arrhenius-type equation, all methods yield similar apparent activation energies (±2 kJ/mol) for the impedance, which range from -20 to -31 kJ/mol for the electrodes. Impedance growth increases with temperature but remains at less than 0.2% per cycle for most electrodes and temperatures. NCA and NMC811 are the exceptions, which yield 0.5% and 1.5% increases in ASI per cycle, respectively, at 40 °C. For cells with the same electrodes, the capacities are similar at 20 and 40 °C but reduce at lower temperatures, with up to a 52% reduction at -20 °C and 2C. The fade in energy of the cells during C/3 cycling is attributed to decreasing capacity as opposed to increasing ASI.

25 ENERGY STORAGE↗

Unlocking the value of recycling scrap from Li-ion battery manufacturing: Challenges and outlook

The growing global trend toward mobile electrification is primarily driven by the rising popularity of electric vehicles, leading to an unprecedented surge in demand for lithium-ion batteries. As a result, the importance of battery recycling has become increasingly apparent. Battery recycling aims to recover valuable materials from both spent batteries and battery manufacturing scraps. By recycling these resources, the reliance on raw material extraction is reduced, which benefits resource conservation and minimizes the need for new mining operations. While significant attention has been given to the recycling of spent batteries, less emphasis has been placed on the recycling and recovery of battery scraps. However, it is important to recognize that many gigafactories are still taking steps to improve their manufacturing processes, and end-of-life batteries take approximately 10 years to become suitable for recycling, the manufacturing scraps will serve as the primary sources for recycling in this decade. This review delves into the progress in recycling technologies associated with battery manufacturing scraps, shedding light on the challenges, opportunities, and evolving perspectives surrounding battery manufacturing scrap recycling. In conclusion, we aim to contribute to the knowledge base of battery manufacturing scrap recycling and promote a more comprehensive understanding of the subject.

25 ENERGY STORAGE↗

Direct reuse of graphite and lithium nickel manganese cobalt oxide (NMC) recovered from ultrafast-laser ablation debris in Li-ion battery electrodes

Here we demonstrate that debris collected from the ultrafast-laser ablation of graphite anodes can be directly reused in a lithium-ion battery with little to no negative effects on electrochemical performance. Further, we show that while post-ablation NMC (LiNi 0.33 Mn 0.33 Co 0.33 O) cathode debris will require additional processing before being incorporated into an electrode, its critical materials (nickel, manganese, and cobalt) are not lost during ablation and can be recovered for recycling. Pre- and post-ablation materials are characterized with a suite of diagnostics, including SEM, TEM, X-ray CT, EDS, and XRD, to study changes in material morphology, composition and crystal structure. Graphite exhibited little to no morphological or compositional changes and a slight annealing of its crystal structure. NMC underwent profound morphological and crystallographic changes, but retained its elemental composition. Finally, post-ablation materials were re-manufactured into electrodes and cycled vs lithium metal. Graphite showed equal or better capacity and Coulombic efficiency compared to pre-ablation electrodes, while the post-ablation NMC exhibited severely reduced electrochemical performance. Furthermore, we discuss the outlook for application of this work to advanced manufacturing lines that produce next-generation, laser-patterned electrodes.

25 ENERGY STORAGE↗

Enabling fast discharge of Li-ion batteries via electrolyte formulations for urban air mobility applications

High-power discharge requirements are critical for lithium-ion batteries (LIBs) used in electric Vertical Takeoff and Landing (eVTOL) vehicles that are increasingly considered in urban mobility. This investigation places a particular emphasis on understanding the impact of electrolytes on discharge processes and rate capability. We aim to compare the discharge behavior of LiBs using a conventional electrolyte (Gen 2: 1.2 M LiPF 6 in EC:EMC) and the dual salt LiTFSI-LiBOB-based electrolyte. Here we carefully examine the profiles of charging and discharging, the behavior during extended cycles, impedance spectroscopy results, and the characteristics of the electrode surface. Our research findings demonstrate the complex relationship between the composition of electrolytes and the specific high-power discharge requirements of electric vertical takeoff and landing (eVTOL) systems. This research highlights the importance of customizing electrolyte compositions to optimize energy storage density while simultaneously enabling higher power extraction to enhance performance in short-range electric aviation.

25 ENERGY STORAGE↗