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At least 73 records · Page 4

Lithium extraction composite for recovery of lithium from brines, and process of using said composition

A lithium extraction composite comprising: (i) a porous support and (ii) particles of a lithium-selective sorbent material coated on at least one surface of the support, wherein the support has a planar membrane, fiber (or rod), or tubular shape. A method for extracting and recovering a lithium salt from an aqueous solution by use of the above-described composition is also described, the method comprising (a) flowing the aqueous source solution through a first zone or over a first surface of the lithium extraction composite to result in selective lithium intercalation in the lithium-selective sorbent material in the first zone or first surface; and (b) simultaneously recovering lithium salt extracted in step (a) from said lithium-selective sorbent material by flowing an aqueous stripping solution through a second zone or over a second surface of the lithium extraction composite in which lithium ions from the first zone or first surface diffuse.

Bhave, Ramesh R.↗

Rechargeable ambient temperature lithium cells

The cycling performance of a secondary lithium cell with a 2-methyl THF lithium hectofluorarsenate electrolyte is discussed. Stripping efficiency, dendritization, passivation on standing, and discharge efficiency are considered.

Holleck, G. L.↗

Overcoming Anode Instability in Solid‐State Batteries through Control of the Lithium Metal Microstructure

Abstract Enabling the lithium metal anode (LMA) in solid‐state batteries (SSBs) is the key to developing high energy density battery technologies. However, maintaining a stable electrode–electrolyte interface presents a critical challenge to high cycling rate and prolonged cycle life. One such issue is the interfacial pore formation in LMA during stripping. To overcome this, either higher stack pressure or binary lithium alloy anodes are used. Herein, it is shown that fine‐grained ( d = 20 µm) polycrystalline LMA can avoid pore formation by exploiting the microstructural dependence of the creep rates. In a symmetric cell set‐up, i.e., LiǀLi 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZO)ǀLi, fine‐grained LMA achieves > 11.0 mAh cm −2 compared to ≈ 3.6 mAh cm −2 for coarse‐grained LMA ( d = 295 µm) at 0.1 mA cm −2 and at moderate stress of 2.0 MPa. Smaller diffusion lengths (≈ 20 µm) and higher diffusivity pathway along dislocations ( D d ≈ 10 −7 cm 2 s −1 ), generated during cell fabrication, result in enhanced viscoplastic deformation in fine‐grained polycrystalline LMA. The electrochemical performances corroborate well with estimated creep rates. Thus, microstructural control of LMA can significantly reduce the required stack pressure during stripping. These results are particularly relevant for “anode‐free” SSBs wherein both the microstructure and the mechanical state of the lithium are critical parameters.

25 ENERGY STORAGE↗

Li Stripping Behavior of Anode‐Free Solid‐State Batteries Under Intermittent‐Current Discharge Conditions

Anode‐free manufacturing holds promise to enable high energy densities and lower Lithium (Li)‐metal solid‐state batteries (LMSSBs). Nevertheless, in contrast to thick Li foil (>50 µm), the stripping capacity of in situ‐formed Li (10–30 µm) is limited due to diminished creep flow, resulting in reduced accessible capacity. This study explores the correlation between stripping capacity and surface roughness of garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. The results reveal that stripping capacity can be enhanced through the surface modification of solid electrolytes. Additionally, this study scrutinizes the stripping behavior of in situ Li under intermittent‐current discharge conditions, which are more relevant to the operational conditions of electric vehicles (EVs). It is demonstrated that, when compared to constant‐current stripping, intermittent‐current stripping effectively suppresses void formation and enhances the stripping capacity of in situ Li by 40%. It is considered that the intermittent current inhibits the accumulation of Li vacancies, thereby delaying the void formation. These findings provide valuable insights into the development of high‐performance anode‐free LMSSBs for EVs.

25 ENERGY STORAGE↗

Evaluating Pressure‐dependent Discharge Behavior of Foil Versus In situ Plated Lithium Metal Anodes in Solid‐State Batteries

Abstract Anode‐free manufacturing of solid‐state batteries (SSBs) shows promise to maximize energy density by eliminating excess lithium (Li) and simplifying battery production. However, high reversibility during discharge (stripping of Li) is necessary for long‐lifetime SSBs with a limited Li reservoir. Further, the plastic flow of Li changes depending on the Li thickness, leading to possible differences in discharge performance under stack pressure. This work investigates the pressure‐dependent discharge performance of anode‐free manufactured SSBs with in situ plated Li and compares the performance to that of conventional thick Li foil cells. Distinct stripping behavior is observed at low pressures (0–1 MPa), where Li diffusivity and initial interfacial contact may control accessible capacity, compared to high pressures (3–10 MPa) where mechanical deformation of Li likely governs stripping behavior. Analysis of impedance spectra collected during stripping shows that additional stack pressure delays the formation of deep, as opposed to lateral, voids in the Li anode. These results provide insights to guide the transition from thick Li foil anodes to anode‐free manufactured SSBs.

Haslam, Catherine G.↗

The stopping of deuterons in lithium

The interaction of 52 MeV deuterons with lithium was investigated, in view of the optimization of a lithium target for an intense neutron source based on the d-Li stripping reaction. The experimental results are compared with theoretical calculations obtained from an updated version of the Bragg code. This code describes in detail the interaction of charged particles with matter. Within the experimental uncertainties the theoretical results are well reproduced by the experiments.

NASA Program Space Medicine↗

Developing a model for the impact of non-conformal lithium contact on electro-chemo-mechanics and dendrite growth

Lithium dendrite growth hinders the use of lithium metal anodes in commercial batteries. We present a 3D model to study the mechanical and electrochemical mechanisms that drive microscale plating. With this model, we investigate electrochemical response across a lithium protrusion characteristic of rough anode surfaces, representing the separator as a porous polymer in non-conformal contact with a lithium anode. The impact of pressure on separator morphology and electrochemical response is of particular interest, as external pressure can improve cell performance. We explore the relationships between plating propensity, stack pressure, and material properties. External pressure suppresses lithium plating due to interfacial stress and separator pore closure, leading to inhomogeneous plating rates. For moderate pressures, dendrite growth is completely suppressed, as plating will occur in the electrolyte-filled gaps between anode and separator. In fast-charging conditions and systems with low electrolyte diffusivities, the benefits of pressure are overridden by ion transport limitations.

25 ENERGY STORAGE↗

The Impact of Lithium Anode Interface on Capacity Fade in Polymer Electrolyte-Based Solid-State Batteries

This study investigates the Li stripping-plating morphology and failure mechanisms in full cells consisting of a solid polymer electrolyte (SPE) with two commercial Li anodes: Li chip and Li foil. The primary identified failure mechanism of the SPE cell is capacity fade, regardless of the Li manufacturer. While the cathode’s role in capacity fade is evident, the Li anode significantly influences cycling performance, with Li foil cells cycling 50% longer than Li chip cells, a statistical difference. Further, post-mortem scanning electron microscopy and X-ray photoelectron spectroscopy results attribute the Li chip’s faster capacity fade to a loss of contact and continuous growth of the solid electrolyte interphase (SEI). Conversely, Li foil maintains consistent contact with the solid polymer, displaying a thin and stable SEI. Additionally, failure mechanisms between a gel electrolyte in previous work and the dry SPE are compared.

25 ENERGY STORAGE↗

Visualizing electrode assembly movement and lithiation heterogeneity in lithium-metal batteries using operando energy dispersive X-ray diffraction

There is renewed interest in Li-metal anodes in order to increase the energy density of battery cells. Here, we demonstrate an operando X-ray crystallography method to visualize lithiation gradients and electrode assembly movement during electrochemical cycling of a Li-metal cell containing a Ni-Mn-Co layered oxide cathode (NMC811). During charge, deposition of Li + ions from the cathode increases the Li foil thickness; during discharge, the thickness decreases as Li + ions are stripped off the foil. Additionally, the resulting periodic movement is observed through tracking of Bragg peaks from the ordered phases of the cathode and separator. In addition to this 3.6 μm/mAh displacement, continuous mossy Li build-up on the anode causes an irreversible drift of the assembly, which is similar to 11.3 μm/cycle. Furthermore, our data indicate significant lithiation gradients in the NMC811 cathode during the oxide relithiation, which is not observed during the delithiation.

25 ENERGY STORAGE↗

Dual Passivation of Cathode and Anode through Electrode–Electrolyte Interface Engineering Enables Long-Lifespan Li Metal–SPAN Batteries

The reliability and durability of lithium metal (Li 0 )–sulfur batteries are largely limited by the undesired Li 0 plating-stripping irreversibility and the detrimental polysulfide dissolution, yet approaches that can simultaneously address the above anodic and cathodic problems are scarce. In this study, we report the stable operation of a Li 0 -SPAN (sulfurized polyacrylonitrile) battery via an anode–cathode dual-passivation approach. By combination of a fluorinated localized high concentration electrolyte (LHCE) and a Li 3 N-forming additive (TMS-N 3 ), robust and highly conductive electrode passivation layers are formed in situ on the surface of both the Li 0 anode and the SPAN cathode. The resulting highly reversible, dendrite-free, and high-density Li 0 plating morphology enables a high Coulombic efficiency of 99.4%. Advanced tender energy X-ray spectroscopy also reveals the eliminated Li 2 S formation and minimized polysulfide dissolution in SPAN cathodes, leading to a high capacity of 580 mAh/g SPAN and stable cycling with negligible capacity decay (0.7%) for 800 cycles. This electrode–electrolyte interphase engineering strategy has tackled the major limitations of Li–S batteries in both ether- and carbonate-based electrolyte systems and under a wide temperature range from –10 to +50 °C, thus providing insightful guidelines for the rational design of highly durable and high-energy-density Li 0 -S batteries.

25 ENERGY STORAGE↗

Main-sequence mass loss and the lithium dip

The significant dip in observed lithium abundances for Population I stars near M about 1.3 solar mass is discussed. It is noted that this dip occurs near where the instability strip crosses the main sequence on the lower edge of the Delta Scuti stars and that stellar pulsations are expected to give rise to mass loss. A total mass loss of 0.05 solar mass over the main-sequence lifetime of these stars would be sufficient to explain the observations of lithium depletion. The absence of a dip in the Pleiades and of significant depletion of beryllium in the Hyades places tight constraints on the rate of mass loss. These constraints make unlikely the high main-sequence mass-loss rates which would significantly affect globular cluster ages.

Schramm, David N.↗

Interfacial Defect of Lithium Metal in Solid‐State Batteries

Abstract All‐solid‐state battery with Li metal anode is a promising rechargeable battery technology with high energy density and improved safety. Currently, the application of Li metal anode is plagued by the failure at the interfaces between lithium metal and solid electrolyte (SE). However, little is known about the defects at Li–SE interfaces and their effects on Li cycling, impeding further improvement of Li metal anodes. Herein, by performing large‐scale atomistic modeling of Li metal interfaces with common SEs, we discover that lithium metal forms an interfacial defect layer of nanometer‐thin disordered lithium at the Li–SE interfaces. This interfacial defect Li layer is highly detrimental, leading to interfacial failure such as pore formation and contact loss during Li stripping. By systematically studying and comparing incoherent, coherent, and semi‐coherent Li–SE interfaces, we find that the interface with good lattice coherence has reduced Li defects at the interface and has suppressed interfacial failure during Li cycling. Our finding discovered the critical roles of atomistic lithium defects at interfaces for the interfacial failure of Li metal anode, and motivates future atomistic‐level interfacial engineering for Li metal anode in solid‐state batteries.

Yang, Menghao↗

The passivity of lithium electrodes in liquid electrolytes for secondary batteries

Rechargeable Li metal batteries are currently limited by electrolyte decomposition and rapid Li consumption. Li plating and stripping greatly depend on the solid electrolyte interphase formed at the Li metal-liquid electrolyte interface. This Review discusses the reactions occurring at this interface from a corrosion science perspective, highlighting the requirements for an ideal passivation layer. Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decomposition and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liquid electrolyte interface. Additionally, the formation of a passivation film (that is, a solid electrolyte interphase) determines ionic diffusion and the structural and morphological evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chemical reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochemical stripping and plating of Li during battery operation. Finally, we discuss solutions to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chemistry, cell engineering and the intrinsic instability of the Li metal-electrolyte interface.

25 ENERGY STORAGE↗

Interfacial Defect of Lithium Metal in Solid-State Batteries

All-solid-state battery with Li metal anode is a promising rechargeable battery technology with high energy density and improved safety. Currently, the application of Li metal anode is plagued by the failure at the interfaces between lithium metal and solid electrolyte (SE). However, little is known about the defects at Li–SE interfaces and their effects on Li cycling, impeding further improvement of Li metal anodes. Herein, by performing large-scale atomistic modeling of Li metal interfaces with common SEs, we discover that lithium metal forms an interfacial defect layer of nanometer-thin disordered lithium at the Li–SE interfaces. Further, this interfacial defect Li layer is highly detrimental, leading to interfacial failure such as pore formation and contact loss during Li stripping. By systematically studying and comparing incoherent, coherent, and semi-coherent Li–SE interfaces, we find that the interface with good lattice coherence has reduced Li defects at the interface and has suppressed interfacial failure during Li cycling. Our finding discovered the critical roles of atomistic lithium defects at interfaces for the interfacial failure of Li metal anode, and motivates future atomistic-level interfacial engineering for Li metal anode in solid-state batteries.

25 ENERGY STORAGE↗

Tuning Solid Electrolyte Interphase Formation before Plating Onset in Anode-Free Sodium Batteries

Sodium (Na) batteries are of growing interest due to the higher earth abundance of sodium than lithium, as well as their promising theoretical energy density when metallic Na anodes are used. However, Na plating and stripping are heavily influenced by the physicochemical properties of the solid electrolyte interphase (SEI), which is directly influenced by the solvent and salt used for the electrolyte. While most studies focus on the SEI that forms on the surface of Na metal after plating, we expand this analysis by identifying a nanoscale “pre-plating” SEI that forms on the current collector (CC) prior to the onset of Na plating. Here, we systematically investigate an array of Na salt and glyme solvents in the electrolyte and determine the associated impacts on pre-plating SEI formation on aluminum CCs. By combining analytical electrochemistry approaches with a multimodal suite of spectroscopy techniques (X-ray, infrared, and Raman), supported by density functional theory calculations, we reveal a direct correlation between the Na + coordination environment and pre-plating SEI composition. We find that longer-chain glymes produce larger proportions of organic alkoxide products in the interphase, consistent with increased Na + −glyme interactions, while the fraction of salt-derived inorganic products (e.g., NaF) correlates with Na + −anion coordination. These insights highlight the critical influence of electrolyte composition particularly solvent identity and Na + coordination on the initial SEI formation in anode-free Na batteries.

anode-free batteries↗

Ambient Rare Earth Metal Electrodeposition in Nitrogen-Coordinated Silylamide Electrolyte

The transition to a sustainable, low-carbon economy demands energy-efficient and environmentally benign methods for rare earth metal (REM) production. Furthermore, while high-temperature molten salt electrolysis remains energy-intensive, corrosive, and environmentally unfriendly, emerging room-temperature processes based on conventional ionic liquids are also hindered by high viscosity and chemical instability. In this study, a nitrogen-coordinated, water-, oxygen-, and fluorine-free silylamide-based electrolyte is presented as a promising system for room-temperature REM electrodeposition. Derived from commercially available lithium silylamide precursors, the system enables facile synthesis, broad electrochemical stability, and tunable metal–ligand interactions. Electrochemical analysis reveals high voltammetric stripping reversibility, stable cathodic and anodic potentials, and selective neodymium (Nd) deposition at appreciable current densities (>1 mA/cm 2 ), with minimal parasitic reactions. Bulk experiments produced high-purity Nd with reproducible performance across multiple batches. Scaled deposition yielded over 1 g of Nd with near-theoretical mass efficiency (0.40 mg/C) and >90% purity. Using sacrificial dysprosium (Dy) and Nd metal anodes, the system maintained constant Nd loading during extended deposition and enabled cathodic codeposition of stripped anode material, demonstrating the electrolyte’s dual functionality for REM electrorefining. Collectively, this silylamide platform offers a compelling combination of electrochemical robustness, chemical resilience, and process scalability for sustainable ambient REM recovery.

36 - MATERIALS SCIENCE↗

Kinetic Parameters and Diffusivity of Uranium in FLiNaK and ClLiK

Anodic stripping voltammetry (ASV) and cyclic voltammetry (CV) measurements at 773, 823, and 873 K were made of uranium trifluoride (UF 3 ) in lithium fluoride-sodium fluoride-potassium fluoride eutectic (FLiNaK) and uranium trichloride (UCl 3 ) in lithium chloride-potassium chloride eutectic (ClLiK). ASV data were used to estimate the charge transfer coefficients, exchange current densities, and activation energies of the uranium reactions. Charge transfer coefficients of both salt systems were within the range of 0.17 to 0.38. Exchange current densities in the fluoride and chloride salts were estimated within the range of 0.060 to 0.12 A cm -2 . Activation energy of uranium exchange current was 16.0 kJ mol -1 in the fluoride salt and 28.9 kJ mol -1 in the chloride salt. Kinetics of charge transfer were found to be faster in FLiNaK. Analyses of the CV data suggest the electrochemical system was diffusion controlled and irreversible in the chloride and fluoride salt mixtures. Diffusion coefficients of uranium in the range of temperatures were on the order of 10-5 cm 2 s -1 in both systems. Greater values of diffusivity in ClLiK are attributed to its lower density compared with FLiNaK. Activation energy of uranium diffusion in the fluoride and chloride salt mixtures were 53.4 and 89.4 kJ mol -1 , respectively.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A Self-Healable Sulfide/Polymer Composite Electrolyte for Long-Life, Low-Lithium-Excess Lithium-Metal Batteries

Solid electrolyte-protected lithium-metal anodes promise energy-dense, safe cells. While sulfide solid electrolytes enable facile processability and fast ion transport, they suffer from complex chemo-mechanical issues, including Li plating-induced fracture and Li stripping-induced contact loss. To address these issues, a grafting approach is implemented to functionalize the sulfide solid electrolyte (Li 3,85 Sn 0.85 Sb 0.15 S 4 ) with a self-healing unit. This leads to a dynamic bonding between the solid electrolyte network and a mechanically robust polymer scaffold, which reversibly accommodates the volume changes of the lithium-metal anode. Thus, the approach improves the interfacial contact between the lithium-metal anode and the composite electrolyte, enabling stable cycling at a mild stack pressure (160 kPa). With a negative to positive capacity ratio equals to 1, pouch full cells with a high-nickel cathode (nickel content > 90%) and lithium-metal anode display 92% capacity retention for 140 cycles. Engineering the interface between solid electrolyte and the polymeric binder offers a promising pathway to address the chemo-mechanical issues.

36 MATERIALS SCIENCE↗