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At least 127 records · Page 7

Magnetic Field-Suppressed Lithium Dendrite Growth for Stable Lithium-Metal Batteries

Lithium metal is the most attractive anode material due to its extremely high specific capacity, minimum potential, and low density. However, uncontrollable growth of lithium dendrite results in severe safety and cycling stability concerns, which hinders the application in next generation secondary batteries. In this paper, a new and facile method imposing a magnetic field to lithium metal anodes is proposed. That is, the lithium ions suffering Lorentz force due to the electromagnetic fields are put into spiral motion causing magnetohydrodynamics (MHD) effect. This MHD effect can effectively promote mass transfer and uniform distribution of lithium ions to suppress the dendrite growth as well as obtain uniform and compact lithium deposition. The results show that the lithium metal electrodes within the magnetic field exhibit excellent cycling and rate performance in a symmetrical battery. Additionally, full batteries using limited lithium metal as anodes and commercial LiFePO 4 as cathodes show improved performance within the magnetic field. In summary, a new and facile strategy of suppressing lithium dendrites using the MHD effect by imposing a magnetic field is proposed, which may be generalized to other advanced alkali metal batteries.

25 ENERGY STORAGE↗

Redox-Active Crown Ether Copolymer for Selective Lithium Recovery from Spent Lithium-Ion Batteries

The increasing demand for lithium, alongside concerns over resource scarcity and supply chain risks, has driven the need for alternative lithium sources, particularly from spent lithium-ion batteries (LIBs). Here, in this work, we introduce a redox-active crown ether copolymer designed for highly selective and electrochemically reversible lithium recovery from organic LIB leachates. A lithium-selective moiety, (12-crown-4)methyl methacrylate (12C4MA), is combined with a redox-active moiety, ferrocenylpropyl methacrylamide (FPMAm), into a redox copolymer electrosorbent to replace acid-based regeneration with electrostatic repulsion. The redox response enhances lithium ingress into the polymer, doubling lithium uptake (0.58 mol Li /mol CrE ) and enabling electrochemical regeneration upon the FPMAm oxidation. Our system exhibits exclusive lithium uptake, even in complex leachates containing competing metals (e.g., iron, nickel, and cobalt) and organic degradants. Techno-economic analysis highlights high energy efficiency and competitive lithium pricing to the market value (∼$12.7 per kg Li ). Overall, our work demonstrates a scalable, electrified adsorbent platform for sustainable and chemical-free critical metal recovery.

adsorption↗

VUV/XUV measurements of impurity emission in plasmas with liquid lithium surfaces on LTX [VUV/XUV measurements of low recycling plasmas with liquid lithium surfaces on LTX]

The VUV/XUV spectrum has been measured on the Lithium Tokamak eXperiment (LTX) using a transmission grating imaging spectrometer (TGIS) coupled to a direct-detection x-ray charge-coupled device camera. TGIS data show significant changes in the ratios between the lithium and oxygen impurity line emission during discharges with varying lithium wall conditions. Lithium coatings that have been passivated by lengthy exposure to significant levels of impurities contribute to a large O/Li ratio measured during LTX plasma discharges. Furthermore, previous results have indicated that a passivated lithium film on the plasma facing components will function as a stronger impurity source when in the form of a hot liquid layer compared to a solid lithium layer. However, recent TGIS measurements of plasma discharges in LTX with hot stainless steel boundary shells and a fresh liquid lithium coating show lower O/Li impurity line ratios when compared to discharges with a solid lithium film on cool shells. In conclusion, these new measurements help elucidate the somewhat contradictory results of the effects of solid and liquid lithium on plasma confinement observed in previous experiments.

36 MATERIALS SCIENCE↗

SOLPS4.3 Modeling of Lithium Transport and Noncoronal Radiation in the T-15 Tokamak with Lithium Emitter−Collector Scheme in Use

The lithium emitter−collector scheme has been successfully used on limiter tokamak T-11M for a long time and is therefore one of the most mature concepts of liquid lithium-assisted power and particle exhaust. In the present paper, a possible application of the emitter−collector scheme to the divertor tokamak T-15 is analyzed with the 2D transport code SOLPS4.3. Modeling indicates that placing the lithium limiter at the outer midplane of the vessel results in the widest possible spreading of lithium over the scrape-off layer, whereas lithium deposition in this case is localized primarily at the upper outer target plate. The power exhaust capability of the lithium emitter−collector scheme is also studied. It is often presumed on the basis of a simple 0D analysis that the noncoronality can bring the lithium radiation capability in line with the other low-Z impurities typically involved in the divertor power exhaust (such as carbon and nitrogen). However, detailed 2D modeling shows that in spite of the significant increase of the Li cooling rate due to the noncoronal effects, the contribution of lithium radiation to divertor power balance remains marginal, unless the lithium inventory in the edge becomes close to the deuterium one.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Isotopic Signatures of Lithium Carbonate and Lithium Hydroxide Monohydrate Measured Using Raman Spectroscopy

Lithium isotopic ratios have wide ranging applications as chemical signatures, including improved understanding of geochemical processes and battery development. Measurement of isotope ratios using optical spectroscopies would provide an alternative to traditional mass spectrometric methods, which are expensive and often limited to a chemical laboratory. In this work, Raman spectra of 7 Li 2 CO 3 , 6 Li 2 CO 3 , 7 LiOH*H 2 O and 6 LiOH*H 2 O have been measured to determine the effect of lithium isotope substitution on the Raman molecular vibrations. Thirteen peaks were observed in the spectrum of lithium carbonate, with discernable isotopic shifts occurring in eleven of the thirteen vibrations, two of which have not been previously reported in the literature. The spectrum of lithium hydroxide monohydrate contained nine peaks, with discernable isotopic shifts occurring in eight of the nine vibrations, four of which have not been previously reported in the literature. The Raman spectral data reported here for lithium carbonate and lithium hydroxide monohydrate are in agreement with the previously reported works in the literature, in which the Raman active modes of these molecules were first identified and assigned. However, due to the stability and resolution of the detection system used in this work, isotopic shifts with a magnitude less than one wavenumber have been identified. Principal Component Regression was used to evaluate the sensitivity to isotopic content of small Raman peak shifts in Li 2 CO 3 and indicates differences greater than 2 atom-% could be reliably determined. These measurements add to the body of work on lithium isotope Raman spectroscopy for these two compounds and increases the number of Raman bands which could be used for lithium isotope content analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recovery of Lithium from Geothermal Brine with Lithium–Aluminum Layered Double Hydroxide Chloride Sorbents

In this paper, we report a three-stage bench-scale column extraction process to selectively extract lithium chloride from geothermal brine. The goal of this research is to develop materials and processing technologies to improve the economics of lithium extraction and production from naturally occurring geothermal and other brines for energy storage applications. A novel sorbent, lithium aluminum layered double hydroxide chloride (LDH), is synthesized and characterized with X-ray powder diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry (ICP-OES), and thermogravimetric analysis. Each cycle of the column extraction process consists of three steps: (1) loading the sorbent with lithium chloride from brine; (2) intermediate washing to remove unwanted ions; (3) final washing for unloading the lithium chloride ions. Our experimental analysis of eluate vs feed concentrations of Li and competing ions demonstrates that our optimized sorbents can achieve a recovery efficiency of ~91% and possess excellent Li apparent selectivity of 47.8 compared to Na ions and 212 compared to K ions, respectively in the brine. Finally, the present work demonstrates that LDH is an effective sorbent for selective extraction of lithium from brines, thus offering the possibility of effective application of lithium salts in lithium-ion batteries leading to a fundamental shift in the lithium supply chain.

25 ENERGY STORAGE↗

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.

36 MATERIALS SCIENCE↗

Understanding and applying coulombic efficiency in lithium metal batteries

Coulombic Efficiency (CE) has been widely used in battery research as a quantifiable monitor to compare the properties and performances of materials, electrolytes, interfaces and the entire electrochemical cells. While CE with ultra high precision effectively predicts the lifespan and health for lithium ion (Li-ion) batteries, it is not necessarily true in rechargeable lithium (Li) metal batteries. A large variation of CE is often seen even from the same materials and electrolytes in Li metal cells. This work discusses the fundamental definition of CE in different configurations of Li metal-based cells. The similarities and differences of CE in Li-ion and Li metal cells have been clarified and used to understand the relevance/irrelevance between CE and cycling. Long-standing goal of this study is to help rational design of cell testing protocols and elaborate electrochemical results. The insights from this work are broadly applicable in many other rechargeable metal cells e.g., Zn, Mg and Na batteries to accelerate reseach innovation.

Xiao, Jie↗

Ultra-high efficient lithium recovery via terephthalic acid from spent lithium-ion batteries

The recovery of lithium from spent lithium-ion batteries (LIBs) is a critical step in advancing sustainability within the battery industry. Traditional lithium extraction methods from end-of-life LIBs predominantly rely on chemical leaching techniques. However, these methods often involve the excessive use of acids, leading to substantial environmental concerns. Additionally, their non-selective nature can compromise the purity of the recovered lithium salt. To achieve battery-grade purity, further purification and recovery processes are necessary. In this study, we introduce a universal and eco-friendly process for lithium recovery, employing terephthalic acid to selectively extract lithium prior to the recycling of other valuable metals. This innovative method achieves lithium recovery rates exceeding 98.53% from layered oxide cathodes and 98.53% from lithium iron phosphate cathodes, delivering an exceptional purity level of 99.95%. By demonstrating applicability across a variety of cathode materials, this approach establishes a universal, sustainable and efficient solution for LIB recycling. The high-purity lithium extraction enabled by this process supports the comprehensive utilization of valuable resources, contributing significantly to the development of a circular economy for battery materials.

Hou, Jiahui [Worcester Polytechnic Institute, MA (↗

Modeling Lithium Movement over Multiple Cycles in a Lithium-Metal Battery

This paper builds on the work by Ferrese et al. [J. Electrochem., 159, A1615 (2012)], where a model of a lithium-metal battery with a LiyCoO2 positive electrode was created in order to predict the movement of lithium in the negative electrode along the negative electrode/separator interface during cell cycling. In this paper, the model is expanded to study the movement of lithium along the lithium-metal anode over multiple cycles. From this model, it is found that when a low percentage of lithium at the negative electrode is utilized, the movement of lithium along the negative electrode/separator interface reaches a quasi steady state after multiple cycles. This steady state is affected by the slope of the open-circuit-potential function in the positive electrode, the rate of charge and discharge, the depth of discharge, and the length of the rest periods. However, when a high percent of the lithium at the negative electrode is utilized during cycling, the movement does not reach a steady state and pinching can occur, where the lithium nearest the negative tab becomes progressively thinner after cycling. This is another nonlinearity that leads to a progression of the movement of lithium over multiple cycles. (C) 2014 The Electrochemical Society.

Ferrese, A↗

Lithium Dendrite-Free Li 7 N 2 I-LiOH Solid Electrolytes for High Energy Lithium Batteries

All-solid-state lithium batteries (ASSLBs) hold great potential to improve the safety and energy density of today’s lithium-ion batteries by using non-flammable inorganic solid electrolytes. Solid electrolytes (SEs) are believed to prevent Li dendrite growth because of high mechanical strength and high Li+ transference numbers. Significant advances in SE have been achieved, among which, Li7La3Zr2O12 (LLZO) and Li2S–P2S5 (LPS) are the most promising SEs for bulk-type solid-state lithium batteries because of high ionic conductivities (>10-4 S/cm2). However, in contrast to our expectations, the growth of lithium dendrites is not suppressed but is facilitated in LLZOs and LPSs regardless of dopants, porosity, and crystallinity of the electrolytes. Despite the unity Li transference number and over two-times of shear modulus than that of Li metal, the critical current densities for Li plating and stripping in these SEs are less than 1.0 mA cm-2, which is one-fourth to one-tenth of that in liquid electrolytes at room temperature. The incompatibility between LLZO and LPS with Li metal seriously limits the energy density of all-solid-state batteries. The mechanism for lithium dendrite formation and growth in SEs are still disputable. Lack of understanding of the Li dendrite formation mechanism seriously impeded the development of solid-state lithium batteries. The development of the criterion for Li dendrite suppression is essential for the success of solid electrolyte lithium batteries. In this project, a criterion for Li dendrite suppression will be developed through thermodynamics and kinetics analysis of lithium dendrite nucleation/growth, which will guide the solid-state electrolyte design. Li7N2I-LiOH, Li5NI2-LiOH and Li3YCl6 solid electrolyte with high ionic conductivity and low electronic conductivity were used to validate the criterion for lithium dendrite suppression. Different surface modifications were also explored to enhance the dendrite suppression capability of SSEs.

25 ENERGY STORAGE↗

Understanding thermal and mechanical effects on lithium plating in lithium-ion batteries

Lithium plating is one of the main concerns for cell durability, as cyclable lithium and cell capacity are decreased during the process. Thermal and mechanical loads can influence cell behavior, including lithium plating driving forces, as suggested by the Arrhenius equation and the Bruggeman relation, respectively. Hence, a 1D and a 3D model are employed to study the thermal and mechanical effects on lithium plating in a lithium-ion battery with a high areal capacity (4 mAh/cm 2 ). The 1D model assumes uniform mechanical and temperature profile, while the 3D model is capable of capturing the nonuniformity of stress and temperature in the cell. Further, the effects of mechanical deformation and different temperatures on the process of lithium plating are investigated in this study. With the help of the 1D charging simulations, it is observed that lower temperatures increase the risk of lithium plating and the presence of mechanical deformations can accelerate its initiation. Furthermore, 3D charging simulations indicated that folds and boundaries of jellyrolls are more susceptible to lithium plating due to the higher stress concentration and lower temperature, respectively.

25 ENERGY STORAGE↗

TiO 2 Microboxes with Controlled Internal Porosity for High‐Performance Lithium Storage

Abstract Titanium dioxide (TiO 2 ) is considered a promising anode material for high‐power lithium ion batteries (LIBs) because of its low cost, high thermal/chemical stability, and good safety performance without solid electrolyte interface formation. However, the poor electronic conductivity and low lithium ion diffusivity of TiO 2 result in poor cyclability and lithium ion depletion at high current rates, which hinder them from practical applications. Herein we demonstrate that hierarchically structured TiO 2 microboxes with controlled internal porosity can address the aforementioned problems for high‐power, long‐life LIB anodes. A self‐templating method for the synthesis of mesoporous microboxes was developed through Na 2 EDTA‐assisted ion exchange of CaTiO 3 microcubes. The resulting TiO 2 nanorods were organized into microboxes that resemble the microcube precursors. This nanostructured TiO 2 material has superior lithium storage properties with a capacity of 187 mAh g −1 after 300 cycles at 1 C and good rate capabilities up to 20 C.

Gao, Xuehui↗

Oxidation of lithium plasma facing components and its effect on plasma performance in the lithium tokamak experiment-β

The characteristics of lithium-coated plasma-facing components (PFCs) have been correlated with plasma performance on the lithium tokamak experiment-β (LTX-β). Previous experiments on LTX showed that the application of lithium to PFCs was needed to achieve higher performance discharges with flat electron temperature profiles and high edge temperatures. Samples that match the LTX-β PFCs were exposed to plasmas before and after PFCs were coated with lithium and transferred under vacuum to a surface analysis station. Measurements using x-ray photoelectron spectroscopy (XPS) revealed that the primary surface constituent was lithium oxide. Earlier XPS analysis of lithium-coated PFCs on LTX was only able to show the presence of surface oxygen. The new XPS data from LTX-β have sufficient resolution to clearly identify lithium compounds for the first time, and enable them to be correlated with how lithium-coated PFCs can reduce impurities and retain hydrogen to reduce recycling.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Operating High-Energy Lithium-Metal Pouch Cells with Reduced Stack Pressure Through a Rational Lithium-Host Design

Transitioning from a liquid electrolyte to an inorganic solid electrolyte offers a potential pathway to enable highly reversible lithium-metal anodes. However, the solid-electrolyte-protected lithium-metal anode suffers from poor interfacial ionic contacts and requires an impractically high stack pressure (>1.0 MPa) to maintain the interfacial contacts. It is demonstrated here that combining a hollow silver/carbon fiber scaffold and an inorganic/organic composite electrolyte enables a highly reversible lithium-metal anode. Since the high surface area of the electrode provides intimate contact and the hollow structure of the electrode relieves the lithium plating-induced stress, the electrode/electrolyte interface remains stable during cycling even under mild stack pressure. This unconventional structural design is validated in practical pouch cells assembled with the 3D lithium host containing a onefold excess of lithium and a high-nickel cathode. At a mild stack pressure of 320 kPa, the pouch cell displays 83% capacity retention for 200 cycles. This work illustrates that combining a hollow electrode architecture and a robust solid electrolyte offers a practical pathway toward rechargeable lithium-metal anodes.

36 MATERIALS SCIENCE↗

High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes

Lithium metal batteries face safety and low Coulombic Efficiency barriers. Superconcentrated electrolyte is stable with lithium metal but exhibits high cost and poor wettability. We report a localized superconcentrated electrolyte by diluting a superconcentrated electrolyte with an ‘inert’ diluent which does not dissolve the salt but miscible with the solvent used in the superconcentrated electrolyte. This electrolyte exhibits low cost, good wettability, and enables dendrite-free lithium cycling with high Coulombic Efficiency (99.3%) and stability (> 95% capacity retention after 300 cycles) of lithium||LiNixMnyCozO2 batteries. The concept of localized superconcentrated electrolyte can also be applied to other multi-functional electrolytes for broad applications.

Coulomic efficiency, anode, batteries↗