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Spatial dynamics of lithiation and lithium plating during high-rate operation of graphite electrodes

The principal inhibitor of fast charging lithium ion cells is the graphite negative electrode, where favorable conditions for lithium plating occur at high charge rates, causing accelerated degradation and safety concerns. The local response of graphite, both at the electrode and particle level, when exposed to fast charging conditions of around 6C is not well understood. Consequently, the conditions that lead to the onset of lithium plating, as well as the local dynamics of lithium plating and stripping, have also remained elusive. Here, we use high-speed (100 Hz) pencil-beam X-ray diffraction to repeatedly raster along the depth of a 101 μm thick graphite electrode in 3 μm steps during fast (up to 6C) charge and discharge conditions. Consecutive depth profiles from separator to current collector were each captured in 0.5 seconds, giving an unprecedented spatial and temporal description of the state of the electrode and graphite's staging dynamics during high rate conditions. The electrode is preferentially activated near the separator, and the non-uniformity increases with rate and is influenced by free-energy barriers between graphite's lithiation stages. The onset of lithium plating and stripping was quantified, occurring only within the first 15 μm from the separator. The presence of lithium plating changed the behavior of the underlying graphite, such as causing co-existence of LiC 6 and graphite in the fully discharged state. Finally, the staging behavior of graphite at different rates was quantified, revealing a high dependency on rate and drastic hysteresis between lithiation and delithiation.

25 ENERGY STORAGE↗

Compact and high-particle-flux thermal-lithium-beam probe system for measurement of two-dimensional electron density profile

A compact and high-particle-flux thermal-lithium-beam source for two-dimensional measurement of electron density profiles has been developed. The thermal-lithium-beam oven is heated by a carbon heater. In this system, the maximum particle flux of the thermal lithium beam was ∼4 × 10{sup 19} m{sup −2} s{sup −1} when the temperature of the thermal-lithium-beam oven was 900 K. The electron density profile was evaluated in the small tokamak device HYBTOK-II. The electron density profile was reconstructed using the thermal-lithium-beam probe data and this profile was consistent with the electron density profile measured with a Langmuir electrostatic probe. We confirm that the developed thermal-lithium-beam probe can be used to measure the two-dimensional electron density profile with high time and spatial resolutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of lithium coating on the optics of Doppler backscatter system

This paper presents the first investigation of the effect of lithium coating on the optics of Doppler backscattering. A liquid lithium limiter has been applied in the Experimental Advanced Superconducting Tokamak (EAST), and a Doppler backscattering has been installed in the EAST. A parabolic mirror and a flat mirror located in the vacuum vessel are polluted by lithium. An identical optical system of the Doppler backscattering is set up in laboratory. The power distributions of the emission beam after the two mirrors with and without lithium coating (cleaned before and after), are measured at three different distances under four incident frequencies. The results demonstrate that the influence of the lithium coating on the power distributions are very slight, and the Doppler backscattering can work normally under the dosage of lithium during the 2014 EAST campaign.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Strong texturing of lithium metal in batteries

Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type of additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO 3 and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. In conclusion, this understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.

25 ENERGY STORAGE↗

Effects of magnetic fields on lithium evolution in F and G stars

To study the effects of magnetic fields on lithium depletion and to explain the characteristics of lithium evolution in F- and G-type stars in open clusters, we construct a stellar model that includes a Tayler-Spruit dynamo-type field. Through examining the features of extra-mixing caused by magnetic fields in stellar interiors and the relationship between lithium depletion and the input parameters (i.e., mass, metallicity, and the initial rotational condition), we find that the magnetic model produces extra-mixing processes different from other models. During pre-main sequence, the model exhibits very efficient extra-mixing, resulting in strong lithium depletion. As a star evolves, the efficiency of extra-mixing rapidly decreases and lithium depletion slows down at old ages. By setting up different initial rotating conditions, the model predicts dispersions of lithium abundance in both main sequence and pre-main sequence stages. The dispersion begins when a radiative core forms in the interior. The number sees a rapid growth afterward, reaching 0.1-0.5 dex at zero age main sequence in G and late-F stars. The increase of dispersion continues in the main sequence, which is slight in G and late-F stars while significant in mid-F stars. Finally, a comparison is carried out between the theoretical results and the observed data in four open clusters. Good agreements are obtained.

79 ASTRONOMY AND ASTROPHYSICS↗

Fusion applications for lithium: wall conditioning in magnetic confinement devices

The application of lithium to plasma facing components (PFCs) has been widely used to improve plasma performance in magnetic confinement devices. The ability of lithium to retain hydrogen isotopes has been exploited to lower wall recycling. Low recycling leads to high edge plasma temperatures, and decreased temperature gradients reduce the free energy source for microinstabilities that cause transport. A variety of techniques have been developed to introduce lithium into fusion research devices, and its beneficial effects have been observed in their plasmas. The mechanism for the retention of hydrogen isotopes has been elucidated by detailed surface science studies, and 'first principles' molecular dynamics simulations. The remaining challenges primarily pertain to long pulse operation. Our knowledge of erosion, transport, and redeposition needs to improve for the mixed material PFCs lithium creates. As a result, flowing liquid lithium systems also must be demonstrated for the replenishable lithium walls that fusion reactors require.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Structured large-pore foams improve thermal performance of LiMIT-style liquid lithium PFC

As magnetically confined fusion devices improve, the conditions at the walls become increasingly intense. Plasma facing components (PFCs) must withstand these extreme heat and particle loads without damage or degradation. Liquid lithium PFCs are known to be quite resilient, and the presence of lithium also serves to improve plasma properties. The liquid metal infused trench (LiMIT) concept is an open surface liquid lithium PFC design that has been tested extensively at the University of Illinois and in fusion devices around the world. LiMIT utilizes thermoelectric magnetohydrodynamics (TEMHD) to passively drive liquid lithium flow. This work demonstrates an extension of the LiMIT trench geometry to three dimensions. Additively manufactured large pore metallic foams maintain TEMHD drive while drastically improving heat flux handling and resistance to lithium dryout, a phenomenon where locally high TEMHD forces depresses the lithium level and exposes underlying solid structure. COMSOL multiphysics modeling of the system yields insight into the forces at play in dryout development, and shows the 3D structures can eliminate dryout. Here, low heat proof-of-concept experimental testing of the system matches computational results, and high heat flux electron beam tests more than double the proven operational range of a LiMIT-style PFC, to 6.8 MW m –2 , with no indications of dryout or impending damage.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Lithium's low-temperature phase transitions: Insights into quantum lattice dynamics and superconductivity

The large lattice dynamics of lithium, driven by its low atomic mass, results in energetically similar structures and significant isotope effects under pressure, posing challenges to current theoretical models. Above 20 GPa and at low temperatures, lithium's electronic properties deviate from simple metallic behavior, with superconductivity emerging in a complex, pressure-dependent manner, alongside an unusual isotope effect. The structural phases of 7 Li reported under these conditions are inconsistent across studies, and the structures of 6 Li remain unexamined. These gaps limit our understanding of the effects of pressure on lithium's electronic properties and the role of quantum lattice effects on its structural behavior under pressure. Here, we integrate experimental and theoretical approaches to investigate the low-temperature structural phase boundaries in lithium isotopes. We map the structural phase diagram of 7 Li from 5 to 55 GPa and 15–75 K, identifying the sequence fcc → ℎ⁡R⁢1 → cI16. A pronounced isotope effect is observed, with 6 Li shifting the fcc → ℎ⁡R⁢1 phase boundary to lower pressures at 15 K. Density functional theory calculations further clarify how these structural changes affect superconducting properties, particularly emphasizing the role of the fcc → ℎ⁡R⁢1 transition in lithium's superconductivity. Furthermore, our findings offer insights into the unique behavior of lithium isotopes under pressure.

36 MATERIALS SCIENCE↗

Simulation of Liquid Lithium Divertor Geometry Using SOLPS-ITER

Here, plasma-facing component (PFC) geometries are evaluated for a Fusion Nuclear Science Facility (FNSF) design to find solutions that are compatible with flowing liquid lithium components while satisfying requirements from the perspective of plasma and neutral particle transport. Flowing liquid metal (LM) divertor systems offer important advantages due to continual regeneration of the surface material, but may require modifications from standard optimized tokamak divertor designs. Scrape Off Layer Plasma Simulator for the International Thermonuclear Experimental Reactor (SOLPS-ITER) simulations are used to compare standard vertical target, open, and balanced baffled geometries. It is found that the open geometry offers little control of neutral particles and has narrow operating windows where the divertor fluxes can be lowered to acceptable levels, while maintaining the required upstream density. The addition of neutral baffles allows greater control over the divertor conditions with less impact on the upstream density. The divertor neutral pressure in the baffled geometry is slightly higher than the open divertor, but not as large with a vertical target. A first-pass coupling of the SOLPS solution with sheath and implantation/erosion models to compute the lithium emission shows that the lithium is largely confined to the near-surface region due to the small ionization mean free path and large main ion flow toward the surface. The lithium source was varied by three orders of magnitude. At the highest rate, when the sourced lithium approaches the level of the main ion recycling flux, a high core lithium concentration (~10%) is observed with only moderate power dissipation to affect the divertor plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Devices for Diagnostics and Lithium Collection on the T-11M and T-10 Tokamaks. First Results

The use of lithium as a material of the tokamak in-vessel plasma-facing components made it necessary to develop appropriate diagnostic instruments. For the T-10 and T-11M tokamaks, devices have been developed that allow one to investigate the processes of lithium transport in the tokamak scrape-off layer, the dynamics of lithium deposition at different temperatures of the collecting surface in real time by using a piezoelectric quartz detector, adsorption and desorption of the plasma-forming gas by lithium, and the influence of the electric field on the process of lithium collection. The plasma parameters are monitored using Langmuir probes. The developed devices can be used to extract lithium deposited on the tokamak vessel wall without breaking vacuum conditions. For these purposes, a gateway and a vacuum input without bellows have been designed on the basis of an innovative liquid-metal coupling.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Impact of External Pressure and Electrolyte Transport Properties on Lithium Dendrite Growth

Practical implementation of metal anodes in commercial lithium-ion batteries has been limited by the growth of dendritic protrusions, which can cause short-circuits and adversely affect battery safety. The impacts of the physical (such as external pressure and electrolyte shear modulus) and electrochemical (for example, conductivity, diffusivity and transference number) properties of a solid electrolyte on the propensity of lithium dendrite growth are investigated here. It is found that over a range of conditions, there are critical pressures above which growth of lithium dendritic protrusions can be prevented. The magnitude of this critical pressure depends on the elastic modulus of the electrolyte. Plastic deformation of lithium at high pressure results in reduced protrusion growth, which helps in obtaining stable deposition. For the first time, phase maps have been developed based on mechanical and transport properties of electrolytes, indicating conditions under which stable deposition of lithium is possible during long-term operation. Suppression of dendrites by individually altering conductivity, or diffusivity, or transference number, or elastic modulus of the electrolyte appears to be a relatively difficult task. Finally, minor tailoring of the transference number and elastic modulus of present-day polymer electrolytes, in a combined fashion, can lead to dendrite-free deposition of lithium.

25 ENERGY STORAGE↗

Edge Plasma Simulations in NSTX and CTF: Synergy of Lithium Coating, Non-Diffusive Anomalous Transport and Drifts

This is the final report for the Research Grant DE-FG02-08ER54989 'Edge Plasma Simulations in NSTX and CTF: Synergy of Lithium Coating, Non-Diffusive Anomalous Transport and Drifts'. The UCSD group including: A.Yu. Pigarov (PI), S.I. Krasheninnikov and R.D. Smirnov, was working on modeling of the impact of lithium coatings on edge plasma parameters in NSTX with the multi-species multi-fluid code UEDGE. The work was conducted in the following main areas: (i) improvements of UEDGE model for plasma-lithium interactions, (ii) understanding the physics of low-recycling divertor regime in NSTX caused by lithium pumping, (iii) study of synergistic effects with lithium coatings and non-diffusive ballooning-like cross-field transport, (iv) simulation of experimental multi-diagnostic data on edge plasma with lithium pumping in NSTX via self-consistent modeling of D-Li-C plasma with UEDGE, and (v) working-gas balance analysis. The accomplishments in these areas are given in the corresponding subsections in Section 2. Publications and presentations made under the Grant are listed in Section 3.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Low-Cost Production of Lithium-Ion Separator Membranes w/ Improved Safety

The purpose of this Cooperative Research and Development Agreement (CRADA) between Oak Ridge National Laboratory (ORNL) and Porous Power Technologies, LLC (PPT) was to validate the performance, durability, and safety of a new type of reinforced, composite lithium ion battery separator produced as either a free-standing product or by a method of direct coating after electrode fabrication. ORNL’s primary roles were to develop novel separator thermophysical and mechanical property characterization methods and assist with fundamental understanding of SYMMETRIX® HPX and HPX-F product line chemical makeup and microstructure. PPT’s primary roles were to implement the understanding gained from the ORNL developed characterization methods into a refined product line featuring nonwoven-reinforced, ceramic-filled composite HPX-F separators for the lithium ion battery industry and quantify long-term cell performance improvements associated with HPX-F separators. Over the course of this CRADA, the product line of PPT was expanded from a pure polyvinylidene fluoride (PVDF) HP and polyester nonwoven-reinforced HPX separator platform to one that includes a variety of ceramic-filled HPX-F separators. In addition, the laminating and direct coating technologies for HPX and HPX-F separators are now more developed and moving towards commercial licensing. PPT’s SYMMETRIX® production process will revolutionize the production of lithium ion batteries by eliminating one of the most expensive components (the free-standing separator membrane) while improving performance and safety. The performance and safety improvements are due primarily to replacement of the conventional polyethylene/polypropylene (PE/PP) separator material with polyvinylidene fluoride (PVDF), and to ceramic materials added to the PVDF to form a short-resistant, thermally-stable composite structure. Ultimately, lithium ion battery manufacturers will be able to produce PPT separators in-house through the laminating or direct coating methods such as those based on the SYMMETRIX® product line, giving them higher performance cells at a fraction of the cost required to purchase separators from existing vendors. Direct coating of separators onto electrodes eliminates the cost of a downstream thermal lamination step and requires little or no change to existing equipment. It is a clear path for lithium ion battery manufacturers to reach the <$1/m2 separator price target set by the U.S. Advanced Battery Consortium (USABC). The technology enabled by this project will have a substantial impact on energy efficiency required to produce cells and is anticipated to save up to $1B annually by 2014 in reduced manufacturing costs. In addition, it will contribute significantly to production energy savings associated with transporting free-standing polyolefin (PE/PP) separators from the vendor to the cell manufacturer locations. SYMMETRIX® separators have shown increased cell capacity, improved thermal stability, and longer cycle life over their PE/PP counterparts and have been repeatedly demonstrated to improve nearly all aspects of lithium ion battery performance Prior to the start of this CRADA, widespread adoption has been limited by three factors: 1) difficulty in handling the material on high-speed processing equipment due to lower tensile strength than oriented PE/PP materials; 2) cost concerns associated with the higher expense of PVDF as a raw material; and 3) questions regarding short resistance and durability. The first factor was addressed through thorough mechanical (ultimate tensile strength and dynamic mechanical analysis, etc.) property characterization of HPX and HPX-F materials against the commercial polyolefin baselines. The second factor was address by shifting the focus of PPT’s product line towards the HPX-F materials with low-PVDF (high ceramic filler) content to reduce overall separator cost. Concerns associated with the third factor were alleviated by evaluating the internal shorting resistance of the separators using a custom developed ORNL measurement method and obtaining long-term cycling data of the new HPX-F separator formulations. A materials emphasis was placed on polyester fiber mats for the nonwoven reinforcement (to boost overall separator tensile strength) and proprietary metal oxides for the HPX-F fillers (to improve thermomechanical properties of the separator and make it more resistant to overcharge and internal shorting).

batteries↗

Liquid Lithium Divertor and Scrape-Off-Layer Interactions on the National Spherical Torus Experiment:2010 ₋2013 Progress Report

The implementation of the liquid Lithium Divertor (LLD) in NSTX presented a unique opportunity in plasma-material interactions studies. A high density Langmuir Probe (HDLP) array utilizing a dense pack of triple Langmuir probes was built at PPPL and the electronics designed and built by UIUC. It was shown that the HDLP array could be used to characterize the modification of the EEDF during lithium experiments on NSTX as well as characterize the transient particle loads during lithium experiments as a means to study ELMs. With NSTX being upgraded and a new divertor being installed, the HDLP array will not be used in NSTX-U. However UIUC is currently helping to develop two new systems for depositing lithium into NSTX-U, a Liquid Lithium Pellet Dripper (LLPD) for use with the granular injector for ELM mitigation and control studies as well as an Upward-Facing Lithium Evaporator (U-LITER) based on a flash evaporation system using an electron beam. Currently UIUC has Daniel Andruczyk Stationed at PPPL and is developing these systems as well as being involved in preparing the Materials Analysis Particle Probe (MAPP) for use in LTX and NSTX-U. To date the MAPP preparations have been completed. New sample holders were designed by UIUC?s Research Engineer at PPPL and manufactured at PPPL and installed. MAPP is currently being used on LTX to do calibration and initial studies. The LLPD has demonstrated that it can produce pellets. There is still some adjustments needed to control the frequency and particle size. Equipment for the U-LITER has arrived and initial test are being made of the electron beam and design of the U-LITER in progress. It is expected to have these ready for the first run campaign of NSTX-U.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

ICP-MS For Analysis of Lithium Isotopic Ratios in Materials Highly Enriched in 7 Li (CRADA 626) Final Report

The intent of this project was to determine appropriate methodologies for analysis of lithium isotopes for 1) quasi-online monitoring of isotope separations, and 2) high-precision characterization of end-products, including lithium fluoride and lithium-beryllium fluoride (FLiBe). Traditionally, isotopic analysis requires the use of expensive, sophisticated instrumentation with often relatively long analytical timelines. We determined that the use of cheaper, smaller, and easier-to-operate instruments are sufficient for rapid analysis of lithium isotopes to monitor isotope separation efficiencies. In addition, we found that the analytical precision afforded by these lower-cost instruments is comparable to the more sophisticated (i.e., more expensive) instrumentation when the isotopic composition of lithium becomes highly depleted in 6Li. This finding will ultimately help lower costs of manufacturing of depleted lithium that is required for operation of certain designs of Generation IV nuclear reactors.

07 ISOTOPE AND RADIATION SOURCES↗

Lithium-ion cell technology demonstration for future NASA applications

NASA requires lightweight rechargeable batteries for future missions to Mars and the outer planets that are capable of operating over a wide range of temperatures, with high specific energy and energy densities. Due to their attractive performance characteristics, lithium-ion batteries have been identified as the battery chemistry of choice for a number of future applications, including planetary orbiters, rovers and landers. For example, under the Mars Surveyor Program MSP 01 lithium-ion batteries were developed by Lithion (each being 28 V, 25 Ah, 8-cells. and 9 kg) and fully qualified prior to mission cancellation. In addition to the requirement of being able to supply at least 90 cycles on the surface of Mars, the battery demonstrated operational capability (both charge and discharge) over a large temperature range (-2O'C to +4OoC), with tolerance to non-operational excursions to -30nd 50Currently, JPL is implementing lithium-ion technology on the 2003 Mars Exploration Rover (MER), which will be coupled with a solar array. This mission has similar performance requirements to that of the 2001 Lander in that high energy density and a wide operating temperature range are necessitated. In addition to planetary rover and lander applications, we are also engaged in determining the viability of using lithium-ion technology for orbiter applications that require exceptionally long life (>20,000 cydes at partial depth of discharge). To assess the viabili of lithium-ion cells for these applications, a number of performance characterization tests have been performed (at the cell and battery level) on state-of-art prototype lihium- ion cells, induding: assessing the cycle life performance (at varying DODs), life characteristics at extreme temperatures (< -10nd >+4OoC), rate capability as a function of temperature (-30' to 4OoC), pulse capability, self-discharge and storage characteristics, as well as, mission profile capability. This paper will describe the current and future NASA missions that are considering lithium ion batteries and will contain results of the cell testing conducted to-date to validate the technology for these missions.

lithium-ion batteries Mars landers Mars rovers↗

Lithium-ion Battery Strain Gauge Monitoring and Depth of Discharge Estimation

Lithium-ion battery diagnostics and prognostics rely on measurements of electrical impedance, capacity, and voltage to infer the internal state of the battery. Mechanical changes to the cell structure represent an additional measure of the battery’s state because these changes are related to the overall battery health. As lithium-ion batteries are charged and discharged, lithium ions are inserted or removed from the anode and cathode, a process called intercalation and de-intercalation. As lithium ions intercalate and de-intercalate, they can cause changes to the lattice of the electrode particles, resulting in volumetric changes. These volumetric changes cause mechanical stresses and strains on the lithium-ion battery electrodes, and subsequently, the whole cell’s thickness varies as it is charged and discharged. This paper presents a study on the use of surface-mounted strain gauges for in-situ measurement of structural changes to lithium-ion batteries, along with a characterization of the unit-to-unit differences in strain response. A neural network modeling structure is then used to predict the battery’s depth of discharge under dynamic discharge conditions.

Lithium-ion batteries, depth of discharge, strain ↗

Lithium Nucleation of Anode-Free Solid-State Batteries with a Dry Compressible Interlayer

Anode-free lithium batteries offer promising advantages, including increased energy density and the ability to address common mechanistic failures within the cell, thus increasing safety. One way that can make this possible is to control lithium nucleation. This could be achieved by reducing the overpotential required and implanting lithophilic nucleation sites in an anodic interlayer to aid in lithium ion transport and plating. The concept has been utilized in solid-state battery systems where electrolytes are solids with further improved safety and structural longevity. In this presentation, we discuss the use of a silver-holey graphene-based anodic interlayer that can be fabricated via direct dry compression without the use of solvent or binder. The addition of silver to the holey graphene matrix creates a route to lithium plating via a lower-energy intermediate. This idea is supported by the presence of a lithium-silver alloy that forms during the activation step. It is understood that the embedded silver acts as a nucleation site for lithium ions, thereby assisting in even plating. This control, combined with the added cushion of the holey graphene itself, can help reduce dendrite formation, ultimately increasing the safety and lifetime of the solid-state batteries.

Solid state batteries↗