Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “lithium metal stabilization”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Mechanical and spectroscopic properties of metal containing polyimides

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymermzation or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Taylor, L. T.↗
DOE OSTI2025

Understanding the Role of Borohydride Doping in Electrochemical Stability of Argyrodite Li 6 PS 5 Cl Solid‐State Electrolyte

This work elucidates the mechanism by which lithium borohydride (LiBH 4 ) doping into argyrodite-type Li 6 PS 5 Cl (LBH-LPSCl) solid-state electrolyte (SSE) enhances electrochemical stability. State-of-the-art electrochemical performance is achieved with 5 wt% borohydride. Symmetric cells achieve critical current density (CCD) of 7.3 mA cm −2 , versus 2.6 mA cm −2 for baseline-LPSCl. All solid-state batteries (ASSBs) employing lithium metal and NMC811 cathode are stable over 400 cycles at 0.5C, with capacity retention of 83%. An anode-free ASSB (AF-ASSB) is stable over 600 cycles, with capacity loss of 0.04% per cycle. 5LBH-LPSCl allows for enhanced low temperature operation, down to −14 °C. Yet the difference in electrolytes’ bulk microstructures and hardnesses are minimal, while ionic conductivity is incrementally improved (≈50%). Theoretical modeling indicates limited effect of substitution on thermodynamic stability of PS 4 3- units, which decompose when contacting Li. Instead, enhanced electrochemical stability is site-specific kinetic effect: In situ electrodeposition experiments using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) reveal tri-layer SEI based predominately on Li 3 P/LiBH 4 /Li 2 S that blocks electrons while facilitating ion transport. This SEI manifests reduced interface resistance and accelerated nucleation and growth of metallic Li. With baseline-LPSCl the SEI based on Li 3 P/Li 2 S is substantially thicker, generating localized stresses that promote interfacial cracking while cycling.

argyrodite↗
DOE OSTI2021

Molecular Layer Deposition of Crosslinked Polymeric Lithicone for Superior Lithium Metal Anodes

In this work, we for the first time developed a novel lithium-containing crosslinked polymeric material, a lithicone that enables excellent protection effects over lithium (Li) metal anodes. This new lithicone was synthesized via an accurately controllable molecular layer deposition (MLD) process, in which lithium tert -butoxide (LTB) and glycerol (GL) were used as precursors. The resultant LiGL lithicone was analyzed using a suite of characterizations. Furthermore, we found that the LiGL thichicone could serve as an exceptional polymeric protection film over Li metal anodes. Our experimental data revealed that the Li electrodes coated by this LiGL lithicone can achieve a superior cycling stability, accounting for an extremely long cyclability of >13,600 Li-stripping/plating cycles and having no failures so far in Li/Li symmetric cells at a current density of 5 mA/cm 2 and an areal capacity of 1 mAh/cm 2 . We found that, with a sufficient protection by this LiGL coating, Li electrodes could realize long-term stable cyclability with little formation of Li dendrites and solid electrolyte interphase. This novel LiGL represents a facile and effective solution to the existing issues of Li anodes and potentially paves a technically feasible route for lithium metal batteries.

Meng, Xiangbo↗
DOE OSTI2024

Barrier reinforcement for enhanced perovskite solar cell stability under reverse bias

Stability of perovskite solar cells (PSCs) under light, heat, humidity and their combinations have been notably improved recently. However, PSCs have poor reverse-bias stability that limits their real-world application. Here we report a systematic study on the degradation mechanisms of p-i-n structure PSCs under reverse bias. The oxidation of iodide by injected holes at the cathode side initialize the reverse-bias-induced degradation, then the generated neutral iodine oxidizes metal electrode such as copper, followed by drift of Cu+ into perovskites and its reduction by injected electrons, resulting in localized metallic filaments and thus device breakdown. A reinforced barrier with combined lithium fluoride, tin oxide and indium tin oxide at the cathode side reduces device dark current and avoids the corrosion of Cu0. It dramatically increases breakdown voltage to above -20 V and improved the T90 lifetime of PSCs to ~1,000 h under -1.6 V. The modified minimodule also maintained over 90% of its initial performance after 720 h of shadow tests.

degradation mechanisms↗
DOE OSTI2020

Sweeping potential regulated structural and chemical evolution of solid-electrolyte interphase on Cu and Li as revealed by cryo-TEM

A fundamental understanding of solid-electrolyte interphase (SEI) is paramount importance for controlling the cycling performance of rechargeable lithium metal batteries. The structural and chemical evolution of SEI with respect to electrochemical operating condition remains barely established. Here we develop a unique method for imaging the evolution of SEI formed on the Cu foil under sweeping electrochemical potential. By using cryogenic TEM imaging combined with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy electronic structure analyses, we reveal that, for the vinylene carbonate (VC)-free electrolyte, the SEI formed at 1.0 V is a monolithic amorphous structure, which evolves to amorphous matrix embedded with Li 2 O particles as the voltage decreases to 0 V. In the case of VC-containing electrolyte, the SEI is featured by an amorphous matrix with Li 2 O particles from 1.0 V to 0 V. The thickness of SEI formed on Cu foil increases with decreasing voltage. Associated with the localized charge modulation by the surface topographic feature and defects in the Cu foil, the SEI layer shows direct spatial correlation with these structural defects in the Cu. In addition, upon Li deposition, the SEI formed on the Li metal has similar thickness with, but different composition from the SEI formed on the Cu foil at 0 V. Furthermore, those results provide insight toward SEI engineering for enhanced cycling stability of Li metal.

25 ENERGY STORAGE↗
DOE OSTI2025

Asymmetric ether solvents for high-rate lithium metal batteries

Recent electrolyte solvent design based on weakening lithium-ion solvation have shown promise in enhancing cycling performance of Li-metal batteries. However, they often face slow redox kinetics and poor cycling reversibility at high rate. Here we report using asymmetric solvent molecules substantially accelerates Li redox kinetics. Asymmetric ethers (1-ethoxy-2-methoxyethane, 1-methoxy-2-propoxyethane) showed higher exchange current densities and enhanced high-rate Li 0 plating/stripping reversibility compared to symmetric ethers. Adjusting fluorination levels further improved oxidative stability and Li 0 reversibility. The asymmetric 1-(2,2,2-trifluoro)-ethoxy-2-methoxyethane, with 2 M lithium bis(fluorosulfonyl)imide, exhibited high exchange current density, oxidative stability, compact solid–electrolyte interphase (~10 nm). This electrolyte exhibited superior performance among state-of-the-art electrolytes, enabling over 220 cycles in high-rate Li (50 μm)||LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811, 4.9 mAh cm −2 ) cells and for the first time over 600 cycles in anode-free Cu | |Ni95 pouch cells (200 mAh) under electric vertical take-off and landing cycling protocols. Our findings on asymmetric molecular design strategy points to a new pathway towards achieving fast redox kinetics for high-power Li-metal batteries.

batteries↗
DOE OSTI2025

Interlayer Design for Halide Electrolytes in All‐Solid‐State Lithium Metal Batteries

Abstract All‐solid‐state lithium‐metal batteries (ASSLMBs) are promising for transportation electrification due to their superior safety and high energy density. Lithium halide electrolytes provide excellent processing flexibility, high ionic conductivity, and anodic stability (>4.1 V), making them highly compatible with high‐voltage cathodes, surpassing sulfide electrolytes (<2.1 V). Nevertheless, halide electrolytes suffer from low cathodic stability and form an electronically conductive interphase with lithium, resulting in a critical current density (CCD) of nearly zero. Herein, Li 3 YbCl 6 electrolytes are synthesized that are kinetically stable with lithium by forming an electronic insulating solid electrolyte interphase. Guided by critical overpotential criteria, a PI 3 interlayer is designed that transforms into Li 6 PI 3 upon contact with lithium, substantially reducing the interfacial resistance of Li 3 YbCl 6 against lithium to 34 Ω and achieving a high critical overpotential of 114 mV. By substituting Yb with Lu, Li 3 LuCl 6 electrolytes with Li 6 PI 3 interlayers reach a CCD of 1.0 mA cm −2 at a capacity of 1.0 mAh cm −2 , comparable to sulfide electrolytes but with higher oxidation stability. Additionally, Li 6 PI 3 enables stable cycling of Li//Li cells with Li 3 LuCl 6 electrolytes at 0.5 mA cm −2 for 400 cycles and maintains 86.5% capacity in Li//LiCoO 2 cells after 220 cycles at 30 °C, paving the way for high‐performance ASSLMBs.

Chemistry↗
DOE OSTI2023

Phase engineering of layered anode materials during ion-intercalation in Van der Waal heterostructures

Transition metal dichalcogenides (TMDs) are a class of 2D materials demonstrating promising properties, such as high capacities and cycling stabilities, making them strong candidates to replace graphitic anodes in lithium-ion batteries. However, certain TMDs, for instance, MoS 2 , undergo a phase transformation from 2H to 1T during intercalation that can affect the mobility of the intercalating ions, the anode voltage, and the reversible capacity. In contrast, select TMDs, for instance, NbS 2 and VS 2 , resist this type of phase transformation during Li-ion intercalation. This manuscript uses density functional theory simulations to investigate the phase transformation of TMD heterostructures during Li-, Na-, and K-ion intercalation. The simulations suggest that while stacking MoS 2 layers with NbS 2 layers is unable to limit this 2H → 1T transformation in MoS 2 during Li-ion intercalation, the interfaces effectively stabilize the 2H phase of MoS 2 during Na- and K-ion intercalation. However, stacking MoS 2 layers with VS 2 is able to suppress the 2H → 1T transformation of MoS 2 during the intercalation of Li, Na, and K-ions. The creation of TMD heterostructures by stacking MoS 2 with layers of non-transforming TMDs also renders theoretical capacities and electrical conductivities that are higher than that of bulk MoS 2 .

25 ENERGY STORAGE↗
DOE OSTI2022

Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

Abstract Spinel‐type LiNi 0.5 Mn 1.5 O 4 (LNMO) is one of the most promising 5 V‐class cathode materials for Li‐ion batteries that can achieve high energy density and low production costs. However, in liquid electrolyte cells, the high voltage causes continuous cell degradation through the oxidative decomposition of carbonate‐based liquid electrolytes. In contrast, some solid‐state electrolytes have a wide electrochemical stability range and can withstand the required oxidative potential. In this work, a thin‐film battery consisting of an LNMO cathode with a solid lithium phosphorus oxynitride (LiPON) electrolyte is tested and their interface before and after cycling is characterized. With Li metal as the anode, this system can deliver stable performance for 600 cycles with an average Coulombic efficiency >99%. Neutron depth profiling indicates a slight overlithiated layer at the interface prior to cycling, a result that is consistent with the excess charge capacity measured during the first cycle. Cryogenic electron microscopy further reveals intimate contact between LNMO and LiPON without noticeable structure and chemical composition evolution after extended cycling, demonstrating the superior stability of LiPON against a high voltage cathode. Consequently, design guidelines are proposed for interface engineering that can accelerate the commercialization of a high voltage cell with solid or liquid electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2020

Impact of Ionic Liquid on Lithium Ion Battery with a Solid Poly(Ionic Liquid) Pentablock Terpolymer as Electrolyte and Separator

In this work, a ternary blend solid polymer electrolyte (SPE) consisting of a poly(ionic liquid) (PIL) multiblock polymer, lithium salt, and ionic liquid (IL) was investigated with the goal of understanding the influence of IL concentration on ion transport mechanisms and electrochemical stability. The physical, transport, mechanical, morphological, and electrochemical properties of the ternary blend SPE were systematically investigated as a function of IL concentration (r = [IL]/[PIL] mole ratio between 0.1 and 0.7). The results indicate that with increasing IL concentration, the continuous conductive domain increases along with the polymer chain segmental mobility, as well as facilitate ionic conductivity, while the mechanical modulus exhibits a percolation threshold (from 52.17 MPa to 0.55 MPa at r = 0.2 to 0.3). Surprisingly, at higher IL concentrations, there is a reduction in the lithium cation mobility (i.e., 9.3 × 10-12 m2 s-1 versus 3.8 × 10-12 m2 s-1 for r = 0.2 versus r = 0.5, respectively) as evidenced by pulsed-field gradient nuclear magnetic resonance (PFG-NMR), which coincides with an increased overpotential (i.e., 50 mV versus 150 mV for r = 0.2 versus r = 0.5, respectively) evidenced by lithium metal stripping and plating. This work provides valuable insights into the impact of IL on lithium ion conducting PIL block polymers, which may enable the design of new SPEs with both high ionic conductivity and improved stability for the future lithium ion batteries.

Chen, Tzu-Ling↗
DOE OSTI2025

Molecular Interlocking Multidimensional Modulations of Cathode‐Electrolyte Interface for Constructing High Energy Density Quasi‐Solid‐State Batteries

Gel polymers are regarded as a promising candidate electrolyte for lithium-metal quasi-solid-state batteries, primarily due to their high ionic conductivity and solid-liquid synergistic properties. However, challenges such as interfacial side reactions, limitations in Li + transport caused by interfacial issues, and leaching of transition metals from the cathode have yet to be effectively solved. Herein, a novel gel electrolyte modulation strategy based on electrostatic filler assembly is proposed to address the issues of ineffective capacity utilization and inadequate cycling stability of high-energy-density cathode materials in solid-state lithium-ion batteries. It constructs a 3D interpenetrating charge-bridge network that effectively tackles the phase-separation challenge between fillers and electrolytes at the molecular level. Meanwhile, the molecular interlocking structure effectively inhibits the electrolyte erosion. More critically, it optimizes and stabilizes the cathode-electrolyte interface film, which facilitates the conduction of Li + -ions through a size-sieving mechanism. Consequently, this strategy enables effective adaptation across diverse high-energy-density cathode materials with satisfactory capacity performance (170.4 mAh g −1 at 4.5 V/1 C for LiNi 0.6 Co 0.2 Mn 0.2 O 2 and 194.0 mAh g −1 at 4.3 V/1 C for LiNi 0.9 Co 0.08 Mn 0.02 O 2 ). In conclusion, this investigation offers a straightforward and effective reference for addressing the critical challenges of ionic transport and interface stabilization in the design of gel electrolytes.

cathode-electrolyte interface↗
DOE OSTI2020

A chemically stabilized sulfur cathode for lean electrolyte lithium sulfur batteries

Lithium sulfur batteries (LSBs) are promising next-generation rechargeable batteries due to the high gravimetric energy, low cost, abundance, nontoxicity, and high sustainability of sulfur. However, the dissolution of high-order polysulfide in electrolytes and low Coulombic efficiency of Li anode require excess electrolytes and Li metal, which significantly reduce the energy density of LSBs. Quasi-solid-state LSBs, where sulfur is encapsulated in the micropores of carbon matrix and sealed by solid electrolyte interphase, can operate under lean electrolyte conditions, but a low sulfur loading in carbon matrix (<40 wt %) and low sulfur unitization (<70%) still limit the energy density in a cell level. Here, we significantly increase the sulfur loading in carbon to 60 wt % and sulfur utilization to ∼87% by dispersing sulfur in an oxygen-rich dense carbon host at a molecular level through strong chemical interactions of C–S and O–S. In an all-fluorinated organic lean electrolyte, the C/S cathode experiences a solid-state lithiation/delithiation reaction after the formation of solid electrolyte interphase in the first deep lithiation, completely avoiding the shuttle reaction. The chemically stabilized C/S composite retains a high reversible capacity of 541 mAh⋅g −1 (based on the total weight of the C/S composite) for 200 cycles under lean electrolyte conditions, corresponding to a high energy density of 974 Wh⋅kg −1 . The superior electrochemical performance of the chemical bonding-stabilized C/S composite renders it a promising cathode material for high-energy and long-cycle-life LSBs.

25 ENERGY STORAGE↗
DOE OSTI2021

An In-Depth Analysis of the Transformation of Tin Foil Anodes during Electrochemical Cycling in Lithium-Ion Batteries

Tin foils have an impressive lithium-storage capacity more than triple that of graphite anodes, and their adoption could facilitate a drastic improvement in battery energy density. However, implementation of a dense foil electrode architecture represents a significant departure from the standard blade-cast geometry with a distinct electrochemical environment, and this has led to confusion with regards to the first cycle efficiency of the system. In this work, we investigate the unique behavior of a tin active material in a foil architecture to understand its performance as an anode. We find shallow cycling of the foil results in an irreversible formation (< 40%) due to diffusional trapping, but intermediate and complete utilization allows for a remarkably reversible formation reaction (> 90%). This striking nonlinearity stems from an in situ transformation from bulk metal to porous electrode that occurs during formation cycles and defines electrode-level lithium-transport on subsequent cycles. As a result, an alternative cycling procedure for assessing the stability of foils is proposed to account for this chemomechanical effect.

25 ENERGY STORAGE↗
DOE OSTI2020

Corrosion in Other Liquid Metals (Li, PbLi, Hg, Sn, Ga)

A wide range of liquid metals have been considered for application in nuclear fission and fusion reactors. Liquid mercury (Hg) was tested as a coolant and working fluid for nuclear fission reactors and as a neutron source target. Liquid lithium and lead lithium eutectic (Li and PbLi) have been extensively studied for fusion reactor designs including plasma facing components (PFCs). Liquid tin and gallium (Sn and Ga) have recently gained attention as alternative PFCs due to their low vapor pressure and chemical stability. To enable successful application of these less common liquid metals, corrosion compatibility with containment materials needs to be investigated. For this purpose, this article reviews corrosion behavior and structural material compatibility, including ferrous alloys, refractory metals, and ceramics, by liquid Li, PbLi, Sn, Ga, and Hg.

Jun, Jiheon↗
DOE OSTI2025

Fine‐Tuning Li‐Ion Solvation Structure by Enhanced Solvent‐Diluent Interactions for Long‐Cycling Lithium Metal Batteries

Achieving durable lithium (Li) metal anodes in liquid electrolytes remains challenging, primarily due to the instability of the formed solid-electrolyte interphases (SEIs). Modulating the Li-ion solvation structures is pivotal in forming a stable SEI for stabilizing Li metal anodes. Here a strategy is developed to fine-tune the Li-ion solvation structures through enhanced dipole–dipole interactions between the Li-ion-coordinated solvent and the non-Li-ion-coordinating diluent, for creating a stable SEI in the developed binary salt electrolyte. The enhanced dipole–dipole interactions weaken the coordination between Li-ions and the solvents while strengthening the interaction between Li-ions and dual anions, thereby facilitating the Li-ion transport and a robust anion-derived SEI with a distinct bilayer structure. Consequently, the developed electrolyte exhibited exceptional electrochemical performance in high energy-density Li||LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cells, with long calendar life, stable cyclability at 1 C, and reliable operation between 25 and −20 °C, and it also demonstrat remarkable cycling stability for a Li||NMC811 pouch cell with projected energy density of 402 Wh kg −1 , maintaining 80% capacity retention over 606 cycles under practical conditions.

25 ENERGY STORAGE↗
DOE OSTI2023

Stabilizing High–Nickel Cathodes with High–Voltage Electrolytes

Electrolytes connect the two electrodes in a lithium battery by providing Li + transport channels between them. Advanced electrolytes are being explored with high-nickel cathodes and the lithium-metal anode to meet the high energy density and cycle life goals, but the origin of the performance differences with different electrolytes is not fully understood. Here, the mechanisms involved in protecting the high-capacity, cobalt-free cathode LiNiO 2 with a model high-voltage electrolyte (HVE) are delineated. The kinetic barrier posed by a thick surface degradation layer with poor Li + -ion transport is found to be the major contributor to the fast capacity fade of LiNiO 2 with the conventional carbonate electrolyte. In contrast, HVE reduces the side reactions between the electrolyte and the electrodes, leading to a thinner nano-interphase layer comprised of more beneficial species. Crucially, the HVE leads to a different surface reorganization pathway involving the formation of a thinner nanoscale LiNi 2 O 4 spinel phase on the LiNiO 2 surface. Finally, with a high 3D Li + -ion and electronic conductivity, the spinel LiNi 2 O 4 reorganization nanolayer preserves fast Li + transport across the cathode–electrolyte interface, reduces reaction heterogeneity in the electrode and alleviates intergranular cracking within secondary particles, resulting in superior long-term cycle life.

25 ENERGY STORAGE↗
DOE OSTI2023

Lattice Oxygen Redox Reversibility Modulation in Enhancing the Cycling Stability of Li-Rich Cathode Materials

The practical application of lithium-rich layered oxides is prohibited by the drawbacks such as severe capacity and voltage degradation resulting from unstable oxygen redox environment and the accompanied irreversible oxygen release. In this report a facile and effective strategy is proposed to regulate the oxygen redox chemistry via foreign Fe doping and its induced intrinsic transition metal (TM) doping as well as the in situ constructed spinel surface layer. The Fe doping, together with the induced intrinsic TM dual doping, can stabilize the lattice oxygen in the bulk due to the formed stronger Fe—O bond, and restrain the irreversible TM migration and then the undesirable phase transformation. More importantly, thermodynamical energy barrier of oxygen activation is dramatically decreased by the O 2p–Fe 3d charge-transfer, allowing stable oxygen redox activity. And the pre-constructed spinel layer can effectively stabilize the surface lattice oxygen and suppress harmful interfacial side-reactions. Such a simple optimizing method make the modified cathode exhibit a high specific capacity of 298 mAh g -1 at 0.2 C, outstanding cycling stability with a superior capacity and voltage retentions of 92.5% and 90.8%, respectively, after 400 cycles at 1 C. This study provides a new direction for developing advanced Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Regulating lithium deposition via electropolymerization of acrylonitrile in rechargeable lithium metal batteries

Here, we report acrylonitrile (AN) as an effective additive in carbonate-based electrolytes to enable uniform and dense lithium (Li) deposition and to improve the coulombic efficiency of Li metal anode. Our electrochemical, spectroscopic, and theoretical study reveal that AN is cathodically electropolymerized on the Li surface prior to the electrochemical decomposition of the electrolyte during Li deposition. The resultant polyacrylonitrile artificial solid electrolyte interphase enables uniform nucleation and growth of Li deposition with significantly reduced side reactions. The effectiveness of the AN additive is demonstrated in 0.4 Ah Li||LiNi 0.6 Mn 0.2 Co 0.2 O 2 pouch cells (using 50-μm Li anode, 3 mAh cm -2 cathode areal capacity, and 4g Ah -1 electrolyte) with excellent cycle stability under realistic charge-discharge condition

25 ENERGY STORAGE↗