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Results for “LITHIUM DENDRITE FORMATION”

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.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries through Electrolytes

Lithium batteries are one of the most advance energy storage devices in the world and have attracted extensive research interests. However, lithium dendrite growth was a safety issue which handicapped the application of pure lithium metal in the negative electrode. In this paper, two solvents, propylene carbonate (PC) and 2-methyl-tetrahydrofuran (2MeTHF), and four Li + salts, LiPF 6 , LiAsF 6 , LiBF 4 and LiClO 4 were investigated in terms of their effects on the kinetics of lithium dendrite formation in eight electrolyte solutions. The kinetic parameters of charge transfer step (exchange current density, j 0 , transfer coefficient, α) of Li + /Li redox system, the mass transfer parameters of Li + (transfer number of Li + , t Li+ , diffusion coefficient of Li + , D Li+ ), and the conductivity (κ) of each electrolyte were studied separately. The results demonstrate that the solvents play a critical role in the measured j 0 , t Li+ , D Li+ , and κ of the electrolyte, while the choice of Li + salts only slightly affect the measured parameters. Finally, the understanding of the kinetics will gain insight into the mechanism of lithium dendrite formation and provide guidelines to the future application of lithium metal.

2-methyl-tetrahydrofuran↗
DOE OSTI2020

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High‐Energy Li‐S Batteries

Abstract Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium–sulfur (Li‐S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li‐S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core–shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm −2 ) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm −2 ) with a low electrolyte/sulfur ratio (10 μL mg −1 ). This research further demonstrates a durable Li‐Se/S pouch cell with high specific capacity, validating the potential practical applications.

Zhao, Chen↗
DOE OSTI2020

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High-Energy Li-S Batteries

Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium-sulfur (Li-S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li-S pouch cells. In this work, we demonstrate that a rational combination of selenium doping, core-shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm -2 ) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm -2 ) with a low electrolyte/sulfur ratio (10 mu L mg(-1)). Overall, this research further demonstrates a durable Li-Se/S pouch cell with high specific capacity, validating the potential practical applications.

25 ENERGY STORAGE↗
DOE OSTI2015

Lithium Dendrite Formation

Scientists at the Department of Energy’s Oak Ridge National Laboratory have captured the first real-time nanoscale images of lithium dendrite structures known to degrade lithium-ion batteries. The ORNL team’s electron microscopy could help researchers address long-standing issues related to battery performance and safety. Video shows annular dark-field scanning transmission electron microscopy imaging (ADF STEM) of lithium dendrite nucleation and growth from a glassy carbon working electrode and within a 1.2M LiPF6 EC:DM battery electrolyte.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Tuning the electrolyte network structure to invoke quasi-solid state sulfur conversion and suppress lithium dendrite formation in Li–S batteries

Here, the lithium-sulfur battery is promising as an alternative to conventional lithium-ion technology due to the high energy density of both sulfur and lithium metal electrodes. Extended life time has been demonstrated, but two notable challenges still exist in battery applications: overcoming the undesired high electrolyte/sulfur ratio, and inhibiting Li dendrite growth and its parasitic reaction with the electrolyte. Here we demonstrate that by tuning the electrolyte structure, the challenges at both electrodes can be tackled simultaneously. The sulfur speciation pathway transforms from a dissolution-precipitation route to a quasi-solid-state conversion in the presence of lowered solvent activity and an extended electrolyte network structure as revealed by ab initio calculations, curtailing the need for high electrolyte volumes. With such an optimized structure, the Li plates dendrite-free and shows 20-fold reduction in parasitic reactions with Li, avoiding electrolyte consumption and greatly extending the life time of a low E/S (5 µl/mg -1 ) sulfur cell.

25 ENERGY STORAGE↗
DOE OSTI2019

High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes

Solid electrolytes (SEs) are widely considered as an ‘enabler’ of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li 7 La 3 Zr 2 O 12 (LLZO) and Li 2 S–P 2 S 5 is actually much easier than that in liquid electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concentration profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li 3 PS 4 ) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concentration in LiPON can be observed, we visualize the direct deposition of Li inside the bulk LLZO and Li 3 PS 4 . Furthermore, our findings suggest the high electronic conductivity of LLZO and Li 3 PS 4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic conductivity, rather than further increasing the ionic conductivity of SEs, is therefore critical for the success of all-solid-state Li batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Visualizing Lithium Dendrite Formation within Solid-State Electrolytes

Solid-state electrolyte (SSE) is promising for application in allsolid-state lithium metal batteries because of its reliable safety and longevity. The failure of SSE to suppress dendrite formation of Li metal anodes has been conventionally explained by uneven Li deposition at Li/SSE interfaces and its subsequent dendritic growth. While Li deposition within SSE has been recently proposed as another key cause for SSE failure, little is known regarding the Li growth details inside the SSE itself. In this work, we performed in situ microscopic observation of Li deposition inside the SSE and obtained visualized evidence regarding the dynamic process of Li dendrite formation and growth. Here, Li is seen to directly nucleate and propagate within the SSE, leading to its structural cracking. Such behavior should be caused by the presence of P- and S-based crystalline defects in Li 3 PS 4 SSE, which is consistent with the cryo-transmission electron microscopy observations and theoretical calculations. This observation provides important insights into the growth mechanisms of Li dendrites within a working lithium battery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries

Dendrite formation during electrodeposition while charging lithium metal batteries compromises their safety. Although high-shear-modulus ( G s ) solid-ion conductors (SICs) have been prioritized to resolve the pressure-driven instabilities that lead to dendrite propagation and cell shorting, it is unclear whether these or alternatives are needed to guide uniform lithium electrodeposition, which is intrinsically density-driven. Here, we show that SICs can be designed within a universal chemomechanical paradigm to access either pressure-driven dendrite-blocking or density-driven dendrite-suppressing properties, but not both. This dichotomy reflects the competing influence of the SIC’s mechanical properties and the partial molar volume of Li + $(V_{\mathrm{Li}^+})$ relative to those of the lithium anode ( G Li and V Li ) on plating outcomes. Within this paradigm, we explore SICs in a previously unrecognized dendrite-suppressing regime that are concomitantly ‘soft’, as is typical of polymer electrolytes, but feature an atypically low $(V_{\mathrm{Li}^+})$ that is more reminiscent of ‘hard’ ceramics. Li plating (1 mA cm -2 ; T = 20 °C) mediated by these SICs is uniform, as revealed using synchrotron hard X-ray microtomography. As a result, cell cycle life is extended, even when assembled with thin Li anodes (~30 µm) and either high-voltage NMC-622 cathodes (1.44 mAh cm -2 ) or high-capacity sulfur cathodes (3.02 mAh cm -2 ).

25 ENERGY STORAGE↗
DOE OSTI2020

Unveiling the mechanisms of lithium dendrite suppression by cationic polymer film induced solid–electrolyte interphase modification

It is crucial to suppress lithium dendrite formation in lithium metal batteries. Formation of a good solid–electrolyte interphase (SEI) has been considered to be effective in limiting lithium dendrite growth. However, how the SEI may be modified during lithium deposition is hard to resolve due to challenges in in situ investigation of the SEI with fine details. Here, we report an in situ study that uncovers the lithium dendrite suppression mechanism arising from SEI modification by a poly(diallyldimethylammonium chloride) (PDDA) cationic polymer film, using electrochemical liquid cell transmission electron microscopy (TEM). Lithium nanogranules are obtained in the presence of the polymer film. Chemical mapping of the deposits provides remarkable details of the SEI on individual nanogranules. It shows that lithium fluorides are uniformly distributed within the inner SEI layer of individual lithium nanogranules, arising from the instantaneous reaction of the deposited lithium with PF 6 – ions accumulated by the cationic polymer film, and thus the dendritic growth of lithium is prohibited. The ability to directly measure SEI chemistry at the nanoscale down to the individual nanograins in situ and unveil its correlation with the lithium deposition behavior opens future opportunities to explore unsolved mechanisms in batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Developing an In-situ Formed Dynamic Protection Layer to Mitigate Lithium Interface Shifting: Preventing Dendrite Formation on Metallic Lithium Surface to Facilitate Long Cycle Life of Lithium Solid-State Batteries

After extensive research on various system, a fully lithiated Si anode material (Li 3.75 Si) was synthesized. The high energy density, long cycle life anode demonstrated no apparent dendrite growth in an all-solid-state Li battery. A flexible solid-state electrolyte film with a thickness less than 50 μm was developed. All-solid-state Li full batteries were built and tested with NMC811, organic, organosulfide and sulfur cathode. Energy density of 1140 Wh/Kg at material level and 376 Wh/Kg at electrode level were demonstrated for over 500 cycles and with no apparent dendrite formation on the Li anode.

25 ENERGY STORAGE↗
DOE OSTI2026

Modeling the influence of the solid electrolyte interphase on the sand’s time and dendrite formation on lithium metal electrodes

Lithium metal is a sought after battery material for its high energy density due to the low electrochemical potential and density. However, lithium metal is also highly reactive, which results in a strong propensity for dendrite formation. The Sand’s time has previously been used to predict the time of dendrite initiation on metals that do not form a solid-electrolyte interphase (SEI), but it has been shown that the Sand’s time is not accurate for lithium electrodes when using transport parameters associated with the electrolyte. Thus, we built a numerical model to simulate lithium ion transport through a growing SEI to predict the Sand’s time. The numerical model is shown to be more accurate than previous analytical solutions, especially for low current densities. We then analyze the sensitivity of the Sand’s time to different SEI properties and the chemical potential gradients present in the SEI, driving lithium transport. The results showed that high lithium concentration has a greater impact at high current density, while fast diffusivity is more important at low current density. Lastly, we modeled the influence of surface roughness on the plating evolution and chemical potential gradients when an SEI is present in comparison to the electrolyte. As a result, we demonstrate that the SEI plays a critical role in lithium electrode stability, and that improved characterization techniques are needed to better understand transport through the SEI and increase lithium metal utilization in energy storage devices.

Chemistry↗
DOE OSTI2020

Insights into lithium ion deposition on lithium metal surfaces

Lithium metal is among the most promising anodes for the next generation of batteries due to its high theoretical energy density and high capacity. Challenges such as extreme reactivity and lithium dendrite formation have kept lithium metal anodes away from practical applications. However, the underlying mechanisms of Li ion deposition from the electrolyte solution onto the anode surface are still poorly understood due to their inherent complexity. In this work, density functional theory calculations and thermodynamic integration via constrained molecular dynamics simulations are conducted to study the electron and ion transfer between lithium metal slab and the electrolyte in absence of an external field. Here, we explore the effect of the solvent chemistry and structure, distance of the solvated complex from the surface, anion–cation separation, and concentration of Li-salts on the deposition of lithium ions from the electrolyte phase onto the surface. Ethylene carbonate (EC), 1,2-dimethoxyethane (DME), 1,3-dioxolane (DOL), and mixtures of them are used as solvents. These species compete with the salt anion and the Li cation for electron transfer from the surface. It is found that the structure and properties of the solvation shell around the lithium cation has a great influence on the ability of the cation to diffuse as well as on its surrounding electron environment. DME molecules allow easier motion of the lithium ion compared with EC and DOL molecules. The slow growth approach allows the study of energy barriers for the ion diffusion and desolvation during the deposition pathway. This method helps elucidating the underlying mechanisms on lithium-ion deposition and provides a better understanding of the early stages of Li nucleation.

25 ENERGY STORAGE↗
DOE OSTI2026

Self-Healing Lithium Dendrites through Spontaneous Passivating Layer Formation for Stable Solid-State Lithium–Metal Batteries

All-solid-state lithium–metal batteries have attracted significant attention, owing to their high energy density and superior safety. However, lithium–metal penetration through the solid electrolyte, leading to short-circuiting, remains a critical failure mode that demands comprehensive mitigation strategies. Most existing strategies are effective only prior to the initiation of lithium-dendrite formation and fail once dendrites begin to propagate through the electrolyte. In this study, we propose a self-healing mechanism in which the penetrated lithium reacts with a self-healing agent to form a passivating layer along the particle boundaries. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated into a Li 6 PS 5 Cl solid electrolyte as the self-healing agent to suppress lithium-dendrite propagation even after dendrite formation initiated under high current densities. The self-healing induced by LiTFSI was verified through comprehensive experimental analyses and was further demonstrated in a full-cell configuration. Moreover, LiTFSI incorporation plays an important role in increasing the critical current density by reducing the overall electronic conductivity of the solid electrolyte and facilitating the formation of a robust LiF-containing solid-electrolyte interphase.

25 ENERGY STORAGE↗
DOE OSTI2018

Tortuosity Effects in Garnet-Type Li 7 La 3 Zr 2 O 12 Solid Electrolytes

Intrinsic material microstructure features, such as pores or void spaces, grains, and defects can affect local lithium-ion concentration profiles and transport properties in solid ion conductors. The formation of lithium-deficient or -excess regions can accelerate degradation phenomena, such as dendrite formation, lithium plating, and electrode/electrolyte delamination. This paper evaluates the effects pores or void spaces have on the tortuosity of a garnet-type Li 7 La 3 Zr 2 O 12 solid electrolyte. Synchrotron X-ray tomography is used to obtain three-dimensional reconstructions of different electrolytes sintered at temperatures between 1050 and 1150 °C. The magnitude of the electrolyte tortuosity and the tortuosity directional anisotropy is shown to increase with sintering temperature. Electrolytes with highly anisometric tortuosity have lower critical current densities. Here, the alignment or elimination of pores within an electrolyte or composite cathode may provide a means or achieving higher critical current densities and higher power densities in all solid-state batteries.

42 ENGINEERING↗
DOE OSTI2016

An Artificial Solid Electrolyte Interphase with High Li-Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes

Here, an artificial solid electrolyte interphase (SEI) is demonstrated for the efficient and safe operation of a lithium metal anode. Composed of lithium-ion-conducting inorganic nanoparticles within a flexible polymer binder matrix, the rationally designed artificial SEI not only mechanically suppresses lithium dendrite formation but also promotes homogeneous lithium-ion flux, significantly enhancing the efficiency and cycle life of the lithium metal anode.

25 ENERGY STORAGE↗
DOE OSTI2024

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↗