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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

In Situ Formation of Polycyclic Aromatic Hydrocarbons as an Artificial Hybrid Layer for Lithium Metal Anodes

Nonuniform Li deposition causes dendrites and low Coulombic efficiency (CE), seriously hindering the practical applications of Li metal. Herein, we developed an artificial solid-state interphase (SEI) with planar polycyclic aromatic hydrocarbons (PAHs) on the surface of Li metal anodes by a facile in situ formation technology. The resultant dihydroxyviolanthron (DHV) layers serve as the protective layer to stabilize the SEI. In addition, the oxygen-containing functional groups in the soft and conformal SEI film can regulate the diffusion and transport of Li ions to homogenize the deposition of Li metal. The artificial SEI significantly improves the CEs and shows superior cyclability of over 1000 h at 4 mAh cm –2 . The LiFePO 4 /Li cell (2.8 mAh cm –2 ) enables a long cyclability for 300 cycles and high CEs of 99.8%. Furthermore, this work offers a new strategy to inhibit Li dendrite growth and enlightens the design on stable SEI for metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Polymer–Ceramic Composite Electrolytes for Lithium Batteries: A Comparison between the Single-Ion-Conducting Polymer Matrix and Its Counterpart

Single-ion-conducting polymer electrolytes are attractive to use in lithium batteries as the transference number of the lithium cation approaches unity. This helps prevent concentration gradients across the electrolyte, which can result in dendrite formation. The addition of ceramic particles to polymer electrolytes at high loadings can increase the mechanical strength of the polymer, which can also help suppress dendrite formation. Here, a single-ion-conducting polymer electrolyte is blended with lithium-conducting oxide ceramic particles to make a composite electrolyte. This electrolyte is studied in comparison to a composite electrolyte containing freely dissolved lithium salt. It is found that the addition of ceramic particles to the single-ion-conducting polymer can result in increased cation dissociation and consequent increased ionic conductivity. The electrolytes are cycled in lithium symmetrical cells, and it is found that the ceramic-containing electrolytes show increased interfacial stability with the lithium metal compared to the pristine polymer electrolytes. Our findings shed light on how to optimize the polymer host chemistry to form composite electrolytes that can meet the challenging requirements to stabilize the lithium metal anode.

25 ENERGY STORAGE↗
DOE OSTI2026

Radiation Damage Mechanisms in Oxide-Based Solid Electrolytes

Ion implantation is a promising approach to mitigate dendrite formation in metal anode solid-state batteries by modifying the chemical and mechanical properties of oxide-based electrolyte surfaces such as Li 7 La 3 Zr 2 O 12 (LLZO). Yet, the detailed atomistic mechanisms and potentially adverse side effects of ion implantation remain poorly understood. In this study, we used molecular dynamics simulations to elucidate the evolution of radiation-induced damage in LLZO. The results reveal that radiation damage is primarily driven by recoils from heavy ions in the lattice, producing antisite defect clusters whose density decreases as recoil energy increases, a counterintuitive finding that highlights complex cascade fragmentation. Radiation-induced disruption to the crystal sublattice connectivity, especially in the La–O network critical for Li-ion transport, leads to degradation in ionic pathways at low energies, while higher energy cascades can form new conduction pathways via enhanced Zr–O network connectivity. These findings provide a mechanistic foundation for optimizing ion implantation strategies that balance disruption of the lattice for surface modification for dendrite resistance with preservation of essential ionic conductivity.

Defects↗
DOE OSTI2022

Stable and Recyclable Photocatalysts of CsPbBr 3 @MSNs Nanocomposites for Photoinduced Electron Transfer RAFT Polymerization

All-inorganic metal halide perovskite CsPbX 3 (X = Cl, Br, I) nanocrystals (NCs) have demonstrated attractive optoelectronic characteristics. However, their photocatalytic properties are limited by their poor stability and easy recombination of photogenerated carriers. Herein, we introduced a CsPbBr 3 @MSNs nanocomposite (CsPbBr 3 NCs embedded in dendritic mesoporous silica nanospheres (MSNs)) as photocatalysts for photoinduced electron transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. In this study, the CsPbBr 3 nanocrystals (~8.1 nm; PLQY of 62 ± 2.1%) were embedded in dendritic MSNs using a nanoconfinement strategy. PET-RAFT polymerization was successfully initiated using the CsPbBr 3 @MSNs nanocomposite as the photocatalyst. Reaction variables, such as catalyst loading, monomer composition, and excitation light wavelengths, were varied to yield polymers with the desired control of molecular weight and dispersity as well as block copolymers with high chain-end fidelity. In addition, the perovskite-based photocatalysts could be readily separated and purified, which allowed effective and rapid recycling of the nanocomposites for multiple polymerization cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Pressure-Tolerant 3D Anodes Enable Short-Circuit Prevention and Low Heat Generation in Argyrodite Solid-State Batteries

Solid-state batteries (SSBs) offer a safer, higher-energy-density alternative to lithium-ion batteries, yet commercialization is hindered by incompatibility with lithium metal. Here, to overcome these challenges, we developed a cost-effective, commercially available prelithiated micro carbon fiber framework (Li-Cf) anode featuring a high-pressure-tolerance, for use with argyrodite solid-state electrolytes (SSEs). This 3D structure accommodates uniform lithium deposition, simplifies cell assembly under elevated pressure, inhibits dendrite growth toward SSEs, reduces heat generation, and enhances overall compatibility. Notably, our architecture enables the cell to tolerate pressures up to 400 MPa without short-circuiting during assembly. Meanwhile, the 3D framework serves as a preferential pathway for lithium deposition, thereby reducing lithium growth toward the SSEs and mitigating the risk of dendrite formation in SSEs. Operando calorimetry and distribution of relaxation times analysis reveal that lithium morphology degradation at the interface with the SSEs is a key failure mechanism in lithium metal argyrodite SSBs, leading to increased diffusion resistance and heat generation. In contrast, the Li-Cf anode mitigates these issues by reducing both heat flux and charge transfer resistance. Full cells with LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li 6 PS 5 Cl/Li-Cf retain ~79% capacity after 600 cycles, demonstrating significantly improved cycling stability and strong potential for practical energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2025

Energizing Robust Sulfur/Lithium Electrochemistry via Nanoscale-Asymmetric-Size Synergism

Sluggish redox kinetics and dendrite growth perplex the fulfillment of efficient electrochemistry in lithium–sulfur (Li–S) batteries. The complicated sulfur phase transformation and sulfur/lithium diversity kinetics necessitate an all-inclusive approach in catalyst design. Herein, a compatible mediator with nanoscale-asymmetric-size configuration by integrating Co single atoms and defective CoTe 2–x (Co SA -CoTe 2–x @NHCF) is elaborately developed for regulating sulfur/lithium electrochemistry synchronously. Substantial electrochemistry and theoretical analyses reveal that CoTe 2–x exhibits higher catalytic activity in long-chain polysulfide transformation and Li 2 S decomposition, while monodispersed Co sites are more effective in boosting sulfur reduction kinetics to regulate Li 2 S deposition. Such cascade catalysis endows Co SA -CoTe 2–x @NHCF with the all-around service of “trapping-conversion-recuperation” for sulfur species during the whole redox reaction. Furthermore, it is demonstrated by in situ transmission electron microscopy that initially formed electronic-conductive Co and ionic-conductive Li 2 Te provide sufficient lithiophilic sites to regulate homogeneous Li plating and stripping with markedly suppressed dendrite growth. Consequently, by coupling the Co SA -CoTe 2–x @NHCF interlayer and Li@Co SA -CoTe 2–x @NHCF anode, the constructed Li–S full batteries deliver superior cycling stability and rate performance, and the flexible pouch cell exhibits stable cycling performance at 0.3 C. In conclusion, the gained insights into the synergistic effect of asymmetric-size structures pave the way for the integrated catalyst design in advanced Li–S systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Facile One-Pot Block Copolymer-Mediated Solvothermal Approach for Synthesis of High-Entropy Alloy with Enhanced OER Activity

Herein, we introduce a straightforward synthesis approach for highly active dendritic multimetallic high-entropy alloy (DMHEA@PtIrPdAgRu) nanoparticles with sufficient entropic mixing, featuring uniform distribution of five noble group metals (Pt, Ir, Pd, Ag, and Ru) via a block copolymer-mediated one-pot solvothermal reduction method for oxygen evolution reaction (OER). In this synthesis, N,N -dimethylformamide (DMF) is used as a reductant as well as solvent and core–shell-corona-type (poly(styrene)- block -poly(vinylpyridine)- block -poly(ethylene oxide)) (PS-PVP-PEO) block copolymer as a structure directing agent. The cooperative effect between the copolymer architecture and the reducing environment of DMF promoted a confined nucleation mechanism for forming a single-phase dendritic structure HEA with high compositional uniformity, thereby mitigating phase segregation, a common challenge in the synthesis of multimetallic nanoparticles. This prepared DMHEA@PtIrPdAgRu catalyst exhibits a low overpotential of 490 mV to attain a high current density of 100 mA cm –2 with a Tafel slope of 442 mV dec –1 for oxygen evolution. The superior OER performance is attributed to the synergistic cooperation among its active and coordinated metal centers as well as the incorporation of corrosion-resistant metal like platinum.

block copolymer↗
DOE OSTI2023

Enabling selective zinc-ion intercalation by a eutectic electrolyte for practical anodeless zinc batteries

Abstract Two major challenges hinder the advance of aqueous zinc metal batteries for sustainable stationary storage: (1) achieving predominant Zn-ion (de)intercalation at the oxide cathode by suppressing adventitious proton co-intercalation and dissolution, and (2) simultaneously overcoming Zn dendrite growth at the anode that triggers parasitic electrolyte reactions. Here, we reveal the competition between Zn 2+ vs proton intercalation chemistry of a typical oxide cathode using ex-situ/ operando techniques, and alleviate side reactions by developing a cost-effective and non-flammable hybrid eutectic electrolyte. A fully hydrated Zn 2+ solvation structure facilitates fast charge transfer at the solid/electrolyte interface, enabling dendrite-free Zn plating/stripping with a remarkably high average coulombic efficiency of 99.8% at commercially relevant areal capacities of 4 mAh cm −2 and function up to 1600 h at 8 mAh cm −2 . By concurrently stabilizing Zn redox at both electrodes, we achieve a new benchmark in Zn-ion battery performance of 4 mAh cm −2 anode-free cells that retain 85% capacity over 100 cycles at 25 °C. Using this eutectic-design electrolyte, Zn | |Iodine full cells are further realized with 86% capacity retention over 2500 cycles. The approach represents a new avenue for long-duration energy storage.

25 ENERGY STORAGE↗
DOE OSTI2023

Promoting multiexciton interactions in singlet fission and triplet fusion upconversion dendrimers

Abstract Singlet fission and triplet-triplet annihilation upconversion are two multiexciton processes intimately related to the dynamic interaction between one high-lying energy singlet and two low-lying energy triplet excitons. Here, we introduce a series of dendritic macromolecules that serve as platform to study the effect of interchromophore interactions on the dynamics of multiexciton generation and decay as a function of dendrimer generation. The dendrimers (generations 1–4) consist of trimethylolpropane core and 2,2-bis(methylol)propionic acid (bis-MPA) dendrons that provide exponential growth of the branches, leading to a corona decorated with pentacenes for SF or anthracenes for TTA-UC. The findings reveal a trend where a few highly ordered sites emerge as the dendrimer generation grows, dominating the multiexciton dynamics, as deduced from optical spectra, and transient absorption spectroscopy. While the dendritic structures enhance TTA-UC at low annihilator concentrations in the largest dendrimers, the paired chromophore interactions induce a broadened and red-shifted excimer emission. In SF dendrimers of higher generations, the triplet dynamics become increasingly dominated by pairwise sites exhibiting strong coupling (Type II), which can be readily distinguished from sites with weaker coupling (Type I) by their spectral dynamics and decay kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Industrializable interlayer with catalytic conversion of dead lithium for Ah–level Nickel–rich lithium metal batteries

The growth of lithium (Li) dendrites and the accumulation of dead Li (i.e., Li metal regions which are electronically disconnected from the current collector) significantly undermine the safety and performance of Li metal batteries. This study employs kilogram-scale atomic layer deposition technology to construct zinc oxide with a preferential (002) crystal orientation, which homogeneously forms on commercial carbon nanotube papers. Our approach emphasizes the importance of achieving a moderate Li adsorption energy and low Li migration energy barriers to suppress Li dendrite growth. In this work, we introduce the concept of "catalytic" effect for dead Li reconversion, as validated through time-of-flight secondary ion mass spectrometry, leading to a Li plating/stripping efficiency of 99.89%. The Ah-level Li metal pouch cells with high-nickel positive electrodes achieve a specific energy of 380 Wh kg -1 (based on the mass of the whole pouch cell) and demonstrate stable cycling under demanding conditions. Analysis of the cycled pouch cells confirms the structural integrity and provides insights into the mechanism of the dead Li "catalytic" conversion.

Shen, Huasen [Jianghan University, Wuhan (China)]↗
DOE OSTI2026

Elimination of detrimental grain boundary segregation in garnets

Garnet Li 7 La 3 Zr 2 O 12 electrolyte is considered a key enabler of solid-state batteries with Li metal electrodes, but the grain boundaries impair its performance. To date, the understanding of grain boundary structures and its impact on performance remains elusive. Here, we show that element segregation at Li 7 La 3 Zr 2 O 12 grain boundaries critically governs Li transport and nucleation. During conventional sintering, Al, Ta, and La segregate at grain boundaries, locally depleting Li and creating space-charge layers that lower total ionic conductivity. Simultaneously, this segregation leads to higher electronic conductivity along grain boundaries, which promotes Li nucleation at grain boundary edges with increased risk of dendrite formation. The underlying mechanism of segregation is governed by both thermodynamic driving forces and diffusion kinetics. Building on this understanding, we develop a strategy to achieve segregation-free grain boundaries through a rapid sintering protocol that utilizes the onset of solid-state softening. This approach yields transparent, polycrystalline Li 7 La 3 Zr 2 O 12 with negligible grain boundary impedance and enhanced dendrite tolerance. By elucidating the structural origins and electrochemical consequences of grain boundary segregation, this work provides a guidance for the rational optimization of solid electrolytes.

Energy - Storage↗
DOE OSTI2024

Methylation enables the use of fluorine-free ether electrolytes in high-voltage lithium metal batteries

Lithium metal batteries represent a promising technology for next-generation energy storage, but they still suffer from poor cycle life due to lithium dendrite formation and cathode cracking. Fluorinated solvents can improve battery longevity by improving LiF content in the solid-electrolyte interphase; however, the high cost and environmental concerns of fluorinated solvents limit battery viability. Here, for this work, we designed a series of fluorine-free solvents through the methylation of 1,2-dimethoxyethane, which promotes inorganic LiF-rich interphase formation through anion reduction and achieves high oxidation stability. The anion-derived LiF interphases suppress lithium dendrite growth on the lithium anode and minimize cathode cracking under high-voltage operation. The Li + -solvent structure is investigated through in situ techniques and simulations to draw correlations between the interphase compositions and electrochemical performances. The methylation strategy provides an alternative pathway for electrolyte engineering towards high-voltage electrolytes while reducing dependence on expensive fluorinated solvents.

25 ENERGY STORAGE↗
DOE OSTI2020

Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface

Stable operation of rechargeable lithium (Li)-based batteries at low temperatures is vital for cold-climate applications but is plagued with dendritic Li plating and unstable solid-electrolyte interphase (SEI). Here we report high-performance Li-metal batteries under low-temperature and high-rate-charging conditions. This is realized by utilizing a self-assembled monolayer of electrochemically active molecules on current collectors that regulates the nanostructure and composition of SEI and deposition morphology of Li metal anodes. A multilayer SEI containing a LiF-rich inner phase and amorphous outer layer effectively seals the Li surface in contrast to the conventional impassive SEI at low temperatures. As a result, galvanic Li corrosion and self-discharge were suppressed; stable Li deposition was realized from -60º to 45ºC; and a Li|LiCoO 2 cell with a capacity of 2.0 mAh cm -2 displayed a 200-cycle life at -15ºC with a recharge time of 45 minutes.

25 ENERGY STORAGE↗
DOE OSTI2024

Single-phase local-high-concentration solid polymer electrolytes for lithium-metal batteries

Solid polymers are promising electrolytes for Li-metal batteries, but they have limitations: they cannot simultaneously achieve high ionic conductivity, good mechanical strength and compatibility with high-voltage cathodes while suppressing Li dendrites. Here, we design a class of locally high-concentration solid polymer electrolytes based on polymer blends, which are termed Li-polymer in F diluter (LPIFD). The Li-polymer (polymer-in-salt) ensures continuous Li-ion conduction channels and contributes to the solid electrolyte interphase (SEI), and the F diluter (inert fluorinated polymer) adds mechanical strength. Studies reveal that a single-phase LPIFD, which is based on a miscible polymer blend, lacks phase boundaries and forms an organic-less and LiF-rich SEI, effectively suppressing lithium dendrites. The single-phase LPIFD delivers ionic conductivity of 3.0 x 10 -4 S cm -1 and enables the Li anode to reach a high coulombic efficiency of 99.1% and a critical current density of 3.7 mA cm -2 . Furthermore, the ability to form an F-rich cathode electrolyte interphase allows LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Li cells to achieve a cycle life of 450 cycles at a high operating voltage of 4.5 V. In conclusion, this design will inspire efforts to commercialize polymer electrolytes for high-energy Li-metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Grain boundary zirconia-modified garnet solid-state electrolyte

Here, we report a method for promoting electrochemical stability in garnet Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 solid-state electrolyte based on a composite two-phase oxide–oxide microstructure. Grain boundary precipitation of the controlled distribution of amorphous zirconium oxide microparticles is achieved through the addition of reactive tantalum carbide. During ambient-atmosphere sintering, the carbide decomposes through an in situ reaction, the ‘extra’ Ta substituting for Zr within the Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 lattice. Density functional theory (DFT) calculations identify a thermodynamically favourable reaction path and show how substituting Ta 5+ at Zr 4+ sites affects the crystal structure as well as bulk ionic and electronic conductivities. Quantitative stereology highlights that zirconia also acts as a sintering aid, reducing compact porosity. Cryogenic focused-ion-beam scanning electron microscopy and fractography analysis of cycled solid-state electrolytes illustrates that near-universally observed intergranular Li-metal dendrite propagation is suppressed by the two-phase microstructure, favouring transgranular dendrites instead. Importantly, DFT demonstrates that compared with the Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 surface, the zirconium oxide surface per se is less electronically conductive and does not trap excess electrons to reduce Li ions. This is a key reason for the substantial improvement in the electrochemical properties over the single-phase baseline.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Surface diffusion manifestation in electrodeposition of metal anodes

Metal anode-based battery systems have been deemed indispensable towards energy storage renaissance engendering extensive research into strategies countering dendritic growth of metal electrodeposition. Fundamentally, the morphological evolution of a material is uniquely characterized by the heights of its self-diffusion barrier across multiple pathways. Herein, based on a coarse-grained kinetic Monte Carlo method, we derive insights into the nucleation and growth of metallic electrodeposits in liquid electrolytes, governed by surface self-diffusion characteristics cognizant of the diverse diffusion routes including terrace, away from step and interlayer pathways. We deconvolve the roles played by each of these surface diffusion mechanisms in conjunction with the electrochemical reaction rate on the deposition morphology regime (film vs. mossy vs. fractal). We identify interlayer diffusion as the predominant morphology-determining mechanism; dendrite-free deposition even at moderate current rates constrains this diffusion barrier to an upper limit. Additionally, we highlight subtle features amidst the realm of the morphological growth assortment that connect to the cell's electrochemical performance. Finally, we delineate morphological features of Li, Na, Mg and Al based on their respective surface diffusion barriers and applied overpotentials, and provide a baseline for the interpretation of experimental observations. This fundamental study sheds light on the mesoscale underpinnings of morphological variances in mono-valent and multi-valent metal electrodeposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A weakly ion pairing electrolyte designed for high voltage magnesium batteries

High-voltage rechargeable magnesium batteries (RMBs) are potential alternatives to lithium-ion batteries owing to the low cost and high abundance of magnesium. However, the parasitic reactions of the latter with many electrolytes greatly hinders the stability and kinetics of Mg plating/stripping. Here we report a new and easily accessible solvent-designed electrolyte, which effectively solves the difficulty of ion pair dissociation and facilitates fast nanoscale Mg nucleation/growth using simple Mg(TFSI)2 as the salt, enabling a facile interfacial charge transfer process. Dendrite-free Mg plating/stripping is maintained for over 7000 hours (∼10 months) at a practical areal capacity of 2 mA h cm−2. The high-voltage stability of these electrolytes is demonstrated by benchmarking with polyaniline||Mg full cells with an operating voltage up to 3.5 V that exhibit stable cycling at a 2C rate with 99% coulombic efficiency after 400 cycles. This work opens up new frontiers in coupling low-cost electrolytes with next-generation high-voltage cathode materials for fast-charging RMBs with long life and high energy densities.

Li, Chang↗