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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes

Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.

25 ENERGY STORAGE↗
DOE OSTI2026

Advanced LiFSI-LiPF6 Electrolyte for Wide-Temperature and Thermally Stable Lithium-Ion Batteries

A new optimized LiFSI–LiPF6 dual-salt controlled-solvation electrolyte (E-DS) is demonstrated to enable practical graphite||LiNi0.8Mn0.1Co0.1O2 cells (˜4.0 mAh cm?²) to achieve exceptional performance and safety under extreme conditions. By optimizing anion coordination with the smaller, more dissociating FSI? anion, the E-DS forms ultrathin, dense, and inorganic-rich electrode/electrolyte interphases that dramatically suppress solvent decomposition, transition-metal dissolution, and surface reconstruction compared to the conventional LiPF6/carbonate electrolyte. Consequently, E-DS cells deliver >78% capacity retention after 300 cycles at 60 °C, retain fast discharging capacity at 30 °C, and operate effectively at -20 °C. Most strikingly, fully charged full cells with E-DS, even under overcharging to 4.8 V, show a lower heat evolution in stable formulations — transforming a traditionally unstable high-voltage/high-temperature configuration into an intrinsically safe state. This work establishes a new benchmark for carbonate-containing electrolytes, simultaneously achieving high energy density, fast-discharging capability, wide-temperature operation (-20 to 60 °C), and outstanding thermal safety in nickel-rich lithium-ion batteries.

electrode/electrolyte interphase↗
DOE OSTI2020

Towards the Commercialization of the All-Solid-State Li-ion Battery: Local Bonding Structure and the Reversibility of Sheet-Style Si-PAN Anodes

A slurry-coated sheet-style Si-based anode is developed for use in all-solid-state Li-ion batteries. Inexpensive, mixed-conducting polyacrylonitrile (PAN) is utilized as both binder and conductive additive, enabling Si-rich electrodes (70 wt%) to attain large reversible capacities ~1,500 mAh g-1 (Si) at 1 C rates (>3 mA cm -2 ). Cross sectional analysis of a discharged all-solid-state half-cell indicates that the Si-PAN anode achieves the largest volumetric specific capacity ever reported for a Li-ion electrode (>1500 mAh cm -3 ). Ex situ Raman spectroscopic studies reveal that the anodes' reversibility is attributed to the preservation of small tetrahedrally coordinated clusters within their Si nanoparticles upon discharge. We therefore argue that careful lithiation limitations should be implemented in all Si-based Li-ion anodes to preserve this local tetrahedral atomic structure. Furthermore, the slurry-coated sheet-style Si-PAN anodes have been successfully cycled in all-solid-state full-cells against high-voltage nickel-rich NMC 811 composite cathodes to encourage future commercialization of similar sheet-style all-solid-state designs.

25 ENERGY STORAGE↗
DOE OSTI2022

Enable High-Energy LiNi0.5Co0.2Mn0.3O2 by Ultra-Thin Coating through Wet Impregnation

A high cut-off voltage is required for nickel-rich layered oxide LiNixCoyMnzO2 (NCM) to meet the high energy density requirement of lithium-ion batteries in electric vehicles. However, such a high voltage application leads to an unstable interface between NCM and liquid electrolytes. To stabilize the interface, the facile wet impregnation method has been developed to apply an ultra-thin Al2O3 coating layer on the NCM particles. This coating layer was found to have a strong interaction with the NCM and resulted in Al-doped NCM at the surface structure of NCM. The change of surface structure can not only reduce the surface resistance of lithium diffusion of LiNi0.5Co0.2Mn0.3O2 (NCM523), but also stabilize the solid electrolyte interface between NCM523 and the electrolyte with the cut-off voltage of 4.5 V vs. Li/Li+. Compared to other coating methods, wet impregnation coating can provide an ultra-thin and uniform coating with surface doping on NCM particles. Furthermore, this scalable coating method can be applied to various electrode materials without adding much additional cost.

25 ENERGY STORAGE↗
DOE OSTI2023

Tackling issues of lithium metal anodes with a novel polymeric lithicone coating

Lithium metal (Li) has been hindered from as anodes in commercial batteries for over 50 years, due to two main issues: continuous formation of solid electrolyte interphase (SEI) and lithium dendritic growth. In this work, we report a new strategy to tackle these issues, i.e., using molecular layer deposition (MLD) to grow an ionically conducting but electrically insulating polymeric lithicone coating, an Li-containing triethanolamine (LiTEA). Our electrochemical tests revealed that this LiTEA coating could serve as an exceptional protection layer over Li anodes. Consequently, the LiTEA-coated Li electrodes could achieve a superior cyclability of > 10000 Li stripping/plating cycles at a current density of 5 mA cm -2 and a long cyclability of > 5500 cycles at 2 mA cm -2 in Li||Li symmetric cells without failures, under a fixed areal capacity of 1 mAh cm -2 . Characterizations using scanning electron microscopy and X-ray photoelectron microscopy verified that Li + ions could be easily extracted through and deposited under the LiTEA coating during the stripping/plating processes. Consequently, this LiTEA coating significantly inhibited the formation of SEI and Li dendrites. This underlies the long cycling lifetime of the LiTEA-coated Li||Li cells. Coupling with the nickel-rich LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes, more encouragingly, the LiTEA-coated Li anodes could remarkably extend the cyclability and sustainable capacity of the resultant Li||NMC full cells. Finally, we also demonstrated that the performance of Li||NMC cells could be further improved through combining an LiTEA-coated Li anode with an Li 2 S-modified NMC811 via atomic layer deposition (ALD). Thus, this study is inspiring for developing high-energy Li||NMC lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Valuation of Surface Coatings in High-Energy Density Lithium-ion Battery Cathode Materials

Artificial barriers, usually with either electrochemically active or inactive coating materials, are deployed on cathode material surfaces to mitigate detrimental side reactions by suppressing direct contact of cathode and electrolyte called surface coatings. These surface coatings are commonly known to increase the wettability of liquid electrolyte and reduce the interfacial charge transfer resistance. An important caveat is the selection of appropriate coating material with appropriate thickness for achieving enhanced electrochemical performance. As modern battery materials are increasingly developed with some type of surface coating, a careful and thorough examination of their role in mitigating the cycle life issues of cathode materials is paramount. Here, this comprehensive review article extensively covers the selection criteria of coating materials based on their chemical and physical properties and electrochemical functionalities. Additionally, the article discusses the concept of critical coating thickness and methods of achieving homogeneous coating architectures that deliver desired performance benefits. Furthermore, this comprehensive article summarizes the recent advancements, effectiveness, necessity of cathode surface coatings and identifies the key aspect of structure-property correlation between coating type/thickness and lithium-ion diffusion through coating layers as the linchpin that validates surface coating approaches especially for high capacity nickel-rich cathodes.

25 ENERGY STORAGE↗
DOE OSTI2023

Solid-state interphases design for high-safety, high-voltage and long-cyclability practical batteries via ethylene carbonate-free electrolytes

In this study, ethylene carbonate (EC) plays a crucial role in current electrolytes for batteries. However, EC reacts exothermically with the electrode to trigger thermal runaway and undergoes continuous oxidative decomposition at high voltages, hindering it application for next-generation batteries. Here we report a simple and effective strategy to design sulfolane(SL)-based electrolyte with reshaped anions-dominated solvation structure, forming highly stable inorganic-dominated electrode-electrolyte interphases that efficiently stabilize nickel-rich cathode and graphite anode. Compared with the conventional electrolyte, practical pouch-type LiNi 0.8 Co 0.1 Mn 0.1 O 2 |Graphite cell with SL-based electrolyte significantly improve self-generated heat T 1 and thermal runaway triggering T 2 by 9.6 and 42.0 °C, respectively. More surprisingly, the pouch cell with SL-based electrolyte exhibits outstanding capacity retention of 88 % after 1000 cycles charged up to 4.5 V. The study brings new insights for unlocking advanced electrolyte candidates to build next-generation practical safer high-energy batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Promising performance of sulfide catholytes compared to halide alternatives in NMC811 cathodes for sheet-type sulfide solid-state batteries

Sulfide-based solid-state batteries (SSBs) show promise in achieving energy densities over 350 Wh/kg, yet challenges persist with their incorporation of high-voltage, nickel-rich layered oxide cathodes, such as LiNi₀.₈Mn₀.₁Co₀.₁O₂ (NMC811), due to the poor oxidation stability of sulfide solid-state electrolytes (SSEs) like Li₆PS₅Cl (LPSCl). Although halide SSEs such as Li₃InCl₆ (LIC) and Li₃YCl₆ (LYC) have previously shown promise in stabilizing high-voltage NMC cathodes, our research reveals that sulfide SSE catholytes, particularly when combined with surface-coated NMC cathodes, deliver superior performance. Here, this investigation assesses the cycling stability of various catholytes—LPSCl, LIC, Li₁₀GeP₂S₁₂ (LGPS), combined LIC-LPSCl, and LYC-LPSCl—in SSBs with LiNbO₃-coated NMC811 cathodes against sheet-type LPSCl separators. Findings indicate that while LGPS-based cathodes maintain higher capacity retention, they yield lower deliverable capacity, and LIC cathodes experience significant electrochemical degradation. Importantly, our results underscore that sulfide SSE catholytes, in conjunction with LiNbO₃-coated cathodes, optimize the cathode-electrolyte interphase (CEI), enhancing both kinetics and mass transport. These insights provide a strategic direction for optimizing catholyte composition in the development of sheet-type sulfide-based SSBs.

Catholyte↗
DOE OSTI2021

Dual-shell silicate and alumina coating for long lasting and high capacity lithium ion batteries

In this work we demonstrate a theory-driven, novel dual-shell coating system of Li 2 SrSiO 4 and Al 2 O 3 , achieved via a facile and scalable sol-gel technique on LiCoO 2 electrode particles. The optimal thickness of each coating can lead to increased specific capacity (~185 mAh/g at 0.5 C-rate) at a cut-off potential of 4.5 V, and greater cycling stability at very high C rates (up to 10 C) in half-cells with lithium metal. The mechanism of this superior performance was investigated using a combination of X-ray and electron characterization methods. It shows that the results of this investigation can inform future studies to identify still better dual-shell coating schemes, achieved by such industrially feasible techniques, for application on similar, nickel-rich cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2020

LiNi x Fe y Al z O 2 , a new cobalt-free layered cathode material for advanced Li-ion batteries

Recently, rapid fluctuations in cobalt prices have created a worsening supply chain constraint that has become a serious cause of concern amidst global battery manufacturers. To address this challenge, we report herein a new class of cobalt-free, nickel-rich layered cathode material termed the NFA class with general formula LiNi x Fe y Al z O 2 (x + y + z = 1). Using co-precipitation reaction in a continuous stirred tank reactor, we synthesized NFA(OH) 2 precursors with the constituent Ni, Fe and Al elements successfully incorporated. The obtained LiNFAO 2 cathode was characterized using X-Ray diffraction, Mössbauer spectroscopy and scanning electron microscopy. Electrochemical behavior was assessed using cyclic voltammetry, galvanostatic charge/discharge, electrochemical impedance spectroscopy and galvanostatic intermittent titration technique at various states of lithiation/delithiation. Electrochemical performance evaluations revealed that our cobalt-free material delivers high capacity of 190 mAh/g at 0.1C. Rate and cycling performance evaluations also indicated good rate capability and cycling stability with 88% capacity retention after 100 cycles at C/3. Using NFA cathodes, we also fabricated a 0.5Ah (C/3) cobalt-free Li-ion battery which demonstrated reasonable cycling stability with ~72% capacity retained after 200 cycles. Overall, our work demonstrates the immense potential of the cobalt-free NFA class cathodes as viable candidates towards development of next generation cost effective lithium ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Interfacial Chemistry Involved in Selective Separation of NMC/LMO and LCO/LMO Binary Cathode Materials by Froth Flotation Using Oleic Acid

The variability in cathode compositions within recycled lithium-ion battery (LIB) feedstocks poses a significant challenge to efficient downstream refining processes. This study demonstrates the feasibility of using froth flotation with oleic acid as a collector to selectively separate lithium nickel-manganese-cobalt oxide (NMC) and lithium cobalt oxide (LCO) from lithium manganese oxide (LMO) materials. Laboratory-scale flotation tests achieved an 80% separation efficiency in a single stage, producing a froth product with >90% purity of NMC/LCO at approximately 90% yield. Concurrently, the LMO materials were enriched in the sink product with ∼90% purity and ∼90% yield. This approach was further validated using recycled cathode materials, confirming its applicability to realistic feedstocks. The underlying mechanism governing the selective separation of NMC/LCO from LMO was investigated using ζ-potential measurements, contact angle measurements, bubble-particle attachment experiments, and X-ray photoelectron spectroscopy (XPS) analysis. Both contact angle and bubble-particle attachment results confirmed that oleic acid adsorption rendered NMC and LCO surfaces hydrophobic, thereby enhancing flotation recovery. At pH 5, oleic acid adsorbed preferentially onto NMC and LCO surfaces via electrostatic interactions, while exhibiting minimal adsorption on LMO surfaces. However, separation efficiency deteriorated at higher pH, which was attributed to the co-flotation of LMO materials caused by oleate chemisorption on MnOH + species. This work establishes froth flotation as a viable cathode/cathode separation strategy, providing a low-cost, scalable pathway to preconcentrate and enrich nickel-rich and cobalt-rich cathode active materials from incompatible cathode chemistries for direct recycling or hydrometallurgical processing. Furthermore, this study reveals, for the first time, the mechanism of oleate adsorption on the surface of different cathode materials.

PH↗
DOE OSTI2021

Nickel–Platinum Nanoparticles as Peroxidase Mimics with a Record High Catalytic Efficiency

While nanoscale mimics of peroxidase have been extensively developed over the past decade or so, their catalytic efficiency as a key parameter has not been substantially improved in recent years. Herein, we report a class of highly efficient peroxidase mimic–nickel–platinum nanoparticles (Ni–Pt NPs) that consist of nickel-rich cores and platinum-rich shells. The Ni–Pt NPs exhibit a record high catalytic efficiency with a catalytic constant (K cat ) as high as 4.5 × 10 7 s –1 , which is ~46- and 10 4 -fold greater than the K cat values of conventional Pt nanoparticles and natural peroxidases, respectively. Density functional theory calculations reveal that the unique surface structure of Ni–Pt NPs weakens the adsorption of key intermediates during catalysis, which boosts the catalytic efficiency. Furthermore, the Ni–Pt NPs were applied to an immunoassay of a carcinoembryonic antigen that achieved an ultralow detection limit of 1.1 pg/mL, hundreds of times lower than that of the conventional enzyme-based assay.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

New Compounds and Phase Selection of Nickel Sulfides via Oxidation State Control in Molten Hydroxides

Molten salts are promising reaction media candidates for the discovery of novel materials; however, they offer little control over oxidation state compared to aqueous solutions. Here, we demonstrated that when two hydroxides are mixed, their melts become fluxes with tunable solubility, which are surprisingly powerful solvents for ternary chalcogenides and offer effective paths for crystal growth to new compounds. We report that precise control of the oxidation state of Ni is achievable in mixed molten LiOH/KOH to grow single crystals of all known ternary K-Ni-S compounds. It is also possible to access several new phases, including a new polytope of β-K 2 Ni 3 S 4 , as well as low-valence KNi 4 S 2 and K 4 Ni 9 S 11 . KNi 4 S 2 is a two-dimensional low-valence nickel-rich sulfide, and β-K 2 Ni 3 S 4 has a hexagonal lattice. Moreover, using KNi 4 S 2 as a template, we obtained a new layered binary Ni 2 S by topotactic deintercalation of K. The new binary Ni 2 S has a van der Waals gap and can function as a new host layer for intercalation chemistry, as demonstrated by the intercalation of LiOH between its layers. The oxidation states of low-valence KNi 4 S 2 and Ni 2 S were studied using X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. Density functional theory calculations showed large antibonding interactions at the Fermi level for both KNi 4 S 2 and Ni 2 S 2 corresponding to the flat-bands with large Ni-d$_{x^2}$$_{y^2}$ character.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thermal-healing of lattice defects for high-energy single-crystalline battery cathodes

Abstract Single-crystalline nickel-rich cathodes are a rising candidate with great potential for high-energy lithium-ion batteries due to their superior structural and chemical robustness in comparison with polycrystalline counterparts. Within the single-crystalline cathode materials, the lattice strain and defects have significant impacts on the intercalation chemistry and, therefore, play a key role in determining the macroscopic electrochemical performance. Guided by our predictive theoretical model, we have systematically evaluated the effectiveness of regaining lost capacity by modulating the lattice deformation via an energy-efficient thermal treatment at different chemical states. We demonstrate that the lattice structure recoverability is highly dependent on both the cathode composition and the state of charge, providing clues to relieving the fatigued cathode crystal for sustainable lithium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Additive engineering for robust interphases to stabilize high-Ni layered structures at ultra-high voltage of 4.8 V

Nickel-rich layered cathode materials promise high energy density for next-generation batteries when coupled with lithium metal anodes. However, the practical capacities accessible are far less than the theoretical values due to their structural instability during cycling, especially when charged at high voltages. Here we demonstrate that stable cycling with an ultra-high cut-off voltage of 4.8 V can be realized by using an appropriate amount of lithium difluorophosphate in a common commercial electrolyte. The Li||LiNi 0.76 Mn 0.14 Co 0.10 O 2 cell retains 97% of the initial capacity (235 mAh g -1 ) after 200 cycles. The cycling stability is ascribed to the robust interphase on the cathode. It is formed by lithium difluorophosphate decomposition, which is facilitated by the catalytic effect of transition metals. The decomposition products (Li 3 PO 4 and LiF) form a protective interphase. This suppresses transition metal dissolution and cathode surface reconstruction. It also facilitates uniform Li distribution within the cathode, effectively mitigating the strain and crack formation.

25 ENERGY STORAGE↗
DOE OSTI2025

A cost-effective all-in-one halide material for all-solid-state batteries

All-solid-state batteries require advanced cathode designs to realize their potential for high energy density and economic viability. Integrated all-in-one cathodes, which eliminate inactive conductive additives and heterogeneous interfaces, hold promise for substantial energy and stability gains but are hindered by materials lacking sufficient Li + /e − conductivity, mechanical robustness and structural stability. Here, in this work, we present Li 1.3 Fe 1.2 Cl 4 , a cost-effective halide material that overcomes these challenges. Leveraging reversible Fe 2+ /Fe 3+ redox and rapid Li + /e − transport within its framework, Li 1.3 Fe 1.2 Cl 4 achieves an electrode energy density of 529.3 Wh kg −1 versus Li + /Li. Critically, Li 1.3 Fe 1.2 Cl 4 shows unique dynamic properties during cycling, including reversible local Fe migration and a brittle-to-ductile transition that confers self-healing behaviour. This enables exceptional cycling stability, maintaining 90% capacity retention for 3,000 cycles at a rate of 5 C. Integration of Li 1.3 Fe 1.2 Cl 4 with a nickel-rich layered oxide further increases the energy density to 725.6 Wh kg −1 . By harnessing the advantageous dynamic mechanical and diffusion properties of all-in-one halides, this work establishes all-in-one halides as an avenue for energy-dense, durable cathodes in next-generation all-solid-state batteries.

25 ENERGY STORAGE↗