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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Toward a Reversible Calcium-Sulfur Battery with a Lithium-Ion Mediation Approach

Calcium represents a promising anode for the development of high-energy-density, low-cost batteries. Yet, a lack of suitable electrolytes has restricted the development of rechargeable batteries with a Ca anode. Furthermore, to achieve a high energy density system, sulfur would be an ideal cathode to couple with the Ca anode. Unfortunately, a reversible calcium-sulfur (Ca-S) battery has not yet been reported. Herein, a basic study of a reversible nonaqueous room-temperature Ca-S battery is presented. The reversibility of the Ca-S chemistry and high utilization of the sulfur cathode are enabled by employing a Li + -ion-mediated calcium-based electrolyte. Mechanistic insights pursued by spectroscopic, electrochemical, microscopic, and theoretical simulation (density functional theory) investigations imply that the Li + -ions in the Ca-electrolyte stimulate the reactivation of polysulfide/sulfide species. The coordination of lithium to sulfur reduces the formation of sturdy Ca-S ionic bonds, thus boosting the reversibility of the Ca-S chemistry. Furthermore, the presence of Li + -ions facilitates the ionic charge transfer both in the electrolyte and across the solid electrolyte interphase layer, consequently reducing the interfacial and bulk impedance of Ca-S batteries. As a result, both the utilization of active sulfur in the cathode and the discharge voltage of Ca-S batteries are significantly improved.

25 ENERGY STORAGE↗
DOE OSTI2019

“Top-Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

Designing Li composite electrodes with host frameworks for accommodating Li metal has been considered to be an effective approach to suppress Li dendrites. Herein, an asymmetric design of a Mo net/Li metal film (MLF) composite electrode is developed by an inverted thermal infusion method. The asymmetric MLF electrode has a dense oxide passivated layer on the top side, a porous Mo net matrix on the back side, and active Li layer in between. The back side has a larger specific area and higher electric field than the top side, which contacts with the separator upon cycling, triggering the preferred Li deposition and stripping of the porous back side of the electrode far from the separator. The surface passivation layer on the top side of the electrode as an artificial solid electrolyte interphase ensures the stable contact with the electrolyte and separator. Meanwhile, the porous structure of the supporting Mo net provides enough space for accommodating the volume change during Li deposition and stripping. This asymmetry design enables a unique “top down” growth pathway for Li deposition in the MLF electrode, suppressing the dendrite growth effectively. In conclusion, the design strategy provides a new direction for high-energy dendrite-free Li metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2019

Localized High‐Concentration Electrolytes Boost Potassium Storage in High‐Loading Graphite

Abstract Reversible intercalation of potassium‐ion (K + ) into graphite makes it a promising anode material for rechargeable potassium‐ion batteries (PIBs). However, the current graphite anodes in PIBs often suffer from poor cyclic stability with low coulombic efficiency. A stable solid electrolyte interphase (SEI) is necessary for stabilizing the large interlayer expansion during K + insertion. Herein, a localized high‐concentration electrolyte (LHCE) is designed by adding a highly fluorinated ether into the concentrated potassium bis(fluorosulfonyl)imide/dimethoxyethane, which forms a durable SEI on the graphite surface and enables highly reversible K + intercalation/deintercalation without solvent cointercalation. Furthermore, this LHCE shows a high ionic conductivity (13.6 mS cm −1 ) and excellent oxidation stability up to 5.3 V (vs K + /K), which enables compatibility with high‐voltage cathodes. The kinetics study reveals that K + intercalation/deintercalation does not follow the same pathway. The potassiated graphite exhibits excellent depotassiation rate capability, while the formation of a low stage intercalation compound is the rate‐limiting step during potassiation.

Qin, Lei↗
DOE OSTI2020

Multimodal Nanoscale Tomographic Imaging for Battery Electrodes

Accurate representations of the 3D structure within a lithium-ion battery are key to understanding performance limitations. However, obtaining exact reconstructions of electrodes, where the active particles, the carbon black and polymeric binder domain, and the pore space are visualized is challenging. In this work, it is shown that multimodal imaging can be used to overcome this challenge. High-resolution ptychographic X-ray computed tomography are combined with lower resolution but higher contrast transmission X-ray tomographic microscopy to obtain 3D reconstructions of pristine and cycled graphite-silicon composite electrodes. This cross-correlation enables quantitative analysis of the surface of active particles, including the heterogeneity of carbon-black and binder domain and solid-electrolyte interphase coverage. Capturing the active particles as well as the carbon black-binder domain allows using these segmented structures for electrochemical simulations to highlight the influence of the particle embedding on local state of charge heterogeneities.

25 ENERGY STORAGE↗
DOE OSTI2020

A High-Rate Aqueous Proton Battery Delivering Power Below -78 °C via an Unfrozen Phosphoric Acid

Lithium-sulfur batteries are attractive for automobile and grid applications due to their high theoretical energy density and the abundance of sulfur. Despite the significant progress in cathode development, lithium metal degradation and the polysulfide shuttle remain two critical challenges in the practical application of Li-S batteries. Development of advanced electrolytes has become a promising strategy to simultaneously suppress lithium dendrite formation and prevent polysulfide dissolution. Here, a new class of concentrated siloxane-based electrolytes, demonstrating significantly improved performance over the widely investigated ether-based electrolytes are reported in terms of stabilizing the sulfur cathode and Li metal anode as well as minimizing flammability. Through a combination of experimental and computational investigation, it is found that siloxane solvents can effectively regulate a hidden solvation-ion-exchange process in the concentrated electrolytes that results from the interactions between cations/anions and solvents. As a result, it could invoke a quasi-solid-solid lithiation and enable reversible Li plating/stripping and robust solid-electrolyte interphase chemistries. The solvation-ion-exchange process in the concentrated electrolytes is a key factor in understanding and designing electrolytes for other high-energy lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Microclusters of Kinked Silicon Nanowires Synthesized by a Recyclable Iodide Process for High-Performance Lithium-Ion Battery Anodes

Silicon shows great promise as a high-capacity anode material for lithium-ion batteries. Nanostructuring silicon minimizes the impact of fracturing during charging and discharging. However, synthesizing nanostructured silicon typically requires complicated procedures with high manufacturing costs. Additionally, these complicated procedures typically have poor secondary particle formation, a requirement to achieve a high tap density. Here, a cost-effective synthesis procedure which generates nearly ideal secondary particle clusters of nanostructured silicon is developed. The cost-effectiveness is a result of the in operando generation of silicon iodide from iodine gas and low-grade silicon microparticle. Decomposition of silicon iodide into crystalline silicon and iodine gas enables recycling of the iodine gas, allowing for near full reutilization of iodine in the following cycles. Additionally, the optimal nanostructures and microstructures of silicon synthesized by the recyclable iodide decomposition reaction enables 83.6% capacity retention over 1000 cycles. The good performance is a result of well-maintained morphology during cycling, enabling reutilization of the solid electrolyte interphase.

25 ENERGY STORAGE↗
DOE OSTI2021

Polymers in Lithium‐Ion and Lithium Metal Batteries

Abstract Lithium‐ion batteries play a significant role in modern electronics and electric vehicles. However, current Li‐ion battery chemistries are unable to satisfy the increasingly heightened expectations regarding energy demand and reliability. To boost the overall energy density while ensuring the safety of Li batteries, researchers have focused on alternative battery materials, such as silicon, sulfur, and Li metal. These represent promising avenues, although numerous obstacles (e.g., Si cracking, polysulfide shuttling, Li dendrites, etc.) must be tackled before batteries based on these materials can enter mass production and penetrate the mainstream market. Polymers are a class of materials that are widely used in current battery systems; however, many novel polymer chemistries may offer better performance and reliability than the current ones, and even overcome the issues of the above‐mentioned new battery materials. In this review, selected polymeric materials for solving these issues are categorized into four parts: polymer electrolytes, polymer artificial solid‐electrolyte interphases, binders, and separators. Both the current progress and the characterization methods are included. Potential future directions of energy materials research are pointed out as well.

Li, Junheng↗
DOE OSTI2022

Enhanced Electrolyte Transport and Kinetics Mitigate Graphite Exfoliation and Li Plating in Fast–Charging Li–Ion Batteries

Despite significant progress in energy retention, lithium-ion batteries (LIBs) face untenable reductions in cycle life under extreme fast-charging (XFC) conditions, which primarily originate from a variety of kinetic limitations between the graphite anode and the electrolyte. Through quantitative Li + loss accounting and comprehensive materials analyses, it is directly observed that the operation of LIB pouch cells at 4 C||C/3 (charging||discharging) results in Li plating, disadvantageous solid-electrolyte-interphase formation, and solvent co-intercalation leading to interstitial decomposition within graphite layers. It is found that these failure modes originate from the insufficient properties of conventional electrolytes, where employing a designed ester-based electrolyte improved the capacity retention of these cells from 55.9% to 88.2% after 500 cycles when operated at the aforementioned conditions. These metrics are the result of effective mitigation of the aforementioned failure modes due to superior Li + transport and desolvation characteristics demonstrated through both experimental and computational characterization. Finally, this work reveals the vital nature of electrolyte design to XFC performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Conjugated Imine Polymer Synthesized via Step‐Growth Metathesis for Highly Stable Silicon Nanoparticle Anodes in Lithium‐Ion Batteries

Abstract This work reports a new method to synthesize polyphenylmethanimine (polyPMI) as a linear or a hyperbranched, conjugated polymer using an aldehyde‐imine metathesis reaction. This work details the reaction mechanisms of this polymerization by characterizing a red‐shift in its absorption spectrum as polymer conjugation length increases and verifies that this optical shift results from extended π‐condensation using density functional theory. This new synthetic approach provides a polymer that can potentially be depolymerized for facile recyclability and is compatible with air‐ and water‐sensitive chemistries. As an example of the utility of this new approach, this work demonstrates that this polymer can be directly grown on silicon nanoparticles to create silicon anodes for lithium‐ion batteries with a high degree of electrochemical interfacial passivation. These silicon anodes exhibit Coulombic efficiencies above 99.9% and can accommodate silicon nanoparticle expansion and contraction during lithiation and delithiation as demonstrated by stable reversible capacities for 500 cycles. Finally, this work demonstrates that polyPMI facilitates the formation of a lithium fluoride rich solid electrolyte interphase that remains chemically and mechanically stable after long term cycling.

25 ENERGY STORAGE↗
DOE OSTI2023

Intermetallics Based on Sodium Chalcogenides Promote Stable Electrodeposition–Electrodissolution of Sodium Metal Anodes

Sodiophilic micro-composite films of sodium-chalcogenide intermetallics (Na 2 Te and Na 2 S) and Cu particles are fabricated onto commercial copper foam current collectors (Na 2 Te@CF and Na 2 S@CF). For the first time a controllable capacity thermal infusion process is demonstrated. Enhanced wetting by the metal electrodeposition leads to state-of-the-art electrochemical performance. For example, Na 2 Te@CF-based half-cells demonstrate stable cycling at 6 mA cm -2 and 6 mAh cm -2 , corresponding to 54 µm of Na electrodeposited/electrodissolved by geometric area. Sodium metal batteries with Na 3 V 2 (PO 4 ) 3 cathodes are stable at 30C (7 mA cm -2 ) and for 10 000 cycles at 5C and 10C. Cross-sectional cryogenic focused ion beam (cryo-FIB) microscopy details deposited and remnant dissolved microstructures. Sodium metal electrodeposition onto Na 2 Te@CF is dense, smooth, and free of dendrites or pores. On unmodified copper foam, sodium grows in a filament-like manner, not requiring cycling to achieve this geometry. Substrate–metal interaction critically affects the metal–electrolyte interface, namely the thickness and morphology of the solid electrolyte interphase. Density functional theory and mesoscale simulations provide insight into support-adatom energetics, nucleation response, and early-stage morphological evolution. On Na 2 Te sodium atomic dispersion is thermodynamically more stable than isolated clusters, leading to conformal adatom coverage of the surface.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The Origin of Improved Performance in Boron‐Alloyed Silicon Nanoparticle‐Based Anodes for Lithium‐Ion Batteries

Stabilizing the solid electrolyte interphase (SEI) remains a key challenge for silicon‐based lithium‐ion battery anodes. Alloying silicon with secondary elements like boron has emerged as a promising strategy to improve the cycle life of silicon anodes, yet the underlying mechanism remains unclear. To address this knowledge gap, how boron concentration influences battery performance is systematically investigated. These results show a near‐monotonic increase in cycle lifetime with higher boron content, with boron‐rich electrodes significantly outperforming pure silicon. Additionally, silicon‐boron alloy anodes exhibit nearly three times longer calendar life than pure silicon. Through detailed mechanistic analysis, alternative contributing factors are systematically ruled out, and it is proposed that improved passivation arises from a strong permanent dipole at the nanoparticle surface. This dipole, formed by undercoordinated and highly Lewis acidic boron, creates a static, ion‐dense layer that stabilizes the electrochemical interface, reducing parasitic electrolyte decomposition and enhancing long‐term stability. These findings suggest that, within the SEI framework, the electric double layer is an important consideration in surface passivation. This insight provides an underexplored parameter space for optimizing silicon anodes in next‐generation lithium‐ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2018

A High‐Energy‐Density Potassium Battery with a Polymer‐Gel Electrolyte and a Polyaniline Cathode

Abstract A safe, rechargeable potassium battery of high energy density and excellent cycling stability has been developed. The anion component of the electrolyte salt is inserted into a polyaniline cathode upon charging and extracted from it during discharging while the K + ion of the KPF 6 salt is plated/stripped on the potassium‐metal anode. The use of a p‐type polymer cathode increases the cell voltage. By replacing the organic‐liquid electrolyte in a glass‐fiber separator with a polymer‐gel electrolyte of cross‐linked poly(methyl methacrylate), a dendrite‐free potassium anode can be plated/stripped, and the electrode/electrolyte interface is stabilized. The potassium anode wets the polymer, and the cross‐linked architecture provides small pores of adjustable sizes to stabilize a solid‐electrolyte interphase formed at the anode/electrolyte interface. This alternative electrolyte/cathode strategy offers a promising new approach to low‐cost potassium batteries for the stationary storage of electric power.

Gao, Hongcai↗
DOE OSTI2019

Synergy of Epoxy Chemical Tethers and Defect‐Free Graphene in Enabling Stable Lithium Cycling of Silicon Nanoparticles

Abstract We report a new approach for nanosilicon–graphene hybrids with uniquely stable solid electrolyte interphase. Expanded graphite is gently exfoliated creating “defect‐free” graphene that is non‐catalytic towards electrolyte decomposition, simultaneously introducing high mass loading (48 wt. %) Si nanoparticles. Silane surface treatment creates epoxy chemical tethers, mechanically binding nano‐Si to CMC binder through epoxy ring‐opening reaction while stabilizing the Si surface chemistry. Epoxy‐tethered silicon pristine–graphene hybrid “E‐Si‐pG” exhibits state‐of‐the‐art performance in full battery opposing commercial mass loading (12 mg cm −2 ) LiCoO 2 (LCO) cathode. At 0.4 C, with areal capacity of 1.62 mAh cm −2 and energy of 437 Wh kg −1 , achieving 1.32 mAh cm −2 , 340.4 Wh kg −1 at 1 C. After 150 cycles, it retains 1.25 mAh cm −2 , 306.5 Wh kg −1 . Sputter‐down XPS demonstrates survival of surface C‐Si‐O‐Si groups in E‐Si‐pG after repeated cycling. The discovered synergy between support defects, chemical‐mechanical stabilization of Si surfaces, and SEI‐related failure may become key LIB anode design rule.

Liu, Wei↗
DOE OSTI2021

Optimization of Magnesium‐Doped Lithium Metal Anode for High Performance Lithium Metal Batteries through Modeling and Experiment

Abstract Lithium (Li)‐magnesium (Mg) alloy with limited Mg amount, which can also be called Mg‐doped Li (Li‐Mg), has been considered as a potential alternative anode for high energy density rechargeable Li metal batteries. However, the optimum doping‐content of Mg in Li‐Mg anode and the mechanism of the improved performance are not well understood. Herein, density functional theory (DFT) calculations are used to investigate the effect of Mg amount in Li‐Mg anode. The Li‐Mg with about 5 wt. % Mg (abbreviated as Li‐Mg5) has the lowest absorption energy of Li, thus all the surface area can be “controlled” by Mg atoms, leading to the smooth and continuous deposition of Li on the surface around the Mg center. A localized high concentration electrolyte enables Li‐Mg5 to exhibit the best cycling stability in Li metal batteries with high‐loading cathode and lean electrolyte under 4.4 V high‐voltage, which is approaching the demand of practical application. This electrolyte also helps generate an inorganic‐rich solid electrolyte interphase, which leads to smooth, compact and less corrosion layer on the Li‐Mg5 surface. Both theoretical simulations and experimental results prove that Li‐Mg5 has optimum Mg content and gives best battery cycling performance.

Gao, Peiyuan↗
DOE OSTI2022

Covalent Organic Framework as an Efficient Protection Layer for a Stable Lithium‐Metal Anode

Abstract Lithium (Li) metal shows great potential for achieving high‐energy‐density rechargeable batteries. However, the practical applications of Li‐metal batteries are still challenged by the formation of Li dendrites and unstable solid‐electrolyte interphase (SEI) on metallic Li. Herein, a thin covalent organic framework layer is in situ fabricated on Li (COF‐Li) to suppress Li dendrite growth and mitigate the side reaction on the Li anode. The COF has a periodic and uniform porosity, allowing for selectively sieving Li ions and guiding a uniform Li deposition. As a result, the COF‐Li exhibits a non‐dendrite morphology during repeated Li plating/stripping and demonstrates a remarkable cycle life over 13 200 h with an extremely low overpotential of only 16 mV at a high current density of 10 mA cm −2 and a high areal capacity of 10 mAh cm −2 .

He, Jiarui↗
DOE OSTI2022

Non‐Flammable Ester Electrolyte with Boosted Stability Against Li for High‐Performance Li Metal Batteries

Abstract In traditional non‐flammable electrolytes a trade‐off always exists between non‐flammability and battery performance. Previous research focused on reducing free solvents and forming anion‐derived solid‐electrolyte interphase. However, the contribution of solvated anions in boosting the stability of electrolyte has been overlooked. Here, we resolve this via introducing anions into Li + solvation sheaths using anions with similar Gutmann donor number (DN) to that of solvents. Taking trimethyl phosphate fire‐retardant (DN=23.0 kcal mol −1 ) and NO 3 − (DN=22.2 kcal mol −1 ) as an example, NO 3 − is readily involved in the Li + solvation sheath and reduces the polarity of solvent. This results in boosted stability of electrolyte against Li. The developed non‐flammable electrolyte has low viscosity, high ionic conductivity and is low cost. The reversibility of Li‐Cu cell was improved to 99.49 % and the lifespan of practical LMBs was extended by >100 %.

Wang, Zhijie↗
DOE OSTI2022

A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine‐Free” SEI

Abstract Realization of practical sodium metal batteries (SMBs) is hindered due to lack of compatible electrolyte components, dendrite propagation, and poor understanding of anodic interphasial chemistries. Chemically robust liquid electrolytes that facilitate both favorable sodium metal deposition and a stable solid‐electrolyte interphase (SEI) are ideal to enable sodium metal and anode‐free cells. Herein we present advanced characterization of a novel fluorine‐free electrolyte utilizing the [HCB 11 H 11 ] 1− anion. Symmetrical Na cells operated with this electrolyte exhibit a remarkably low overpotential of 0.032 V at a current density of 2.0 mA cm −2 and a high coulombic efficiency of 99.5 % in half‐cell configurations. Surface characterization of electrodes post‐operation reveals the absence of dendritic sodium nucleation and a surprisingly stable fluorine‐free SEI. Furthermore, weak ion‐pairing is identified as key towards the successful development of fluorine‐free sodium electrolytes.

Tomich, Anton W.↗