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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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

A method to remove intercalates from bromine and iodine intercalated carbon fibers

Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers which were intercalated with 18 percent bromine by weight, 1 hr of fluorine exposure results in a large weight increase, but causes only a small decrease in thermal stability. More than l hr of fluorine exposure time results in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena do not occur if the fluorine exposure is at 250 C. These observations suggest the mechanism that at room temperature, fluorine is absorbed quickly by the intercalated fibers and intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. Under an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for two weeks, the brominated fibers lost about 45 percent of their bromine, and their resistivity increased from 64 omega-cm to a range of 95 to 170 micro omega-cm. This is still much lower than the 300 micro omega-cm value for pristine P-100. For practical purposes, in order to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature, or to any intercalate at a temperature where, upon direct contact to graphite, an intercalation compound can easily be formed.

Hung, Ching-Cheh↗
DOE OSTI2021

In Situ Probing Potassium-ion Intercalation-induced Amorphization in Crystalline Iron Phosphate Cathode Materials

Na-ion and K-ion batteries are promising alternatives for large-scale energy storage applications due to their abundance and low cost. Intercalation of these large ions could cause irreversible structural deformation and partial to complete amorphization in the crystalline electrodes. The designing of new amorphous electrodes is another route to develop electrodes to store these ions reversibly. Lack of understanding of dynamic changes in the amorphous nanostructures during battery operation is the bottleneck for further developments. Here, we report the utilization of in situ digital image correlation and in-operando X-ray diffraction (XRD) techniques to probe dynamic changes in the amorphous phase of iron phosphate during potassium intercalation. In-operando XRD demonstrates amorphization in the electrode’s nanostructure during the first charge/discharge cycle. Additionally, the ex-situ high-resolution transmission electron microscopy further confirms the amorphization after potassium insertion. In situ strain analysis detects the reversible deformation associated with redox reactions in the amorphous phases. Our approach offers new insights on the mechanisms of ion intercalation in the amorphous nanostructures which are highly potent for development of next-generation batteries.

Ozdogru, Bertan↗
DOE OSTI2021

The impact of alkali‐ion intercalation on redox chemistry and mechanical deformations: Case study on intercalation of Li, Na, and K ions into FePO 4 cathode

Abstract Batteries made of charge carriers from Earth‐crust abundant materials (e.g., Na, K, and Mg) have received extensive attention as an alternative to Li‐ion batteries for grid storage. However, a lack of understanding of the behavior of these larger ions in the electrode materials hinders the development of electrode structures suitable for these large ions. In this study, we investigate the impact of alkali ions (Li, Na, and K) on the redox chemistry and mechanical deformations of iron phosphate composite cathodes by using electrochemical techniques and in situ digital image correlation. Na‐ion and Li‐ion intercalation demonstrate a nearly linear correlation between electrochemical strains and the state of charge and discharge. The strain development shows nonlinear dependance on the state of charge and discharge for K ions. Strain rate calculations show that K ion intercalation results in a progressive increase in the strain rate for all cycles. Li and Na intercalation induce nearly constant strain rates with the exception of the first discharge cycle of Na intercalation. When the same amount of ions are inserted into the electrode, the electrode shows the lowest strain generation upon Li intercalation compared to larger alkali ions. Na and K ions induce similar volumetric changes in the electrode when the state of charge and discharge is around 30%. Although the electrode experiences larger absolute strain generation at the end of the discharge cycles upon Na intercalation, strain rates were found to be greater for K ions. Potential‐dependent behaviors also demonstrate more sluggish redox reactions during K intercalation, compared to Li and Na. Our quantitative analysis suggests that the strain rate, rather than the absolute value of strain, is the critical factor in amorphization of the crystalline electrode.

25 ENERGY STORAGE↗
NASA NTRS1985

Graphite fiber intercalation: Dynamics of the bromine intercalation process

The resistance of pitch-based graphite fibers was monitored, in situ, during a series of bromine intercalation experiments. The threshold pressure for the bromine intercalation of pitch-based fibers was estimated to be 102 torr. When the bromine atmosphere was removed from the reaction chamber, the resistivity of the intercalated graphite fibers increased consistently. This increase was attributed to loss of bromine from the perimeter of the fiber. The loss was confirmed by mapping the bromine concentration across the diameter of single intercalated fibers with either energy dispersive spectroscopy or scanning Auger microscopy. A statistical study comparing fibers intercalated in bromine vapor with fibers intercalated in bromine liquid showed that similar products were obtained with both methods of intercalation.

Jaworske, D. A.↗
DOE OSTI2020

Effects of Intercalating Molecules on the Polymer Properties of DNA

Atomic force microscopy (AFM) enables determination of physical properties from single DNA molecules. Insertion of aromatic molecules into the structure of DNA results in morphological changes. However, the accompanying changes to elastic properties due to this insertion are not fully understood. AFM was used to examine the morphological effects of intercalator binding and report changes in the elastic properties of intrinsically straight DNA molecules. The persistence length and polymer extension were characterized in the presence of three intercalating molecules: ethidium bromide and the less well studied chloroquine and acridine. It was found that all three intercalators significantly increased the bending persistence length. In addition, an analysis of the normal bending modes of the static molecules corroborated these results. Furthermore, this approach of measuring binding effects of intercalators on DNA physical properties using a model system of intrinsically straight DNA is applicable to other DNA binding ligands and other modes of DNA interaction.

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

Modification of Catalytic Properties of Hollandite Manganese Oxide by Ag Intercalation for Oxidative Acetalization of Ethanol to Diethoxyethane

The effect of addition of Ag to the catalytic properties of hollandite manganese oxide (HMO) was investigated for the oxidative acetalization of ethanol to diethoxyethane. Based on analysis with HRTEM, XRD, and EXAFS, Ag introduced onto HMO by deposition/precipitation was found to be present in different forms in the final catalyst depending on the calcination temperature. It could exist as nanoparticles on the outside surface of HMO nanorods for samples calcined at 60 °C, and as Ag atoms intercalated into the tunnels of the HMO structure for samples calcined at 500 °C. NH 3 desorption results showed that intercalation of Ag resulted in stronger Lewis acidic sites on HMO, which DFT computational results suggested to be due to Ag-induced electron redistribution in the HMO framework. Here, the intercalation of Ag atoms also made the HMO more easily reducible by lowering the H 2 reduction temperature from 500 to 200 °C. Consequently, the sample with intercalated Ag was more active for ethanol oxidation to acetaldehyde, achieving nearly 100% conversion of ethanol and acetaldehyde by 360 °C, and acetalization of acetaldehyde with ethanol to produce diethoxyethane selectively, resulting in 93.5% diethoxyethane yield, which was 10% higher than with samples containing Ag nanoparticles on HMO. This study demonstrated a little-studied phenomenon in which a metal alters the catalytic properties of an oxide electronically but not structurally and without direct participation in the reaction.

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

Tuning the Solvation Structure in Aqueous Zinc Batteries to Maximize Zn-Ion Intercalation and Optimize Dendrite-Free Zinc Plating

Aqueous zinc batteries are recognized to suffer from H + /Zn 2+ coinsertion in the cathode, but few approaches have been reported to suppress deleterious H + intercalation. We realize this goal by tuning the solvation structure, using LiV 2 (PO 4 ) 3 (LVP) as a model cathode. Phase conversion of LVP induced by H + intercalation is observed in 4 m Zn(OTf) 2 , whereas dominant Zn 2+ insertion is confirmed in a ZnCl 2 water-in-salt electrolyte (WiSE). This disparity is ascribed to the complete absence of free water and a strong Zn 2+ –H 2 O interaction in the latter that interrupts the H 2 O hydrogen bonding network, thus suppressing H + intercalation. On the basis of this strategy, a novel PEG-based hybrid electrolyte is designed to replace the corrosive ZnCl2 WiSE. This system exhibits an optimized Zn 2+ solvation sheath with a similar low free water content, showing not only much better suppression of H + intercalation but also highly reversible Zn plating/stripping with a CE of ~99.7% over 150 cycles.

25 ENERGY STORAGE↗
DOE OSTI2022

Asphericity Can Cause Nonuniform Lithium Intercalation in Battery Active Particles

Uniform intercalation is desired to enable next-generation Li-ion batteries. While we expect nonuniformity in materials undergoing a phase change, single-phase intercalation materials such as nickel manganese cobalt oxide are believed to lithiate uniformly at the particle/electrolyte interface. However, recent imaging reveals nonuniform lithiation. Motivated by this discrepancy, we examine if aspherical particle shape can cause such nonuniformity since the conventional belief is based on spherical particle theory. We obtain real particle geometries using rapid lab-based X-ray computed tomography and subsequently perform physics-based calculations accounting for electrochemical reactions at the particle/electrolyte interface and lithium transport inside the particle bulk. The aspherical geometry breaks the symmetry and causes nonuniform reaction distribution. Such nonuniformity is exacerbated as the particle becomes more aspherical. We report the proposed mechanism represents a fundamental limit on achievable lithiation uniformity in aspherical particles in the absence of other mechanisms causing inhomogeneity, such as grain structure, nonuniform carbon-binder coating, etc.

25 ENERGY STORAGE↗
DOE OSTI2021

High-Capacity Aqueous Storage in Vanadate Cathodes Promoted by the Zn-Ion and Proton Intercalation and Conversion–Intercalation of Vanadyl Ions

Aqueous Zn-ion batteries (AZIBs) are promising alternatives to lithium-ion batteries in stationary storage. However, limited storage capacity and cyclic life impede their large-scale implementation. In this study, we report reversible electrochemical insertion of multi-ions into sodium vanadate (NaV 3 O 8 ) cathode materials for AZIBs, achieving a maximum storage capacity of 450 mAh g –1 at 0.05 A g –1 and a capacity retention of 82% after 500 cycles at 0.4 A g –1 . In addition to Zn 2+ and H + insertion, in situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) collectively provide explicit evidence on vanadyl ions (VO 2+ ) conversion–intercalation at the NaV 3 O 8 cathode, showing the deintercalation of VO 2+ from NaV 3 O 8 and the consequent conversion of VO 2+ into V 2 O 5 on charging, and vice versa on discharging. Our study is the first to report on the cation conversion–intercalation mechanism in AZIBs. This reversible multi-ion storage mechanism provides a design principle for developing high-capacity aqueous electrode materials by engaging both the intercalation and conversion of charge carriers.

25 ENERGY STORAGE↗
DOE OSTI2022

Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Rechargeable aqueous Zn-MnO 2 technology combines one of the oldest battery chemistries with favourable sustainability characteristics, including safety, cost and environmental compatibility. However, the ambiguous charge storage mechanism presents a challenge to fulfil the great potential of this energy technology. In this work, we leverage on advanced electron microscopy, electrochemical analysis and theoretical calculations to look into the intercalation chemistry within the cathode material, or α-MnO 2 more specifically. We show that Zn 2+ insertion into the cathode is unlikely in the aqueous system; rather, the charge storage process is dominated by proton intercalation to form α-H x MnO 2 . We further reveal anisotropic lattice change as a result of entering protons proceeding from the surface into the bulk of α-MnO 2 , which accounts for the structural failure and capacity decay of the electrode upon cycling. Our work not only advances the fundamental understanding of rechargeable zinc batteries but also suggests the possibility to optimize proton intercalation kinetics for better-performing cell designs. A rechargeable aqueous Zn-MnO 2 battery features a combination of favourable sustainability characteristics from safety to cost. The authors deploy advanced characterizations and theoretical calculations to provide fresh insight into the charge storage mechanism, which not only closes an ongoing debate but suggests ways forward.

25 ENERGY STORAGE↗
DOE OSTI2022

Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species

Systematic synthesis studies of the formation of tetrahedral FeS-ethylenediamine intercalates resulted in the synthesis of a new compound, [Fe 9.4(2) S 10 ][Fe(en) 3 ] 0.6(1) ·en 0.9 ( 3 ). The composition and complex crystal structure were determined based on a synergistic combination of elemental composition, decomposition behavior, high-resolution synchrotron X-ray diffraction and total scattering, 57 Fe Mössbauer spectroscopy, and electron diffraction. The structural model was derived based on a systematic comparison to the previously reported structures [Fe 8 S 10 ][Fe(en) 3 ] 1 ·en 0.5 and tetragonal FeS. The new compound has flat Fe 9.4 S 10 layers, analogous to those in superconducting binary FeS. In the crystal structure of [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 ·en 0.9 , the interlayer space is occupied by [Fe(en) 3 ] 2+ complexes and neutral ethylenediamine molecules in a ~2:3 ratio. Interlayer species are not randomly oriented but ordered as evidenced by superstructural diffraction peaks in both high-resolution X-ray diffraction and electron diffraction patterns. Magnetic studies reveal no superconducting transition down to 2 K, indicating that the presence of minute amounts (~6%) of iron vacancies at the Fe-S layer in [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 ·en 0.9 is still sufficient to shift the position of the Fermi level resulting in an adjustment of the properties. Here, our work shows the importance of detailed characterization of the crystal structure of intercalated compounds to understand the origin of the observed properties and develop proper structure–property relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Spin-Valley Locking in 2 H -TaS 2 and Its Co-Intercalated Counterpart: Roles of Surface Domains and Co Intercalation

Tuning and probing spin-valley coupling is key to understanding correlated ground states in 2H-TaS 2 . Its magnetically intercalated analogue, Co 1/3 TaS 2 , introduces additional degrees of freedom, including modified interlayer coupling and magnetism, to modulate spin-valley physics. Surface-sensitive probes like ARPES are essential for accessing surface spin texture, yet previous studies on 2H-TMDs have reported conflicting results regarding spin-polarized bands, leaving open whether these discrepancies are intrinsic or extrinsic. Here, in this study, we performed spatially resolved spin-ARPES measurements on 2H-TaS 2 and Co 1/3 TaS 2 . Our results reveal robust spin-valley locking on both compounds. Importantly, Co intercalation enhances interlayer hybridization and introduces magnetism while preserving the TaS 2 -derived spin texture. We further observe a spatial reversal of the out-of-plane spin polarization, which we attribute to different surface domains. This effect complicates quantifying spin textures and may underlie prior inconsistent observations. Our findings provide microscopic insight into how interlayer interactions and surface domains together govern spin-valley phenomena in layered TMDs.

Spin-resolved angle-resolved photoemission spectro↗
NASA NTRS1986

Graphite fiber intercalation: Basic properties of copper chloride intercalated fibers

In situ resistance measurements were used to follow the intercalation of copper chloride in pitch-based fibers. Subsequent single fiber resistivity measurements reveal a large range of resistivities, from 13 to 160 micro-ohms cm. Additional density measurements reveal a bimodal distribution of mass densities. The dense fibers have lower resistivities and correspond to the stage III compound identified by X-ray diffraction. Neither resistivity nor density correlate with diameter. Both energy dispersive spectroscopy and mass density data suggest that excess chlorine resides in the intercalated fiber, resulting in a stoichiometry of C4.9n CuCl2.5 (where n is the stage number) for the denser fibers. Finally, thermogravimetric analysis shows a 33 percent loss in mass upon heating to 700C. This loss in mass is attributed to loss of both chlorine and carbon.

Jaworske, D. A.↗
NASA NTRS1994

Graphite intercalation compound with iodine as the major intercalate

Halogenated graphite CBr(x)I(y) (I less than y/x less than 10) was made by exposing graphite materials to either pure Br2 or an I2/Br2/HBr mixture to initiate the reaction, and then to iodine vapor containing a small amount of Br2/HBr/IBr to complete the intercalation reaction. Wetting of the graphite materials by the I2/Br2/HBr mixture is needed to start the reaction, and a small amount of Br2/HBr/IBr is needed to complete the charge transfer between iodine and carbon. The interplanar spacings for the graphite materials need to be in the 3.35 to 3.41 A range. The X-ray diffraction data obtained from the halogenated HOPG indicate that the distance between the two carbon layers containing intercalate is 7.25 A. Electrical resistivity of the fiber product is from 3 to 6.5 times the pristine value, The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine-to-bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 percent to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to structural damage during subsequent fluorination to fabricate graphite fluoride fibers.

Hung, Ching-Cheh↗
NASA NTRS1992

Graphite intercalation compound with iodine as the major intercalant

Halogenated CBr(sub x)I(sub y) (1 less than y/x less than 10) was made by exposing graphite materials with interplanar spacing in the 3.35 to 3.41 A range to either pure Br2 or an I2-Br2 mixture, and then to iodine vapor containing a small amount of Br2. The electrical resistivity of this product is from 3 to 6.5 times the pristine value. The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine to bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to fluorine attack during subsequent fluorination to fabricate graphite fluoride fibers.

Hung, Ching-Cheh↗