Twisting two-dimensional iron sulfide layers into coincident site superlattices via intercalation chemistry.

Layered van der Waals (vdW) materials are susceptible not only to various stacking polymorphs through translations but also twisted structures due to rotations between layers. Here, we study the influence of such layer-to-layer twisting through the intercalation of ethylenediamine (EDA) molecules into tetragonal iron sulfide (Mackinawite FeS). Selected area electron diffraction patterns of intercalated FeS display reflections corresponding to multiple square lattices with a fixed angle between them, contrary to a single square lattice seen in the unintercalated phase. The observed twist angles of 49.13° and 22.98° result from a superstructure formation well described by the coincident site lattice (CSL) theory. According to the CSL theory, these measured twist angles lead to the formation of larger coincident site supercells. We build these CSL models for FeS using crystallographic group-subgroup transformations and find simulated electron diffraction patterns from the model to agree with the experimentally measured data.

High voltage electrolytes for lithium-ion batteries with micro-sized silicon anodes.

Micro-sized silicon anodes can significantly increase the energy density of lithium-ion batteries with low cost. However, the large silicon volume changes during cycling cause cracks for both organic-inorganic interphases and silicon particles. The liquid electrolytes further penetrate the cracked silicon particles and reform the interphases, resulting in huge electrode swelling and quick capacity decay. Here we resolve these challenges by designing a high-voltage electrolyte that forms silicon-phobic interphases with weak bonding to lithium-silicon alloys. The designed electrolyte enables micro-sized silicon anodes (5 µm, 4.1 mAh cm-2) to achieve a Coulombic efficiency of 99.8% and capacity of 2175 mAh g-1 for >250 cycles and enable 100 mAh LiNi0.8Co0.15Al0.05O2 pouch full cells to deliver a high capacity of 172 mAh g-1 for 120 cycles with Coulombic efficiency of >99.9%. The high-voltage electrolytes that are capable of forming silicon-phobic interphases pave new ways for the commercialization of lithium-ion batteries using micro-sized silicon anodes.

Photovoltaic amorphous feroxyhyte nanostructures synthesized by atmospheric AC microplasma.

Feroxyhite (δ-FeOOH) nanomaterials were successfully synthesized through the atmospheric AC microplasma method at room temperature from ferrous sulfate aqueous solutions. Various syntheses conditions, including electric voltage, electric field strength, ferrous concentration, hydrogen peroxide concentration, and reaction duration, were systematically investigated. The synthesized products were characterized through x-ray diffraction, UV-vis absorption spectroscopy, photoluminescence spectroscopy, infra-red spectroscopy, and electron microscopy. The bandgap of the produced materials were strongly dependent of the ferrous concentration while the product ratio was dependent on all experimental conditions. The synthesis mechanism was thoroughly discussed. The synthesized nanomaterials were amorphous nanospheres, showing superparamagnetic properties at room temperature. The synthesized oxyhydroxide is a potential photovoltaic material besides its reported applications in photocatalysts and supercapacitors. The application of this synthesis technique could be extended to synthesize other oxy-hydroxide nanomaterials for renewable energy applications facilely, scalablely, cost-effectively, and environmentally.

Investigation of iron oxide shell and iron core in magnetically-assisted synthetized wire-like nanochains.

The zerovalent iron (Fe0) nanomaterials tend to be spontaneously oxidized in the presence of oxygen. This leads to the formation of interface composed of iron core and thin iron oxide shell. These structures are frequently observed with transmission electron microscope but, at the same time, it is hard to determine the precise structural and chemical composition of oxide shell. This feature is very important for possible applications of Fe0nanostructures. Hence, the present work aims to deliver more detailed insights in this topic. The investigations are performed for the iron nanochains prepared in the magnetic-field-induce reduction of FeCl3by NaBH4. The high-resolution transmission electron microscopy, electron energy loss spectroscopy, and x-ray photoemission spectroscopy confirm that the iron nanochains are covered by very thin oxide layer not exceeding over 3 nm. Moreover, the detailed XPS analyses of O 1s and Fe 2p lines indicate that the iron oxide shell reveals Fe3O4nature. Moreover, this work demonstrated that some by-products of the reaction containing boron are presented in the sample even after a removal of the thin iron oxide shell by Ar+treatment.

Iron-Iron Oxide Core-Shell Nanochains as High-Performance Adsorbents of Crystal Violet and Congo Red Dyes from Aqueous Solutions.

The main aim of this work was to use the iron-iron oxide nanochains (Fe NCs) as adsorbents of the carcinogenic cationic crystal violet (CV) and anionic Congo red (CR) dyes from water. The investigated adsorbent was prepared by a magnetic-field-induced reduction reaction, and it revealed a typical core-shell structure. It was composed of an iron core covered by a thin Fe3O4 shell (<4 nm). The adsorption measurements conducted with UV-vis spectroscopy revealed that 15 mg of Fe NCs constituted an efficient dose to be used in the CV and CR treatment. The highest effectiveness of CV and CR removal was found for a contact time of 90 min at pH 7 and 150 min at pH 8, respectively. Kinetic studies indicated that the adsorption followed the pseudo-first-order kinetic model. The adsorption process followed the Temkin model for both dyes taking into account the highest value of the R2 coefficient, whereas in the case of CR, the Redlich-Peterson model could be also considered. The maximal adsorption capacity estimated from the Langmuir isotherms for the CV and CR was 778.47 and 348.46 mg g-1, respectively. Based on the Freundlich model, both dyes adsorbed on the Fe NCs through chemisorption, but Coulombic interactions between the dye and adsorbent cannot be excluded in the case of the CV dye. The obtained results proved that the investigated Fe NCs had an excellent adsorption ability for both dye molecules within five cycles of adsorption/desorption, and therefore, they can be considered as a promising material for water purification and environmental applications.

Poly(Vinylidene Fluoride-co-Hexafluoropropylene) Films Filled in Iron Nanoparticles for Infrared Shielding Applications.

In order to use the infrared (IR) radiation shielding materials, they should take a form of thin film coatings deposited on glass/polymer substrates or be used as fillers of glass/polymer. The first approach usually suffers from several technological problems. Therefore, the second strategy gains more and more attention. Taking into account this trend, this work presents the usage of iron nanoparticles (Fe NPs) embedded into the poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) films as the shielding material in near-infrared (NIR) and mid-infrared (MIR) region. The performed investigations show that the transmittance of copolymer films decreases with increasing content of the Fe NPs inside them. It is found that the average fade of IR transmittance for 1, 2.5, 5, 10, and 50 mg of Fe NPs is about 13%, 24%, 31%, 77%, and 98%, respectively. Moreover, it is observed that the PVDF-HFP films filled in the Fe NPs almost does not reflect the NIR and MIR radiation. Hence, the IR shielding properties of the PVDF-HFP films can be effectively tuned by the addition of proper amount of the Fe NPs. This, in turn, shows that the PVDF-HFP films filled in the Fe NPs constitute a great option for IR antireflective and shielding applications.

Investigation of the excitations of plasmons and surface exciton polaritons in monoclinic gadolinium sesquioxide by electron energy-loss spectroscopy and plasmon spectroscopic imaging.

The monoclinic gadolinium sesquioxide (denoted as m-Gd2O3) with its lower crystal symmetry exhibits larger dielectric permittivity (κ) than the cubic Gd2O3 (denoted as c-Gd2O3). Recently, a few nanometers thick m-Gd2O3 thin film has been successfully epitaxially grown on a GaN substrate as a promising candidate gate oxide in metal-oxide-semiconductor field-effect transistors (MOSFETs). Thus, it is important to understand the electronic excitations in m-Gd2O3 and investigate them by electron energy loss spectroscopy (EELS) performed with aloof electron beams and electron diffraction to gain the spatial and momentum resolutions. In this study, using scanning transmission electron microscopy combined with EELS (STEM-EELS) in the aloof electron beam setup, we observed low-loss spectral features at 13 eV and 14.5 eV at the specimen edge in a grazing incidence and the material interior, which can be interpreted as a surface plasmon (SP) and a volume plasmon (VP), respectively. Surface exciton polaritons (SEPs), which represents surface resonances associated with excitonic onsets above the bandgap, were also observed at about 7, 10.2, and 36 eV energy loss. Their surface excitation character was confirmed by energy-filtered transmission electron microscopy spectrum imaging (EFTEM-SI) and using relativistic energy versus-momentum (E-k) map calculations. The momentum (q)-dependent EELS indicates that the SEP features near the bandgap represented a function of q and revealed a nondispersive behavior for VP and SEP at 36 eV. The oscillator strengths for VP and SEP at 36 eV dropped at different q values along with different q directions, revealing the anisotropic electronic structures of m-Gd2O3.

The glass-like structure of iron-nickel nanochains produced by the magnetic-field-induced reduction reaction with sodium borohydride.

Preparation and detailed structural characterization of iron-nickel wire-like nanochains with Fe0.75Ni0.25, Fe0.50Ni0.50, and Fe0.25Ni0.75 compositions are reported. The investigated nanomaterials were produced by the novel template-free magnetic-field-induced reduction reaction with NaBH4 as the reducing agent. It is demonstrated that this method leads to the formation of Fe-Ni nanochains composed of spherical nanoparticles with an average diameter of 50-70 nm and with a very high degree of atomic disorder manifested as the lack of clearly developed bcc and fcc phases, which are usually observed for nano- and polycrystalline Fe-Ni species. The recorded wide-angle X-ray scattering data for the obtained Fe-Ni nanochains exhibit a strong resemblance to those obtained for bulk metallic glasses. The atomic scale structure of the investigated nanochains has been studied using pair distribution function analysis of the recorded total scattering data. The best fits to the experimental pair distribution functions have been achieved assuming two-phase models of hcp and bcc networks with the size of coherently scattering regions of about 2.5 nm in diameter, for each Fe-Ni composition. The transmission electron microscopy images indicate that the glass-like bimetallic alloy cores are covered by amorphous oxide/hydroxide shells with their thickness ranging from 2 to 5 nm. Moreover, electron energy loss spectroscopy, X-ray photoelectron spectroscopy, and Mössbauer spectroscopy results confirm the core-shell structure of the Fe-Ni nanochains and the complex character of the shell layer which consists of several iron- and nickel-containing phases.

Decoupling Ionic and Electronic Pathways in Low-Dimensional Hybrid Conductors.

The construction of two-dimensional (2D) layered compounds for nanofluidic ion transport has recently attracted increasing interest due to the facile fabrication, tunable channel size, and high flux of these materials. Here we design a nacre-mimetic graphite-based nanofluidic structure in which the nanometer-thick graphite flakes are wrapped by negatively charged nanofibrillated cellulose (NFC) fibers to form multiple 2D confined spacings as nanochannels for rapid cation transport. At the same time, the graphite-NFC structure exhibits an ultralow electrical conductivity (σe ≤ 10-9 S/cm), even when the graphite concentration is up to 50 wt %, well above the percolation threshold (∼1 wt %). By tuning the hydration degree of graphite-NFC composites, the surface-charge-governed ion transport in the confined ∼1 nm spacings exhibits nearly 12 times higher ionic conductivity (1 × 10-3 S/cm) than that of a fully swollen structure (∼1.5 nm, 8.5 × 10-5 S/cm) at salt concentrations up to 0.1 M. The resulting charge selective conductor shows intriguing features of both high ionic conductivity and low electrical conductivity. Moreover, the inherent stability of the graphite and NFC components contributes to the strong functionality of the nanofluidic ion conductors in both acidic and basic environments. Our work demonstrates this 1D-2D material hybrid system as a suitable platform to study nanofluidic ion transport and provides a promising strategy to decouple ionic and electronic pathways, which is attractive for applications in new nanofluidic device designs.

The dp type π-bond and chiral charge density waves in 1T-TiSe2.

Based on the atomic electronic configuration and Ti-Se coordination, a valence bond model for the layered transition metal dichalcogenide (TMDC) 1T-TiSe2 is proposed. 1T-TiSe2 is viewed as being composed of edge-sharing TiSe4-plaquettes as TiSe2-ribbon chains in each layer via a directional valence shell electron distribution as chemical bonds, in contrast to the conventional layer view of face-sharing TiSe6-octahedra. The four valence electrons per Ti in the hybridized dsp2-orbitals of square coordination form σ-bonds with the four nearest neighbor Se atoms in the chain. The electrons in the lone pair of the Se-4pz orbital are proposed to form a dp type π-bond via side-to-side orbital overlap with the empty Ti-3dxz/3dyz orbitals within each chain, which is positively supported by quantum chemistry calculations. A study of electron energy loss spectroscopy (EELS) with transmission electron microscopy (TEM) for 1T-TiSe2 is presented to show an energy loss near ∼7 and ∼20 eV, which confirms the existence of collective plasmon oscillations with the predicted effective electron numbers for the π- and (π + σ)-bond electrons, respectively.

Author Correction: Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries.

In the version of this Article originally published, in the first paragraph of the Methods, HFE was incorrectly given as 2,2,2-Trifluoroethyl-3',3',3',2',2'-pentafluoropropyl ether; it should have been 1,1,2,2-tetrafluoroethyl-2',2',2'-trifluoroethyl ether. This has now been corrected in the online versions of the Article.

Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries.

Rechargeable Li-metal batteries using high-voltage cathodes can deliver the highest possible energy densities among all electrochemistries. However, the notorious reactivity of metallic lithium as well as the catalytic nature of high-voltage cathode materials largely prevents their practical application. Here, we report a non-flammable fluorinated electrolyte that supports the most aggressive and high-voltage cathodes in a Li-metal battery. Our battery shows high cycling stability, as evidenced by the efficiencies for Li-metal plating/stripping (99.2%) for a 5 V cathode LiCoPO4 (~99.81%) and a Ni-rich LiNi0.8Mn0.1Co0.1O2 cathode (~99.93%). At a loading of 2.0 mAh cm-2, our full cells retain ~93% of their original capacities after 1,000 cycles. Surface analyses and quantum chemistry calculations show that stabilization of these aggressive chemistries at extreme potentials is due to the formation of a several-nanometre-thick fluorinated interphase.

High energy-density and reversibility of iron fluoride cathode enabled via an intercalation-extrusion reaction.

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh kg-1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g-1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh kg-1 with a decay rate of 0.03% per cycle is achieved. The anion's and cation's co-substitutions thermodynamically reduce conversion reaction potential and shift the reaction from less-reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. The co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.

Proton and ammonia intercalation into layered iron chalcogenides.

Structurally related to the iron-based superconductors, two new intercalated iron chalcogenides (H0.5NH3)Fe2Ch2 where Ch = S, Se have been prepared. By topochemical conversion, the protons were exchanged by lithium to form (Li0.5NH3)Fe2Ch2. Hydrogen bonding plays a significant role in the guest-host interactions of these intercalated phases.

Superconductivity and magnetism in iron sulfides intercalated by metal hydroxides.

Inspired by naturally occurring sulfide minerals, we present a new family of iron-based superconductors. A metastable form of FeS known as the mineral mackinawite forms two-dimensional sheets that can be readily intercalated by various cationic guest species. Under hydrothermal conditions using alkali metal hydroxides, we prepare three different cation and metal hydroxide-intercalated FeS phases including (Li1-x Fe x OH)FeS, [(Na1-x Fe x )(OH)2]FeS, and K x Fe2-y S2. Upon successful intercalation of the FeS layer, the superconducting critical temperature Tc of mackinawite is enhanced from 5 K to 8 K for the (Li1-x Fe x OH) δ+ intercalate. Layered heterostructures of [(Na1-x Fe x )(OH)2]FeS resemble the natural mineral tochilinite, which contains an iron square lattice interleaved with a hexagonal hydroxide lattice. Whilst heterostructured [(Na1-x Fe x )(OH)2]FeS displays long-range magnetic ordering near 15 K, K x Fe2-y S2 displays short range antiferromagnetism.

Red phosphorus-single-walled carbon nanotube composite as a superior anode for sodium ion batteries.

Sodium ion batteries (SIBs) have been considered as a top alternative to lithium ion batteries due to the earth abundance and low cost of sodium compared with lithium. Among all proposed anode materials for SIBs, red phosphorus (P) is a very promising candidate because it has the highest theoretical capacity (∼2600 mAh/g). In this study, a red P-single-walled carbon nanotube (denoted as red P-SWCNT) composite, in which red P is uniformly distributed between tangled SWCNTs bundles, is fabricated by a modified vaporization-condensation method. Benefiting from the nondestructive preparation process, the highly conductive and mechanically strong SWCNT network is preserved, which enhances the conductivity of the composite and stabilizes the solid electrolyte interphase. As a result, the red P-SWCNT composite presents a high overall sodium storage capacity (∼700 mAh/gcomposite at 50 mA/gcomposite), fast rate capability (∼300 mAh/gcomposite at 2000 mA/gcomposite), and stable long-term cycling performance with 80% capacity retention after 2000 sodiation-desodiation cycles. The red P-SWCNT composite fabricated by the vaporization-condensation method significantly extends the cycling stability of P/carbon composite from current ∼100 cycles to ∼2000 cycles.

Tunable and stable UV-NIR photoluminescence from annealed SiOx with Si nanoparticles.

We demonstrate stable and tunable light emission in ultraviolet to near infrared regime by using annealed SiOx sample. By adjusting the ratio of Si and O of SiOx, different wavelengths such as ultraviolet, visible and near infrared photoluminescence can be tuned. From the results of transmission electron microscope, various sizes (1~4 nm) of the embedded Si nanoparticles were formed. Nanoparticles with smaller sizes were indeed formed for UV-blue emitting samples and the origin of light emission may be misattributed to the quantum confinement effects. However, we found the efficient and stable light emission in UV-blue regime, with lifetime on the order of nanoseconds, is dominantly from the defects.

Observation of room-temperature ballistic thermal conduction persisting over 8.3 µm in SiGe nanowires.

In ballistic thermal conduction, the wave characteristics of phonons allow the transmission of energy without dissipation. However, the observation of ballistic heat transport at room temperature is challenging because of the short phonon mean free path. Here we show that ballistic thermal conduction persisting over 8.3 µm can be observed in SiGe nanowires with low thermal conductivity for a wide range of structural variations and alloy concentrations. We find that an unexpectedly low percentage (∼0.04%) of phonons carry out the heat conduction process in SiGe nanowires, and that the ballistic phonons display properties including non-additive thermal resistances in series, unconventional contact thermal resistance, and unusual robustness against external perturbations. These results, obtained in a model semiconductor, could enable wave-engineering of phonons and help to realize heat waveguides, terahertz phononic crystals and quantum phononic/thermoelectric devices ready to be integrated into existing silicon-based electronics.