Carbon-Nanotube-Encapsulated-Sulfur Cathodes for Lithium-Sulfur Batteries: Integrated Computational Design and Experimental Validation.

To mitigate lithium-polysulfides (Li-PSs) shuttle in lithium-sulfur batteries (LiSBs), a unique carbon-nanotube-encapsulated-sulfur (S@CNT) cathode material with optimum open-ring sizes (ORSs) on the CNT walls were designed using an integrated computational approach followed by experimental validation. By calculating the transport barrier of Li+ ion through ORSs on the CNT walls and comparing the molecular size of solvents and Li-PSs with ORSs, optimum open-rings with 16-30 surrounding carbon atoms were predicted to selectively allow transportation of Li+ ion and evaporated sulfur while blocking both Li-PS and solvent molecules. A CNT oxidation process was proposed and simulated to generate these ORSs, and the results indicated that the optimum ORSs can be achieved by narrowly controlling the oxidation parameters. Subsequently, S@CNT cathodes were experimentally synthesized, confirming that optimum ORSs were generated in CNT oxidized at 475 K and exhibited more stable cycling behavior.

Imaging Arrangements of Discrete Ions at Liquid-Solid Interfaces.

The individual and collective behavior of ions near electrically charged interfaces is foundational to a variety of electrochemical phenomena encountered in biology, energy, and the environment. While many theories have been developed to predict the interfacial arrangements of counterions, direct experimental observations and validations have remained elusive. Utilizing cryo-electron microscopy, here we directly visualize individual counterions and reveal their discrete interfacial layering. Comparison with simulations suggests the strong effects of finite ionic size and electrostatic interactions. We also uncover correlated ionic structures under extreme confinement, with the channel widths approaching the ionic diameter (∼1 nm). Our work reveals the roles of ionic size, valency, and confinement in determining the structures of liquid-solid interfaces and opens up new opportunities to study such systems at the single-ion level.

Boron-doped few-walled carbon nanotubes: novel synthesis and properties.

Few-walled carbon nanotubes offer a unique marriage of graphitic quality and robustness to ink-processing; however, doping procedures that may alter the band structure of these few-walled nanotubes are still lacking. This report introduces a novel solution-injected chemical vapor deposition growth process to fabricate the first boron-doped few-walled carbon nanotubes (B-FWNTs) reported in literature, which may have extensive applications in battery devices. A comprehensive characterization of the as-grown B-FWNTs confirms successful boron substitution in the graphitic lattice, and reveals varying growth parameters impact the structural properties of B-FWNT yield. An investigation into the optimal growth purification parameters and ink-making procedures was also conducted. This study introduces the first process technique to successfully grow intrinsically p-doped FWNTs, and provides the first investigation into the impact factors of the growth parameters, purification steps, and ink-making processes on the structural properties of the B-FWNTs and the electrical properties of the resulting spray-coated thin-film electrodes.

Radiation-induced solidification of ionic liquid under extreme electric field.

An extreme electric field on the order of 10(10) V m(-1) was applied to the free surface of an ionic liquid to cause electric-field-induced evaporation of molecular ions from the liquid. The point of ion emission was observed in situ using a TEM. The resulting electrospray emission process was observed to create nanoscale high-aspect-ratio dendritic features that were aligned with the direction of the electric field. Upon removal of the stressing field the features were seen to remain, indicating that the ionic liquid residue was solidified or gelled. Similar electrospray experiments performed in a field-emission scanning electron microscope revealed that the features are created when the high-energy electron beam damages the molecular structure of the ionic liquid. While the electric field does not play a direct role in the fluid modification, the electric stress was critical in detecting the liquid property change. It is only because the electric stress mechanically elongated the fluid during the electrospray process and these obviously non-liquid structures persisted when the field was removed that the damage was evident. This evidence of ionic liquid radiation damage may have significant bearing on electrospray devices where it is possible to produce high-energy secondary electrons through surface impacts of emitted ions downstream of the emitter. Any such impacts that are in close proximity could see reflected secondary electrons impact the emitter causing gelling of the ionic liquid.

Ammonium Laurate Surfactant for Cleaner Deposition of Carbon Nanotubes.

Experiments probing the properties of individual carbon nanotubes (CNTs) and those measuring bulk composites show vastly different results. One major issue limiting the results is that the procedures required to separate and test CNTs introduce contamination that changes the properties of the CNT. These contamination residues often come from the resist used in lithographic processing and the surfactant used to suspend and deposit the CNTs, commonly sodium dodecyl sulfate (SDS). Here we present ammonium laurate (AL), a surfactant that has previously not been used for this application, which differs from SDS only by substitution of ionic constituents but shows vastly cleaner depositions. In addition, we show that compared to SDS, AL-suspended CNTs have greater shelf stability and more selective dispersion. These results are verified using transmission electron microscopy, atomic force microscopy, ζ-potential measurements, and Raman and absorption optical spectroscopy. This surfactant is simple to prepare, and the nanotube solutions require minimal sonication and centrifugation in order to outperform SDS.

A measurement technique for circumventing hysteresis and conductance drift in carbon nanotube field-effect transistors.

We present a measurement protocol that effectively eliminates both the hysteresis and the temporal drift typically observed in the channel conductance of single-walled carbon nanotube field-effect transistors (SWNT FETs) during the application of gate voltages. Before each resistance measurement, the gate is first stepped through a series of alternating positive and negative voltages to produce a neutral charge distribution within the device. This process is highly effective at removing the hysteresis in the channel conductance, and time-dependent measurements further demonstrate that the drain current is stable and single-valued, independent of the prior measurement history. The effectiveness of this method can be understood within the Preisach hysteresis model, which we demonstrate as a useful framework to predict the observed results.

Diagnosing nanoelectronic components using coherent electrons.

We present the direct observation, using off-axis electron holography (EH), of the electric potential distribution in the vicinity of a single carbon nanotube electrically biased by two closely spaced contacts. When our results are combined with finite element modeling, we demonstrate the ability to separately observe the electrostatic potential drops across the metal contacts at the interface with the nanotube and along the length of the nanotube itself. We demonstrate that the uneven resistivity of different contacts can cause an asymmetric EH phase shift, which can readily be identified and quantified. EH thus offers a unique and precise approach for in-depth understanding and quick diagnosis of many similar nanoscale electronic devices.

Environmental damping and vibrational coupling of confined fluids within isolated carbon nanotubes.

Because of their large surface areas, nanotubes and nanowires demonstrate exquisite mechanical coupling to their surroundings, promising advanced sensors and nanomechanical devices. However, this environmental sensitivity has resulted in several ambiguous observations of vibrational coupling across various experiments. Herein, we demonstrate a temperature-dependent Radial Breathing Mode (RBM) frequency in free-standing, electron-diffraction-assigned Double-Walled Carbon Nanotubes (DWNTs) that shows an unexpected and thermally reversible frequency downshift of 10 to 15%, for systems isolated in vacuum. An analysis based on a harmonic oscillator model assigns the distinctive frequency cusp, produced over 93 scans of 3 distinct DWNTs, along with the hyperbolic trajectory, to a reversible increase in damping from graphitic ribbons on the exterior surface. Strain-dependent coupling from self-tensioned, suspended DWNTs maintains the ratio of spring-to-damping frequencies, producing a stable saturation of RBM in the low-tension limit. In contrast, when the interior of DWNTs is subjected to a water-filling process, the RBM thermal trajectory is altered to that of a Langmuir isobar and elliptical trajectories, allowing measurement of the enthalpy of confined fluid phase change. These mechanisms and quantitative theory provide new insights into the environmental coupling of nanomechanical systems and the implications for devices and nanofluidic conduits.

Silicon nanowires: electron holography studies of doped p-n junctions and biased Schottky barriers.

We report an in situ examination of individual Si p-n junction nanowires (NWs) using off-axis electron holography (EH) during transmission electron microscopy. The SiNWs were synthesized by chemical vapor deposition with an axial dopant profile from n- to p-type, and then placed inside the transmission electron microscope as a cantilever geometry in contact with a movable Pt probe for in situ biasing measurements during simultaneous EH observations. The phase shift from EH indicates the potential shift between the p- and n-segments to be 1.03 ± 0.17 V due to the built-in voltage. The I-V characteristics of a single SiNW indicate the formation of a Schottky barrier between the NW tip and the movable Pt contact. EH observations show a strong concentration of electric field at this contact, preventing a change in the Si energy bands in the p-n junction region due to the applied bias.

Lithium-assisted electrochemical welding in silicon nanowire battery electrodes.

From in situ transmission electron microscopy (TEM) observations, we present direct evidence of lithium-assisted welding between physically contacted silicon nanowires (SiNWs) induced by electrochemical lithiation and delithiation. This electrochemical weld between two SiNWs demonstrates facile transport of lithium ions and electrons across the interface. From our in situ observations, we estimate the shear strength of the welded region after delithiation to be approximately 200 MPa, indicating that a strong bond is formed at the junction of two SiNWs. This welding phenomenon could help address the issue of capacity fade in nanostructured silicon battery electrodes, which is typically caused by fracture and detachment of active materials from the current collector. The process could provide for more robust battery performance either through self-healing of fractured components that remain in contact or through the formation of a multiconnected network architecture.

Electrolyte stability determines scaling limits for solid-state 3D Li ion batteries.

Rechargeable, all-solid-state Li ion batteries (LIBs) with high specific capacity and small footprint are highly desirable to power an emerging class of miniature, autonomous microsystems that operate without a hardwire for power or communications. A variety of three-dimensional (3D) LIB architectures that maximize areal energy density has been proposed to address this need. The success of all of these designs depends on an ultrathin, conformal electrolyte layer to electrically isolate the anode and cathode while allowing Li ions to pass through. However, we find that a substantial reduction in the electrolyte thickness, into the nanometer regime, can lead to rapid self-discharge of the battery even when the electrolyte layer is conformal and pinhole free. We demonstrate this by fabricating individual, solid-state nanowire core-multishell LIBs (NWLIBs) and cycling these inside a transmission electron microscope. For nanobatteries with the thinnest electrolyte, ≈110 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. With electrolyte thickness increased to 180 nm, the self-discharge rate is reduced substantially, and the NWLIBs maintain a potential above 2 V for over 2 h. Analysis of the nanobatteries' electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes directly through the electrolyte. Our study illustrates that, at these nanoscale dimensions, the increased electric field can lead to large electronic current in the electrolyte, effectively shorting the battery. The scaling of this phenomenon provides useful guidelines for the future design of 3D LIBs.

Anisotropic swelling and fracture of silicon nanowires during lithiation.

We report direct observation of an unexpected anisotropic swelling of Si nanowires during lithiation against either a solid electrolyte with a lithium counter-electrode or a liquid electrolyte with a LiCoO(2) counter-electrode. Such anisotropic expansion is attributed to the interfacial processes of accommodating large volumetric strains at the lithiation reaction front that depend sensitively on the crystallographic orientation. This anisotropic swelling results in lithiated Si nanowires with a remarkable dumbbell-shaped cross section, which develops due to plastic flow and an ensuing necking instability that is induced by the tensile hoop stress buildup in the lithiated shell. The plasticity-driven morphological instabilities often lead to fracture in lithiated nanowires, now captured in video. These results provide important insight into the battery degradation mechanisms.

Reducing disorder in artificial kagome ice.

Artificial spin ice has become a valuable tool for understanding magnetic interactions on a microscopic level. The strength in the approach lies in the ability of a synthetic array of nanoscale magnets to mimic crystalline materials, composed of atomic magnetic moments. Unfortunately, these nanoscale magnets, patterned from metal alloys, can show substantial variation in relevant quantities such as the coercive field, with deviations up to 16%. By carefully studying the reversal process of artificial kagome ice, we can directly measure the distribution of coercivities, and, by switching from disconnected islands to a connected structure, we find that the coercivity distribution can achieve a deviation of only 3.3%. These narrow deviations should allow the observation of behavior that mimics canonical spin-ice materials more closely.

In situ observation of reversible nanomagnetic switching induced by electric fields.

We report direct observation of controlled and reversible switching of magnetic domains using static (dc) electric fields applied in situ during Lorentz microscopy. The switching is realized through electromechanical coupling in thin film Fe(0.7)Ga(0.3)/BaTiO(3) bilayer structures mechanically released from the growth substrate. The domain wall motion is observed dynamically, allowing the direct association of local magnetic ordering throughout a range of applied electric fields. During application of approximately 7-11 MV/m electric fields to the piezoelectric BaTiO(3) film, local magnetic domains rearrange in the ferromagnetic Fe(0.7)Ga(0.3) layer due to the transfer of strain from the BaTiO(3) film. A simulation based on micromagnetic modeling shows a magnetostrictive anisotropy of 25 kPa induced in the Fe(0.7)Ga(0.3) due to the strain. This electric-field-dependent uniaxial anisotropy is proposed as a possible mechanism to control the coercive field during operation of an integrated magnetoelectric memory node.

Electron beam-induced crystallization of Al2O3 gate layer on ß-Ga2O3 MOS capacitors.

Electron irradiation was observed to induce crystallization of amorphous Al2O3 films grown by atomic layer deposition on ß-Ga2O3 substrates. Growth of large, strongly oriented crystalline γ-Al2O3 regions was induced using conventional-mode transmission electron microscopy (TEM) and observed to propagate outward from the interface as well as from the previously crystallized Al2O3. A few nm of epitaxial Al2O3 was already visible at the beginning of the crystallization front propagation. The phenomenon is not explained by electron beam-induced heating, which amounted to less than 1 K at all times. Direct measurement of the beam current permitted quantitative correlation between electron dose rates and crystallization rates. Enlarging the electron beam to reduce current density was found to slow the propagation of the crystallization front. Furthermore, a factor of 4 smaller electron dose was required for a given rate using 100 keV electrons as compared to 200 keV, indicating that crystallization is driven by ionization-induced atomic rearrangement within the gate layer. Lattice spacing between the oxygen sub-lattices of ß-Ga2O3 and γ-Al2O3 are favorable for the nucleation of crystallites at the interface. Multivariate statistical analysis of electron energy loss spectroscopy (EELS) data also showed evidence of diffusion between Al and Ga in the substrates and gate oxides, respectively. These structural transformations at the semiconductor-insulator interface are expected to influence the device electrical behavior and are relevant to the continued refinement of ß-Ga2O3 device technology.

A structure and activity relationship for single-walled carbon nanotube growth confirmed by in situ observations and modeling.

The structure and phase transformation of a cobalt (Co) catalyst, during single walled carbon nanotube (SWCNT) growth, is elucidated for inactive, active and deactivated nanoparticles by in situ imaging using an environmental transmission electron microscope. During nanotube growth, the structure was analyzed using Miller indices to determine the types of planes that favor anchoring or liftoff of nanotubes from the Co catalyst. Density functional theory was further applied to model the catalyst interactions to compare the work of adhesion of the catalyst's faceted planes to understand the interactions of different Miller planes with the graphene structure. Through in-depth studies of multiple distinct Co nanoparticles, we established a dominant nanoparticle phase for SWCNT growth. In addition, we identified the preferred lattice planes and a threshold for work of adhesion to allow the anchoring and liftoff of SWCNTs.

Field-Dependent Heat Dissipation of Carbon Nanotube Electric Currents.

We study heat dissipation of a multi-wall carbon nanotube (MWCNT) device fabricated from two crossed nanotubes on a SiNx substrate under the influence of a constant (DC) electric bias. By monitoring the temperature of the substrate, we observe negligible Joule heating within the nanotube lattice itself and instead heating occurs in the insulating substrate directly via a remote-scattering heating effect. Using finite element analysis, we estimate a remote heating parameter, ß, as the ratio of the power dissipated directly in the substrate to the total power applied. The extracted parameters show two distinct bias ranges; a low bias regime where about 85% of the power is dissipated directly into the substrate and a high bias regime where ß decreases, indicating the onset of traditional Joule heating within the nanotube. Analysis shows that this reduction is consistent with enhanced scattering of charge carriers by optical phonons within the nanotube. The results provide insights into heat dissipation mechanisms of Joule heated nanotube devices that are more complex than a simple heat dissipation mechanism dominated by acoustic phonons, which opens new possibilities for engineering nanoelectronics with improved thermal management.

Topological frustration of artificial spin ice.

Frustrated systems, typically characterized by competing interactions that cannot all be simultaneously satisfied, display rich behaviours not found elsewhere in nature. Artificial spin ice takes a materials-by-design approach to studying frustration, where lithographically patterned bar magnets mimic the frustrated interactions in real materials but are also amenable to direct characterization. Here, we introduce controlled topological defects into square artificial spin ice lattices in the form of lattice edge dislocations and directly observe the resulting spin configurations. We find the presence of a topological defect produces extended frustration within the system caused by a domain wall with indeterminate configuration. Away from the dislocation, the magnets are locally unfrustrated, but frustration of the lattice persists due to its topology. Our results demonstrate the non-trivial nature of topological defects in a new context, with implications for many real systems in which a typical density of dislocations could fully frustrate a canonically unfrustrated system.

Development of a Nanoindenter for In Situ Transmission Electron Microscopy.

In situ transmission electron microscopy is an established experimental technique that permits direct observation of the dynamics and mechanisms of dislocation motion and deformation behavior. In this article, we detail the development of a novel specimen goniometer that allows real-time observations of the mechanical response of materials to indentation loads. The technology of the scanning tunneling microscope is adopted to allow nanometer-scale positioning of a sharp, conductive diamond tip onto the edge of an electron-transparent sample. This allows application of loads to nanometer-scale material volumes coupled with simultaneous imaging of the material's response. The emphasis in this report is qualitative and technique oriented, with particular attention given to sample geometry and other technical requirements. Examples of the deformation of aluminum and titanium carbide as well as the fracture of silicon will be presented.

Miniature all-solid-state heterostructure nanowire Li-ion batteries as a tool for engineering and structural diagnostics of nanoscale electrochemical processes.

Complex interfacial phenomena and phase transformations that govern the operation of Li-ion batteries require detailed nanoscale 3D structural and compositional characterization that can be directly related to their capacity and electrical transport properties. For this purpose, we have designed model miniature all solid-state radial heterostructure Li-ion batteries composed of LiCoO2 cathode, LiPON electrolyte and amorphous Si anode shells, which were deposited around metallized high-aspect-ratio Si nanowires as a scaffolding core. Such diagnostic batteries, the smallest, complete secondary Li-ion batteries realized to date, were specifically designed for in situ electrical testing in a field-emission scanning electron microscope and/or transmission electron microscope. The results of electrochemical testing were described in detail in a previous publication (Nano Lett., 2012, 12, 505-511). The model Li-ion batteries allow analysis of the correlations between electrochemical properties and their structural evolution during cycling in various imaging, diffraction and spectroscopic modes down to the atomic level. Employing multimode analytical scanning/transmission electron microscopy imaging coupled with correlative multivariate statistical analysis and tomography, we have analyzed and quantified the 3D morphological and structural arrangement of the batteries, including textured platelet-like LiCoO2 nanocrystallites, buried electrode-electrolyte interfaces and hidden internal defects to clarify effects of scaling on a battery's electrochemical performance. Characterization of the nanoscale interfacial processes using model heterostructure nanowire-based Li-ion batteries provides useful guidelines for engineering of prospective nano-sized building blocks in future electrochemical energy storage systems.