Carbon nanotube survivability in marine environments and method for biofouling removal.

The deep sea survivability and biofouling characteristics of corrosion-resistant bulk carbon nanotubes (CNTs) have been studied after deployment in the Atlantic Ocean over the course of 12 months. Quantification of barnacle count, biofouling density, and non-combustible residue shows cyanoacrylate coatings increase durability and reduce the colonization of biofouling compared to as-received CNTs. Scanning electron microscopy was performed on the biofouled CNTs, and the majority of species were identified as diatoms, consisting of an ordered silica cell wall. Both the as-received and cyanoacrylate-treated CNTs were successfully acid purified to remove biogrowth, leading to complete recovery of tensile strength and electrical transport properties. Thermogravimetric analysis, scanning electron microscopy, contact angle, dynamic mechanical analysis, and current carrying capacity measurements validated the refunctionalization results. Thus, the multifunctional property recovery and enhanced durability confirms that CNTs are electrochemically stable in saltwater environments and are resilient to biofouling conditions in real-world environments after extended exposure.

Graphene Strained by Defects.

Using graphene nanomechanical resonators we demonstrate the extent to which the mechanical properties of multilayer graphene films are controllable, in real time, through introduction and rearrangement of defects. We show both static and re-entrant (cyclical) changes in the tensile stress using a combination of ion implantation, chemical functionalization, and thermal treatment. While the dramatic increase in static tensile stress achievable through laser annealing can be of importance for various MEMS applications, we view the direct observation of a time-variable stress as even more significant. We find that defect-rich films exhibit a slow relaxation component of the tensile stress that remains in the resonator long after the laser exposure is finished (trelax ≈ 100 s ≫ tcooling), analogous to a wind-up toy. We attribute this persistent component of the time-variable stress to a set of metastable, multivacancy structures formed during the laser anneal. Our results indicate that significant stress fields generated by multivacancies, in combination with their finite lifetime, could make them a powerful and flexible tool in nanomechanics.

Removal of sodium dodecyl sulfate surfactant from aqueous dispersions of single-wall carbon nanotubes.

A reagent-based treatment method was developed for the removal of sodium dodecyl sulfate (SDS) from aqueous dispersions of single-wall carbon nanotubes (SWCNTs). Based on a survey of various reagents, organic solvents emerged as the most effective at interrupting the SDS:SWCNT interaction without producing deleterious side reactions or causing precipitation of the surfactant. Specifically, treatment with acetone or acetonitrile allows for the facile isolation of SWCNTs with near complete removal of SDS through vacuum filtration, resulting in a 100x reduction in processing time. These findings were validated via quantitative analysis using thermogravimetric analysis, Raman spectroscopy, 4-point probe electrical measurement, and X-ray photoelectron spectroscopy. Subsequent thermal oxidation further enhances the purity of the reagent treated samples and yields bulk SWCNT samples with >95% carbonaceous purity. The proposed reagent treatment method thus demonstrates potential for large volume SWCNT processing.

Modification of Silver/Single-Wall Carbon Nanotube Electrical Contact Interfaces via Ion Irradiation.

Introduction of defects via ion irradiation ex situ to modify silver/single-wall carbon nanotube (Ag-SWCNT) electrical contacts and the resulting changes in the electrical properties were studied. Two test samples were fabricated by depositing 0.1 µm Ag onto SWCNT thin films with average thicknesses of 10 and 60 nm, followed by ion irradiation (150 keV 11B+ at 5 × 1014 ions/cm2). The contact resistance (Rc) between the Ag and SWCNT thin films was determined using transfer length method (TLM) measurements before and after ion irradiation. Rc increases for both test samples after irradiation, while there is no change in Rc for control structures with thick Ag contacts (1.5 µm), indicating that changes in Rc originate from changes in the SWCNT films and at the Ag-SWCNT interface caused by ion penetration through the Ag contact electrodes. Rc increases by ∼4× for the 60 nm SWCNT structure and increases by ∼2.4× for the 10 nm SWCNT structure. Raman spectroscopy measurements of the SWCNTs under the contacts compared to the starting SWCNT film show that the degradation of the 10 nm SWCNT structure was less significant than that of the 60 nm SWCNT structure, suggesting that the smaller change in Rc for the 10 nm SWCNT structure is a result of the thickness-dependent damage profile in the SWCNTs. Despite the increase in overall contact resistance, further TLM analysis reveals that the specific contact resistance actually decreases by ∼3.5-4× for both test samples, suggesting an enhancement of the electrical properties at the Ag-SWCNT interface. Irradiation simulations provide a physical description of the underlying mechanism, revealing that Ag atoms are forward-scattered into the SWCNTs, creating an Ag/C interfacial layer several nanometers in depth. The collective results indicate competing effects of improvement of the Ag-SWCNT interface versus degradation of the bulk SWCNT films, which has implications for scaled high-performance devices employing thinner SWCNT films.

Carbon Nanotube Thin-Film Antennas.

Multiwalled carbon nanotube (MWCNT) and single-walled carbon nanotube (SWCNT) dipole antennas have been successfully designed, fabricated, and tested. Antennas of varying lengths were fabricated using flexible bulk MWCNT sheet material and evaluated to confirm the validity of a full-wave antenna design equation. The ∼20× improvement in electrical conductivity provided by chemically doped SWCNT thin films over MWCNT sheets presents an opportunity for the fabrication of thin-film antennas, leading to potentially simplified system integration and optical transparency. The resonance characteristics of a fabricated chlorosulfonic acid-doped SWCNT thin-film antenna demonstrate the feasibility of the technology and indicate that when the sheet resistance of the thin film is >40 ohm/sq no power is absorbed by the antenna and that a sheet resistance of <10 ohm/sq is needed to achieve a 10 dB return loss in the unbalanced antenna. The dependence of the return loss performance on the SWCNT sheet resistance is consistent with unbalanced metal, metal oxide, and other CNT-based thin-film antennas, and it provides a framework for which other thin-film antennas can be designed.

Enhanced Electrical Conductivity in Extruded Single-Wall Carbon Nanotube Wires from Modified Coagulation Parameters and Mechanical Processing.

Single-wall carbon nanotubes (SWCNTs) synthesized via laser vaporization have been dispersed using chlorosulfonic acid (CSA) and extruded under varying coagulation conditions to fabricate multifunctional wires. The use of high purity SWCNT material based upon established purification methods yields wires with highly aligned nanoscale morphology and an over 4× improvement in electrical conductivity over as-produced SWCNT material. A series of eight liquids have been evaluated for use as a coagulant bath, and each coagulant yielded unique wire morphology based on its interaction with the SWCNT-CSA dispersion. In particular, dimethylacetamide as a coagulant bath is shown to fabricate highly uniform SWCNT wires, and acetone coagulant baths result in the highest specific conductivity and tensile strength. A 2× improvement in specific conductivity has been measured for SWCNT wires following tensioning induced both during extrusion via increased coagulant bath depth and during solvent evaporation via mechanical strain, over that of as-extruded wires from shallower coagulant baths. Overall, combination of the optimized coagulation parameters has yielded acid-doped wires with the highest reported room temperature electrical conductivities to date of 4.1-5.0 MS/m and tensile strengths of 210-250 MPa. Such improvements in bulk electrical conductivity can impact the adoption of metal-free, multifunctional SWCNT materials for advanced cabling architectures.

Economic and environmental characterization of an evolving Li-ion battery waste stream.

While disposal bans of lithium-ion batteries are gaining in popularity, the infrastructure required to recycle these batteries has not yet fully emerged and the economic motivation for this type of recycling system has not yet been quantified comprehensively. This study combines economic modeling and fundamental material characterization methods to quantify economic trade-offs for lithium ion batteries at their end-of-life. Results show that as chemistries transition from lithium-cobalt based cathodes to less costly chemistries, battery recovery value decreases along with the initial value of the raw materials used. For example, manganese-spinel and iron phosphate cathode batteries have potential material values 73% and 79% less than cobalt cathode batteries, respectively. A majority of the potentially recoverable value resides in the base metals contained in the cathode; this increases disassembly cost and time as this is the last portion of the battery taken apart. A great deal of compositional variability exists, even within the same cathode chemistry, due to differences between manufacturers with coefficient of variation up to 37% for some base metals. Cathode changes over time will result in a heavily co-mingled waste stream, further complicating waste management and recycling processes. These results aim to inform disposal, collection, and take-back policies being proposed currently that affect waste management infrastructure as well as guide future deployment of novel recycling techniques.

Prelithiation of silicon-carbon nanotube anodes for lithium ion batteries by stabilized lithium metal powder (SLMP).

Stabilized lithium metal powder (SLMP) has been applied during battery assembly to effectively prelithiate high capacity (1500-2500 mAh/g) silicon-carbon nanotube (Si-CNT) anodes, eliminating the 20-40% first cycle irreversible capacity loss. Pressure-activation of SLMP is shown to enhance prelithiation and enable capacity matching between Si-CNT anodes and lithium nickel cobalt aluminum oxide (NCA) cathodes in full batteries with minimal added mass. The prelithiation approach enables high energy density NCA/Si-CNT batteries achieving >1000 cycles at 20% depth-of-discharge.

High-performance, lightweight coaxial cable from carbon nanotube conductors.

Coaxial cables have been constructed with carbon nanotube (CNT) materials serving as both the inner and outer conductors. Treatment of the CNT outer and inner conductors with KAuBr(4) was found to significantly reduce the attenuation of these cables, which demonstrates that chemical agents can be used to improve power transmission through CNT networks at high frequencies (150 kHz-3 GHz). For cables constructed with a KAuBr(4)-treated CNT outer conductor, power attenuation per length approaches parity with cables constructed from metallic conductors at significantly lower weight per length (i.e., 7.1 g/m for CNT designs compared to 38.8 g/m for an RG-58 design). A relationship between the thickness of the CNT outer conductor and the cable attenuation was observed and used to estimate the effective skin depth at high frequency. These results establish reliable, reproducible methods for the construction of coaxial cables from CNT materials that can facilitate further investigation of their performance in high-frequency transmission structures, and highlight a specific opportunity for significant reduction in coaxial cable mass.

Carbon nanotube wires and cables: near-term applications and future perspectives.

Wires and cables are essential to modern society, and opportunities exist to develop new materials with reduced resistance, mass, and/or susceptibility to fatigue. This article describes how carbon nanotubes (CNTs) offer opportunities for integration into wires and cables for both power and data transmission due to their unique physical and electronic properties. Macroscopic CNT wires and ribbons are presently shown as viable replacements for metallic conductors in lab-scale demonstrations of coaxial, USB, and Ethernet cables. In certain applications, such as the outer conductor of a coaxial cable, CNT materials may be positioned to displace metals to achieve substantial benefits (e.g. reduction in cable mass per unit length (mass/length) up to 50% in some cases). Bulk CNT materials possess several unique properties which may offer advantages over metallic conductors, such as flexure tolerance and environmental stability. Specifically, CNT wires were observed to withstand greater than 200,000 bending cycles without increasing resistivity. Additionally, CNT wires exhibit no increase in resistivity after 80 days in a corrosive environment (1 M HCl), and little change in resistivity with temperature (<1% from 170-330 K). This performance is superior to conventional metal wires and truly novel for a wiring material. However, for CNTs to serve as a full replacement for metals, the electrical conductivity of CNT materials must be improved. Recently, the conductivity of a CNT wire prepared through simultaneous densification and doping has exceeded 1.3 × 10(6) S/m. This level of conductivity brings CNTs closer to copper (5.8 × 10(7) S/m) and competitive with some metals (e.g. gold) on a mass-normalized basis. Developments in manipulation of CNT materials (e.g. type enrichment, doping, alignment, and densification) have shown progress towards this goal. In parallel with efforts to improve bulk conductivity, integration of CNT materials into cabling architectures will require development in electrical contacting. Several methods for contacting bulk CNT materials to metals are demonstrated, including mechanical crimping and ultrasonic bonding, along with a method for reducing contact resistance by tailoring the CNT-metal interface via electroless plating. Collectively, these results summarize recent progress in CNT wiring technologies and illustrate that nanoscale conductors may become a disruptive technology in cabling designs.

Material and energy intensity of fullerene production.

Fullerenes are increasingly being used in medical, environmental, and electronic applications due to their unique structural and electronic properties. However, the energy and environmental impacts associated with their commercial-scale production have not yet been fully investigated. In this work, the life cycle embodied energy of C(60) and C(70) fullerenes has been quantified from cradle-to-gate, including the relative contributions from synthesis, separation, purification, and functionalization processes, representing a more comprehensive scope than used in previous fullerene life cycle studies. Comparison of two prevalent production methods (plasma and pyrolysis) has shown that pyrolysis of 1,4-tetrahydronaphthalene emerges as the method with the lowest embodied energy (12.7 GJ/kg of C(60)). In comparison, plasma methods require a large amount of electricity, resulting in a factor of 7-10× higher embodied energy in the fullerene product. In many practical applications, fullerenes are required at a purity >98% by weight, which necessitates multiple purification steps and increases embodied energy by at least a factor of 5, depending on the desired purity. For applications such as organic solar cells, the purified fullerenes need to be chemically modified to [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM), thus increasing the embodied energy to 64.7 GJ/kg C(60)-PCBM for the specified pyrolysis, purification, and functionalization conditions. Such synthesis and processing effects are even more significant for the embodied energy of larger fullerenes, such as C(70), which are produced in smaller quantities and are more difficult to purify. Overall, the inventory analysis shows that the embodied energy of all fullerenes are an order of magnitude higher than most bulk chemicals, and, therefore, traditional cutoff rules by weight during life cycle assessment of fullerene-based products should be avoided.

Enhanced capacity and rate capability of carbon nanotube based anodes with titanium contacts for lithium ion batteries.

Carbon nanotubes are being considered for adoption in lithium ion batteries as both a current collector support for high-capacity active materials (replacing traditional metal foils) and as free-standing electrodes where they simultaneously store lithium ions. The necessity to establish good electrical contact to these novel electrode designs is critical for success. In this work, application of nickel and titanium as both separable and thin film electrical contacts to free-standing single-wall carbon nanotube (SWCNT) electrodes is shown to dramatically enhance both the reversible lithium ion capacity and rate capability in comparison with stainless steel. Scanning electron microscopy showed that evaporation of Ni and Ti can effectively coat the SWCNT bundles in a bulk electrode which is capable of providing an improved electrical contact. A thin film of titanium emerged as the preferred electrical contact promoting the highest capacity ever measured for a SWCNT free-standing electrode of 1250 mAh/g. In addition, the titanium contacting approach demonstrated a 5-fold improvement in lithium ion capacity at extraction rates greater than 1C for a high-energy density Ge-SWCNT electrode. The overall performance improvement with Ti contacts is attributed to a lower contact resistance, nanoscale "wetting" of SWCNT bundles to improve contact uniformity, and effective electron coupling between Ti and SWCNTs due to work function-energy level alignment. The experimental results provide the basis for a Ragone analysis (power vs energy parameters), whereby Ge-SWCNT-Ti anodes paired with a LiFePO(4) cathode can lead to a 60% improvement over conventional graphite anodes in both power and energy density for a complete battery.

Multi-walled carbon nanotube paper anodes for lithium ion batteries.

The lithium ion capacity has been measured for multi-walled carbon nanotubes (MWCNTs) synthesized by injection chemical vapor deposition (CVD) using a cyclopentadienyl iron dicarbonyl dimer catalyst. The high quality of the as-synthesized MWCNTs has enabled free-standing electrodes to be fabricated independent of polymeric binder or copper support. Galvanostatic cycling of these electrodes demonstrates excellent reversibility and coulombic efficiency (> 97% after cycle 3) using propylene carbonate based electrolytes, with no evidence for material degradation. A reversible capacity exceeding 225 mAh/g was measured after 20 cycles when using the electrolyte combination of (1:1:1 v/v) ethylene carbonate (EC):propylene carbonate (PC):diethyl carbonate (DEC) at a constant current of 74 mA/g (equivalent of C/5 for LiC6). Modification of the catalyst solvent during synthesis from xylenes to pyridine improved the lithium ion capacity in the resulting MWCNT paper to 340 mAh/g. In addition, this MWCNT paper showed a stable reversible capacity after 10 cycles, exceeding 225 mAh/g when cycled at an equivalent 1C rate. Therefore, the use of a nitrogen source during synthesis can lead to improved lithium ion capacity in novel MWCNT anodes.

Effects of carrier gas dynamics on single wall carbon nanotube chiral distributions during laser vaporization synthesis.

We report on the utility of modifying the carrier gas dynamics during laser vaporization synthesis to alter the single wall carbon nanotube (SWNT) chiral distribution. SWNTs produced from an Alexandrite laser using conventional Ni/Co catalysts demonstrate marked differences in chiral distributions due to effects of helium gas and reactor chamber pressure, in comparison to conventional subambient pressures and argon gas. Optical absorption and Raman spectroscopies confirm that the SWNT diameter distribution decreases under higher pressure and with helium gas as opposed to argon. Fluorescence mapping of the raw soots in sodium dodecylbenzene sulfonate (SDBS)-D2O was used to estimate the relative (n, m)-SWNT content of the semiconducting types. A predominance of type II structures for each synthesis condition was observed. The distribution of SWNT chiral angles was observed to shift away from near-armchair configurations under higher pressure and with helium gas. These results illustrate the importance of gas type and pressure on the condensation/cooling rate, which allows for synthesis of specific SWNT chiral distributions.

Purity assessment of single-wall carbon nanotubes, using optical absorption spectroscopy.

A demand currently exists for a method of assessing the purity of single-wall carbon nanotubes (SWNTs), which will allow for meaningful material comparisons. An established metric and protocol will enable accurate and reproducible purity claims to be substantiated. In the present work, the ability to accurately quantify the mass fraction of SWNTs in the carbonaceous portion of a given sample is demonstrated, using optical absorption spectroscopy on both laser and arc discharge-generated SWNT-N,N-dimethylacetamide (DMA) dispersions. Verification of purity assessment protocols is based upon constructed sample sets comprising designed mass fractions of purified SWNTs and representative carbonaceous synthesis byproducts. Application of a previously reported method based on a ratio of the areal absorbance from linear subtractions of the second interband electronic transitions of semiconducting SWNTs ((S)E(22)) has shown a severe overestimation of SWNT purity (average error >24%). Instead, the development of a nonlinear pi-plasmon model, which considers overlap of electronic transitions and peak broadening, has dramatically improved the purity assessment accuracy (average error <7%), derived from a strong correlation to the constructed sample sets. This approach has enabled corroboration of rapid assessment procedures, such as absorbance peak maxima ratio and Beer's law analysis, directed at purification monitoring and synthesis sample screening. Specifically, a simple protocol for purity assessment of laser and arc-discharge SWNTs has been established that can be extended to other synthetic types (i.e. CVD, HiPco, etc.) and diameter distributions.