Roberta A. DiLeo

Carbon nanotubes for lithium ion batteries

Lithium ion batteries are receiving considerable attention in applications, ranging from portable electronics to electric vehicles, due to their superior energy density over other rechargeable battery technologies. However, the societal demands for lighter, thinner, and higher capacity lithium ion batteries necessitate ongoing research for novel materials with improved properties over that of state-of-the-art. Such an effort requires a concerted development of both electrodes and electrolyte to improve battery capacity, cycle life, and charge–discharge rates while maintaining the highest degree of safety available. Carbon nanotubes (CNTs) are a candidate material for use in lithium ion batteries due to their unique set of electrochemical and mechanical properties. The incorporation of CNTs as a conductive additive at a lower weight loading than conventional carbons, like carbon black and graphite, presents a more effective strategy to establish an electrical percolation network. In addition, CNTs have the capability to be assembled into free-standing electrodes (absent of any binder or current collector) as an active lithium ion storage material or as a physical support for ultra high capacity anode materials like silicon or germanium. The measured reversible lithium ion capacities for CNT-based anodes can exceed 1000 mAh g−1 depending on experimental factors, which is a 3× improvement over conventional graphite anodes. The major advantage from utilizing free-standing CNT anodes is the removal of the copper current collectors which can translate into an increase in specific energy density by more than 50% for the overall battery design. However, a developmental effort needs to overcome current research challenges including the first cycle charge loss and paper crystallinity for free-standing CNT electrodes. Efforts to utilize pre-lithiation methods and modification of the single wall carbon nanotube bundling are expected to increase the energy density of future CNT batteries. Other progress may be achieved using open-ended structures and enriched chiral fractions of semiconducting or metallic chiralities that are potentially able to improve capacity and electrical transport in CNT-based lithium ion batteries.

Purity assessment of multiwalled carbon nanotubes by Raman spectroscopy

Carbonaceous purity assessment for chemical vapor deposition multiwalled carbon nanotubes (MWNTs) using Raman spectroscopy was investigated. Raman spectroscopy was performed on a reference sample set containing predetermined ratios of MWNTs and representative synthesis by-products. Changes in the characteristic Raman peak ratios (i.e., ID∕IG, IG′∕IG, and IG′∕ID) as a function of MWNT content were measured. Calibration curves were generated from the reference samples and used to evaluate MWNTs synthesized under different conditions with varying purity. The efficacy of using Raman spectroscopy in conjunction with thermogravimetric analysis for quantitative MWNT purity assessment is discussed.

Germanium–single-wall carbon nanotube anodes for lithium ion batteries

High-capacity thin-film germanium was coupled with free-standing single-wall carbon nanotube (SWCNT) current collectors as a novel lithium ion battery anode. A series of Ge–SWCNT compositions were fabricated and characterized by scanning electron microscopy and Raman spectroscopy. The lithium ion storage capacities of the anodes were measured to be proportional to the Ge weight loading, with a 40 wt% Ge–SWCNT electrode measuring 800 mAh/g. Full batteries comprising a Ge–SWCNT anode in concert with a LiCoO2 cathode have demonstrated a nominal voltage of 3.35 V and anode energy densities 3× the conventional graphite-based value. The higher observed energy density for Ge–SWCNT anodes has been used to calculate the relative improvement in full battery performance when capacity matched with conventional cathodes (e.g., LiCoO2, LiNiCoAlO2, and LiFePO4). The results show a >50% increase in both specific and volumetric energy densities, with values approaching 275 Wh/kg and 700 Wh/L.

Ion irradiation of electronic-type-separated single wall carbon nanotubes: A model for radiation effects in nanostructured carbon

The structural and electrical properties of electronic-type-separated (metallic and semiconducting) single wall carbon nanotube (SWCNT) thin-films have been investigated after irradiation with 150 keV 11B+ and 150 keV 31P+ with fluences ranging from 1012 to 1015 ions/cm2. Raman spectroscopy results indicate that the ratio of the Raman D to G′ band peak intensities (D/G′) is a more sensitive indicator of SWCNT structural modification induced by ion irradiation by one order of magnitude compared to the ratio of the Raman D to G band peak intensities (D/G). The increase in sheet resistance (Rs) of the thin-films follows a similar trend as the D/G′ ratio, suggesting that the radiation induced variation in bulk electrical transport for both electronic-types is equal and related to localized defect generation. The characterization results for the various samples are compared based on the displacement damage dose (DDD) imparted to the sample, which is material and damage source independent. Therefore, it is poss...

Ultra-Lightweight Hybrid Thin-Film Solar Cells: A Survey of Enabling Technologies for Space Power Applications

The development of hybrid inorganic/organic thin-film solar cells on flexible, lightweight, space-qualified, durable substrates provides an attractive solution for fabricating solar arrays with high mass specific power (W/kg). Next generation thin-film technologies may well involve a revolutionary change in materials to organic-based devices. The high-volume, low-cost fabrication potential of organic cells will allow for square miles of solar cell production at one-tenth the cost of conventional inorganic materials. Plastic solar cells take a minimum of storage space and can be inflated or unrolled for deployment. We will explore a cross-section of in-house and sponsored research efforts that aim to provide new hybrid technologies that include both inorganic and polymer materials as active and substrate materials. Research at University of Texas at Arlington focuses on the fabrication and use of poly(isothianaphthene-3,6-diyl) in solar cells. We describe efforts at Norfolk State University to design, synthesize and characterize block copolymers. A collaborative team between EIC Laboratories, Inc. and the University of Florida is investigating multijunction polymer solar cells to more effectively utilize solar radiation. The National Aeronautics and Space Administration (NASA)/Ohio Aerospace Institute (OAI) group has undertaken a thermal analysis of potential metallized substrates as well as production of nanoparticles of CuInS2 and CuInSe2 in good yield at moderate temperatures via decomposition of single-source precursors. Finally, preliminary work at the Rochester Institute of Technology (R.I.T.) to assess the impact on performance of solar cells of temperature and carbon nanotubes is reported. Technologies that must be developed to enable ultra-lightweight solar arrays include: monolithic interconnects, lightweight array structures, and new ultra-light support and deployment mechanisms. For NASA applications, any solar cell or array technology must not only meet weight and AMO efficiency goals, but also must be durable enough to survive launch conditions and space environments.

Dye-sensitized bulk heterojunction polymer solar cells

At present, there is a real limitation one can achieve with state-of-the-art fullerene-polymer solar cell materials in a fully optimized device based upon the poor mismatch to the solar spectrum. Empirical modeling has been performed using device parameters from current-voltage and spectral response measurements. The limiting Jsc has been simulated from the spectral response profile of PCBM[70]-MEH-PPV and PCBM[60]-P3HT devices. The maximum efficiency for these systems is calculated to be between 6 and 9%, under 1 sun illumination. Empirical simulations show that molecular dyes absorbing between 800-900 nm in a properly structured device can theoretically increase the device photocurrent sufficient to reach a power conversion efficiency of 16% in a bulk heterojunction polymer solar cell under 1 sun AM1.5 illumination. We have investigated the use of soluble organic dyes with measured bandgaps in the nearinfrared (NIR) to extend the spectral conversion in polymeric solar cells. An appropriate energy level structure (to promote exciton dissociation and charge transport to the fullerene derivatives and polymer) has been measured using cyclic voltammetry for certain indolylidene dyes. The incorporation of these dyes into a PCBM-P3HT device structure has shown an enhancement in the spectral response at 1.5 eV.

Single Wall Carbon Nanotube – LiCoO 2 Lithium Ion Batteries

The electrochemical cycling performance of high purity single wall carbon nanotube (SWCNT) paper electrodes has been measured for a series of electrolyte solvent compositions. The effects of varying the galvanostatic charge rate and cycling temperature on lithium ion capacity have been evaluated between 25-100 °C. The measured reversible lithium ion capacities for SWCNT anodes range from 600-1000 mAh/g for a 1M LiPF 6 electrolyte, depending on solvent composition and cycling temperature. The solid-electrolyte-interface (SEI) formation and first cycle charge loss are also shown to vary dramatically with carbonate solvent selection and illustrate the importance of solvent alkyl chain length and polarity on SWCNT capacity. SWCNT anodes have also been incorporated into full battery designs using LiCoO 2 cathode composites. An electrochemical pre-lithiation sequence, prior to battery assembly, has been developed to mitigate the first cycle charge loss of SWCNT anodes. The pre-lithiated SWCNT anodes show reversible cycling at varying charge rates and depths of discharge with the cathode system. The summary of data shows that the structural integrity of individual SWCNTs is preserved after cycling, and that free-standing SWCNT paper electrodes represent an attractive material for lithium ion batteries.

Determination of nanomaterial energy levels for organic photovoltaics by Cyclic voltammetry

A wide variety of nanomaterials and associated nanomaterial/polymer composites are being developed in an effort to produce higher efficiency organic solar cells. This development requires a fundamental understanding of the energy levels for the individual materials, and their composites, to enable device designs which posess appropriate energy level matching. Cyclic voltammetry (CV) allows for the determination of the band gaps (E g ) and energy levels of these various nanomaterials and composites by measuring their oxidation and reduction potentials. These potentials correspond to a given materials ionization potential (IP) and electron affinity (EA), respectively. The results for the EA, IP, and E g have been determined by CV for derivatized fullerenes and CdSe quantum dots (QD), measured in isolation, and in conjugated polymer composites with MEH-PPV. In addition, CV measurements conducted under dark and illuminated conditions were used to investigate the relationship between energy levels within the composites.