Design of electrode for electrochemical energy storage and conversion devices using multiwall carbon nanotubes

• Main Author: Lee, Seung Woo, Ph. D. Massachusetts Institute of Technology
• Other Authors: Yang Shao-Horn and Paula T. Hammond.
• Format: Others
• Language: English
• Published: Massachusetts Institute of Technology 2010
• Subjects: Chemical Engineering.
• Online Access: http://hdl.handle.net/1721.1/59878

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2010. === Cataloged from PDF version of thesis. === Includes bibliographical references. === All-multiwall carbon nanotube (MWNT) thin films are created by layer-by-layer (LbL) assembly of surface functionalized MWNTs. Negatively and positively charged MWNTs were prepared by surface functionalization, allowing the incorporation of MWNTs into highly tunable thin films via the LbL technique. The pH dependent surface charge on the MWNTs gives this system the unique characteristics of LbL assembly of weak polyelectrolytes, controlling thickness and morphology with assembly pH conditions. We demonstrate that these MWNT thin films have randomly oriented interpenetrating network structure with well developed nanopores using SEM, which is an ideal structure of functional materials for various applications. LbL-MWNT electrodes show high electronic conductivity in comparison with polymer composites with single wall nanotubes, and high capacitive behavior in aqueous electrolyte with precise control of capacity. Of significance, additive-free LbL-MWNT electrodes with thicknesses of several microns can deliver high energy density (200 Wh/kg) at an exceptionally high power of 100 kW/kg in lithium nonaqueous cells. Utilizing the redox reactions on the surface functional groups in a wide voltage window (1.5 - 4.5 V vs. lithium) in nonaqueous electrolytes, asymmetric electrochemical capacitors consisting of LbL-MWNT and either lithium or a lithium titanium oxide negative electrode exhibit gravimetric energy density -5 times higher than conventional electrochemical capacitors with comparable gravimetric power and cycle life. Thin-film LbL-MWNT electrodes could potentially lead to breakthrough power sources for microsystems and flexible electronic devices such as smart cards and ebook readers, while thicker LbL-MWNT electrodes could expand the application of electrochemical capacitors into heavy vehicle and industrial systems, where the ability to deliver high energy at high power will be an enabling technological development. Furthermore, nanoscale pseuduocapactive oxides and electrocatalysts were incorporated into LbL-MWNT electrodes for energy storage and conversion. Inorganic oxides such as MnO2 and RuO2 are incorporated to increase volumetric capacitance in LbLMWNT electrodes using electroless deposition and square wave pulse potential deposition methods. Preliminary results show that we can increase volumetric capacitance of LbLMWNT/ MnO2 and LbL-MWNT/RuO2 composite up to 1000 F/cm3 in aqueous electrolytes. In addition, Pt and Pt/Ru alloy electrocatalysts are introduced into LbL-MWNT electrodes using square wave pulse potential deposition, which show higher CO and methanol oxidation activities. Tailored incorporation of metal and oxide nanoparticles into LbLMWNT electrodes by square wave pulse potential opens a new strategy for novel energy storage and conversion electrodes with superior electrochemical properties. === by Seung Woo Lee. === Ph.D.