Dissertation/Thesis Abstract

Recycling Carbon Dioxide into Sustainable Hydrocarbon Fuels: Electrolysis of Carbon Dioxide and Water
by Graves, Christopher Ronald, Ph.D., Columbia University, 2010, 281; 3448327
Abstract (Summary)

Great quantities of hydrocarbon fuels will be needed for the foreseeable future, even if electricity based energy carriers begin to partially replace liquid hydrocarbons in the transportation sector. Fossil fuels and biomass are the most common feedstocks for production of hydrocarbon fuels. However, using renewable or nuclear energy, carbon dioxide and water can be recycled into sustainable hydrocarbon fuels in non-biological processes which remove oxygen from CO2 and H2O (the reverse of fuel combustion). Capture of CO2 from the atmosphere would enable a closed-loop carbon-neutral fuel cycle.

The purpose of this work was to develop critical components of a system that recycles CO2 into liquid hydrocarbon fuels. The concept is examined at several scales, beginning with a broad scope analysis of large-scale sustainable energy systems and ultimately studying electrolysis of CO 2 and H2O in high temperature solid oxide cells as the heart of the energy conversion, in the form of three experimental studies. The contributions of these studies include discoveries about electrochemistry and materials that could significantly improve the overall energy use and economics of the CO2-to-fuels system.

The broad scale study begins by assessing the sustainability and practicality of the various energy carriers that could replace petroleum-derived hydrocarbon fuels, including other hydrocarbons, hydrogen, and storage of electricity on-board vehicles in batteries, ultracapacitors, and flywheels. Any energy carrier can store the energy of any energy source. This sets the context for CO2 recycling — sustainable energy sources like solar and wind power can be used to provide the most energy-dense, convenient fuels which can be readily used in the existing infrastructure. The many ways to recycle CO2 into hydrocarbons, based on thermolysis, thermochemical loops, electrolysis, and photoelectrolysis of CO2 and/or H 2O, are critically reviewed. A process based on high temperature co-electrolysis of CO2 and H2O to produce syngas (CO/H2 mixture) is identified as a promising method. High temperature electrolysis makes very efficient use of electricity and heat (near-100% electricity-to-syngas efficiency), provides high reaction rates, and the syngas produced can be catalytically converted to hydrocarbons in well-known fuel synthesis reactors (e.g. Fischer-Tropsch).

The experimental studies of high temperature electrolysis are made at different scales — at the cell level, electrode level, and in materials and microstructure development. The results include cell performance and durability, insight into electrode reaction mechanisms, and new high-performance electrode materials. The experimental studies make extensive use of electrochemical impedance spectroscopy and systematic variation of test conditions to examine the electrochemical phenomena. Variation of the material composition itself within families of related materials was an additional parameter used in the electrode level and materials studies that revealed more information than studying a single material would have.

Using full cells, the performance and durability of a solid oxide cell applied for co-electrolysis of CO2 and H2O was investigated. High initial performance was observed but the long-term durability needs to be improved. Based on these results, an analysis of the energy balance and economics of an electrolysis-based synthetic fuel production process, including CO2 air capture and Fischer-Tropsch fuel synthesis, determined that the system can feasibly operate at 70% electricity-to-liquid fuel efficiency (higher heating value basis) and that the price of electricity needed to produce competitive synthetic gasoline (at USD$2/gal, or $0.53/L, wholesale) is 2-3 U.S. cents per kWh. For $3/gal ($0.78/L) gasoline, 4-5 cents per kWh is needed. Fuel production may already be economical in some regions that have inexpensive renewable electricity, such as Iceland. The dominant costs of the process are the electricity cost and the capital cost of the electrolyzer, and this capital cost is significantly increased when operating intermittently (on renewable power sources such as solar and wind). Low cell internal resistance, low degradation, and low manufacturing cost each contribute to a low electrolyzer capital cost, and can be traded off. One straightforward path to affordability is by improving the durability of the high current density cell operation (≥1 A/cm2) that is already possible with these cells. The negative-electrode, a composite of nickel and yttria-stabilized zirconia (YSZ), is often the major site of cell degradation, including in the co-electrolysis results presented here.

To better understand the reaction mechanisms at the negative-electrode that limit performance and durability, different metal electrodes including nickel were studied using a simplified point-contact electrode geometry with a well-defined three-phase boundary (TPB; the electrode/electrolyte/gas interface where the electrochemical reactions take place). The simple geometry is useful for isolating the electrochemical properties without the effects of the complex microstructure of technological porous electrodes. Widely different impedance responses of the different metals to the same changes in test conditions (gas composition, temperature, and polarization) were observed, indicating that the same reaction mechanisms are not shared by the different metals, contrary to some recent studies. Evidence was also found that supports the explanation that impurities segregated to the TPB play a major role and are largely responsible for inconsistencies in the electrode kinetics literature. The significance of microstructure at the TPB was also revealed — the electrode polarization resistance was reduced by an order of magnitude when subjected to extreme conditions of oxidation-reduction and strong cathodic polarization, which induced the formation of a micro/nanostructured TPB. Possible reaction mechanisms for H2O/CO2 reduction and H2/CO oxidation are discussed.

Novel ceramic materials based on molybdates with varying Mo valence were synthesized as possible alternative negative-electrode materials. The phase, stability, microstructure and electrical conductivity were characterized. The electrochemical activity for H2O/CO2 reduction and H2/CO oxidation was studied using simplified geometry electrodes, similar to the metals study. Unique phenomena were observed for some of the molybdate materials — they decomposed into multiple phases and formed a nanostructured surface upon exposure to operating conditions (in certain reducing atmospheres). The new phases and surface features enhanced the electronic conductivity and electrocatalytic activity. Preparing an electrode by performing controlled decomposition to form multiple desirable phases and a desirable microstructure (which can take place in situ) using these materials is a novel way to produce potentially high-performance electrodes for solid oxide cells. By modifying the composition, it was possible to prevent decomposition. Other members of the molybdate family exhibited similarly high electronic conductivity and electrocatalytic activity but did not decompose. The high activity was the result of a different mechanism, probably related to the defect chemistry of the material. The polarization resistances of the best molybdate materials were two orders of magnitude lower than that of donor-doped strontium titanates. Many of the molybdate materials were significantly activated by cathodic polarization, and they exhibited higher performance for cathodic (electrolysis) polarization than anodic (fuel cell) polarization, which makes them especially interesting for use in electrolysis electrodes. Whereas nearly all of the molybdates showed higher performance for H2O electrolysis than CO2 electrolysis, one with vanadium showed nearly equal performance, and a non-molybdate which exhibits some complementary properties to the best molybdates, Gd-doped ceria in nanoparticle form, was found to be an excellent electrocatalyst for CO2 electrolysis and CO oxidation (moreso than for H2O/H2 for which it is known to be good).

Indexing (document details)
School: Columbia University
School Location: United States -- New York
Source: DAI-B 72/05, Dissertation Abstracts International
Subjects: Alternative Energy, Chemical engineering, Sustainability, Environmental engineering, Materials science
Keywords: Carbon dioxide, Ceramic electrodes, Electrolysis, Hydrocarbon fuels, Sustainable energy, Syngas
Publication Number: 3448327
ISBN: 9781124543222
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