abstract: A new type of electronics was envisioned, namely edible electronics. Edible electronics are made by Food and Drug Administration (FDA) certified edible materials which can be eaten and digested by human body. Different from implantable electronics, test or treatment using edible electronics doesn’t require operations and perioperative complications. This dissertation bridges the food industry, material sciences, device fabrication, and biomedical engineering by demonstrating edible supercapacitors and electronic components and devices such as pH sensor. Edible supercapacitors were fabricated using food materials from grocery store. 5 of them were connected in series to power a snake camera. Tests result showed that the current generated by supercapacitor have the ability to kill bacteria. Next more food, processed food and non-toxic level electronic materials were investigated. A “preferred food kit” was created for component fabrication based on the investigation. Some edible electronic components, such as wires, resistor, inductor, etc., were developed and characterized utilizing the preferred food kit. These components make it possible to fabricate edible electronic/device in the future work. Some edible electronic components were integrated into an edible electronic system/device. Then edible pH sensor was introduced and fabricated. This edible pH sensor can be swallowed and test pH of gastric fluid. PH can be read in a phone within seconds after the pH sensor was swallowed. As a side project, an edible double network gel electrolyte was synthesized for the edible supercapacitor. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2019

Supercapacitors, as promising energy storage devices, have been of interest for their long lifespan compared to secondary batteries, high capacitance and excellent reliability compared to conventional dielectric capacitors. Transition metal oxides can be applied as the electrode materials for pseudocapacitors and offer a much higher specific capacitance. Co3O4 is one of the most investigated transition metal oxides for supercapacitor. Besides simple monometallic oxides, bimetallic transition oxides have recently drawn growing attention in electrochemical energy storage. They present many unique properties such as achievable oxidation states, high electrical conductivities because of the coexistence of two different cations in a single crystal structure. This study focuses on the bimetallic iron cobalt oxide based materials for the application of energy storage. We selected iron as the substituent in spinel Co3O4, by virtue of its abundant and harmless character. Four types of iron cobalt oxides based electrode materials with different morphologies and components have been synthesized for the first time. The hydrothermal method was the main strategy for the synthesis of iron cobalt based materials, which achieved the control of morphology and ratio of components. Multiple characterization methods, including SEM, TEM, XRD, XPS, TGA, BET, have been applied to study the morphologies and nano/submicron structures. The electrochemical properties of as-fabricated samples were performed by electrochemical workstation. In addition, in order to investigate the practical application of electrode materials, asymmetric supercapacitors have been assembled by using as-prepared samples as the positive electrodes and activated carbon as the negative electrodes.

To meet the predicted increase in demand for energy storage in tomorrow's society, the development of inexpensive, flexible, lightweight and sustainable energy-storage materials is essential. In this respect, devices based on electroactive organic molecules, such as conducting polymers, are highly interesting. The aim of this thesis was to evaluate the use of nanocellulose as a matrix material in composites of cellulose and the electroactive polymer polypyrrole (PPy), and the use of these composites in all-polymer paper-based energy-storage devices.   Pyrrole was polymerized using FeCl3 onto cellulose nanofibers in the form of a hydrogel. The resulting PPy-coated fibers were washed with water and dried into a high surface area, conductive paper material. Variations in the drying technique provided a way of controlling the porosity and the surface area of wood-based cellulose nanofibers, as the properties of the cellulose were found to have a large influence on the composite structure. Different nanocellulose fibers, of algal and wood origin, were evaluated as the reinforcing phase in the conductive composites. These materials had conductivities of 1–6 S/cm and specific surface areas of up to 246 m2/g at PPy weight fractions around 67%.   Symmetrical supercapacitor devices with algae-based nanocellulose-PPy electrodes and an aqueous electrolyte showed specific charge capacities of around 15 mAh/g and specific capacitances of around 35 F/g, normalized with respect to the dry electrode weight. Potentiostatic charging of the devices was suggested as a way to make use of the rapid oxidation and reduction processes in these materials, thus minimizing the charging time and the effect of the IR drop in the device, and ensuring charging to the right potential. Repeated charging and discharging of the devices revealed a 10–20% loss in capacity over 10 000 cycles. Upon up-scaling of the devices, it was found that an improved cell design giving a lower cell resistance was needed in order to maintain high charge and discharge rates.   The main advantages of the presented concept of nanocellulose-PPy-based electrical energy storage include the eco-friendly raw materials, an up-scalable and potentially cost-effective production process, safe operation, and the controllable porosity and moldability offered by the nanocellulose fiber matrix. Integrating energy storage devices into paper could lead to un- precedented opportunities for new types of consumer electronics. Future research efforts should be directed at increasing the energy density and improving the stability of this type of device as well as advancing the fundamental understanding of the current limitations of these properties.

Porous carbons are versatile materials with applications in different fields. They are used in filtration, separation and sequestration of fluids and gases, as conductive additives in many energy storage materials, as coloring agents, as pharmaceutical and food additives, and in many other vital technologies. Porous carbons produced by pyrolysis and activation of organic precursors commonly suffer from poorly controlled morphology, microstructure, chemistry, and pore structure. In addition, the poorly controlled parameters of porous carbons make it challenging to elucidate the underlying key physical parameters controlling their performance in energy storage devices, including electrochemical capacitors (ECs) and lead-acid batteries (LABs). Zeolite-templated carbons (ZTCs) are a novel class of porous carbon materials with uniform and controllable pore size, microstructure, morphology, and chemistry. In spite of their attractive properties, they have never been explored for use in LABs and their studies for ECs have been very limited. Here I report a systematic study of ZTCs applications in ECs operating at temperatures as low as - 70 C and in LABs. Greatly improved power and energy performance, compared to state of the art devices, has been demonstrated in the investigated ECs. Moreover, the application of ZTCs in LABs has resulted in a dramatic enhancement of their cycle life and power and energy densities.

Presently there are deep concerns over the environmental consequences and the consumption of non-renewable energy sources, with the accelerated greenhouse effect, triggered enormous interest in the use of renewable energy sources e.g., solar, hydropower, wind and geothermal. However the intermittent nature of harvesting renewable energy sources has recently gained considerable attention in the alternative reliable, cost effective, and environmentally friendly energy storage devices. The supercapacitor and lithium ion batteries are considered more efficient electrical energy storage devices than conventional energy storage systems. Both devices have many useful and important applications; they could be an excellent source for high power and high energy density, especially in portable electronic devices and Electrical Vehicles (EVs) or Hybrid Electrical Vehicles (HEVs). In order to make the efficient usage of these stationary energy storage devices, state of the art research on new and advanced electrode materials is highly needed. The aim of this dissertation is to investigate the scope of graphene/metal oxide-conducting polymer nanocomposites electrodes for light weight, high power density and wider voltage window supercapacitor devices. The facile chemical polymerization approach was used to synthesize the aromatic and heterocyclic conducting polymer nanocomposites. For aromatic nanocomposites, several materials were synthesized includes ZnO-PANI, ZnO/G-PANI,RuO2-PANI and G-PANI. Subsequently these materials have been characterized by physical, structural techniques e.g Raman Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), Xray-Diffraction (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM). In addition to material characterization the prepared material was also characterized by electrochemical measurements using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chrono potentiometry for supercapacitor electrodes. Since graphene is a two-dimensional single-atom-thick sp2 hybridized carbon structure due to its extraordinary characteristic, high electrical conductivity, chemical stability and large theoretical surface area (over 2600 m2 g−1) has gained immense interest in the future generation of renewable energy devices. Therefore, among all aromatic based nanocomposites, the Graphene-Polyaniline (G-PANI) rendered promisingly high specific capacitance around 440 F/g with the excellent cyclic stability. The higher specific capacitance of G-PANI might be due to the high conductivity and superior electrochemical properties of graphene in G-PANI nanocomposites. However, besides the G-PANI, other aromatic nanocomposites e.g., RuO2-PANI, ZnO-PANI and G/ZnO-PANI also showed the potential of low cost and flexible supercapacitor electrodes with the reasonably good specific capacitance as 360 F/g, 300 F/g, and 275 F/g. We have further investigated the role of conductivity by adding different amount of graphene in G-PANI nanocomposites to optimize device performance with the specific capacitance and columbic efficiency of 440 F/g and 90% respectively.Further the other important parameters, relate with the electrode thickness, type of electrolytes, concentration of electrolytes and the effect of the solvent has also been studied to achieve the overall performance and reliability of the device. Moreover, in order to have the comprehensive study of conducting polymer besides the aromatic conducting polymer the heterocyclic polymers e.g., polythiophene and poly (3, 4-ethylenedioxythiophenes) (PEDOT) nanocomposites were studied at length to evaluate their role for the cost effective, large surface area and flexible green energy storage devices and has shown great prospects for commercial application. Therefore, G-Cps nanocomposites have proved to be a promising electrode material choice to facilitate the ionic diffusion and contact of the electrolytes to improve the specific capacitance and performance of the device.

The objective of this dissertation is to develop task scheduling guidelines and algorithms for wireless sensor nodes that harvest energy from ambient environment and use supercapacitor based storage systems to buffer the harvested energy. This dissertation makes five contributions. First, a physics based equivalent circuit model for supercapacitors is developed. The variable leakage resistance (VLR) model takes into account three mechanisms of supercapacitors: voltage dependency of capacitance, charge redistribution, and self-discharge. Second, the effects of time and supercapacitor initial state on supercapacitor voltage change and energy loss during charge redistribution are investigated. Third, the task scheduling problem in supercapacitor based environmentally powered wireless sensor nodes is studied qualitatively. The impacts of supercapacitor state and energy harvesting on task scheduling are examined. Task scheduling rules are developed. Fourth, the task scheduling problem in supercapacitor based environmentally powered wireless sensor nodes is studied quantitatively. The modified earliest deadline first (MEDF) algorithm is developed to schedule nonpreemptable tasks without precedence constraints. Finally, the modified first in first out (MFIFO) algorithm is proposed to schedule nonpreemptable tasks with precedence constraints. The MEDF and MFIFO algorithms take into account energy constraints of tasks in addition to timing constraints. The MEDF and MFIFO algorithms improve the energy performance and maintain the timing performance of the earliest deadline first (EDF) and first in first out (FIFO) algorithms, respectively.

Graphene has great potential for energy storage and conversion applications due to its outstanding electrical conductivity, large surface area and chemical stability. However, the pristine graphene offers unsatisfactory performance as a result of several intrinsic limitations such as aggregation and inertness. The functionalization of graphene is considered as a powerful way to modify the physical and chemical properties of graphene, and improve the material performance, which unfortunately still being preliminary and need further knowledge on controllable functionalization methods and the structure-property relationships. This thesis aims to provide in-depth understanding on these aspects. We firstly explored oxygen-functionalized graphene for supercapacitor electrodes. A mild solvothermal method was developed for graphene preparation from the reduction of graphene oxide; the solvent-dependent reduction kinetics is an interesting finding in this method that could be attributed to the solvent-graphene oxide interactions. Using the solvothermal method, oxygen-functionalized graphene with controlled density of oxygen functional groups was prepared by tuning the reduction time. The oxygen-containing groups, primarily phenols and quinones, reduce the graphene aggregation, improve the wetting properties and introduce the pseudocapacitance. Consequently, excellent supercapacitive performance was achieved. Nitrogen-doped graphene was synthesized by the pyrolysis of graphene oxide with nitrogen-containing molecules and used as an electrocatalyst for oxygen reduction reactions. We achieved the structural control of the nitrogen-doped graphene, mainly the content of graphitic nitrogen, by manipulating the pyrolysis temperature and the structure of nitrogen-containing molecules; these experiments help understand the evolution of the bonding configurations of nitrogen dopants during pyrolysis. Superior catalytic activity of the prepared nitrogen-doped graphene was found, due to the enriched content of graphitic nitrogen that is most active for the oxygen reduction reaction. Moreover, we demonstrated a facile strategy of producing superhydrophobic octadecylamine-functionalized graphite oxide films. The long hydrocarbon chain in octadecylamine reduces the surface energy of the graphene oxide film, resulting in a high water contact angle and low hysteresis. The reaction mechanism and the effect of hydrocarbon chain length were systematically investigated. In addition to the researches on graphene-based materials, some results on advanced carbon nanomaterials and polymer composites for electronic packaging will also be discussed as appendix to the thesis. These include carbon nanotube-based capacitive deionizer and gas sensor, and hexagonal boron nitride-epoxy composites for high thermal conductivity underfill.

Energy storage devices are generally evaluated on two main requirements; power and energy. In supercapacitors these two performance criteria are altered by the capacitance, resistance and voltage. (For complete abstract open document)

abstract: The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all the processes at the interface. The following work presents different systems in which the electrode-electrolyte interface is highly important. The first is a charge storage electrode utilizing percolation theory to develop an electrode architecture producing high capacities. This is followed by Zn deposition in an ionic liquid in which the deposition morphology is highly dependant on the charge transfer and surface adsorption at the interface. Electrode Architecture: A three-dimensional manganese oxide supercapacitor electrode architecture is synthesized by leveraging percolation theory to develop a hierarchically designed tri-continuous percolated network. The three percolated phases include a faradaically-active material, electrically conductive material and pore-former templated void space. The micropores create pathways for ionic conductivity, while the nanoscale electrically conducting phase provides both bulk conductivity and local electron transfer with the electrochemically active phase. Zn Electrodeposition: Zn redox in air and water stable N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [C2nmm][NTf2] is presented. Under various conditions, characterization of overpotential, kinetics and diffusion of Zn species and morphological evolution as a function of overpotential and Zn concentration are analyzed. The surface stress evolution during Zn deposition is examined where grain size and texturing play significant rolls in compressive stress generation. Morphological repeatability in the ILs led to a novel study of purity in ionic liquids where it is found that surface adsorption of residual amine and chloride from the organic synthesis affect growth characteristics. The drivers of this work are to understand the processes occurring at the electrode-electrolyte interface and with that knowledge, engineer systems yielding optimal performance. With this in mind, the design of a bulk supercapacitor electrode architecture with excellent composite specific capacitances, as well as develop conditions producing ideal Zn deposition morphologies was completed. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

abstract: Carbon nanomaterials have caught tremendous attention in the last few decades due to their unique physical and chemical properties. Tremendous effort has been made to develop new synthesis techniques for carbon nanomaterials and investigate their properties for different applications. In this work, carbon nanospheres (CNSs), carbon foams (CF), and single-walled carbon nanotubes (SWNTs) were studied for various applications, including water treatment, energy storage, actuators, and sensors. A facile spray pyrolysis synthesis technique was developed to synthesize individual CNSs with specific surface area (SSA) up to 1106 m2/g. The hollow CNSs showed adsorption of up to 300 mg rhodamine B dye per gram carbon, which is more than 15 times higher than that observed for conventional carbon black. They were also evaluated as adsorbents for removal of arsenate and selenate from water and displayed good binding to both species, outperforming commercial activated carbons for arsenate removal in pH > 8. When evaluated as supercapacitor electrode materials, specific capacitances of up to 112 F/g at a current density of 0.1 A/g were observed. When used as Li-ion battery anode materials, the CNSs achieved a discharge capacity of 270 mAh/g at a current density of 372 mA/g (1C), which is 4-fold higher than that of commercial graphite anode. Carbon foams were synthesized using direct pyrolysis and had SSA up to 2340 m2/g. When used as supercapacitor electrode materials, a specific capacitance up to 280 F/g was achieved at current density of 0.1 A/g and remained as high as 207 F/g, even at a high current density of 10 A/g. A printed walking robot was made from common plastic films and coatings of SWNTs. The solid-state thermal bimorph actuators were multifunctional energy transducers powered by heat, light, or electricity. The actuators were also investigated for photo/thermal detection. Electrochemical actuators based on MnO2 were also studied for potential underwater applications. SWNTs were also used to fabricate printable electrodes for trace Cr(VI) detection, which displayed sensitivity up to 500 nA/ppb for Cr(VI). The limit of detection was shown to be as low as 5 ppb. A flow detection system based on CNT/printed electrodes was also demonstrated. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2015