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Development and 3D Printing of Intrinsically Stretchable Materials for MicrosupercapacitorsEngman, Alexander January 2020 (has links)
The purpose of this thesis is to develop a simple Direct Ink Writing (DIW) method for fabricating intrinsically stretchable microsupercapacitors as ef- fective on-chip energy storage devices for the emerging stretchable electron- ics. Using the printing method for fabricating intrinsically stretchable elec- tronic components remains a novel approach. In this thesis, interdigitated structures of intrinsically stretchable electrodes were printed on a stretchable thermoplastic polyurethane (TPU) substrate using a formulated ink based on Poly(3,4-ethylenedioxythiophene):Polystyrene Sulfonate. Formulated elec- trolytes based on Poly(4-styrene Sulfonic Acid) and Phosphoric Acid were applied to the electrodes to complete the fabrication of microsupercapacitors. Cyclic Voltammetry (CV), Galvanostatic Charge-Discharge (GCD) and Elec- trochemical Impedance Spectroscopy (EIS) were used to characterize the per- formance of the devices. The stretchability of the electrodes was also mea- sured. Results from CV-measurements revealed a maximum capacitance of740 µF cm−2 at a scan rate of 5 mV s−1. GCD-measurements showed a capaci- tance of 952 µF cm−2 for the same device and an equivalent series resistance of approximately 7 kΩ. The printed electrodes exhibited a stretchability of 80%. The results show the feasibility of fabricating intrinsically stretchable energystorage devices using commercially available materials and a simple 3D print- ing technique. This method could be used as a high-throughput and low-cost method for stretchable electronics applications. / Syftet med detta arbete är att utveckla en simpel Direct Ink Writing (DIW) metod för framställning av intrinsiskt sträckbara mikrosuperkondensatorer som effektiva on-chip energilagrinsenheter i kommande sträckbar elektronik. Användandet av DIW för att tillverka intrinsiskt sträckbara elektroniska kom- ponenter är ett nytt tillvägagångssätt. I detta arbete trycktes interdigiterade strukturer av intrinsiskt sträckbara elektroder på ett sträckbart termoplastiskt polyuretan (TPU) substrat genom att använda ett formulerat bläck baserat på Poly(3,4-etylendioxitiofen):Polystyren Sulfonat (PEDOT:PSS). Formuler- ade elektrolyter baserade på Poly(4-styrensulfonsyra) och Fosforsyra applicer- ades på elektroderna för att färdigställa tillverkningen av mikrosuperkonden- satorer. Cyklisk Voltammetri (CV), Galvanostatisk uppladdning-urladdning (eng. GCD) och Elektrokemisk Impedansspektroskopi (EIS) användes för att karaktärisera enheternas prestanda. Bläckets sträckbarhet uppmättes också. Resultaten från CV-mätningar visade att den maximala kapacitansen var 742µF cm−2 vid skanningsfrekvensen 5 mV s−1. Kapacitansen från GCD-mätningar var 952 µF cm−2 för samma enhet och den ekvivalenta serieresistansen var cirka 7 kΩ. Sträckbarheten som de tryckta elektroderna uppvisade var 80%. . Re- sultaten påvisar möjligheten att kunna framställa intrinsiskt sträckbara en-ergilagringsenheter genom att använda kommersiellt tillgängliga material och en simpel metod för friformsframställning. Denna metod skulle kunna använ- das för att framställa sträckbara elektroniska komponenter till låg kostnad och med hög produktionstakt.
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Polyacrylonitrile-based Hierarchical Porous Carbons for SupercapacitorsZhu, Shijin 19 September 2022 (has links)
The globally increasing energy demand that results from the rapid development of modern society has created intensive attention towards the importance of energy efficiency. The areas of energy storage and energy conversion have become one of the most important topics in scientific community at present. As new generation energy storage elements, supercapacitors have exhibited promising practical prospects in the information, transportation, electronics and other sectors due to their charge and discharge performance at high rate, high power density as well as long cycle life. Energy density, including gravimetric energy density, areal energy density and volumetric energy density, is one of the most critical indicator evaluating the performance of supercapacitors. The electrochemical performance of supercapacitors depends mainly on the electrochemical activities and kinetic properties of electrode materials. Carbonaceous materials are deemed to be highly promising, and therefore are extensively investigated energy storage materials for supercapacitors because of their environmental friendliness, low-cost production and outstanding chemical inertness during charging-discharging processes. The specific surface area has been long thought to be the main factor influencing the capacitance of carbonaceous materials. However, the pore structure is of similar importance. High specific surface areas are always arising from a high content of micropores. However, pore radii in the sub-nanometer range impede the ionic charge transfer ability significantly and thus cause a damping of capacitance.
In this thesis, hierarchical porous carbons and their composite materials were fabricated by using polyacrylonitrile as carbon precursor for a tailored step-by-step pore forming method, including phase inversion, CaCO3 activation and KOH activation. The materials were thoroughly characterized by XRD, SEM, TEM, BET, XPS and Raman spectroscopy to ascertain the chemical and structural features. The electrochemical properties were studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) in detail to analyze the pore effect, which strongly influence their electrochemical properties.
Porous carbons with high specific surface areas up to 2315 m2 g-1 and high pore volume of 1.9 cm3·g-1 were prepared. A step-wise pore forming method was employed to ensure a high specific surface area and high content of macro/mesopore at the same time. The relationship between pore structure, electrochemical capacitance and rate capability was investigated by changing the content of micropores. For a same specific surface area, a higher micropore content led to a lower capacitance and poorer rate capability. Based on these results, the capacitance was optimized to be 286.8 F g-1.
The areal energy density of the supercapacitors can be improved by increasing the mass loading in a certain area directly. However, insufficient electrochemical reaction may be caused by a lack of unhindered electrical and ionic charge transfer routes, resulting in inefficient material utilization. This problem is addressed by designing hierarchical pore structures with embedded conductive additives. Thus, hierarchical porous carbons were modified by embedding carbon nanotubes (CNTs), followed by coverage with thin layers of birnessite. Owing to the hierarchical pore design and the very high pore volume, the birnessite coverage did not cause pore blocking. At the same time, an intimate contact between carbon and birnessite was established. A high area energy density of 627.8 μWh·cm-2 was obtained based on an optimized mass loading of 13.9 mg cm-2.
The volumetric energy density of supercapacitors was determined by the density and porosity of active materials. Similarly, the dense active materials not always generate high specific capacitance because of an increased dead mass. However, too porous active materials do not provide sufficient volumetric capacitance due to a waste of space. Thus, density and porosity must be balanced by hierarchical pore structure design so that all pores are interconnected and can be accessed by ions. At the same time, the content of these pores should be as low as possible to save space. Based on the results, highly hierarchical porous carbons were synthesized and embedded into conductive carbon foam to combine electronic conductivity with ionic transfer. In that way, a volumetric energy density as high as 19.44 µWh cm-3 at a volumetric power density of 500 mW cm-3 was generated.
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