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No. of bitstreams: 1 klem_ms_me_bauru.pdf: 4012228 bytes, checksum: f1af56b8b0b9f5e19934e197b4755874 (MD5) Previous issue date: 2017-09-27 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Realizou-se primeiramente neste trabalho o estudo de um supercapacitor padrão utilizando coletores de aço inox e eletrodos de grafite Aquadag®. Este dispositivo apresentou uma capacitância máxima de 22 F/g, e seu espectro de impedância foi modelado por um circuito do tipo R(C(RW))(RC)(RC). Com este dispositivo foi possível testar os métodos de produção dos supercapacitores, e identificar as características desejáveis no supercapacitor impresso. Foram testadas duas técnicas de impressão distintas visando o preparo de eletrodos e coletores de corrente impressos em papel para aplicação em supercapacitores. O material ativo utilizado nos eletrodos foi basicamente o PEDOT:PSS, com a adição de óxido de grafeno, grafite aquadag® e nanotubos de carbono de paredes múltiplas (MWNT) para a formação compósitos condutores. Foram realizadas caracterizações morfológicas e elétricas nas superfícies dos eletrodos impressos em papel filtro, vegetal e sulfite. Os eletrodos produzidos por serigrafia utilizando o compósito de PEDOT:PSS com MWNT impressos em papel filtro apresentaram os menores resultados de resistência de folha (17 Ω/sqr), sendo assim utilizados na produção dos supercapacitores. O supercapacitor impresso em papel apresentou um bom comportamento capacitivo através de medidas de espectroscopia de impedância e voltametria cíclica. A curva de impedância foi modelada através de um circuito do tipo R(RC)(C(RQ))(RC), evidenciando uma alta capacitância de dupla camada. Foi encontrada uma capacitância específica máxima de 20,3 F/g.para uma corrente de carga/descarga de 1 mA, e uma resistência equivalente em série de 60 Ω. Estes valores levaram a densidades de energia e potência de 3,1 Wh/kg e 420 W/kg, respectivamente. Realizaram-se também simulações e ajustes a partir das análises em corrente contínua, usando um circuito equivalente RC paralelo com uma resistência em série. Através destes ajustes foi possível extrair parâmetros de grande importância na utilização prática dos supercapacitores. / In this study, we first produced a standard supercapacitor using stainless steel collectors and Aquadag® graphite electrodes. The device exhibited a maximum capacitance of 22 F/g, and an R(C(RW))(RC)(RC) circuit modeled its impedance spectrum. With this device was possible to test the production methods of supercapacitors, and identify its desirable characteristics. Two different printing techniques were tested to produce electrodes/current collectors. The active material used in the electrodes was PEDOT: PSS, with addition of graphene oxide, Aquadag® graphite and multi-walled carbon nanotubes (MWNT), in order to obtain conductive composites. Morphological and electrical characterizations were performed over the surfaces of printed electrodes onto filter, vegetable and bond paper. The electrode produced by screen-printing using the PEDOT: PSS/MWNT composite printed onto filter paper exhibited low sheet resistance (17 Ω /sqr), being used in the production of supercapacitors. Printed supercapacitor showed good capacitive behavior through impedance spectroscopy and cyclic voltammetry measurements. An R(RC)(C(RQ)(RC) circuit modeled the impedance spectrum, evidencing a high double layer capacitance. A maximum specific capacitance of 20.3 F / g was found for a charge/discharge current of 1 mA, and an equivalent series resistance of 60 Ω. These values led to energy and power densities of 3.1 Wh / kg and 420 W / kg, respectively. Simulations and curve fitting were also performed from DC analyzes, using a parallel RC circuit coupled with a series resistance, obtaining important parameters for the practical use of supercapacitors. / FAPESP: 2015/18091-8

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.