Investigation of Bipolar Electrochemically Exfoliated Graphene for Supercapacitor Applications

Developing a reliable, simple, cost-efficient and eco-friendly method for scale-up production of high-quality graphene-based materials is essential for the broad applications of graphene. Up to now, various manufacturing methods have been employed for synthesizing high quality graphene, however aggregation and restacking has been a major issue and the majority of commercially available graphene products are actually graphite microplates. In this study, bipolar electrochemistry techniques have been used to exfoliate and deposit graphene nanosheets in a single-step process to enable high performance device application. In the first part of this study, bipolar electrochemistry concept is utilized to design a single-step and controllable process for simultaneously exfoliating a graphite source and depositing both graphene oxide (GO) and reduced graphene oxide (rGO) layers on conductive substrates. The electrochemical performance of the fabricated graphene-based materials as the electrode for supercapacitors has been investigated. Areal capacitance of 1.932 mF cm-2 for the rGO, and 0.404 mF cm-2 for GO at a scan rate of 2 mV s-1 were achieved. Moreover, a cut-off frequency of 1820 Hz was obtained, which is a promising characteristic for AC filtering applications. Although the physicochemical characteristics of produced graphene have been evaluated in the first part, the exfoliation and deposition mechanisms were still unclear. In the second part of this dissertation, a novel modified BPE system with an electrically connected graphite-platinum couple acting as the bipolar electrode has been designed in order to decouple and investigate the contribution of anodic/cathodic exfoliation and deposition of graphene in the BPE process. Electron microscopy and infrared spectroscopy results indicate that both anodic and cathodic exfoliation of graphene could take place regardless of the type of polarization; however, the morphology and deposition rate highly depend on the polarization. Furthermore, the graphene fabricated by anodic exfoliation was found to show higher levels of oxidation compared to the graphene produced by cathodic exfoliation. In the last part of this study, for the first time, a vertically aligned graphene layer was deposited on a micro-sized interdigitated gold current collector by a modified bipolar electrochemistry method. Both time domain and frequency domain electrochemical performance of on-chip micro-supercapacitors (MSCs) were evaluated. An areal capacity of 640.9 μF cm-2 at a scan rate of 2 mV s-1 and 239.31 μF cm-2 at discharge current density of 25 μA cm-2 was delivered with an excellent cyclability. Most importantly, the MSC exhibited a very fast response (cut-off frequency of 3486 Hz) and very close to ideal performance (phase angle reached -83.2°) at low frequencies. For the first time, this dissertation reported the modified BPE method as a novel approach for three in one exfoliation, deposition and reduction of high-quality graphene with vertically aligned and porous structure. The unique design of the BPE cell enabled the author to study the BPE mechanisms and measure the bipolar current for the first time. The method could successfully be employed to fabricate fast response microsupercapacitors based on vertically aligned graphene nanosheets

Novel application of electrochemical bipolar exfoliated graphene for highly sensitive disposable label-free cancer biomarker aptasensors

Label-free aptasensors can be a promising point-of-care biosensor for detecting various cancer diseases due to their selectivity, sensitivity, and lower cost of production and operation. In this study, a highly sensitive aptasensor based on gold-covered polyethylene terephthalate electrodes (PET/Au) decorated with bipolar exfoliated graphene is proposed as a possible contender for disposable label-free aptasensor applications. Bipolar electrochemical exfoliation enables simultaneous exfoliation, reduction, and deposition of graphene nanosheets on prospective electrodes. Our comparative study confirms that the bipolar exfoliated graphene deposited on the negative feeding electrode (i.e., reduced graphene oxide) possesses better electrochemical properties for aptasensing. The optimized aptasensor based on bipolar exfoliated graphene deposited on PET/Au electrodes exhibits a highly sensitive response of 4.07 μA log c−1(unit ofc, pM) which is linear in the range of 0.0007-20 nM, and has a low limit of detection of 0.65 pM (S/N = 3). The aptasensor establishes highly selective performance with a stability of 91.2% after 6 days. This study demonstrates that bipolar electrochemistry is a simple yet efficient technique that could provide high-quality graphene for biosensing applications. Considering its simplicity and efficiency, the BPE technique promises the development of feasible and affordable lab-on-chip and point-of-care cancer diagnosis technologies

Bipolar electrochem graphene microsupercaps

This study introduces a successful modification of the bipolar electrochemistry (BPE) method to efficiently produce and deposit high-quality reduced graphene oxide onto a conductive substrate. This innovative approach integrates material production and device fabrication into a single-step process that is straightforward, controllable, cost-efficient, and environmentally friendly. Microstructural analysis of the deposited material reveals the formation of oriented graphene sheets on the substrate. For micro-supercapacitor fabrication, interdigitated gold microelectrode arrays are generated through regular photolithography and subsequently employed as the conductive substrate in the BPE process. The electrochemical assessment of the fabricated device through cyclic voltammetry and galvanostatic charge/discharge verifies its outstanding specific areal capacitance. Notably, electrochemical impedance spectroscopy unveils exceptional high-frequency responses, promising potential applications in AC/DC filter systems. A comprehensive presentation of the detailed results will be delivered at the upcoming conference

Design Rules for a Wearable Micro-Fabricated Piezo-Resistive Pressure Sensor

Wearable flexible piezo-resistive pressure sensors hold a wide-ranging potential in human health monitoring, electronic skin, robotic limbs, and other human–machine interfaces. Out of the most successful recent efforts for arterial pulse monitoring are sensors with micro-patterned conductive elastomers. However, a low-current output signal (typically in the range of nano-amperes) and bulky and expensive measurement equipment for useful signal acquisition inhibits their wearability. Herein, through a finite element analysis we establish the design rules for a highly sensitive piezo-resistive pressure sensor with an output that is high enough to be detectable by simple and inexpensive circuits and therefore ensure wearability. We also show that, out of four frequently reported micro-feature shapes in micro-patterned piezo-resistive sensors, the micro-dome and micro-pyramid yield the highest sensitivity. Furthermore, investigations of different conductivity values of micro-patterned elastomers found that coating the elastomer with a conductive material (usually metallic) leads to higher current response when compared to composited conductive elastomers. Finally, the geometric parameters and spatial configurations of micro-pyramid design of piezo-resistive sensors were optimized. The results show that an enhanced sensitivity and higher current output is achieved by the lower spatial density configuration of three micro-features per millimeter length, a smaller feature size of around 100 μm, and a 60–50 degrees pyramid angle

Unraveling the Corrosion of the Ti–6Al–4V Orthopedic Alloy in Phosphate-Buffered Saline (PBS) Solution: Influence of Frequency and Potential

This paper addresses the interplay between electrical fields in the human body and the corrosion behavior of Ti-6Al-4V alloy, a prevalent orthopedic material. The study investigates the impact of alternative electrical signals at different frequencies on the alloy’s electrochemical behavior in a simulated body environment. The human body always has natural sinusoidal potential due to, e.g., heart palpitations and brain/nervous system activities. Ignoring such natural activities may lead to underestimating the corrosion performance of the Ti-6Al-4V alloy in the body. By analyzing anodic and cathodic responses and the net faradaic current induced by alternating current potential, the research sheds light on the influence of electrical fields on corrosion rates. Understanding these dynamics could lead to improved implant materials, mitigating corrosion-related challenges and enhancing implant performance over the long term. Results of this work indicated that frequent oxidation and reduction at certain frequencies may induce corrosion and hinder biomimetic apatite formation, impacting osseointegration. Natural alternative currents in the body affect the corrosion performance of Ti-based implant alloys, highlighting the need for consideration in biomedical applications