Supercapacitors (SCs) have generated significant interest due to their advantages including lightweight, rapid charge-discharge, good rate capability and high cyclic stability. Electrodes are one of the most important factors influencing the performance of SCs. MXene is a promising candidate for supercapacitor electrodes, which is a relatively new material with formula Mn+1XnTx, where M is a transitional metal, X stands for C or N, and Tx is surface terminations. Due to its multi-layered structure, high surface area and rich redox chemistry, good electrochemical performance can be expected. To further enhance the conductivity of the MXene electrodes, multi-walled carbon nanotubes (MCNT) were applied as the conducting additive. The as-fabricated composite electrodes showed reduced resistance and enhanced electrochemical performance. Advanced co-dispersants such as cationic celestine blue (CCB) and anionic catechol violet (ACV) were employed to improve the dispersion of components. CCB and ACV can adsorb strongly on the MXene and MCNT surface to form a homogenous suspension and thus improve the mixing between them. Another advanced dispersant 3,4,5-trihydroxybenzamide (THB) also showed adsorption on both MXene and MCNT particles, favored their dispersive mixing and improved electrochemical performance. Iron oxides are promising materials for negative electrodes for supercapacitors. The attempt to combine highly capacitive Fe3O4 with MXene-MCNT composites proved the synergistic effect of individual components. Investigation of Zn-doped FeOOH as high active mass loading anode with MCNT as conducting additive allowed for enhanced performance. Zn-Fe double hydroxide materials are promising for the fabrication of advanced supercapacitor electrodes. A safe and neutral Na2SO4 electrolyte was was beneficial for the development of asymmetric devices with enlarged voltage window. For cathodes working in an overlapping window with Zn-FeOOH anode, polypyrrole coated carbon nanotube electrode was fabricated with a comparable capacitance. The advanced dopant eriochrome cyanine R (ECR) allowed for the uniform thickness of PPy coating on MCNT and enhanced charge transfer between PPy and MCNT was achieved. Enhanced capacitive properties of cathodes and anodes at high active mass loading working in complimentary voltage windows allowed for fabrication of high-performance supercapacitor, which was a promising device for practical applications. / Thesis / Doctor of Philosophy (PhD) / To reduce the consumption of fossil fuel and meet the surging demand of electric energy, intensive attention has been drawn to new energy storage device, such as capacitors, batteries and supercapacitors. Owing to their higher energy density compared with conventional capacitors and higher power density compared with batteries, supercapacitors are attracting tremendous research interest. The advantages of supercapacitors are fast charge-discharge rate, high power and energy density and excellent cyclic stability. The objective of this work was to fabricate high-performance supercapacitor devices based on the development of advanced electrode materials. MXene and Fe-based composite materials were synthesized by conceptually new colloidal approach and some efficient dispersants were developed during the process. The enlarged voltage window and superior performance were recorded for asymmetric supercapacitors. The results presented in this work showed much more promising performance compared with that reported in the literature and paved the way for future research.

Ti3C2Tx MXene has gained significant attention for biosensor and supercapacitor applications because of 1) its metallic conductivity, large surface area, and reversible surface redox reactions led to high pseudocapacitance and high-rate performance; 2) the unique 2D morphology and high biocompatibility drive great motivation to design advanced nanohybrid systems with bio-receptors; 3) the high density of surface functional groups offers improved biomolecule loading and flexibility for further functionalization. In this thesis, biosensors and electrochemical energy storage devices based on Ti3C2Tx MXene are proposed. Specifically, Ti3C2Tx nanosheets were uniformly functionalized with aminosilane to provide a covalent binding for the immobilized bio-receptor (anti-CEA) for label-free ultrasensitive detection of cancer biomarker (CEA). [Ru(NH3)6]3+ is discovered as the preferable redox probe for biosensing. The fabricated MXene-based sensor exhibits a more comprehensive linear detection range and high sensitivity. Further, Ti3C2Tx nanosheets were introduced as the transducer, and Ti3C2Tx /Prussian blue (Ti3C2Tx/PB) composite was synthesized for sensitive detection of hydrogen peroxide. Meanwhile, a one-step patterning process for highly conductive nitrogen-doped laser-scribed graphene (N-LSG) has been developed. Working electrodes (Ti3C2Tx/PB/N-LSG) were extended by using different enzymes for corresponding biomarker detection, namely glucose, lactate, and alcohol. The enzyme/Ti3C2Tx/PB/N-LSG electrodes exhibit significantly improved electrocatalytic activity and outperform previously reported on-chip graphene-based biosensors. Further, a stretchable, wearable, and multifunctional Ti3C2Tx-based biosensor were designed for durable and sensitive detection of biomarkers in sweat. A unique modular design enabled a simple exchange of the specific sensing electrode to target the desired analytes, while an implemented three-phase interface design for the constant supply of oxygen led to superior sensor performance and stability. As expected, during in-vitro perspiration monitoring of human subjects, the physiochemistry signals (glucose and lactate level) could be measured simultaneously with high sensitivity and good repeatability, outperforming traditional reported graphene/PB- and CNTs/PB-based biosensors. Finally, we developed an in-plane hybrid microsupercapacitor, employing battery-type CuFe-Prussian blue analog (CuFe-PBA) as the positive electrode and pseudocapacitive Ti3C2Tx as the negative electrode. Due to the excellent match of the two types of high-rate performance materials in proton-based electrolyte, the designed on-chip device achieved excellent electrochemical performance.

Wearables for health monitoring are rapidly advancing as evidenced by the number of wearable products on the market. More recently, the US Food and Drug Administration approved the Apple Watch for heart monitoring, indicating that wearables are going to be a part of our lives sooner than expected. However, wearables are still based on rigid, conventional electronic materials and fabrication procedures. The use of flexible conducting materials fabricated on flexible substrates allows for more comprehensive health monitoring because of the seamless integration and conformability of such devices with the human skin. Many materials can be used to fabricate flexible electronics such as thin metals, liquid metals, conducting polymers, and 1D and 2D materials. Ti3C2 MXene is a promising 2D material that shows flexibility as well as desirable electronic properties. Ti3C2 MXene is easily processable in aqueous solutions and can be an excellent functional ink for inkjet printing. Here we report the fabrication and the properties of Ti3C2 MXene films inkjet-printed from aqueous dispersions with a nonionic surfactant. The films are uniform and formed with only a few layers on glass and tattoo paper. The MXene films printed on tattoo are used to record ECG signals with comparable signal-to-noise ratio to commercial Ag/AgCl electrodes despite the absence of gels to lower skin-contact impedance. Due to their high charge storage capacity and mixed (ionic and electronic) conductivity, inkjet-printed MXene films open up a new avenue for applications beyond health monitoring.

In this thesis, we capitalize on the two-dimensional (2D) nature of MXenes by using them as precursors for the synthesis of 2D functional material. MXenes are easily intercalated with monovalent cations K, Na, Li due to their expanded d-spacing after etching. Based on these ideas, we have developed new synthesis processes of texture functional materials using MXenes as precursors. We have successfully synthesized two-dimensional Nb2C MXene based high aspect ratio ferroelectric potassium niobate (KNbO3) and well-oriented photoluminescent rare earth doped lithium niobate (LiNbO3:Pr3+) crystals, which have great potential in opto-electronics applications. In addition, this thesis demonstrates that poly(vinylidene fluoride) (PVDF)-based percolative composites using two-dimensional (2D) MXene nanosheets as fillers exhibit significantly enhanced dielectric permittivity. Furthermore, we fabricated MXene/in-plane aligned PVDF photo-thermo-mechanical solar tracking actuator for energy harvesting applications.

Acetone in exhaled breath is gaining attention as a non-invasive means of quantifying blood glucose levels in Diabetics. This calls for development of novel biosensors for the detection of trace concentrations of acetone present in human breath. Traditional gas detection systems, such as GC/MS and chemiresistive sensors, are currently used for this purpose. However, these systems have limitations with regards to size, cost, and operating temperature. This work presents the K2W7O22/Ti3C2 nanocomposite sensor as breath acetone sensor that overcomes the limitations in traditional detection systems. Sensing experiments were conducted using 5 different sensor materials in varying ratios. KWO/Ti3C2 - ratio 2:1 (annealed) and KWO/Ti3C2 - ratio 2:1 (Unannealed) showed excellent sensitivity to 2.85ppm and 5.4ppm acetone concentration. These materials were then implemented in a prototype device. Material and device test results confirm the potentials of the novel KWO/Ti3C2 nanocomposite as a good sensor for breath acetone detection.

The adrenal medulla is the inner part of adrenal glands located above each kidney, that produces catecholamines. Neuroblastoma and pheochromocytoma are the most prevalent malignancies of the adrenal medulla. Quantitative diagnosis of urinary catecholamines using HPLC-coupled Mass detectors is the current method for the diagnosis of neuroblastoma and pheochromocytoma. There are two major problems with this approach, (i) Because the catecholamines concentrations have short half-life (10-100 s), a series of urine tests must be performed throughout 24hr, detecting each catecholamine separately, is inconvenient and time-consuming; (ii) mass detectors are expensive, bulky, and require highly skilled personal. Vanillylmandelic (VMA), and homavanillic acid (HVA) are the by-products of catecholamines and are emerging alternative biomarker for catecholamines due to their high stability. Here, we developed a rapid, sensitive, miniaturized, and cheaper sensing platform for simultaneous quantifications of dopamine (DA), VMA, and HVA, with the aid of iron single-atom catalysts (Fe-SACs), based electrochemical sensor. SACs are atomically distributed metal atoms that have a maximum atomic utility rate of nearly 100%, compared to 30% for traditional metal nanoparticles. MXene sheets are employed to stabilize Fe-SACs, where, the exposed lone pairs of MXene serve as sites covalently linking high-energy single Fe atoms. MXene/Fe-SACs were synthesized by treating Ti3C2TxMXene with Iron chloride via freeze-drying followed by annealing. The successful formation of the material was verified by state-of-the-art characterizations. The MXene/Fe-SACs show superior electrocatalytic performance to the commonly used Fe- nanomaterials. Then, it was coated on the electrode surface and used to analyze DA, VMA, and HVA simultaneously via cyclic voltammetry (CV) and square-wave voltammetry (SWV). Under optimized conditions, the MXene/Fe-SACs electrochemical sensor showed detection limits as low as 1 nM and a linear range between 1 nM-100 μM for DA, LOD of 5 nM & linear range of 10 nM-100 μM VMA, and LOD of 10 nM & linear range of 20 nM-100 μM HAV. The method proved successful in detecting biomarkers in (spiked) synthetic urine and human serum. Furthermore, the method was successfully demonstrated in the determination of DA release from PC12 live cells, suggesting the wide practical use of SACs in sensing catecholamines-related metabolites.

The emergence of micropower-type applications such as self-powered sensors and miniaturized electronic systems has increased interest in on-chip electrochemical energy storage such as microsupercapacitors. Microsupercapacitors (MSCs) are high rate and high power yet miniaturized versions of macroscopic supercapacitors. MSCs with planar configuration have higher power density at potentially comparable energy density to thin-film batteries, while possessing essentially infinite cycle life. They could also offer compatible integration with smart electronic devices on an integrated chip (IC). In this dissertation, state-of-the-art microsupercapacitors based on Ti3C2Tx MXene and other pseudocapacitive electrode materials are proposed. The proposed strategies involve engineering both intrinsic properties of materials, fabrication methods and device architecture.

Yes / Arsenic (As) contamination of surface water has become a global concern, especially for the third world countries, and it is imperative to develop advanced materials and an effective treatment method to address the issue. In this paper, iron doped ZIF-8@MXene (Fe-ZIF-8@MXene) was prepared as a potential adsorbent to effectively and simultaneously remove As(III/V) from wastewater. To investigate this, Fe-ZIF-8@MXene was characterized before and after the removal of mixed As(III/V). The results of Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), specific surface area (BET) and point of zero charge (pHpzc) showed that Fe-ZIF-8@MXene was prepared successfully and kept a stable structure after As(III) and As(V) adsorption. The particle size of Fe-ZIF-8@MXene was in the range of 0.5 μm to 2.5 μm, where its BET was 531.7 m2/g. For both contaminants, adsorption was found to follow pseudo-second-order kinetics and was best-fitted by the Langmuir adsorption model with correlation coefficients (R2) of 0.998 and 0.997, for As(III) and As(V), respectively. The adsorbent was then applied to remove As from two actual water samples, giving maximum removal rates of 91.07% and 98.96% for As(III) and As(V), respectively. Finally, removal mechanisms for As(III/V) by Fe-ZIF-8@MXene were also explored. During the adsorption, multiple complexes were formed under the effect of its abundant surface functional groups involving multiple mechanisms, which included Van der Waals force, surface adsorption, chemical complexation and electrostatic interactions. In conclusion, this study demonstrated that Fe-ZIF-8@MXene was an advanced and reusable material for simultaneous removal of As(III/V) in wastewater.

Les phases MAX sont des carbures ou des nitrures ternaires nano-lamellaires comportant un métal de transition (M), un élément des colonnes 13-16 (A), X=C ou N.Ces phases combinent certaines des meilleures propriétés des céramiques à celles des métaux. Leurs propriétés physiques (rigidité, résistance aux chocs mécaniques et thermiques, bonnes conductivités thermique et électrique), associées à la possibilité d’usinage, les rend très attractives en termes d’applications technologiques potentielles.En 2011, il a été établi qu’un traitement à l’acide fluorhydrique (HF) des phases MAX comprenant de l’aluminium permet une élimination sélective des plans d’atomes Al, avec pour résultat la formation de matériaux bi-dimensionnels (2D) appelés MXènes pour souligner la perte des atomes de Al. Ces nouveaux membres de la famille des matériaux 2D sont plus résistants, chimiquement plus polyvalents et possèdent une conductivité supérieure à nombre d’autres matériaux. Ils se révèlent par conséquent très intéressants pour de nouvelles applications, par exemple pour des systèmes de délivrance de médicaments in vivo, le stockage d’hydrogène, ou pour remplacer d’autres matériaux dans des batteries, le traitement des eaux usées ou divers capteurs.Dans cette thèse, nous présentons notre travail sur la synthèse, la caractérisation structurale et le transport électronique dans les phases MAX et leurs dérivés 2D, les MXènes. En ce qui concerne les phases MAX, et motivés par les propriétés fortement anisotropes attendues de tels matériaux nano-lamellaires, produire des monocristaux massifs est le moyen le plus naturel d’obtenir des échantillons où l’anisotropie des propriétés physiques peut être sondée expérimentalement. En utilisant avec succès la méthode de croissance en solution à haute température associée à un refroidissement lent, nous avons obtenu des monocristaux de divereses phases MAX, incluant Cr2AlC, V2AlC, Ti3SiC2, etc.La caractérisation structurale confirme le caractère mono-cristallin des échantillons. Expérimentalement, nous avons acquis un jeu exhaustif de mesures de magnéto-transport de monocristaux en fonction de la température et du champ magnétique. De plus, nous obtenons un rapport d’anisotropie très important entre la résistivité dans le plan ab et celle parallèle à l’axe c, allant de plusieurs centaines à plusieurs milliers. A partir des courbes de magnétorésistance et d’effet Hall, nous avons étudié en détail le comportement du transport dans le plan basal. D’un point de vue théorique, nous avons proposé un modèle général mais simple pour décrire les propriétés de magnéto-transport d’électrons presque libres dans des métaux 2D hexagonaux. Ce modèle a été modifié pour être appliqué aux propriétés de transport des phases MAX nano-lamellaires.En ce qui concerne les MXènes, nous avons synthétisé avec succès des écailles de MXènes V2CTx de grande surface à partir du traitement HF conventionnel de monocristaux de V2AlC. La délamination mécanique de ces écailles multi-couches de V2CTx en échantillons comportant peu de monocouches a aussi été réalisée. Nous avons établi la morphologie typique de ces couches à partir d’images de microscopies MEB ou TEM. A partir d’analyse EDX, nous concluons que les terminaisons -OH dominent et sont les plus stables énergétiquement. Nous détaillons ensuite le procédé de fabrication des dispositifs électriques utilisés pour obtenir les résultats de mesures de transport électrique jusqu’à basse température. Nous avons obtenu avec succès des résultats originaux sur les MXènes V2CTx, avec une valeur moyenne de résistivité de l’ordre de 2 × 10-5 ohmm. La mesure d’effet de champ indique une mobilité de 22.7 cm2/Vs. Du fait de l’intensité des recherches portées actuellement sur les MXènes, nous espérons que ces résultats contribueront de manière significative à une meilleure compréhension de cette classe de matériaux et de la façon dont leurs propriétés peuvent être contrôlées. / MAX phases are layered early transition metal ternary carbides and nitrides so called because they are composed of M, an early transition metal, A, a group A element and X is C and/or N. MAX phase structure is composed of near close-packed planes of M atoms with the X atoms occupying all the octahedral sites between them. Their physical properties (stiffness, damage and thermal shock resistance, high thermal and electrical conductivity) along with the fact they are readily machinable, make them extremely attractive in terms of the potential technological applications.In 2011, it was discovered that by immersing Al-containing MAX phases in HF acid, it was possible to selectively etch the Al, resulting in two-dimensional (2D) materials, that were labeled MXene to denote the removal of the A-group element and make the connection to another conducting 2D material, graphene. This new member of 2D materials family owns stronger, more chemically versatile, and have higher conductivity than other materials. As such they are highly interesting on new applications, e.g. specialized in vivo drug delivery systems, hydrogen storage, or as replacements of common materials in e.g. batteries, sewage treatment, and sensors.In this thesis, as its self-telling title indicated, we present our work on the synthesis, structural characterization and the electron transport in the MAX phases and their 2D derivatives, MXenes.For MAX phase: motivated by the theoretically expected anisotropic properties of these layered materials, producing bulk single crystals is a natural way to obtain samples where the anisotropy of the physical properties can be experimentally probed. Also, knowledge of low-temperature behavior of single crystal is vital because it can provide insight into MAX intrinsic physical properties. Using high temperature solution growth and slow cooling technique, several MAX phases single crystals have been successfully grown, including Cr2AlC, V2AlC, Ti3SiC2, etc. Structural characterization confirms the single crystalline character of the samples. Experimentally, a set of experimental data was obtained from single crystals of V2AlC and Cr2AlC as a function of temperature and magnetic field. In particular, we obtain a very high ratio between the in-plane and parallel to the c-axis resistivity, which is very substantial, in the range of a few hundreds to thousands. From MR and Hall effect measurement, in-plane transport behaviors of MAX phases have been studied. The extracted mobility is in the range from 50 to 120 cm2/V·s, which is the same order of magnitude of polycrystalline sample. Theoretically, a general, yet simple model was proposed for describing the weak field magneto-transport properties of nearly free electrons in two-dimensional hexagonal metals. It was then modified to be applicable for the transport properties of layered MAX phases.For MXene: Large scale V2CTx MXene flakes was successfully synthesized by conventional HF-etching of V2AlC single crystals. Mechanical delamination of multilayered V2CTx flakes into few layer flakes and transfer on Si/SiO2 substrate was also achieved. Structural characterization demonstrated an enlarged interplane distance, while prior DMSO intercalation seems to have no effect on this type of MXenes. From EDS results, we concluded that -OH terminations on V2CTx is the dominated, and the most energetically favorable, compared to -F and -O functional groups. We then detail the electrical device fabrication process and proceed with electrical measurements results, performed down to low temperature, with the aim to extract useful information on charge carrier behavior. We successfully obtained some first hand transport data on V2CTx MXenes, the average value for the resistivity of V2CTx MXenes is 2 × 10-5 Ω ∙m, which is in consistent with reported other MXene samples. The mobility, 22.7 cm2/V·s , which stays in the same order of magnitude as its parent MAX phase.

Forskningsområdet för bärbar elektronik är fortfarande relativt ungt och det finns ett stort behov av utveckling av nya material inom området. Olika typer av kompositer är mycket intressanta och de ska uppvisa såväl hög hållfasthet som goda ledande egenskaper. I detta avseende är silkes fibroin och MXene mycket intressanta utgångsmaterial eftersom silkestrådarna kan ge en struktur med god jonledningsförmåga och god flexibilitet och MXene kan bidra med hög styvhet och god elektrisk ledningsförmåga. Med detta som bakgrund beslöts att undersöka om kompositer av silkestrådar och MXene kan användas i kompositer som kan användas i bärbar elektronik. 3 olika typer av hydrogeler studerades och de innehöll silkes fibroin med 0, 1 och 5% MXene. De egenskaper som utvärderades var struktur, mekaniska egenskaper, stabilitet i vatten, bionedbrytbarhet och både statisk och dynamisk ledningsförmåga. Resultaten visar att de tillverkade nanokompositerna har lovande förutsättningar inom området eftersom en kombination av silkes fibroin med 5 % MXene har god stabilitet, konduktivitet och en hög och stabil Gauge-faktor. / As the research area of wearable electronics is still relatively new, material science with this focus opens plenty of unexplored fields. That is why a study characterizing the unexplored composite system of silk fibroin and MXene (Silk/MXene) was conducted. These two biocompatible materials are complementary with regard to the requirements for wearable electronics materials. Silk fibroin dispose an ionic conductivity and solid flexibility, while MXene brings mechanical strength and significant increase of electrical conductivity. The reinforced hydrogel materials were studied at two concentrations of fillers, 1% and 5% and compared to pristine silk fibroin. All three materials were studied from the point of view of their structure, mechanical properties, behaviour in aqueous environment, biodegradability and electrical conductivity, both static and dynamic. Nanocomposite systems of silk fibroin and MXene have shown a potential for being used in the intended application area, as Silk/MXene 5% film displays good stability, conductivity with high andstable Gauge factor.