Measurement of the combined quantum and electrochemical capacitance of a carbon nanotube.
ABSTRACT: The nature of the electronic interface between a nanotube and solvated ions in a liquid electrolyte is governed by two distinct physical phenomena: quantum and chemical. The quantum component arises from the sharply varying electronic density of states and the chemical component arises from ion screening and diffusion. Here, using an integrated on-chip shield technology, we measure the capacitance of one to a few nanotubes quantitatively as a function of both bias potential (from -0.7 V to 0.3 V) and ionic concentration (from 10 mM to 1 M KCl) at room temperature. We determine the relative contributions of the quantum and electrochemical capacitance, and confirm the measurements with theoretical models. This represents an important measurement of the quantum effects on capacitance in reduced dimensional systems in contact with liquid electrolytes, an important and emerging theme in the interface between nanotechnology, energy, and life.
Project description:Multi-colored, water soluble fluorescent carbon nanodots (C-Dots) with quantum yield changing from 4.6 to 18.3% were synthesized in multi-gram using dated cola beverage through a simple thermal synthesis method and implemented as conductive and ion donating supercapacitor component. Various properties of C-Dots, including size, crystal structure, morphology and surface properties along with their Raman and electron paramagnetic resonance spectra were analyzed and compared by means of their fluorescence and electronic properties. ?-Manganese Oxide-Polypyrrole (PPy) nanorods decorated with C-Dots were further conducted as anode materials in a supercapacitor. Reduced graphene oxide was used as cathode along with the dicationic bis-imidazolium based ionic liquid in order to enhance the charge transfer and wetting capacity of electrode surfaces. For this purpose, we used octyl-bis(3-methylimidazolium)diiodide (C8H16BImI) synthesized by N-alkylation reaction as liquid ionic membrane electrolyte. Paramagnetic resonance and impedance spectroscopy have been undertaken in order to understand the origin of the performance of hybrid capacitor in more depth. In particular, we obtained high capacitance value (C?=?17.3??F/cm2) which is exceptionally related not only the quality of synthesis but also the choice of electrode and electrolyte materials. Moreover, each component used in the construction of the hybrid supercapacitor is also played a key role to achieve high capacitance value.
Project description:We present a comprehensive study of the electrochemical capacitance between a one-dimensional electronic material and an electrolyte. In contrast to a conventional, planar electrode, the nanoscale dimension of the electrode (with diameter smaller than the Debye length and approaching the size of the ions in solution) qualitatively changes the capacitance, which we measure and model herein. Furthermore, the finite density of states in these low dimensional electronic systems results in a quantum capacitance, which is comparable to the electrochemical capacitance. Using electrochemical impedance spectroscopy (EIS), we measure the ensemble average, complex, frequency dependent impedance (from 0.1 Hz to 1 MHz) between a purified (99.9%) semiconducting nanotube network and an aqueous electrolyte (KCl) at different concentrations between 10 mM and 1 M. The potential dependence of the capacitance is convoluted with the potential dependence of the in-plane conductance of the nanotube network, which we model using a transmission-line model to account for the frequency dependent in-plane impedance as well as the total interfacial impedance between the network and the electrolyte. The ionic strength dependence of the capacitance is expected to have a root cause from the double layer capacitance, which we model using a modified Poisson-Boltzmann equation. The relative contributions from those two capacitances can be quantitatively decoupled. We find a total capacitance per tube of 0.67-1.13 fF/?m according to liquid gate potential varying from -0.5 to -0.7 V.
Project description:Light-sensitive capacitance variation of Bi0.95La0.05FeO3 (BLFO) ceramics has been studied under violet to UV irradiation. The reversible capacitance enhancement up to 21% under 405 nm violet laser irradiation has been observed, suggesting a possible degree of freedom to dynamically control this in high dielectric materials for light-sensitive capacitance applications. By using ultraviolet photoemission spectroscopy (UPS), we show here that exposure of BLFO surfaces to UV light induces a counterintuitive shift of the O2p valence state to lower binding energy of up to 243 meV which is a direct signature of negative electronic compressibility (NEC). A decrease of BLFO electrical resistance agrees strongly with the UPS data suggesting the creation of a thin conductive layer on its insulating bulk under light irradiation. By exploiting the quantum capacitance model, we find that the negative quantum capacitance due to this NEC effect plays an important role in this capacitance enhancement.
Project description:We explore the stability, electronic properties, and quantum capacitance of doped/co-doped graphene with B, N, P, and S atoms based on first-principles methods. B, N, P, and S atoms are strongly bonded with graphene, and all of the relaxed systems exhibit metallic behavior. While graphene with high surface area can enhance the double-layer capacitance, its low quantum capacitance limits its application in supercapacitors. This is a direct result of the limited density of states near the Dirac point in pristine graphene. We find that the triple N and S doping with single vacancy exhibits a relatively stable structure and high quantum capacitance. It is proposed that they could be used as ideal electrode materials for symmetry supercapacitors. The advantages of some co-doped graphene systems have been demonstrated by calculating quantum capacitance. We find that the N/S and N/P co-doped graphene with single vacancy is suitable for asymmetric supercapacitors. The enhanced quantum capacitance contributes to the formation of localized states near the Dirac point and/or Fermi-level shifts by introducing the dopant and vacancy complex.
Project description:Ionic-liquid gates have a high carrier density due to their atomically thin electric double layer (EDL) and extremely large geometrical capacitance Cg. However, a high carrier density in graphene has not been achieved even with ionic-liquid gates because the EDL capacitance CEDL between the ionic liquid and graphene involves the series connection of Cg and the quantum capacitance Cq, which is proportional to the density of states. We investigated the variables that determine CEDL at the molecular level by varying the number of graphene layers n and thereby optimising Cq. The CEDL value is governed by Cq at n < 4, and by Cg at n > 4. This transition with n indicates a composite nature for CEDL. Our finding clarifies a universal principle that determines capacitance on a microscopic scale, and provides nanotechnological perspectives on charge accumulation and energy storage using an ultimately thin capacitor.
Project description:Electrified solid/liquid interfaces are the key to many physicochemical processes in a myriad of areas including electrochemistry and colloid science. With tremendous efforts devoted to this topic, it is unexpected that molecular-level understanding of electric double layers is still lacking. Particularly, it is perplexing why compact Helmholtz layers often show bell-shaped differential capacitances on metal electrodes, as this would suggest a negative capacitance in some layer of interface water. Here, we report state-of-the-art ab initio molecular dynamics simulations of electrified Pt(111)/water interfaces, aiming at unraveling the structure and capacitive behavior of interface water. Our calculation reproduces the bell-shaped differential Helmholtz capacitance and shows that the interface water follows the Frumkin adsorption isotherm when varying the electrode potential, leading to a peculiar negative capacitive response. Our work provides valuable insight into the structure and capacitance of interface water, which can help understand important processes in electrocatalysis and energy storage in supercapacitors.
Project description:The distribution of electric fields within the electrochemical double layer depends on both the electrode and electrolyte in complex ways. These fields strongly influence chemical dynamics in the electrode-electrolyte interface but cannot be measured directly with submolecular resolution. We report experimental capacitance measurements for aqueous interfaces of CO-terminated Pt(111). By comparing these measurements with first-principles density functional theory (DFT) calculations, we infer microscopic field distributions and decompose contributions to the inverse capacitance from various spatial regions of the interface. We find that the CO is strongly electronically coupled to the Pt and that most of the interfacial potential difference appears across the gap between the terminating O and water and not across the CO molecule, as previously hypothesized. This "gap capacitance" resulting from hydrophobic termination lowers the overall capacitance of the aqueous Pt-CO interface and makes it less sensitive to electrolyte concentration compared to the bare metal.
Project description:We study the quantum capacitance in a topological insulator thin film system magnetized in the in-plane direction in the presence of an out-of-plane magnetic field and hexagonal warping. To first order, the modification in quantum capacitance due to hexagonal warping compared to the clean case, where both the in-plane magnetization and hexagonal warping are absent, is always negative, and increases in magnitude monotonically with the energy difference from the charge neutrality point. In contrast, the change in the quantum capacitance due to in-plane magnetization oscillates with the energy in general, except when a certain relation between the inter-surface coupling, out of plane Zeeman energy splitting and magnetic field strength is satisfied. In this special case, the quantum capacitance remains unchanged by the in-plane magnetization for all energies.
Project description:Peripheral events in olfaction involve odorant binding proteins (OBPs) whose role in the recognition of different volatile chemicals is yet unclear. Here we report on the sensitive and quantitative measurement of the weak interactions associated with neutral enantiomers differentially binding to OBPs immobilized through a self-assembled monolayer to the gate of an organic bio-electronic transistor. The transduction is remarkably sensitive as the transistor output current is governed by the small capacitance of the protein layer undergoing minute changes as the ligand-protein complex is formed. Accurate determination of the free-energy balances and of the capacitance changes associated with the binding process allows derivation of the free-energy components as well as of the occurrence of conformational events associated with OBP ligand binding. Capacitance-modulated transistors open a new pathway for the study of ultra-weak molecular interactions in surface-bound protein-ligand complexes through an approach that combines bio-chemical and electronic thermodynamic parameters.
Project description:We demonstrate that single-layer graphene (SLG) decorated with a high density of Ag adatoms displays the unconventional phenomenon of negative quantum capacitance. The Ag adatoms act as resonant impurities and form nearly dispersionless resonant impurity bands near the charge neutrality point (CNP). Resonant impurities quench the kinetic energy and drive the electrons to the Coulomb energy dominated regime with negative compressibility. In the absence of a magnetic field, negative quantum capacitance is observed near the CNP. In the quantum Hall regime, negative quantum capacitance behavior at several Landau level positions is displayed, which is associated with the quenching of kinetic energy by the formation of Landau levels. The negative quantum capacitance effect near the CNP is further enhanced in the presence of Landau levels due to the magnetic-field-enhanced Coulomb interactions.