Browsing by Subject "Electrolytes"

Now showing 1 - 16 of 16

Open Access
Broadband terahertz modulators using self-gated graphene capacitors
(Optical Society of America, 2015) Kakenov, N.; Balci, O.; Polat, E. O.; Altan, H.; Kocabas, C.
We demonstrate a terahertz intensity modulator using a graphene supercapacitor which consists of two large-area graphene electrodes and an electrolyte medium. The mutual electrolyte gating between the graphene electrodes provides very efficient electrostatic doping with Fermi energies of 1 eV and a charge density of 8 × 1013 cm-2. We show that the graphene supercapacitor yields more than 50% modulation between 0.1 and 1.4 THz with operation voltages less than 3 V. The low insertion losses, high modulation depth over a broad spectrum, and the simplicity of the device structure are the key attributes of graphene supercapacitors for THz applications.
Open Access
Continuous mesoporous pd films by electrochemical deposition in nonionic micellar solution
(American Chemical Society, 2017) Iqbal, M.; Li C.; Wood, K.; Jiang B.; Takei, T.; Dag, Ö.; Baba, D.; Nugraha, A. S.; Asahi, T.; Whitten, A. E.; Hossain, M. S. A.; Malgras, V.; Yamauchi, Y.
Mesoporous metals that combine catalytic activity and high surface area can provide more opportunities for electrochemical applications. Various synthetic methods, including hard and soft templating, have been developed to prepare mesoporous/nanoporous metals. Micelle assembly, typically involved in soft-templates, is flexible and convenient for such purposes. It is, however, difficult to control, and the ordering is significantly destroyed during the metal deposition process, which is detrimental when it comes to designing precisely mesostructured materials. In the present work, mesoporous Pd films were uniformly electrodeposited using a nonionic surfactant, triblock copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide), as a pore-directing agent. The interaction between micelles and metal precursors greatly influences the metal growth and determines the final structure. The water-coordinated species interact with the ethylene oxide moiety of the micelles to effectively drive the Pd(II) species toward the working electrode surface. From small-angle neutron scattering data, it is found that spherical P123 micelles, with an average diameter of ∼14 nm, are formed in the electrolyte, and the addition of Pd ions does not significantly modify their structure, which is the essence of the micelle assembly approach. The uniformly sized mesopores are formed over the entire mesoporous Pd film and have an average pore diameter of 10.9 nm. Cross-sectional observation of the film also shows mesopores spanning continuously from the bottom to the top of the film. The crystallinity, crystal phase, and electronic coordination state of the Pd film are also confirmed. Through this study, it is found that the optimized surfactant concentration and applied deposition potential are the key factors to govern the formation of homogeneous and well-distributed pores over the entire film. Interestingly, the as-prepared mesoporous Pd films exhibit superior electrocatalytic activity toward the ethanol oxidation reaction by fully utilizing the accessible active surface area. Our approach combines electrochemistry with colloidal and coordination chemistry and is widely applicable to other promising metals and alloy electrocatalysts.
Open Access
Electrostatic interactions in charged nanoslits within an explicit solvent theory
(Institute of Physics Publishing, 2015) Buyukdagli, S.
Within a dipolar Poisson-Boltzmann theory including electrostatic correlations, we consider the effect of explicit solvent structure on solvent and ion partition confined to charged nanopores. We develop a relaxation scheme for the solution of this highly non-linear integro-differential equation for the electrostatic potential. The scheme is an extension of the approach previously introduced for simple planes (Buyukdagli and Blossey 2014 J. Chem. Phys. 140 234903) to nanoslit geometry. We show that the reduced dielectric response of solvent molecules at the membrane walls gives rise to an electric field significantly stronger than the field of the classical Poisson-Boltzmann equation. This peculiarity associated with non-local electrostatic interactions results in turn in an interfacial counterion adsorption layer absent in continuum theories. The observation of this enhanced counterion affinity in the very close vicinity of the interface may have important impacts on nanofluidic transport through charged nanopores. Our results indicate the quantitative inaccuracy of solvent implicit nanofiltration theories in predicting the ionic selectivity of membrane nanopores.
Open Access
Electrostatics of Polymer Translocation Events in Electrolyte Solutions
(American Institute of Physics Inc., 2016) Buyukdagli, S.; Ala-Nissila, T.
We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ∼10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.
Open Access
Femtosecond pulse generation from a Ti3+: Sapphire laser near 800 nm with voltage reconfigurable graphene saturable absorbers
(OSA - The Optical Society, 2017) Baylam, Işınsu; Özharar, Sarper; Kakenov, Nurbek; Kocabaş, Coşkun; Sennaroglu, Alphan
We experimentally show that a voltage-controlled graphene-gold supercapacitor saturable absorber (VCG-gold-SA) can be operated as a fast saturable absorber with adjustable linear absorption at wavelengths as low as 795 nm. This was made possible by the use of a novel supercapacitor architecture, consisting of a high-dielectric electrolyte sandwiched between a graphene and a gold electrode. The high-dielectric electrolyte allowed continuous, reversible adjustment of the Fermi level and, hence, the optical loss of the VCG-gold-SA up to the visible wavelengths at low bias voltages of the order of a few volts (0-2 V). The fast saturable absorber action of the VCG-gold-SA and the bias-dependent reduction of its loss were successfully demonstrated inside a femtosecond Ti3+:sapphire laser operating near 800 nm. Dispersion compensation was employed by using dispersion control mirrors and a prism pair. At a bias voltage of 1.2 V, the laser operated with improved power performance in comparison with that at zero bias, and the VCG-gold-SA initiated the generation of nearly transform-limited pulses as short as 48 fs at a pulse repetition rate of 131.7 MHz near 830 nm. To the best of our knowledge, this represents the shortest wavelength where a VCG-gold-SA has been employed as a mode locker with adjustable loss. © 2017 Optical Society of America.
Open Access
Graphene-gold supercapacitor as a voltage controlled saturable absorber for femtosecond pulse generation
(Optical Society of America, 2016-02) Baylam, I.; Balci, O.; Kakenov, N.; Kocabas, C.; Sennaroglu, A.
We report, for the first time to the best of our knowledge, use of a graphene-gold supercapacitor as a voltage controlled fast saturable absorber for femtosecond pulse generation. The unique design involving only one graphene electrode lowers the insertion loss of the device, in comparison with capacitor designs with two graphene electrodes. Furthermore, use of the high-dielectric electrolyte allows reversible, adjustable control of the absorption level up to the visible region with low bias voltages of only a few volts (0-2 V). The fast saturable absorber action of the graphene-gold supercapacitor was demonstrated inside a multipass-cavity Cr:forsterite laser to generate nearly transform-limited, sub-100 fs pulses at a pulse repetition rate of 4.51 MHz at 1.24 μm.
Open Access
Ionic current inversion in pressure-driven polymer translocation through nanopores
(American Physical Society, 2015) Buyukdagli, S.; Blossey, R.; Ala-Nissila, T.
We predict streaming current inversion with multivalent counterions in hydrodynamically driven polymer translocation events from a correlation-corrected charge transport theory including charge fluctuations around mean-field electrostatics. In the presence of multivalent counterions, electrostatic many-body effects result in the reversal of the DNA charge. The attraction of anions to the charge-inverted DNA molecule reverses the sign of the ionic current through the pore. Our theory allows for a comprehensive understanding of the complex features of the resulting streaming currents. The underlying mechanism is an efficient way to detect DNA charge reversal in pressure-driven translocation experiments with multivalent cations. © 2015 American Physical Society.
Open Access
Like-Charge Attraction And Opposite-Charge Decomplexation Between Polymers and DNA Molecules
(American Physical Society, 2017) Buyukdagli, S.
We scrutinize the effect of polyvalent ions on polymer-DNA interactions. We extend a recently developed test-charge theory [S. Buyukdagli, Phys. Rev. E 94, 042502 (2016)1539-375510.1103/PhysRevE.94.042502] to the case of a stiff polymer interacting with a DNA molecule in an electrolyte mixture. The theory accounts for one-loop level electrostatic correlation effects such as the ionic cloud deformation around the strongly charged DNA molecule as well as image-charge forces induced by the low DNA permittivity. Our model can reproduce and explain various characteristics of the experimental phase diagrams for polymer solutions. First, the addition of polyvalent cations to the electrolyte solution results in the attraction of the negatively charged polymer by the DNA molecule. The glue of the like-charge attraction is the enhanced shielding of the polymer charges by the dense counterion layer at the DNA surface. Second, through the shielding of the DNA-induced electrostatic potential, mono- and polyvalent cations of large concentration both suppress the like-charge attraction. Within the same formalism, we also predict a new opposite-charge repulsion effect between the DNA molecule and a positively charged polymer. In the presence of polyvalent anions such as sulfate or phosphate, their repulsion by the DNA charges leads to the charge screening deficiency of the region around the DNA molecule. This translates into a repulsive force that results in the decomplexation of the polymer from DNA. This opposite-charge repulsion phenomenon can be verified by current experiments and the underlying mechanism can be beneficial to gene therapeutic applications where the control over polymer-DNA interactions is the key factor.
Open Access
Like-charge polymer-membrane complexation mediated by multivalent cations: one-loop-dressed strong coupling theory
(American Institute of Physics, 2019) Büyükdağlı, Şahin; Podgornik, R.
We probe the electrostatic mechanism driving adsorption of polyelectrolytes onto like-charged membranes upon the addition of tri- and tetravalent counterions to a bathing monovalent salt solution. We develop a one-loop-dressed strong coupling theory that treats the monovalent salt at the electrostatic one-loop level and the multivalent counterions within a strong-coupling approach. It is shown that the adhesive force of the multivalent counterions mediating the like-charge adsorption arises from their strong condensation at the charged membrane. The resulting interfacial counterion excess locally maximizes the screening ability of the electrolyte and minimizes the electrostatic polymer grand potential. This translates into an attractive force that pulls the polymer to the similarly charged membrane. We show that the high counterion valency enables this adsorption transition even at weakly charged membranes. Additionally, strongly charged membranes give rise to monovalent counterion-induced correlations and intensify the interfacial multivalent counterion condensation, strengthening the complexation of the polymer with the like-charged membrane, as well as triggering the orientational transition of the molecule prior to its adsorption. Finally, our theory provides two additional key features as evidenced by previous adsorption experiments: first, the critical counterion concentration for polymer adsorption decreases with the rise of the counterion valency and, second, the addition of monovalent salt enhances the screening of the membrane charges and suppresses monovalent counterion correlations close to the surface. This weakens the interfacial multivalent counterion condensation and results in the desorption of the polymer from the substrate.
Open Access
Lithium salt-nonionic surfactant lyotropic liquid crystalline gel-electrolytes with redox couple for dye sensitized solar cells
(Royal Society of Chemistry, 2016) Yılmaz, E.; Olutaş, E. B.; Barım, G.; Bandara, J.; Dag, Ö.
Lithium salt (LiCl, LiBr, LiI, or LiNO3) and a non-ionic surfactant (such as 10-lauryl ether, C12E10) form lyotropic liquid crystalline (LLC) mesophases in the presence of a small amount of water. The mesophases can be prepared as gels by mixing all the ingredients in one pot or in the solution phase that they can be prepared by coating over any substrate where the LLC phase is formed by evaporating excess solvent. The second method is easier and produces the same mesophase as the first method. A typical composition of the LLC phases consists of 2-3 water per salt species depending on the counter anion. The LiI-C12E10 mesophases can also be prepared by adding I2 to the media to introduce an I-/I3 - redox couple that may be used as a gel-electrolyte in a dye-sensitized solar cell. Even though the mesophases contain a large amount of water in the media, this does not affect the cell performance. The water molecules in the mesophase are in the hydration sphere of the ions and do not act like bulk water, which is harmful to the anode of the dye-sensitized solar cells (DSSC). There are two major drawbacks of the salt-surfactant LLC mesophases in the DSSCs; one is the diffusion of the gels into the pores of the anode electrode and the other is the low ionic conductivity. The first issue was partially overcome by introducing the gel content as a solution and the gelation was carried in/over the pores of the dye modified titania films. To increase the ionic conductivity of the gels, other salts (such as LiCl, LiBr, and LiNO3) with better ionic conductivity were added to the media, however, those gels behave less effectively than pure LiI/I2 systems. Overall, the DSSCs constructed using the LLC electrolyte display high short circuit current (Isc of around 10 mA), high open circuit voltage (Voc of 0.81 V) and good fill factor (0.69) and good efficiency (3.3%). There is still room for improvement in addressing the above issues in order to enhance the cell efficiency by developing new methods of introducing the gel-electrolytes into the mesopores of the anode electrode.
Open Access
Lyotropic liquid-crystalline mesophase of lithium triflate-nonionic surfactant as gel electrolyte for graphene optical modulator
(American Chemical Society, 2023) Balci, F. M.; Balci, S.; Kocabas, C.; Dag, Ö.
Lithium salt (noncoordinating anions, such as lithium triflate (Ltf)) gel electrolytes may be key for the practical use of electrochemical devices. We introduce a new lyotropic liquid-crystalline (LLC) mesophase using Ltf, a small amount of water (as low as 1.3 water per Ltf), and nonionic surfactant (C18H37(OCH2CH2)10OH, C18E10). The LLC phase forms over a broad range of Ltf/C18E10 mole ratios, 2-18. The clear ethanol solution of the ingredients can be either directly spin-coated over a glass substrate to form a gel phase or it can be prepared as a gel by mixing Ltf, water, and C18E10. The mesophase leaches out surfactant molecules at low salt concentrations, but at a salt/surfactant mole ratio of above 8, the phase is homogeneous with a cubic mesostructure, fully transparent in the visible optical region, mechanically flexible, and an effective gel electrolyte. We have observed a large electrostatic doping on graphene with the Fermi energy level of ∼1.0 eV using Ltf-C18E10 gel electrolytes. The Ltf-based gels demonstrate better properties than commonly used ionic liquid electrolyte in graphene optical modulators. The stability of the new gel electrolytes and their superior performance make them suitable electrolytes for use in graphene-based optical modulators.
Open Access
Probing the dynamics of non-faradaic processes in Ionic liquids at extended time and length scales using XPS with AC modulation
(American Chemical Society, 2021-05-06) Aydoğan Göktürk, Pınar; Süzer, Şefik
Charging dynamics of ionic liquid (IL) electrolytes play important roles in various aspects of electrochemical processes. However, the precise understanding of such processes at extended time and length scales is incomplete due to the experimental difficulties in probing the electrochemical potential and other relevant parameters. In principle, such shortcomings should not apply to theoretical/computational approaches; however, existing works have mostly concentrated on or around electrode/electrolyte interfaces and short timescales due mostly to prohibitive demands on computational efforts. To fill this gap, we have utilized X-ray photoelectron spectroscopy to study the charging dynamics of ILs in contact with two wire electrodes under AC square wave excitation, with frequencies ranging from hundreds of kHz down to the mHz region. Using the changes in the binding energy position of the IL-related core-level peaks, electrical potential profiles along the lines in between the electrodes and on the entire surface of the electrolyte have been investigated in situ. From these results, we identify two widely different time constants. The timescale of the fast process was shown to be on the order of RC time constant, while the slow process takes place on a timescale of seconds. Our method in the present study is expected to open up a new way for extracting novel dynamic information for gaining a better understanding of such processes and designing efficient IL-based electrochemical devices with a novel perspective on the charging.
Open Access
Response of polyelectrolyte layers to the SiO2 substrate charging as probed by XPS
(2009) Conger, C. P.; Süzer, Şefik
A single layer of the Cationic polyelectrolyte poly(allyamine) hydrochloride (PAH) deposited, using the layer-by-layer technique, on a silicon substrate containing 5 nm oxide layer is investigated by XPS while applying an external potential bias to the sample to control and manipulate the charge built-up on the oxide layer. Under application of a -10 V bias, the oxide layer is positively charged due to Photoemission process, evidenced by the measured Si2p binding energy of 104.4 eV. Application of a +10 V bias attracts the low energy neutralizing electrons, stemming from a hot filament, and leads to a negatively charged oxide layer, also evidenced by the measured Si2p binding energy of 102.9 eV. The single polyelectrolyte overlayer also responds to this polarity change of the oxide layer underneath by displaying a somewhat larger shifts both in the C1s and Nls peaks. In addition to the shifts in the positions, the N1s peaks undergo a significant intensity depletion, mostly on the positively charged -N+ component. We interpret this intensity depletion to be the result of reorientation of some of the dangling positively charged groups by moving toward the negatively charged oxide underlayer. To our knowledge this is the first time that a chemically specific response to an electrical stimuli is reported using XPS. A bilayer LbL film consisting of PAH and PSS, exhibits even a larger charging shift, but this time no intensity alteration is observed, most probably due to locking of the -N+ groups by the -SO3 + counterions of the second layer. © 2009 American Chemical Society.
Open Access
Role of water in the lyotropic liquid crystalline lithium Iodide–Iodine–water–C12E10 mesophase as a gel electrolyte in a dye-sensitized solar cell
(American Chemical Society, 2021-07-13) Yılmaz Topuzlu, Ezgi; Ülgüt, Burak; Dağ, Ömer
By replacing volatile and flammable organic-based electrolytes with gel electrolytes, dye-sensitized solar cells (DSSCs) may be a viable and more practical alternative to other clean energy sources. Although they present a promising alternative, gel electrolytes still have some drawbacks for practical applications, such as low ionic conductivity and infusion difficulties into the pores of the working electrode. Here, we introduce a new one-step fabrication method that uses a lyotropic liquid crystalline (LLC) gel electrolyte (LiI:I2:H2O:C12H25(OCH2CH2)10OH) and a dye (N719) to construct a DSSC that performs (7.32%) 2.2 times better compared with a traditional two-step production. Water plays a key role in the gel electrolyte, where the H2O/LiI mole ratio is around 2.57 under ambient laboratory conditions (ALCs); however, this ratio linearly increases to 4.00 and then to 5.85 at 40 and 75% humidities, respectively, without affecting the two-dimensional (2D) hexagonal structure of the mesophase. The ionic conductivity of the gel electrolyte linearly increases accordingly, by 2.2 (4.8 × 10–5 to 10.6 × 10–5) and 13.1 times (63.0 × 10–5 S/cm) from ALC to 40 and ALC to 75% humidity, respectively. Increasing water in the gel phase improves the conductivity of the LLC mesophase and the short-circuit current (Isc) of the DSSC, but negatively influences the open-circuit voltage (Voc) of the cell, equilibrium reaction between the LiI and I2, and the anchoring of the dye molecules over the titania surface.
Open Access
Tuning the degree of oxidation and electron delocalization of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) with solid-electrolyte
(Elsevier, 2017-10) Vempati, Sesha; Ertaş, Yelda; Çelebioğlu, Aslı; Uyar, Tamer
We report on the effects of ionic interaction on the electronic structure of PEDOT:PSS where the oxidation state of PEDOT is an import aspect for various applications. Additional ionic interactions are introduced and controlled by varying the fraction of poly(ethylene oxide) (PEO). These interactions are balanced against the inherent cohesive forces within each of the polymers constituting intertwined networks. Raman spectra evidenced a peak-shift as high as ∼14 cm−1 for C[dbnd]C vibrational region which suggested increasing degree of oxidation of PEDOT for higher PEO fractions. Changes to the single and bipolaronic absorption bands support the results from the Raman spectra. For highest PEO fraction neutral-PEDOT and lowered bipolaron density is attributed to localization of PEDOT chains within PEO matrix. Interestingly, for higher PEO fractions the electronic density of states (DOS) of HOMO and core-levels (S2p, C1s and O1s) suggested increased degree of oxidation and electron localization on PEDOT. Near and below (∼12 eV) Fermi level, contribution to the O2p and C2p atomic orbitals depicted significantly different DOS. Also we note energetic shift for O2s/C2s and bonding σCC atomic and molecular DOS, respectively. The correlation between some surface and bulk-related properties suggests the uniformity of the blend material which might be vital for the application in electrochemical devices.
Open Access
XPS-evidence for in-situ electrochemically-generated carbene formation
(Elsevier Ltd., 2017) Gokturk, A. P.; Salzner, U.; Nyulászi, L.; Ulgut, B.; Kocabas, C.; Süzer, Şefik
Stable N-heterocyclic carbenes (NHC) are a class of compounds that has attracted a huge amount of interest in the last decade. One way to prepare NHCs is through chemical or electrochemical reduction of 1,3-disubstituted imidazolium cations. We are presenting an in-situ electrochemical X-ray Photoelectron Spectroscopy (XPS) study where electrochemically reduced imidazolium cations lead to production of stable NHC. The electroactive imidazolium species is not only the reactant, but also part of the ionic liquid which serves as the electrolyte, the medium and the electroactive material. This allows us to directly probe the difference between the parent imidazolium ion and the NHC through the use of XPS. The interpretation of the results is supported by both observation of reversible redox peaks in the voltammogram and the density functional theory calculations.