Search results for: graphene

Authors: Somnath Bhattacharyya

Abstract:

The mobile adsorbed surface charge on hydrophobic surfaces can modify the velocity slip condition as well as create a Marangoni stress at the interface. The functionalized hydrophobic walls of micro/nanopores, e.g., graphene nanochannels, may possess physio-sorbed ions. The lateral mobility of the physisorbed absorbed ions creates a friction force as well as an electric force, leading to a modification in the velocity slip condition at the hydrophobic surface. In addition, the non-uniform distribution of these surface ions creates a surface tension gradient, leading to a Marangoni stress. The impact of the mobile surface charge on streaming potential and electrochemical energy conversion efficiency in a pressure-driven flow of ionized liquid through the nanopore is addressed. Also, enhanced electro-osmotic flow through the hydrophobic nanochannel is also analyzed. The mean-filed electrokinetic model is modified to take into account the short-range non-electrostatic steric interactions and the long-range Coulomb correlations. The steric interaction is modeled by considering the ions as charged hard spheres of finite radius suspended in the electrolyte medium. The electrochemical potential is modified by including the volume exclusion effect, which is modeled based on the BMCSL equation of state. The electrostatic correlation is accounted for in the ionic self-energy. The extremal of the self-energy leads to a fourth-order Poisson equation for the electric field. The ion transport is governed by the modified Nernst-Planck equation, which includes the ion steric interactions; born force arises due to the spatial variation of the dielectric permittivity and the dielectrophoretic force on the hydrated ions. This ion transport equation is coupled with the Navier-Stokes equation describing the flow of the ionized fluid and the 3fourth-order Poisson equation for the electric field. We numerically solve the coupled set of nonlinear governing equations along with the prescribed boundary conditions by adopting a control volume approach over a staggered grid arrangement. In the staggered grid arrangements, velocity components are stored on the midpoint of the cell faces to which they are normal, whereas the remaining scalar variables are stored at the center of each cell. The convection and electromigration terms are discretized at each interface of the control volumes using the total variation diminishing (TVD) approach to capture the strong convection resulting from the highly enhanced fluid flow due to the modified model. In order to link pressure to the continuity equation, we adopt a pressure correction-based iterative SIMPLE (Semi-Implicit Method for Pressure-Linked Equations) algorithm, in which the discretized continuity equation is converted to a Poisson equation involving pressure correction terms. Our results show that the physisorbed ions on a hydrophobic surface create an enhanced slip velocity when streaming potential, which enhances the convection current. However, the electroosmotic flow attenuates due to the mobile surface ions.

Keywords: microfluidics, electroosmosis, streaming potential, electrostatic correlation, finite sized ions

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Authors: Ling Ai, Ziyu Zhao, Zeyu Zhou, Xiaochen Yang, Heng Zhai, Stuart Holmes

Abstract:

Optimizing the catalyst layer structure is crucial for enhancing the performance of proton exchange membrane fuel cells (PEMFCs) with low Platinum (Pt) loading. Current works focused on the utilization, durability, and site activity of Pt particles on support, and performance enhancement has been achieved by loading Pt onto porous support with different morphology, such as graphene, carbon fiber, and carbon black. Some schemes have also incorporated cost considerations to achieve lower Pt loading. However, the design of the catalyst layer (CL) structure in the membrane electrode assembly (MEA) must consider the interactions between the layers. Addressing the crucial aspects of water management, low contact resistance, and the establishment of effective three-phase boundary for MEA, multi-walled carbon nanotubes (MWCNTs) are promising CL support due to their intrinsically high hydrophobicity, high axial electrical conductivity, and potential for ordered alignment. However, the drawbacks of MWCNTs, such as strong agglomeration, wall surface chemical inertness, and unopened ends, are unfavorable for Pt nanoparticle loading, which is detrimental to MEA processing and leads to inhomogeneous CL surfaces. This further deteriorates the utilization of Pt and increases the contact resistance. Robust chemical oxidation or nitrogen doping can introduce polar functional groups onto the surface of MWCNTs, facilitating the creation of open tube ends and inducing defects in tube walls. This improves dispersibility and load capacity but reduces length and conductivity. Consequently, a trade-off exists between maintaining the intrinsic properties and the degree of functionalization of MWCNTs. In this work, MWCNTs were modified based on the operational requirements of the MEA from the viewpoint of interlayer interactions, including the search for the optimal degree of oxidation, N-doping, and micro-arrangement. MWCNT were functionalized by oxidizing, N-doping, as well as micro-alignment to achieve lower contact resistance between CL and proton exchange membrane (PEM), better hydrophobicity, and enhanced performance. Furthermore, this work expects to construct a more continuously distributed three-phase boundary by aligning MWCNT to form a locally ordered structure, which is essential for the efficient utilization of Pt active sites. Different from other chemical oxidation schemes that used HNO3:H2SO4 (1:3) mixed acid to strongly oxidize MWCNT, this scheme adopted pure HNO3 to partially oxidize MWCNT at a lower reflux temperature (80 ℃) and a shorter treatment time (0 to 10 h) to preserve the morphology and intrinsic conductivity of MWCNT. The maximum power density of 979.81 mw cm-2 was achieved by Pt loading on 6h MWCNT oxidation time (Pt-MWCNT6h). This represented a 59.53% improvement over the commercial Pt/C catalyst of 614.17 (mw cm-2). In addition, due to the stronger electrical conductivity, the charge transfer resistance of Pt-MWCNT6h in the electrochemical impedance spectroscopy (EIS) test was 0.09 Ohm cm-2, which was 48.86% lower than that of Pt/C. This study will discuss the developed catalysts and their efficacy in a working fuel cell system. This research will validate the impact of low-functionalization modification of MWCNTs on the performance of PEMFC, which simplifies the preparation challenges of CL and contributing for the widespread commercial application of PEMFCs on a larger scale.

Keywords: carbon nanotubes, electrocatalyst, membrane electrode assembly, proton exchange membrane fuel cell

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