Fuel cell-powered microfluidic platform for lab-on-a-chip applications

The achievement of a higher degree of integration of components--especially micropumps and power sources--is a challenge currently being pursued to obtain portable and totally autonomous microfluidic devices. This paper presents the integration of a micro direct methanol fuel cell (μDMFC) in a microfluidic platform as a smart solution to provide both electrical and pumping power to a Lab-on-a-Chip system. In this system the electric power produced by the fuel cell is available to enable most of the functionalites required by the microfluidic chip, while the generated CO(2) from the electrochemical reaction produces a pressure capable of pumping a liquid volume through a microchannel. The control of the fuel cell operating conditions allows regulation of the flow rate of a liquid sample through a microfluidic network. The relation between sample flow rate and the current generated by the fuel cell is practically linear, achieving values in the range of 4-18 μL min(-1) while having an available power between 1-4 mW. This permits adjusting the desired flow rate for a given application by controlling the fuel cell output conditions and foresees a fully autonomous analytical Lab-on-a-Chip in which the same device would provide the electrical power to a detection module and at the same time use the CO(2) pumping action to flow the required analytes through a particular microfluidic design.     

采用甲烷燃料的管状固体氧化物燃料电池浸渍阳极电化学性能

以NiO和8％（摩尔分数）氧化钇稳定的氧化锆为原料,采用注凝成型工艺制备了管状同体氧化物燃料电池阳极支撑体．用离子浸渍法对阳极支撑体进行表面修饰．用电化学工作站测单电池交流阻抗和输出性能并且用化学气相色谱仪对电池尾气进行分析．测试结果表明修饰后的阳极在通甲烷的情况下出现了一定程度的积炭,但是积炭现象在一定的测试时间内达到平衡,没有对电池造成破坏,并且显著地提高了电池阳极的电化学性能．单电池存通入氯气和甲烷的情况下最大输出功率密度分别达到了225和400mW／cm^2．     

Membraneless, room-temperature, direct borohydride/cerium fuel cell with power density of over 0.25 W/cm2

The widespread adoption and deployment of fuel cells as an alternative energy technology have been hampered by a number of formidable technical challenges, including the cost and long-term stability of electrocatalyst and membrane materials. We present a microfluidic fuel cell that overcomes many of these obstacles while achieving power densities in excess of 250 mW/cm(2). The poisoning and sluggish reaction rate associated with CO-contaminated H(2) and methanol, respectively, are averted by employing the promising, high-energy density fuel borohydride. The high-overpotential reaction of oxygen gas at the cathode is supplanted by the high-voltage reduction of cerium ammonium nitrate. Expensive, ineffective membrane materials are replaced with laminar flow and a nonselective, porous convection barrier to separate the fuel and oxidant streams. The result is a Nafion-free, room-temperature fuel cell that has the highest power density per unit mass of Pt catalyst employed for a non-H(2) fuel cell, and exceeds the power density of a typical H(2) fuel cell by 50%.     

Optimization of a permeation-based microfluidic direct formic acid fuel cell (DFAFC)

A design for a passive, air-breathing microfluidic fuel cell utilizing formic acid (FA) as a fuel is described and its performance characterized. The fuel cell integrates high surface area platinum (cathode) and palladium-platinum (anode) alloy electrodes within a PDMS microfluidic network that keeps them fully immersed in a liquid electrolyte. The polymer network that comprises the device also serves as a self-supporting membrane through which FA and oxygen are supplied to the alloy anode and cathode, respectively, by passive permeation from external sources. The cell is based on a planar form-factor and in its operation exploits FA concentration gradients that form across the PDMS membrane. These latter gradients allow the device to operate stably, producing a nearly constant limiting power density of ~0.2 mW/cm2, without driven laminar flow of fluids or the incorporation of an in-channel separator between the anodic and the cathodic compartments. The power output of this elementary device in air is subject to electrolyte mass transport impacts, which can be reduced for a given design rule by decreasing the internal ohmic resistance of the cell. The results suggest that operational stability can be improved by decreasing the kinetic losses imposed on the cathode side of the cell due to FA crossover and modalities for doing so, such as by increasing the efficiency of fuel capture at the anode.     

Ba_(0.95)Ce_(0.9)Y_(0.1)O_(3-α)固体氧化物的离子导电性及其燃料电池性能

以Ba0 .95Ce0 .9Y0 .1O3-α氧化物陶瓷为固体电解质 ,以多孔性Pt为电极材料 ,分别组成氢、氧浓差电池和氢_空气燃料电池 ,测定了 6 0 0～ 10 0 0℃范围内的浓差电池电动势 ,燃料电池的放电性能和电极极化性能 .结果表明 ,Ba0 .95Ce0 .9Y0 .1O3-α在氢气氛中几乎是一个纯质子导体 ,在氧气氛中是氧离子与电子空穴的混合导体 ,氧离子迁移数在 0 .3～ 0 .5之间 ,在氢_空气燃料电池条件下显示出混合离子 (质子 +氧离子 )导电性 ,总离子迁移数大于 0 .9.该燃料电池性能良好 ,Pt电极极化性能很小 ,最大输出电流密度为 6 80mA·cm- 2 (10 0 0℃ ) ,最大输出功率密度为 16 0mW·cm- 2 (10 0 0℃ ) .     

Design and characterization of flow-through coulometric cells with porous working electrodes made of crushed vitreous carbon

Summary Three types of flow-through, three-electrode cells with porous working electrodes made of crushed vitreous carbon were tested. The electrochemical properties of the cells were studied by hydrodynamic and cyclic voltammetry using potassium ferrocyanide test solutions. Depending on the volume of the porous working electrode, Nernstian behaviour and electrochemical yields up to 100% were observed for flow rates 1 to 7 ml/min. In the stopped-flow regime the cells exhibit thin-layer cell properties. The utility of the cells is demonstrated for on-line coulometric detection, continuous removal of impurities and dissolved oxygen and for anodic stripping coulometry of trace copper.On leave from: Department of Analytical Chemistry, Slovak Technical University, CS-812 37 Bratislava, Czechoslovakia     

A passive microfluidic hydrogen-air fuel cell with exceptional stability and high performance

We describe an advanced microfluidic hydrogen-air fuel cell (FC) that exhibits exceptional durability and high performance, most notably yielding stable output power (>100 days) without the use of an anode-cathode separator membrane. This FC embraces an entirely passive device architecture and, unlike conventional microfluidic designs that exploit laminar hydrodynamics, no external pumps are used to sustain or localize the reagent flow fields. The devices incorporate high surface area/porous metal and metal alloy electrodes that are embedded and fully immersed in liquid electrolyte confined in the channels of a poly(dimethylsiloxane) (PDMS)-based microfluidic network. The polymeric network also serves as a self-supporting membrane through which oxygen and hydrogen are supplied to the cathode and alloy anode, respectively, by permeation. The operational stability of the device and its performance is strongly dependent on the nature of the electrolyte used (5 M H2SO4 or 2.5 M NaOH) and composition of the anode material. The latter choice is optimized to decrease the sensitivity of the system to oxygen cross-over while still maintaining high activity towards the hydrogen oxidation reaction (HOR). Three types of high surface area anodes were tested in this work. These include: high-surface area electrodeposited Pt (Pt); high-surface area electrodeposited Pd (Pd); and thin palladium adlayers supported on a "porous" Pt electrode (Pd/Pt). The FCs display their best performance in 5 M H2SO4 using the Pd/Pt anode. This exceptional stability and performance was ascribed to several factors, namely: the high permeabilities of O2, H2, and CO2 in PDMS; the inhibition of the formation of insoluble carbonate species due to the presence of a highly acidic electrolyte; and the selectivity of the Pd/Pt anode toward the HOR. The stability of the device for long-term operation was modeled using a stack of three FCs as a power supply for a portable display that otherwise uses a 3 V battery.     

Using layer-by-layer assembly of polyaniline fibers in the fast preparation of high performance fuel cell nanostructured membrane electrodes

Membrane electrode assemblies (MEA) for fuel cells require optimization of their nanoscale organization to reach performance parameters, which include enhanced power density, increased catalyst utilization and reduced cost. We applied sprayed layer-by-layer assembly to produce a high activity MEA for H(2)/O(2) fuel cells from polyaniline fibers (PANI-F). This technique produces "fast-prepared" membranes with nanoscale structure, which allows to adequately address specific tuning of their porosity, platinum loading, electronic conductivity, and proton conductivity. Pt nanoparticles were attached to the PANI-F in a reaction of selective heterogeneous nucleation. After functionalization, Pt/PANI-F were assembled with Nafion. Microscopic investigation revealed that functionalized polyaniline fibers formed a highly porous yet tight network of interpenetrating conductors connected to the catalytic Pt particles. The Pt/PANI-F LBL ultrathin MEA demonstrated a power densitiy of 63 mW cm(-2) and yielded a Pt utilization of 437.5 W g(-1) Pt which is comparable to the traditional fuel cell using carbon black as Pt support. Moreover, the amount of Pt used in this work is almost 2 times lower than for usual carbon-supported Pt catalysts.     

碱性直接甲醇燃料电池含氟阴离子交换膜的制备及性能研究

以甲基丙烯酸二甲基氨基乙酯和甲基丙烯酸三氟乙酯为单体,经过自由基聚合反应、成膜和碱化3个步骤制备氢氧型的DMAEMA/TFMA聚合物阴离子交换膜,系统表征该聚合物膜的结构和性能.结果表明:室温下其电导率可达10-2 S.cm-1;该膜的甲醇渗透系数低于10-7 cm2.s-1;以该膜组装的单电池在室温下的最大功率密度为43.2 mW/cm2,在燃料电池中有良好的应用前景.     

Characterization of Pt nanoparticles deposited onto carbon nanotubes grown on carbon paper and evaluation of this electrode for the reduction of oxygen

Multiwalled carbon nanotubes (MWCNTs) were grown on the fibers of a commercial porous carbon paper used as carbon-collecting electrodes in fuel cells. The tubes were then covered with Pt nanoparticles in order to test these gas diffusion electrodes (GDEs) for oxygen reduction in H2SO4 solution and in H2/O2 fuel cells. The Pt nanoparticles were characterized by cyclic voltammetry, transmission electron microscopy, and X-ray photoelectron spectroscopy. The majority of the Pt particles are 3 nm in size with a mean size of 4.1 nm. They have an electrochemically active surface area of 60 m2/g Pt for Pt loadings of 0.1-0.45 mg Pt/cm2. Although the electroactive Pt surface area is larger for commercial electrodes of similar loadings, Pt/MWCNT electrodes largely outperform the commercial electrode for the oxygen reduction reaction in GDE experiments using H2SO4 at pH 1. On the other hand, when the same electrodes are used as the cathode in a H2/O2 fuel cell, they perform only slightly better than the commercial electrodes in the potential range going from approximately 0.9 to approximately 0.7 V and have a lower performance at lower voltages.     

Air-breathing laminar flow-based microfluidic fuel cell

This communication reports the design and characterization of an air-breathing laminar flow-based microfluidic fuel cell (LFFC). The performance of previous LFFC designs was cathode-limited due to the poor solubility and slow transport of oxygen in aqueous media. Introduction of an air-breathing gas diffusion electrode as the cathode addresses these mass transfer issues. With this design change, the cathode is exposed to a higher oxygen concentration, and more importantly, the rate of oxygen replenishment in the depletion boundary layer on the cathode is greatly enhanced as a result of the 4 orders of magnitude higher diffusion coefficient of oxygen in air as opposed to that in aqueous media. The power densities of the present air-breathing LFFCs are 5 times higher (26 mW/cm2) than those for LFFCs operated using formic acid solutions as the fuel stream and an oxygen-saturated aqueous stream at the cathode ( approximately 5 mW/cm2). With the performance-limiting issues at the cathode mitigated, these air-breathing LFFCs can now be further developed to fully exploit their advantages of direct control over fuel crossover and the ability to individually tailor the chemical composition of the cathode and anode media to enhance electrode performance and fuel utilization, thus increasing the potential of laminar flow-based fuel cells.     

非贵金属催化的碱性硫离子燃料电池放电特性

燃料的选择对于燃料电池电极催化剂的选择、燃料电池的成本及其商业化有着至关重要的影响寻求电化学活性好、成本低,并且能够为非贵金属催化剂所催化的燃料是一项有前景的工作.硫离子的电化学活性及其低成本使之成为一个具有吸引力的选择.本文以碱性硫离子作为燃料构建了碱性硫离子燃料电池.在室温条件下,单体电池在以非贵金属为催化剂的条件下获得了12.3 mW· cm-2的功率密度,此时的电流密度达到了42.8 mA·cm-2; 50 h寿命测试显示了碱性硫离子燃料电池良好的稳定性.此外,通过离子色谱分析,在放电产物中检测到了硫代硫酸盐、亚硫酸盐以及硫酸盐.深度氧化使得硫离子具有更高的放电容量.与之前研究的燃料相比,硫离子具有成本低、运输容易、电化学活性高并且能够被非贵金属催化剂催化的优点.     

A miniature, nongassing electroosmotic pump operating at 0.5 V

Electroosmotic pumps are arguably the simplest of all pumps, consisting merely of two flow-through electrodes separated by a porous membrane. Most use platinum electrodes and operate at high voltages, electrolyzing water. Because evolved gas bubbles adhere and block parts of the electrodes and the membrane, steady pumping rates are difficult to sustain. Here we show that when the platinum electrodes are replaced by consumed Ag/Ag(2)O electrodes, the pumps operate well below 1.23 V, the thermodynamic threshold for electrolysis of water at 25 °C, where neither H(2) nor O(2) is produced. The pumping of water is efficient: 13?000 water molecules are pumped per reacted electron and 4.8 mL of water are pumped per joule at a flow rate of 0.13 mL min(-1) V(-1) cm(-2), and a flow rate per unit of power is 290 mL min(-1) W(-1). The water is driven by protons produced in the anode reaction 2Ag(s) + H(2)O → Ag(2)O(s) + 2H(+) + 2e(-), traveling through the porous membrane, consumed by hydroxide ions generated in the cathode reaction Ag(2)O(s) + 2 H(2)O + 2e(-) → 2Ag(s) + 2 OH(-). A pump of 2 mm thickness and 0.3 cm(2) cross-sectional area produces flow of 5-30 μL min(-1) when operating at 0.2-0.8 V and 0.04-0.2 mA. Its flow rate can be either voltage or current controlled. The flow rate suffices for the delivery of drugs, such as a meal-associated boli of insulin.     

微型氢气/空气自呼吸式质子交换膜燃料电池

数码相机、手提电脑和移动电话等各种新型的电子产品对电池的能量要求越来越高．例如,配备最新的Li离子电池的数码相机只能连续工作30min,手提电脑只运行3h．显然传统电池的发展已越来越不能满足便携式电子设备的用电需求．微型质子交换膜燃料电池(μPEMFC)由于具有高比能量、无需充电和无自放电等优点,在便携式电子设备中具有广阔的应用前景．然而,用传统技术制作μPEMFC不能适应PEMFC微型化要求．因此基于微机电系统(MEMS)技术的微型质子交换膜燃料电池(μPEMFC)已成为国际上的研究热点．2000年,Kelley等基于MEMS技术制作了μPEMFC,随后又在30℃,用加湿氢气作燃料,压缩空气为氧化剂(流速为0．2L／min),电池峰值功率约为120mW／cm^2等条件下进一步研究了μPEMFC。     

单室固体氧化物燃料电池阴极材料La0.75Sr0.25Cr0.5Mn0.5O3的电化学性能研究

采用高温固相法制备了La0.75Sr0.25Cr0.5Mn0.5O3(LSCM)并利用XRD,SEM以及电化学阻抗谱(EIS)分别对粉体及电极进行研究。结果发现LSCM在C3H8-O2-N2混合气氛下能够保持很好的高温化学稳定性,且与电解质材料YSZ在1400℃空气气氛下不发生化学反应。电化学测试结果表明,阳极支撑型单室固体氧化物燃料电池Ni-YSZ|YSZ|LSCM在700℃、C3H8-O2-N2混合气氛下的短路电流密度达317 mA·cm-2,最大功率密度73 mW·cm-2。将LSCM与CGO形成梯度阴极,相同测试条件下,单室电池的短路电流密度为560 mA·cm-2,功率密度达到110 mW·cm-2,电池输出性能提高约50%。     

A dual electrolyte H2/O2 planar membraneless microchannel fuel cell system with open circuit potentials in excess of 1.4 V

A dual electrolyte H2/O2 fuel cell system employing a planar microfluidic membraneless fuel cell has been investigated and compared to single electrolyte H2/O2 systems under analogous conditions. The fuel is H2 dissolved in 0.1 M KOH (pH 13), and the oxidant is O2 dissolved in 0.1 M H2SO4 (pH 0.9), comprising a system with a calculated thermodynamic potential of 1.943 V (when 1 M H2 and O2 concentrations are assumed). This value is well above the calculated thermodynamic maximum of 1.229 V for an acid, or alkaline, single electrolyte H2/O2 fuel cell. Experimentally, open-circuit potentials in excess of 1.4 V have been achieved with the dual electrolyte system. This is a 500 mV increase in the open circuit potentials observed for single electrolyte H2/O2 systems also studied. The dual electrolyte fuel cell system shows power generation of 0.6 mW/cm2 from a single device, which is nearly 0.25 mW/cm2)greater than the values obtained for single electrolyte H2/O2 fuel cell systems studied. Microchannels of varying dimensions have been employed to study both the single and dual electrolyte H2/O2 systems. Channel thickness variation and the flow rate dependences of power generation are also addressed.     

Combinatorial approach toward high-throughput analysis of direct methanol fuel cells

A 40-member array of direct methanol fuel cells (with stationary fuel and convective air supplies) was generated by electrically connecting the fuel cells in series. High-throughput analysis of these fuel cells was realized by fast screening of voltages between the two terminals of a fuel cell at constant current discharge. A large number of voltage-current curves (200) were obtained by screening the voltages through multiple small-current steps. Gaussian distribution was used to statistically analyze the large number of experimental data. The standard deviation (sigma) of voltages of these fuel cells increased linearly with discharge current. The voltage-current curves at various fuel concentrations were simulated with an empirical equation of voltage versus current and a linear equation of sigma versus current. The simulated voltage-current curves fitted the experimental data well. With increasing methanol concentration from 0.5 to 4.0 M, the Tafel slope of the voltage-current curves (at sigma=0.0), changed from 28 to 91 mV.dec-1, the cell resistance from 2.91 to 0.18 Omega, and the power output from 3 to 18 mW.cm-2.     

An air-breathing microfluidic fuel cell with a finny anode

Using COMSOL multiphysics software and a previously validated 3D numerical model, performances of a novel air-breathing microfluidic fuel cell (MFFC) are discussed. The microfluidic fuel cell employs a simple structure composed of a flow channel with sloped upper wall, a gas diffusion cathode and a finny anode. Furthermore it can reduce the losses related to mixing in fuel-electrolyte interface and also promote the replenishment of the depletion layer on anode surfaces. Thus, high fuel utilization can be achieved. Numerical simulations show that the fuel utilization can be up to 70%.     

Highly Efficient Oxygen Reduction Reaction Fe-N-C Cathode in Long-durable Direct Glycol Fuel Cells

The oxygen reduction reaction in direct glycol fuel cells heavily relies on noble metal-based electrocatalysts. In this work, novel Pt group metal-free catalysts based on porous Fe-N-C materials are successfully synthesized as catalysts with high activity and durability for the cathode oxygen reduction reaction (ORR). Through the encapsulation of NH₄SCN salt, the surface elements and pore structure of the catalyst are effectively changed, and the active sites of Fe effectively are increased. The half-wave potential of the best Fe-N-C catalyst was –0.02 V vs. Hg/HgO in an alkaline environment. The porous Fe-N-C catalyst possesses a large specific surface area(1158 m²/g) and shows good activity and tolerance to glycol. The direct glycol fuel cell with the Fe-N-C cathode achieved a maximum power density of 62.2 mW/cm² with 4 mol/L KOH and 4 mol/L glycol solution at 25 °C and maintained discharge for more than 250 h at a 50 A/cm² current density.