A program of study has been established for the quantitative study of electrode reactions in solid oxide fuel cells. The initial focus of the program is the mixed conducting cathode material strontium-doped lanthanum manganate (LSM). A formalism was established treating reactions taking place at the gas-exposed surface of mixed conducting electrodes. This formalism was incorporated into a phenomenological model for oxygen reduction in LSM, which treats the phenomenon of sheet resistance. Patterned electrodes were designed that reduce the dimensionality of the appropriate model, and these electrodes were successfully fabricated using DC sputtering and photolithography. A new model for the bulk defect equilibrium in LSM was proposed and shown to be a better fit to nonstoichiometry data at low temperatures. The fitting was carried out with a particle swarm optimizer and a rigorous method for identification. It was shown that a model for the interface structure between LSM and yttria-stabilized zirconia (YSZ) that assumes free oxygen vacancies in YSZ does not accord with experimental observations. Cluster variation method (CVM) was adapted for analysis of the problem, and a new analytical method combining CVM and electrical contributions to the free energy was proposed.

In the study, micro-PEM fuel cells are designed and fabricated in-house through a deep UV lithography SU-8 process and a wet etching technique for perforated holes plates (diameter is 750 £gm) of 50 £gm thickness of pure copper. Measurements of cell performance are performed using the low percentage of the weight concentration (1-10 wt. %) of NaOH solution, Al paper as the source material for hydrogen production, and different open ratios of the perforated plates to determine which best improves cell power density. Experimental results are presented in the form of polarization VI and PI curves under the above operating conditions. The experimental results show cell performance is enhanced by the self-heating, humidifying of hydrogen production, hydrogen internal circulation and accumulated pressure. Finally, the micro-PEM fuel cell system with DC/DC boost converter can generate 4.99 V for use in cellular phone accumulators charging.

This thesis proposes an adaptive control approach to regulate the hydrogen feed of a fuel cell. The goal of the controller is to maintain the so-called hydrogen excess ratio, defined as the ratio between the hydrogen fed to the cell stake and those consumed in the stake, at a desired level when the fuel cell is under load variation. Maintaining the hydrogen excess ratio at an appropriate level would avoid hydrogen starvation, which is crucial for slowing degeneration of the fuel cell membranes and prolonging the life of the cell stake. The control approach we propose is based on the receding horizon linear quadratic optimal control algorithm with an on-line turning scheme which updates the plant model according to real-time measurement. To ease the computational complexity and make real-time turning realizable, we adopt a simple autoregressive with external disturbance (ARX) model to approximate the complicate chemical/electrical process of the fuel cell. The proposed adaptive control approach is implemented on an experimental platform. The experimental results show that the proposed control works with reasonably good performance.

The proton exchange membrane fuel cells should have three major advantages: 1. micro-phase separation, 2. mechanical properties and 3. thermal stability. According to the recent literature and the material of core benzene ring poly (arylene ether)s studied by our group, this paper synthesize a series of the locally and densely sulfonated polymer. We use core benzene ring as the diol monomer and the containing CF3 groups as the fluorine monomer to synthesis poly (arylene ether)s via nucleophilic displacement reactions, and then use the different concentrations synthesized sulfonated polymer by sulfonic acid reaction. According to NMR¡¦s result we confirmed that the structure of synthetic materials is correct. By using GPC we get that the KP1, KP2, and KP3¡¦s molecular weight about 20000 (g/mol) ; The thermal stability up to 530OC for 5% loss in TGA under nithtrogen, to prove thisseries of polymer excellent thermal stability. After sulfonation, SKP1, SKP2 and SKP3¡¦s decomposition temperature decreased about 200OC ~ 250OC ranging with increasing degree of sulfonation. By DSC analysis, K1, K2 and K3 monomer's Tg followed up with the increase of the benzene ring number, however, the polymer does not have any apparent peak. About the Proton conductive, SKP2C IEC 2.23mequiv / g, water uptake 94%, the highest proton conductivity can be as high as 68.2 mS / cm, has been similar to Nafion 117 of 70 mS / cm.

Proton Exchange Membrane Fuel Cell has the potential to become an important energy conversion technigne. Lots of efforts oriented toward the electrochemical conversion of energy using proton exchange membrane (PEM) fuel cells have been enormously accelerated with the hope to promote as an alternative power source for transport and portable purposes. However, they still suffer from such disadvantages as limited operation temperature, high cost, insufficient durability and high methanol permeability.Good membranes should meet several strict requirements as follows; reasonable proton conductivity, high stability and durny the performance of a fuel cell environment,outstanding mechanical toughness, high heat endurance, and impermeability to fuel gas or liquid. Presently,a lot of references have mentioned some sulfonatied polymer sulfonated of poly(ether ether ketone) (SPEEK), sulfonatedpolysulfone (SPSF), sulfonated polysulfide sulfone(SPSS), and polybenzimidazole(PBI) and so on.To achieve high proton conductivity usually match with a high degree of sulfonation that means owning a large Ion Exchange Capacity, IEC.But which in turn leads to a decrease in the electrochemical¡Bdimensional stability¡Bwater uptake¡Boxidative stability. Therefore they suffer from such disadvantages as limited operation range of temperature.Three aromatic poly(arylene ether)s P4b¡BP4c¡BP4d were synthesized from the polymer consists nine of polyaromatic groups with bisfluoride monomer at studying long time in our laboratory with S1¡BS2¡BS3 diol monomer.The molecular weight of the polymer (Mw:1.49¡Ñ105~5.3¡Ñ105 g/mol ,PDI: 1.82~2)This polymer has high strength,thermal stability and all of polymers own very high Td ,which are over than 500oC.We sulfonatied the polymer in order to apply as the proton exchange membrane of a fuel cell.The results showed after sulfonation of P4b¡BP4c¡BP4d.All IEC reaches 3.9~1(meq/g).According to above result, we propose the aromatic poly(arylene ether)s is good matenal can be used on all application as a proton exchange membrane.

This research mainly investigated how the hydrophilic and hydrophobic properties of gas diffusion layer, and the different open ratio of the flowfield may affect the performance of the micro proton exchange membrane fuel cell (£gPEMFC). The flow plate used in this experiment was made through deep UV lithography manufacturing processes and micro-electroforming manufacturing processes. Four different open ratios, 52.8 %, 50.8 %, 75.2 % and 75.75 %, of the flowfield were designed for the flow plate composed of serpentine-parallel and serpentine geometrical micro configurations. Acrylic (PMMA: Polymethylmethacrylate) was used to make the terminal plate placed on both sides of the micro proton exchange membrane fuel cell. By varying values of the hydrophilic and hydrophobic properties of the anode gas diffusion layer, the effects of these two parameters on the polarization curve and power density of the cell were explored. All results obtained in the experiment are presented by P-I curve and V-I curve. The experiment results show that, with 1: 5 flow ratio of anode to cathode, a design with the gas diffusion layer made of the material with hydrophobic factor 20 wt.% and with open ratio of 50.8 % for anode flow channel as well as open ratio of 75.75 % for cathode flow channel may have the best performance.

The purpose of this thesis is to design hardware and a control strategy for a fuel cell/battery hybrid power supply. Modern fuel cell/battery hybrid power supplies can have 2 DC/DC converters: one converter for the battery and one for the fuel cell. The hardware for the power supply proposed in this thesis consists of a single DC/DC buck converter at the output terminals of the fuel cell. The battery does not have a DC/DC converter, and it is therefore passive in the system. The use of one single converter is attractive, because it reduces the cost of this power supply. This thesis proposes a method of controlling the fuel cell's DC/DC buck converter to act as a current source instead of a voltage source. This thesis will explain why using the fuel cell's buck converter to act as a current source is most appropriate. The proposed design techniques for the buck converter are also based on stiff systems theory. Combining a fuel cell and a battery in one power supply allows exploitation of the advantages of both devices and undermines their disadvantages. The fuel cell has a slow dynamic response time, and the battery has a fast dynamic response time to fluctuations in a load. A fuel cell has high energy density, and a battery has high power density. And the performance of the hybrid power supply exploits these advantages of the fuel cell and the battery. The controller designed in this thesis allows the fuel cell to operate in its most efficient region: even under dynamic load conditions. The passive battery inherits all load dynamic behavior, and it is therefore used for peaking power delivery, while the fuel cell delivers base or average power. Simulations will be provided using MATLAB/Simulink based models. And the results conclude that one can successfully control a hybrid fuel cell/battery power supply that decouples fluctuations in a load from the fuel cell with extremely limited hardware. The results also show that one can successfully control the fuel cell to operate in its most efficient region.

The characteristics of the proton exchange membrane fuel cell (called PEMFC) stacks made with the graphite unipolar/bipolar plates are studied in this thesis. Using pure hydrogen as fuel, certain experimental work is conducted to help us to understand the factors which influence on the performance of a HFC stack. The experimental work under various operating conditions starts from single cell stacks to multi-cell stacks. The maximum power is about 200 W, which is made with two 10-cell stacks in series. For simplification, all of the flow channels in the cathode are open type in which air is directly supplied from ambient by fan. The comparison of the performance of two single cells, which are made with both a graphite unipolar plate and a new-type carbon fiber unipolar plate, is conducted. The total resistances of the two types of bipolar plates with gas diffusion layers are tested to help us to understand their strong or weak points. The experimental results display that the double inlets has better performance than the single inlet due to larger entrance space. Increasing the applied torque will reduce the contact resistance between bipolar plate and diffusion layer and also the gaps between the fibers of carbon cloth. Reducing the contact resistance is helpful in increasing the performance of the cell, but reducing the gaps between fibers will inhibit the entering of reactive gas and is unfavorable for performance; therefore, the proper torque is necessary to obtain the best voltage output. When air is used as an oxidizer and the flow channel is an open type channel, the fan in high rotating speed is helpful at high current density. The high air volume flow rate can supply sufficient oxidizer and avoid the decay of the voltage output at high current density. At the current density 1 A/cm2, the power density of the single-cell stack is about 400 mW/cm2 and the power density of the 10-cell stack is down to about 310 mW/cm2 in our experiment. The rib of the carbon fiber unipolar/bipolar plate is soft, so there is no deformation in the gas diffusion layer in stack assembly. Only slight compression is needed to assemble a stack; therefore, the reactive gas can easily flow into the most of active area. This type unipolar/bipolar plate is made with low density plastic except that the rib is made with carbon fiber bunches. Thus the new plate is weight light, cost low and volume small. So it is quite possible that the new-type of carbon fiber plate is used as substitution for the graphite bipolar plate in the future. In that case the light, low cost and high performance choice can be achieved.

For the past few decades, Ni-YSZ (yttria-stabilized zirconia) has been the dominate anode material of high temperature (>1000¢J) solid oxide fuel cells (SOFCs). However, the conductivity of Ni/YSZ is not enough when the operation temperature is in the intermediate rage of 500~700¢J. Instead, Ni/CGO is a good candidate as the anode material of intermediate temperature SOFCs (IT-SOFC), due to its enhanced conductivity. This work was aimed at the preparation of Ni/CGO composite anodes using the electrostatic assisted ultrasonic spray pyrolysis (EAUSP) method. By properly adjusting the deposition parameters, highly porous composite films with desired phases and microstructure rendering low electrode impedances were obtained. The results indicated that deposition temperature and the applied voltage dictated the evolution of film morphology and hence the interface impedance between the electrode and the electrolyte. Therefore, the optimum deposition parameters for the best microstructure and hence minimum interface impedance were 12 kV for the applied voltage, 6 : 4 for the Ni-CGO mole ratio, 450¢J for the deposition temperature. The microstructure thus obtained possessed a cauliflower-like structure with high porosity. The resultant interface impedance at 550¢J was 0.09 Ωcm2, lower than that obtained from the conventional anode preparation routes of dip-casting (0.14 Ωcm2) or mechanical mixing (0.12 Ωcm2).

In this research the effects of the fabrication processes of MEA on the output power of a DMFC stack are studied by changing hot-pressing conditions including pressure, temperature and time. Additionally, the effects of the various treatments of the MEAs on the output voltage and power are also studied after the hot-pressing process of MEA is finished. In the first experimental study the catalyst of cathode is 4.0mg/cm unsupported HP Pt black, Anode is 4.0mg/cm 80% HP Pt-Ru Alloy (1: 1), membrane is Nafion 117, and bipolar plates is heterogeneous carbon fiber bipolar plate developed by our fuel cell laboratory. The MEA for single cell includes the area of membrane 3*3 cm2 the active area of electrode 1.5*1.5 cm2. Under the hot-pressing conditions 120 oC, 100 bar and 90s, the maximum power density can reach a value of 18 mW/cm2 at the conditions of methanol concentration 3 M, air-breathing, and room temperature After several experiments, we observed that performances of MEAs decayed with time. So we designed a series of experiments to inspect the various possible reasons and try to solve this problem. The cylindrical DMFC is one of the most important developments in our lab. However, the MEAs made for plate-type DMFC do not fit the cylindrical DMFC stack properly. The electrodes easily pealed off from the membrane and the contact resistance increases after certain periods. So the hot-pressing device had been redesigned to fit the cylindrical DMFC stack. After that the total power of the 6-cell stack with total active area 15 cm2 can reach a value 135 mW. If the performance of each cell of the 6-cell stack is uniform, we expect that the total power of this stack can reach a higher value 195 mW, which can be applied to some portable electronic products.