PEM Fuel Cell

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Chapter.1 INTRODUCTION

Recent advances in miniaturization of both electronics and MEMS devices have resulted in a considerable power reduction .On the other hand, the size of power supplies for such miniaturized devices has scaled down only marginally. Downsizing conventional batteries to wafer level causes various problems. For example electrode materials or liquid electrolytes of the chip-integrated batteries just as those of conventional systems have to be hermetically sealed in order to prevent defects caused by interaction with oxygen or water in ambient atmosphere. The system presented in this paper consists of fuel cells(FCs) connected in series, so called fuel cell cascades (FCCs)(Fig. 1.1), a core system to control the output voltage by a low dropout voltage regulator (LDO) (Fig. 2) and circuitry to check and bypass empty or defective FCs to keep the FCCs functional.

Fig 1.1 Prototype of the fuel cell cascades, 7 cascades consisting of 8 single chipintegrated fuel cells in a PLCC68 ceramic package

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CHAPTER.2 INTEGRATED FUEL CELLS

2.1. SETUP OF A SINGLE INTEGRATED FUEL CELL

Conventional PEM fuel cells consist of a polymer electrolyte membrane (PEM), two gas diffusion electrodes, two diffusion layers and two flow fields. The reactants e.g., hydrogen and oxygen are supplied to the gas diffusion electrodes over feedpipes out of external tanks. The amount of supplied fuel is often controlled by active system periphery like pressure reducers and valves. For the chip integration a new setup principle of PEM fuel cells was developed, the new kind of fuel cell is made up of a palladium based hydrogen storage and an air breathingcathode both separated by a PEM. The layout of an integratedfuel cell is depicted in Fig. 2.2. Advantages of the new approachare the omission of active devices for fuel supply and the reductionof system components like flow fields and diffusion layers.Due to the simple assembly process, the fuel cells can be producedby thin film technologies and can be fabricated within anextended CMOS process.

Fig 2.1 Chip photo after CMOS fabrication depicting the core system

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Fig. 2.2Layout of a chip-integrated fuel cell and its performance data compared to state of the art wafer level batteries (WLB).

2.2 THE INTEGRATED HYDROGEN STORAGE

Palladium is used for the storage of hydrogen. This metal isknown for its extraordinary ability to store huge amounts of hydrogen.At room temperature and atmospheric pressure palladiumcan store about 900 times as much hydrogen as its own volume, which corresponds to an atomic relation of hydrogento palladium (H/Pd) of at least 70% (Fig. 2.3). The theoretical capacityof palladium is calculated to 2.12 Ah/cm , which is in the same range as Lithium (2.09 Ah/cm ). Calculating the theoreticalcapacity of the chip integrated fuel cell, the thicknesses ofall the active fuel cell components have to be considered. In theactual assembly the hydrogen storage represents approximately1/4 of the total volume of the micro energy device, the capacityof the chip integrated fuel cell results in 2.12/4 Ah/cm^2 500 mAh cm^2 .

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Therefore, the fuel cell has the potential to providehigher capacity than state-ofthe-art wafer level batteries(WLB) based on lithium-ion technology (Fig. 2.2) .Since theoptimization of the system components is still in progress, acomprehensive characterization of the chip-integrated fuel cellsystem could not yet be completed. The values for energy densityare based on the considerations made above; power densityresults were gained by the characterization of the hybrid system. Data about shelf life of the micro energysystem are based on the characterization of single chipintegratedfuel cells. These measurements revealed open circuitvoltage values above 500 mV for more than 100 days. Advantages of palladium compared to lithium based cells areits non toxicity and the fact that it is inert to environmental gases like oxygen or nitrogen. Thus, the integrated, thick sealinglayer which prevents the intrusion of gases and humidity inlithium-based wafer level batteries can be omitted. The metal palladium is already being used in CMOS compatible semiconductorprocesses like the fabrication of hydrogen sensorsand the backside conduction of silicon wafers .When apalladium layer is evaporated onto a silicon chip, directly connectedto the circuitry and loaded with hydrogen, a storage withhigh capacity, fully integrated onto a chip, can be realized. Theamount of stored hydrogen and therefore the fuel cells capacityof electrical energy can be controlled by the thickness of thepalladium layer. Thin films can be fabricated by evaporationonto silicon substrates; thicker films up to some 100 m can befabricated by electroplating of palladium or by thick film techniqueslike screen printing. Despite the unique scalability of thethickness of the fuel cells hydrogen storage up to some hundredmicrometers, the power and energy density of wafer level batteries, cannot be compared to conventionalmacroscopic systems since the volume fraction of thepassive components (electrodes, substrate and sealing) becomesvery dominant compared to the volume of the active storage materials.Thus, the achievable maximum energy density in microscopicsystems is significantly smaller than that of conventional systems.

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Fig2.3. Pressure-Isotherm of the Palladium-hydrogen system [3].

2.3WORKING PRINCIPLE OF THE INTEGRATED FUEL CELL

When operating the fuel cell, the hydrogen atoms storedwithin the palladium storage are split up into protons and electrons.The electrons are conducted through the external circuit to the cathode of the fuel cell driving the load. The protons aretransported to the cathode by proton hopping through the protonconductive PEM. At the cathode the electrons, the protons andoxygenwhich is supplied by the ambient aircatalyticallyrecombine to water. The integrated fuel cells do not needcomplex sealing layers. In the cathode of the system no reactiveelectrode material has to be stored, since ambient oxygen isused. The electrochemical reactions in fuel cell happen simultaneously on both sides of the membrane the anode and the cathode. The basic fuel cell reactions are: At the anode: H2 2H+ + 2e At the cathode: O2 + 2H+ + 2e H2O Overall: H2 + O2 H2O The maximum amount of electrical energy generated in a fuel cell correspondsto Gibbs free energy, G, of the above reaction:

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Wel = G The theoretical potential of fuel cell, E, is then: E= G /nF

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Where n is the number of electrons involved in the above reaction, and F isthe Faradays constant (96,485 Coulombs/electron-mol). Since G, n and F are allknown, the theoretical hydrogen/oxygen fuel cell potential can also be calculated:

E= G /nF =(237,340 J mol^-1)/(2.96,485 As mol^-1) =1.23 volts

2.4THE FUEL CELL CASCADES

Within its operation range, each single fuel cell delivers a characteristic output voltage between 500 mV and 800 mV. The layout of the integrated fuel cells brings the contacts of the anode and the cathode back to the silicon substrate. This fact allows the connection of several fuel cells in series or in parallel, so the desired output voltage can be adjusted by the number of connected fuel cells. The currently developed process enables the integration ofintelligent energy sources withCMOScircuitry. Another uniqueaspect of this technology is the possibility to adapt the capacityand the power density of the cells independent of each other.The capacity is adapted by the volume of the hydrogen storage,the power output by the area of the fuel cells and the outputvoltage by the number of connected fuel cells in series within acascade. By integrating several fuel cell cascades onto a siliconchip a highly reliable power supply for autonomous systems canbe realized.

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Chapter.3
INTEGRATED ELECTRONICS

3.1 SYSTEM APPROACH

The underlying 0.45 m CMOS process enables an integratedwake up and power supply system directly connectedto the FCCs. Thereby the FCs can be combined with an energymanagement without the need of external components oruser intervention. The proposed electronic control circuitry isdesigned to optimize the lifetime of e.g., autonomous sensorsystems (Fig. 3.1). Therefore, a periodic system wake-up isimplemented, controlled by an on-chip oscillator and a programmabletiming network. To generate a constant output voltage of 3.3 V for duty-cycled measurement tasks, the FCCsare activated after each single cell is checked for functionalityand shorted by a bypass if found faulty. After check-up completion,an LDO is switched on to power the load during one measurement event. As presented in Section 2.4 several fuel cells can be stackedto increase the output voltage. The presented realization uses7 fuel cells per cascade for an open circuit voltage of 6.3 V.To increase the systems maximum output current 6 fuel cellcascades have been implemented in parallel.

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Fig. 3.1 Schematic of the integrated power supply and FC control system. The circuit is supplied by Vcore (1 V1.5 V).

3.2 CORE SYSTEM For the benefit of the systems lifetime, the core system is restricted to fundamental control elements like an oscillator and an asynchronous timing network to avoid current peaks. It is powered by a redundant 2-FC-stack generating 1 V to 1.5 V depending on the charging level of the fuel cells. The implemented low power oscillator is realized as a currentstarved inverter chain with 9 stages S1 to S9 (Fig. 3.2) .To cancel out the simulated frequency drift with temperature of208 Hz/K, the oscillator is supplied by a complementary-to-absolute-temperature (CTAT) current source. Due to the

currentstarved architecture a very constant system cycle time withoutthe need of external components can be realized.

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The current source feeding the current starved oscillator(Fig3.2) delivers a voltage Vosc of around 0.74 V at the 10inverter stages. Thus, a buffer is required to shift the output level toVcore by up to a factor of 2. To minimize the currentconsumption, no classical level shifter is used but the firstoutput buffer stage is cascaded with an nMOS transistor driven by , to prevent dynamical current losses caused by the slowrising edge of this stage. The D-FF guarantees a duty cycle of50%. The connected timer realized as a D-FF frequency divider chain provides system cycle times adjustable between 30 msand 4 years.

The asynchronous realization relaxes the dynamic performancerequirements of the small fuel cells supplying the coresystem. The current consumption spreads over time and thereare no current peaks as would be present in the case of asynchronous design. As soon as the externally programmablesystem cycle time is elapsed, all fuel cell cascades are tested in parallel from bottom to top. After the check is completedand if not more than 3 cells within one FCC are damaged, thiscascade is handled as usable. When at least 3 FCCs have reached this status, the LDO is powered up by all functionalfuel cell cascades and the output voltage is stabilized to 3.3 V.The system shutdown has to be triggered externally, e.g., by the driven system. Hereby the LDO is deactivated again and thetimer is reset to allow for a wake up after a preset time.

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Fig. 3.2 Schematic of the 620 nW 33.3 kHz current starved ring oscillator.

3.3 BYPASS SYSTEM For high reliability of the proposed power supply system theFCCs, that is all single fuel cells within each cascade, have to bechecked for functionality, before they are used to drive the LDO(Fig. 3.3). Each cells anode is compared to its slightly loadedcathode. In case of defective or empty fuel cells, a load current ofapproximately 2.8 nA results in a significant voltage drop acrossthe cell, enabling a dynamic comparator to classify this cell as not usable. These defective or empty fuel cells are shorted byCMOS transmission gates to prevent loss of a complete FCC orto keep the output resistance of the FCC as low as possible The cells within one FCC are checked consecutively frombottom to top. Thus, each cells cathode potential is comparedto a well defined anode potential. Therefore,
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each dynamic comparatoris powered up by Vn , which is the larger voltage of thetwo; the cathode of the current fuel cell +FCn or the output ofthe cascade of the fuel cells below the current cell (Vn-1) , asshown in Fig. 3.3. In this case n is the number of the fuel cell being tested within the cascade ranging from 1 to 7 .Vo,which is theinput Vn-1 for the first FC within each cascade, is connectedto the unregulated output voltage of the core system Vcore (seeFig. 3.1). With ongoing FC test in each cascade, the highest securedvoltage is defined as the FCCs power supply. Thus, theinput signal for the transmission gate is shifted from Vn to Vmax (the maximum of the two voltagesVn andV7 ), decreasing thetransmission gates Ron as soon as the cascade is completelytested. The FCC check is initiated by the core system at the beginningof each measurement cycle. A reset pulse Rst1 causesthe loading for each fuel cell and resets all comparators to anunstable state, where both differential outputs are high. The decisionof the comparators is triggered by the falling edge of theparticular reset signal. That means disabling Rst1 starts thebottom comparator while the others remain in their reset state.As soon as the comparators differential output signals becomeunequal,Rst2 is released and thereby FC2 is checked for functionality.The FC check status is transmitted to the core system by statusflags.

Fig 3.3. Schematic of the Bypass circuit parallel to each FC in the cascade. Grey box: symbol, schematic and dimensions of the implemented transmission gate.

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3.4 LDO

By stacking the fuel cells to cascades with an output voltagehigher than 3.3 V for load currents up to 7 A, a classicalLDO can be used to stabilize the output voltage to 3.3 V. Aspresented 6 fuel cell cascades are integrated on chip. To increasethe systems driving capability, these FCCs are connected in parallelto the output by separate pMOS pass elements (Fig. 3.1). Asall pass elements are driven by the same gate voltage, their draincurrent Id depends on the pMOS source voltage and thereby onthe particular cascades output voltage. Thus, the required loadcurrent is distributed to the FCCs with respect to their drivingcapability. Furthermore, the separate pass elements are avoidingequalizing currents between the different cascades, as long aseach FCCs open circuit voltage is greater than Vout.

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Chapter.4 ADVANTAGES AND DISADVANTAGES

ADVANTAGES

It can generate power from a fraction of a watt to hundreds of kilowatts.Because of this, they may be used in almost every application where local electricity generation is needed. Applications such as automobiles, buses, utility vehicles, scooters, bicycles, submarines have been already demonstrated. Fuel cells are ideal for distributed power generation, at a level of individual homes, buildings or a community, offering tremendous flexibility in power supply. In some cases both power and heat produced by a fuel cell may be utilized, resulting in very high overall efficiency. As a backup power generator, fuel cells offer several advantages over either internal combustion engine generators (noise, fuel, reliability, maintenance) or batteries (weight, lifetime, maintenance).

Small fuel cells are attractive for portable power applications, either as replacement for batteries (in various electronic devices and gadgets) or as portable power generators.

DISADVANTAGES

Though high performance achieved in single cells, it is difficult to achieve high performance in multi cell stacks-requires more stack design studies Power density of stacks to be improved-for lighter, smaller, less expensive fuel cell stacks Fuel cell efficiency to be improved-Fuel cell Performance low at high cell voltage > 0.6-0.7V. High performance at higher cell voltage is required for higher efficiency

Low cost mass flow controllers / gas feed systems, load-matching gas feed systems not available commercially.

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Air management-suitable compressors/blowers for fuel cell applications-with high efficiency and low cost is not available Lot of research &development required for Control and safety system for fuel cells System integration / System packaging difficulty due to non-availability of small, light weight , low cost accessories required for high density fuel cell system-

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Chapter.5 APPLICATIONS

5.1 AUTOMOTIVE APPLICATIONS

All major car manufacturers have demonstrated prototype fuel cell vehicles and announced plans for production and commercialization. The major drivers fordevelopment of automotive fuel cell technology are their efficiency, low or zeroemissions, and fuel that could be produced from indigenous sources rather thanbeing imported. The main obstacles for fuel cell commercialization in automobilesare the cost of fuel cells and the cost and availability of hydrogen. The fuel cell may be connected to the propulsion motor in several ways namely: 1) Fuel cell is sized to provide all the power needed to run the vehicle. A batterymay be present but only for startup (such as a 12V battery). This configurationis typically possible only with direct hydrogen fuel cell systems. A system witha fuel processor would not have as good dynamic response. Also, a small batterywould not be sufficient to start up a system with a fuel processor. 2) Fuel cell is sized to provide only the base load, but the peak power for accelerationof the vehicle is provided by the batteries or similar peaking devices (suchas ultracapacitors). This may be considered as a parallel hybrid configurationsince the fuel cell and the battery operate in parallel the fuel cell providescruising power, and the battery provides peak power (such as for acceleration).The presence of a battery in the system results in much faster response to loadchanges. The vehicle can be started without preheating of the fuel cell system,particularly the fuel processor, and operated as a purely battery-electric vehicle

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until the fuel cell system becomes operational. A battery allows for recapturingof the braking energy, resulting in a more efficient system. The disadvantages ofhaving the battery are extra cost, weight and volume. 3) Fuel cell is sized only to re-charge the batteries. The batteries provide all thepower needed to run the vehicle. This may be considered as serial hybrid configuration(fuel cell charges the battery and battery drives the electric motor). Thesame advantages and disadvantages of having a battery apply as for the parallelhybrid configuration. The fuel cell nominal power output depends on how fast thebatteries would have to be recharged. A smaller battery would have to be rechargedfaster and would result in a larger fuel cell. 4) Fuel cell serves only as an auxiliary power unit, i.e. another engine is used for propulsion, but the fuel cell is used to run the entire or a part of the vehicle electricalsystem. This may be particularly attractive for trucks, since it wouldallow operation of an air-conditioning or refrigeration unit while the vehicle isnot moving without the need to run the main engine . 5.2 PORTABLE POWER APPLICATION

A portable power system is a small grid-independent electric power unit rangingfrom a few watts to roughly one kilowatt, which serves mainly the purpose of conveniencerather than being a primarily a result of environmental or energy-saving considerations.These devices may be divided into two main categories: 1) battery replacements, typically well under 100 W 2) portable power generators, up to 1 kW The key feature of small fuel cells to be used as battery replacements is the runningtime without recharging. Obviously, by definition, the size and weight arealso important. Power units with either significantly higher power densities orlarger energy storage capacities than those of existing secondary batteries may findapplications in portable computers, communication and transmission devices,power tools, remote

meteorological or other observation systems, and in militarygadgets.

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Chapter.6 CONCLUSION

The hybrid integration of a chip-integrated micro energysystem based on fuel cells and a CMOS control circuitry thatstabilizes the output voltage of the system to a constant levelof 3.3 V was demonstrated successfully. At a voltage level of3.3 V the system has a power density of 440 W/cm referringto the active chip area covered by fuel cells. In sleep mode, acore system with a power consumption of 620 nW enables aperiodic system wake-up after a preset time adjustable between30 ms and 4 years. In active mode the output voltage is stabilizedto 3.3 V up to a power consumption of 54.5 W, whichrelates to a current efficiency of 92%.In future work the monolithic integration of fuel cell cascadesand the electronic control circuitry will be realized. A detailedcharacterization of the fully integrated system with fuel cell cascadesand the CMOS circuitry on a single chip will be carriedout. Further integration of a sensor and a signal processing unitwill allow the realization of autonomous sensor devices.

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REFERENCES
1. F. Barbir, Fuel Cell Tutorial, presented at Future Car Challenge Workshop, Dearborn, MI, October 2526, 1997 2. F. Barbir, PEM Fuel Cells: Theory and Practice, Elsevier Academic Press, New York, 2005 3. S.Gottesfeld and T.A. Zawodzinski, Polymer Electrolyte Fuel Cells, in R.C. Alkire, H. Gerischer, D.M. Kolb, and C.W. Tobias (Eds.) Advances in Electrochemical Science and Engineering, Volume 5, Wiley-VCH, New York, 1997 4. T.A. Zawodzinski, Jr., T.E. Springer, J. Davey, R. Jestel, C. Lopez, J. Valerio, and S. Gottesfeld, A Comparative Study of Water Uptake By and Transport Through Ionomeric Fuel Cell Membranes, Journal of the Electrochemical Society, Vol. 140, 1993, p. 19811985 5. T.E. Springer, T.A. Zawodzinski, and S. Gottesfeld, Polymer Electrolyte Fuel Cell Model, Journal of the Electrochemical Society, Vol. 138, No. 8, pp. 233442, 1991. 6. T.R. Ralph and M.P. Hogarth, Catalysis for Low Temperature Fuel Cells, Part I: The Cathode Challenges, Platinum Metals Review, Vol. 46, No. 1, pp.314 , 2002 7. H.A. Gasteiger, W. Gu, R. Makharia and M.F. Mathias, Catalyst utilization and mass transfer limitations in the polymer electrolyte fuel cells, Electrochemical Society Meeting, Orlando, September, 2003 8. T.A. Zawodzinski, Jr., M. Eikerling, L. Pratt, R.Antonio, R. Tommy, M. Hickner, J. McGrath, Membranes for Operation Above 100oC, in Proc. 2002 National Laboratory R&D Meeting DOE Fuel Cells for Transportation Program (Golden, CO, May 9,
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2002).[M.F. Mathias, J. Roth, J. Fleming and W. Lehnert, Diffusion media materials and characterization, in W. Vielstich, A. Lamm, and H.A. Gastegier (Eds.) Handbook of Fuel Cells, Fundamentals, Technology and Applications, Vol. 3 Fuel Cell Technology and Applications, pp. 517537, John Wiley & Sons, Ltd., New York, 2003.

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