Preliminary Investigation of Plasma Activated Fuel Cell Preliminary Investigation of Plasma Activated Fuel Cell Preliminary Investigation of Plasma
Activated Fuel Cell y g
A t f hi h ffi i f l ll A new concept of high efficiency fuel cells A new concept of high efficiency fuel cells A new concept of high efficiency fuel cells W k Ki H k D d M k A C lli M h i l E i i D t t St f d U i it Wookyung Kim, Hyungrok Do and Mark A. Cappelli, Mechanical Engineering Department, Stanford University Wookyung Kim, Hyungrok Do and Mark A. Cappelli, Mechanical Engineering Department, Stanford University Ab t t Ab t t N ilib i Pl Di h N ilib i Pl Di h Integration of a DBD into a PEMFC Integration of a DBD into a PEMFC Modeling of Radicals Generated by USRD (Scheme) Modeling of Radicals Generated by USRD (Scheme) Abstract Abstract Nonequilibrium Plasma Discharges Nonequilibrium Plasma Discharges Integration of a DBD into a PEMFC Integration of a DBD into a PEMFC Modeling of Radicals Generated by USRD (Scheme) Modeling of Radicals Generated by USRD (Scheme) Abstract Abstract Nonequilibrium Plasma Discharges Nonequilibrium Plasma Discharges gg Schematic We discuss the potential use of non-equilibrium plasma discharges n Schematic Boltzmann Boltzmann We discuss the potential use of non equilibrium plasma discharges t di it ithi th i l t h l f f l ll t h f l T nrad Vpulse Boltzmann solver (BOLSIG) Boltzmann Solver BOLSIG generatedin-situ, withintheinlet channels of fuel cells, to enhancefuel Te # d it solver (BOLSIG) Solver BOLSIG g cell efficiency A Dielectric Barrier Discharge (DBD) and a ultra short Temp. # density cell efficiency. A Dielectric Barrier Discharge (DBD) and a ultra short l d titi di h (USRD) b dd ddi tl i t th f l p Volt. nsteady Non Maxwellian EEDF (E/n; ) pulsed repetitivedischarge(USRD) areembeddeddirectly into thefuel Volt. p p g ( ) y and air channel assemblies of common fuel cell designs While Fuel (H2 or CH4) N2 + e N + N + e N2 + e N + N + e Electron mobility and air channel assemblies of common fuel cell designs. While did t f l ll fi ti it bl f h l di h 2 4 N2 e N N e O O O N2 e N N e O O O Electron mobility Dissociation rate candidate fuel cell configurations suitable for such a plasma discharge T O2 + e O + O + e O2 + e O + O + e Dissociation rate constants g p g activation include Proton Exchange Membrane Fuel Cells (PEMFC) Ttr CH + CH + H + CH + CH + H + constants activation include Proton Exchange Membrane Fuel Cells (PEMFC), Di t M th l F l C ll (DMFC) d S lid O id F l C ll CH4 + e CH3 + H + e CH4 + e CH3 + H + e Direct Methanol Fuel Cells (DMFC), and Solid Oxide Fuel Cells Ai r O2 -, O- El I ( ), (SOFC) weinvestigateonly thePEMFC inthis exploratory phase The eq d pulse Initial Yield Initial Electron Impact (SOFC), weinvestigateonly thePEMFC inthis exploratory phase. The li ti f l di h ithi th f l/ i h l i th rc Ppulse of Radical Radical DissociationReactions application of a plasma discharge within the fuel/air channels in the (G value) Yield DissociationReactions Considered; pp p g proximity of the gas diffusion layer (GDL) and the catalyst film is Photograph of Fuel Cell Assembly (half of the actual cell) (G value) Yield Considered; s proximity of the gas diffusion layer (GDL) and the catalyst film is l t d t h t ti ll b fi i l ff t Fi t d
l << << P < g p y ( ) f d d l speculated to have many potentially beneficial effects. First and
pulse << eq pulse << P pulse < rc formed radicals G # p y p y foremost when methane (CH4) is used as the primary fuel the non- i t d V f G = foremost, when methane (CH4) is used as the primary fuel, the non- ilib i di h ill i i l f Energyefficient: lowtranslational temperaturebut highelectron Di schar ge* invested eV Power equilibrium discharge will serve as an in-situ plasma reformer, Energy efficient: low translational temperaturebut high electron t t g Power deposition by q g p , converting the methane to reactive hydrogen and reactive carbon temperature. deposition by plasma converting the methane to reactive hydrogen and reactive carbon. S d h h d ill b i h f f i d i d i p Non equilibriumstate: obtainedbyapulsed plasmadischarge Gas i nl et Gas out l et plasma # of Second, thehydrogenwill beintheformof reactiveandexcitedspecies Non-equilibriumstate: obtainedby a pulsed plasmadischarge Gas i nl et Gas out l et # of R di l , y g p (evenions) whichmay diffusemorereadily across theGDL andreact Radicals (evenions), whichmay diffusemorereadily across theGDL, andreact ffi i l h l i l l Thi d h i d more efficiently at the platinum catalyst layer. Third, the activated Two Types of Pulsed Plasmas Implemented Two Types of Pulsed Plasmas Implemented y p y y , carbon reacts more readily with transported oxygen to form CO2 Two Types of Pulsed Plasmas Implemented Two Types of Pulsed Plasmas Implemented carbon reacts more readily with transported oxygen to form CO2. Fi ll i i f h i h i l l Modeling of Radicals Generated by USRD (Results) Modeling of Radicals Generated by USRD (Results) Finally, activation of the oxygen in the air stream may also lower HV l i ne Modeling of Radicals Generated by USRD (Results) Modeling of Radicals Generated by USRD (Results) DBD vs USRD: Voltage and current profiles y, yg y transport and reaction barriers which limit performance at high cell Ac r yl housi ng g y ( ) g y ( ) DBD vs. USRD: Voltage and current profiles transport and reaction barriers which limit performance at high cell 3.8c m 1c m 1c m c avi t y currents. DBD USRD *Dischargecondition: 8kV p p 10mA peak current 30kHz rep rateand 10WAC DBD DBD USRD *Dischargecondition: 8kV p-p, 10mA peak current, 30kHz rep. rateand~10W AC DBD 15 Power = 10W Power = 10W 15 Power = 10W Power = 10W Typical Fuel Cell Structure Typical Fuel Cell Structure M t f OCV (DBD MEA i ti ) M t f OCV (DBD MEA i ti ) Typical Fuel Cell Structure Typical Fuel Cell Structure 10 Measurement of OCV (DBD,MEA variations) Measurement of OCV (DBD,MEA variations) N in air 0 Measurement of OCV (DBD,MEA variations) Measurement of OCV (DBD,MEA variations) N 2 in air T i l f l H h l CH in air Typical fuels: H 2 , methanol, or 5 CH 4 in air yp 2 , , CH Typeof MEA NoPlasma Plasma O i i CH 4 . yp Nafion+Pt +C cloth 08V 08V O 2 in air Typical chargecarriers: H + OH - or 0 Nafion+Pt +C cloth 0.8V 0.8V 2 Typical chargecarriers: H , OH, or O 2 Nafion+Pt 0.8V 0.8V O 2- . Nafion 0V 18V Typical catalysts: platinum nickel GDL GDL -5 Nafion 0V 1.8V Typical catalysts : platinum, nickel, C t l t C t l t 5 15 25 35 45 55 *Fuel: Hydrogen or perovskites Catalyst Catalyst 5 15 25 35 45 55 y g or perovskites i l l l l O Fuel Electrolyte Fuel Electrolyte Noimprovement wasmeasuredwhenaconventional MEA anda Typical electrolyte: polymer, KOH, Fuel Fuel No improvement was measuredwhen aconventional MEA, anda N fi P MEA df h DBD i df l ll yp y p y , , or ceramic USRDhasasingleandcleandischargeper cyclewhileDBDhas Nafion +Pt MEA areusedfor theDBD activatedfuel cell. Significant radical concentrationisexpectedevenwhenthree or ceramic USRD has asingleandclean dischargeper cyclewhileDBD has lti l d t ll bl l Wh N fi l MEA i d th OCV i hi h th th t Significant radical concentration is expectedeven when three fundamental dissociationreactionsareconsidered Dimensionsof theelements multipleanduncontrollablepulses When aNafion only MEA is used, theOCV is even higher than that fundamental dissociation reactions areconsidered. Dimensions of theelements p p y g of anideal PEMFC Order of magnitudedifferenceof radical number betweenair and GDL: ~200m of an ideal PEMFC. Order of magnitudedifferenceof radical number between air and h h df f i di id ll i i ddi h GDL: 200m Air Air DBD vs USRD: Degree of nonequilibrium Appropriatecurrent collector for NafiononlyMEA isrequired(on- methaneshows aneedfor useof individually optimizeddischarges Catalyst: submicron DBD vs. USRD: Degree of nonequilibrium Appropriatecurrent collector for Nafion only MEA is required(on goingwork) y p g for eachstream Caays: sub c o El l 100 DBD USRD goingwork) for each stream Electrolyte: ~100m DBD USRD y C l i C l i Implementation of the USRD to PEMFC Implementation of the USRD to PEMFC Conclusions Conclusions Implementation of the USRD to PEMFC Implementation of the USRD to PEMFC Conclusions Conclusions pp P f Li it f th R l F l C ll P f Li it f th R l F l C ll Performance Limit of the Real Fuel Cell Performance Limit of the Real Fuel Cell N ilib i l (DBD dUSRD) di Performance Limit of the Real Fuel Cell Performance Limit of the Real Fuel Cell Nonequilibriumplasmas (DBD andUSRD) weregeneratedin a q p ( ) g PEMFC toinvestigateapossibleenhancement of itsefficiency Voltage-current curve PEMFC to investigateapossibleenhancement of its efficiency. Activationloss: theinefficienciesat Voltage current curve Activation loss: theinefficiencies at hi h f i d which reactants formions and CombinedwithabareNafionMEA, aDBDactivatedfuel cell Ideal (thermodynamic) fuel cell voltage electronsat thecatalyst surface Combinedwith abareNafion MEA, aDBD activatedfuel cell resultedinahigher OCV thaninanideal PEMFC electrons at thecatalyst surface. resultedin ahigher OCV than in an ideal PEMFC. Ohmicloss: linear duetoion Ohmic loss: linear dueto ion Gas out l et )diffusionthroughtheelectrolyte Rubber seal Gas out l et A preliminaryinvestigationof USRD-activatedfuel cell was V )diffusion through theelectrolyte. A preliminary investigation of USRD-activatedfuel cell was d t d f ddiff t di h h t i ti i i o ( V Concentrationloss: limited B thdi h h hi hl ilib i h t i ti conducted: wefounddifferent dischargecharacteristics in air, E oConcentration loss: limited i f i i h Both discharges show highly nonequilibriumcharacteristic g , hydrogenandmethane E concentration of ions in theGDL. g g y q hydrogen andmethane. USRDshowshigher greater degreeof nonequilibriuminspectral features All threelosses can bereducedby USRD shows higher greater degreeof nonequilibriumin spectral features ee ossesc be educedby l di h ti ti Gas i nl et HV l i ne Preliminary plasmasimulations wereconductedto estimatethe plasmadischargeactivation Copper El ec t r ode Cavi t y Gas i nl et HV l i ne e yp s s u o sweeco duc ed oes e e number of radicalsproducedbytheplasma: A significant Aviation Ohmic Mass (plasmaassistedactivation higher DBD vs. USRD: General characteristics Copper El ec t r ode number of radicals producedby theplasma: A significant Aviation i Ohmic i transport (plasmaassistedactivation, higher DBD vs. USRD: General characteristics dissociation reaction was expectedfor thecurrent devices fabricated. region region t a spo t region diffusionrateandhigher DBD USRD dissociation reaction was expectedfor thecurrent devices fabricated. region diffusion rateandhigher t ti f i ) DBD USRD F W k F W k Current Density (A/cm 2 ) concentrations of ions). P AC DC V i ti f G i USRD (P li i ) V i ti f G i USRD (P li i ) Future Work Future Work Current Density (A/cm 2 ) Power source AC DC Variation of Gases in USRD (Preliminary) Variation of Gases in USRD (Preliminary) Future Work Future Work a at o o Gases US ( e a y) a at o o Gases US ( e a y) Sankey diagram of PEMFC Typical peak voltage 5kV 5kV Sankey diagram of PEMFC Typical peak voltage 5kV 5kV USRD i n ai r USRD i n hydr ogen USRD i n ai r USRD i n hydr ogen Ideal maximumpower: 3.84kW Typical peak current 0.5A 25A Devisinganovel way to collect current fromthemembrane: Ideal maximumpower: 3.84kW Typical peak current 0.5A 25A ev s g ove w y oco ec cu e o e e b e: loosely packedconductingfibers(carbonnanotube/foam?) T i l f 25 40kH 15 50kH loosely-packedconductingfibers (carbon nanotube/foam?). P t ti 20kW Typical frequency 25~40kHz 15~50kHz 1.84 kWof Power extraction: 2.0kW ( ) ( ) Heat Typical pulse width 10 ns (multiple) 10 ns (single) Obtainingperformancecurvesaswell asOCV for various yp p ( p ) ( g ) Obtainingperformancecurves as well as OCV for various di h diti dt f f l 3.84 kW 1.64 kW power neededfor operatingsystem EM noise Moderate Very high E t i 1/50 dischargeconditions andtypes of fuels. Hydrogen 2 0 kW Net power neededfor operatingsystem i d ( 9%) EM noise Moderate Very high Ex posur e t i me: 1/50 s Ex posur e t i me: 1/50 s Hydrogen 2.0 kW Net electrical is moderate(~9%). Electrode Metal-dielectric Metal-metal Total electrical power power ( ) Electrode Metal-dielectric Metal-metal Better understandingof thein situreformingprocesswhich output Pulse controllability Difficult Easy USRD i t h Better understandingof thein-situ reformingprocess which i l d Lossesd etoabo ethree Pulse controllability Difficult Easy USRD i n met hane Di h th h d t b includes Losses dueto abovethree D f G d B tt Dischargethehydrogen seems to be M t F i t f i f d t limitations: ~48% Degree of noneq. Good Better g y g moreconcentrated Measurements - Fourier transforminfraredspectroscopy limitations: 48% g q moreconcentrated. p py MoreComprehensiveSimulations usingBoltzmannequation Cost Low High Dischargecondition: 6kV (for air MoreComprehensiveSimulations - usingBoltzmann equation P i l ffi i 427%( 1/2 Cost o g Dischargecondition: 6kV (for air andinitial yieldcalculations, coupledtokineticssimulations Practical efficiency: ~42.7% (~1/2 andH 2 ), and8kV (for methane) peak andinitial yieldcalculations, coupledto kinetics simulations suchasCHEMKIN (withGRI MECH30) andPREMIX 200 W 70 W 40 W 50 W y ( of ideal efficiency) andH 2 ), and8kV (for methane) peak lt 15kH titi t such as CHEMKIN (with GRI MECH 3.0) andPREMIX 200 W R t t 70 W C li 40 W H d 50 W of ideal efficiency) DBDiseasier (andlessexpensive) initsimplementation voltages, 15kHz repetition rate. Ex posur e t i me: 1/50 s Reactant air Cooling air Hydrogen circulation Electronic controller DBD is easier (andless expensive) inits implementation. g , p Ex posur e t i me: 1/50 s air blower air blower circulation pump controller USRDi di bl i i fi i d id hi h di l blower blower pump USRD is morepredictablein its firingandcan providehigher radical p g p g concentrations concentrations.