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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.

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