Post on 23-Aug-2020
NanoscaleNanoscale Materials: Exploring Materials: Exploring the Energy Frontierthe Energy Frontier
PrashantPrashant N. N. KumtaKumtaDepartment of Materials Science and Engineering,Department of Materials Science and Engineering,
Biomedical EngineeringBiomedical EngineeringCarnegie Mellon University,Carnegie Mellon University,
Pittsburgh, PA 15213Pittsburgh, PA 15213
Hybrid Electric Vehicle
Backup Power Source
Telecommunication
Electronic Devices
Laser
Military Use
Particle Accelerator
Nissan DieselSizuki ElectricPower Systems
www.hondacorporate.com
www.maxwell.com
www.nissandiesel.co.jp
www.nissandiesel.co.jp
www.maxwell.com
Need for Energy Storage SystemsNeed for Energy Storage Systems
Potential Energy Storage SystemsPotential Energy Storage Systems
LiLi--ion Batteriesion Batteries**
SuperSuper--capacitorscapacitors**
Direct Methanol Fuel CellsDirect Methanol Fuel Cells**
Hydrogen StorageHydrogen Storage
*Focus of the current presentation
LithiumLithium--Ion Systems: Anodes and CathodesIon Systems: Anodes and Cathodes
Comparison of Battery Energy Density(gravimetric and volumetric)
Considerable improvement in area of cathodes with identification of newlayered compounds, LiFePO4 and LiNi0.5Mn0.5O2, LiMn1/3Ni1/3Co1/3O2.Improvements in the anode area are still warranted.
° Li-alloy (LixM) : Anodes for Li ion cells- Intermetallic phases containing lithium
LixM xLi+ + xe- + M
(M = Mg, Ca, Al, Si, Ge, Sn, Sb, Bi, Zn, etc)1
- Higher theoretical capacity than graphite
(LiC6 : 372 mAh/g, 832 Ah/L,
Li22Sn5 : 990 mAh/g, 14780 Ah/L
Li22Si5 : 4000 mAh/g, 10997 Ah/L)1, 2
° Major problems of Li-alloys for use as anodes- Poor reversibility caused by large volume changes
(Sn: 593%, Si: 412% volume change)
- Cracking or crumbling during cycling1. M. Winter & J. O. Besenhard, Electrochimica Acta, 1999, 45, 31.
2. B. A. Boukamp & R. A. Huggins, J. Electrochemical Soc., 1981, 128, 729.
Introduction and Background3
3. L.Y. Beaulieu, K.W. Eberman, R.L. Turner, L.J. Krause and J.R. Dahn, Elect. Sol. St. Lett. 2001, A137.
- No secondary phase observed at the interface
Si/Transition metal non-oxide system is stable during HEMM.
20nm 20nm
Bright Field Dark Field
Nanoscale structureis the key to attainingthe high capacity
2 nm
Amorphous active phase
- Theoretical Capacity = 636 mAh/g- Higher capacity than graphite (~480mAh/g or 1450Ah/l) with stability (0.15%loss/cycle).
Electrochemical Response(Sn:C=1:1)
(Tetraethyl tin+Ps-resin powder heat-treated at 600 oC for 5h in UHP-Ar, current rate = 100µA/cm2 )
0
100
200
300
400
500
600
700
800
0 5 10 15 20 25 30
Cycle Number
Sp.C
apac
ity (m
Ah/
g)
0
500
1000
1500
2000
2500
Vol.C
apac
ity (A
h/l)
Graphite
-5000
-4000
-3000
-2000
-1000
0
1000
2000
3000
0 0.5 1 1.5 2 2.5 3
Cell Potential (V)dQ
/dV
(mA
h/g.
V)
Cycle between 0.02 and 1.2V
HEMM derived Si-C nanocompositesNanostructured inactive matrix can endurelarge volumetric stresses of the active material due to possiblesuperplastic deformation that can provide compressive stresses to accommodate large strains*.
* M.J. Mayo, Nanostructured Materials, Vol. 9 (1997) 717)Q/RTexp(Ddε op-n −=
•
σ
XTEM of sputter deposited XTEM of sputter deposited SiSi film film (250 nm as(250 nm as--deposited film)deposited film)
100 nm
Si
Cu2 nm
Conventional XTEM High Resolution XTEM
Galvanostatic Cycling of 250 nm Si Thin Film (C/2.5 and 2C rates)High Capacity and Excellent Rate Capability of 250 nm Silicon Thin Film Anode (Area = 1 cm2)
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0 5 10 15 20 25 30 35
Cycle Number
Spec
ific
Cap
acity
(mA
h/g)
C/2.5 ChargeC/2.5 Discharge2C Charge2C Discharge
C/2.5 rate (100uA/cm2)
2C rate (500uA/cm2)
372 mAh/g : Theoretical Capacity of Conventional Graphite Anode Material Used in Commercial Lithium-Ion Batteries
4199 mAh/g : Theoretical Capacity of Pure Silicon Anode Material
SEM : C/2.5 rate – 30 cycles2 µm 2 µm
Si EDAX : C/2.5 rate – 30 cycles
2 µm
Also note low irreversible loss ~14% and 0.1 % loss per cycle.Increase of capacity with cycle # for the 2C sample may be due to kinetic limitation of the amorphous Si sample in the initial cycles, which is mitigated gradually in later cycles by morphological changes in the electrode, decreasing the effective diffusion distance for the lithium ions from the electrolyte.
As-Deposited
Multilayer Film SchematicMultilayer Film Schematic
Silicon (250 nm)Carbon (50nm)
Cr (10 nm)
Copper Foil (25 µm)
Note: Drawing not to scale
Note: Ecarbon ~ 50 – 500 GPa
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
0 5 10 15 20 25 30 35 40 45 50
Cycle Number
Spec
ific
Cap
acity
(mA
h/g-
Si)
dischargecharge
Cycling of Multilayer Film, C/2.5 rate
-160000
-140000
-120000
-100000
-80000
-60000
-40000
-20000
0
20000
40000
0 0.2 0.4 0.6 0.8 1 1.2
Cell Potential (V)
dQ/d
V (m
Ah/
gV)
SEM image of a 500°C-4h annealed 250 nm Si/50nm C/10 nm Cr/Cu multilayer thin film cycled at 0.4 C after 75 cycles, 5000x.
Interface dynamics control of the nanoscalefilms is the key to improved electrochemical performance
Energy Density (Wh/kg)
Pow
er D
ensi
ty (W
/kg)
1 h
6 min40s4s
10 h
100 h
1000 h
10
100
1000
10000
10 100 1000 100001
Pb/Acid
Supercapacitor
Ni-Cd
NiMH
Primary Li
Li-ion
Leclanche
Alkaline
Zinc-Air
Fuel Cell
Electrochemical Capacitor
“Ultracapacitor”“Supercapacitor”
Primary Battery
• Leclanche• Primary Li • Alkaline
Secondary Battery
• Pb/Acid• Zinc-Air• Ni-Cd• NiMH• Li-ion
Fuel Cell
Ragone Plot
Supercapacitors: Potential Energy Storage Systems
Gouy-ChapmanDiffuse Layer
Stern Layer
+
_
-
-
-
-
-
-
Cation
Anion
Neutral Molecule
+
-
1/k
ψ0 ψd
Inner Helmholtz Layer
Outer Helmholtz Layer
(≈ ζ )
H2O (Solvent)
+_
−−−+
=)exp(1)exp(1ln
2xx
zeTkB
κγκγψ
=
Tkze
B
o
4tanh ϕγ
KB : Boltzmann constant ϕ0 : Potential at (x=0)z : Ion valency x : Distance from the surface T : Temperature εo : Permittivity of free spaceεr : Solvent dielectric constantCo : Electrolyte concentration
Non-Faradaic : No electron transfer
Ex) Dielectric CapacitorElectric Double Layer Capacitor
= ∗
TkzeTckB
orooB 2
sinh)8( 2/1 ϕεεσ
θB= f (V)
Cφ
Cφ∆V0.5
∆V0.5
θA= f (V)
θ
Cφ
(= q
·dθ/
dV)
(g = 0) (g > 0)
)exp(exp1
θθ
θ gRTVFK ±
=
−
2
exp1
exp
+
⋅=≈
RTVFK
RTVFK
RTF
dVdC θ
φ
1θ
2θ
Faradaic : electron transfer
Ex) Battery, Pseudocapacitor
θ : CoverageV : VoltageK : Reaction rate constantg : Adsorption isotherm constantF : Faraday constant
dzeOx Re↔+
Lin Lin et al. et al. 5050--1.1 1.1 −− 0.80.81M KOH1M KOH291291Co(OH)Co(OH)22 XerogelXerogel
Prasad Prasad et al.et al.2002000 0 −− 0.750.751M LiClO1M LiClO44 in PCin PC650~1300650~1300Polyaniline (PANI) Polyaniline (PANI) on Stainless Steelon Stainless Steel
Clement Clement et al.et al.50500 0 −− 1.21.2Poly(methylmethacrylate) Poly(methylmethacrylate) –– PMMAPMMA2525Polyaniline (PANI)Polyaniline (PANI)
Arbizzani Arbizzani et al.et al.50500 0 −− 0.30.3Poly(ethylene oxide) Poly(ethylene oxide) –– PEOPEO1515Poly(dithienothiophene)Poly(dithienothiophene)--pDTTpDTT
Searson Searson et al.et al.2525--2 2 −− 00Poly(acrylonitrile)Poly(acrylonitrile)23 ~ 30mAh/g23 ~ 30mAh/gPoly3Poly3--(3,5(3,5--difluorophenylthiophene)difluorophenylthiophene)Polym
erPolym
er
Wu Wu et al.et al.22--1.2 1.2 −− 1.21.21M Na1M Na22SOSO443838FeFe33OO44
Liu Liu et alet al. . 1010--0.4 0.4 –– 0.50.51M KOH1M KOH260260NiONiOxx
Lee Lee et alet al..10100.1 0.1 −− 0.850.851M KCl1M KCl153153Amorphous MnOAmorphous MnO22⋅⋅HH22OO
Long Long et al. et al. 220.2 0.2 −− 0.70.70.5M H0.5M H22SOSO44900900RuORuO2 2 on Carbon Tapeon Carbon Tape
Zheng Zheng et alet al. . 2250500 0 −− 110.5M H0.5M H22SOSO44
720 ~ 760720 ~ 760250250RuORuO22··xHxH22OO
Raistrick Raistrick et al.et al.1001000 0 −− 110.5M H0.5M H22SOSO44350350RuORuO22Transition Metal O
xideTransition M
etal Oxide
Zhou Zhou et al.et al.550.75 0.75 –– 3.753.751M LiPF1M LiPF669595MesoporousMesoporous CarbonCarbon
Ma Ma et al.et al.10mA10mA0 0 −− 0.90.938wt% H38wt% H22SOSO4415 ~ 2515 ~ 25Carbon nanoCarbon nano--tubestubes
Niu Niu et alet al. . --0038wt% H38wt% H22SOSO44113113MultiMulti--walled carbon walled carbon nanonano--tubestubes
Carbon
Carbon
ReferenceReferenceScan rateScan rate(mV/s)(mV/s)
Potential Potential WindowWindow
(V)(V)ElectrolyteElectrolyte
Gravimetric Gravimetric Capacitance Capacitance
(F/g)(F/g)MaterialMaterial
Competitive Systems
Good Electrical Conductivity
• High rate electrochemical response of the capacitor depends onelectrical conductivity of the electrode and the ionic conductivity of the electrolyte
Chemical Stability
• The electrolyte widely used are corrosive (H2SO4 or KOH)
Cost
High Mass Density (g/cm3)
• To increase volumetric capacitance (F/cc)
High Specific Surface Area (m2/g )
• To increase the electrode-electrolyte interface area for charge storage
Transition Metal Nitrides: Novel Capacitor Materials
194.96194.965.555.55××10104414.114.1Cubic (Fm3m)Cubic (Fm3m)TaNTaN
612.87612.87< 10< 10--44Orthorhombic Orthorhombic (Cmcm)(Cmcm)TaTa33NN55
197.89197.8912.1212.12Cubic (Pn3m)Cubic (Pn3m)WNWN
205.88205.885.055.05××1010448.48.4Cubic (Pm3m)Cubic (Pm3m)MoMo22NN
106.91106.911.281.28××1010448.38.3Cubic (Fm3m)Cubic (Fm3m)NbNNbN
105.23105.235.555.55××1010447.097.09Cubic (Fm3m)Cubic (Fm3m)ZrNZrN
64.9564.951.671.67××1010446.046.04Cubic (Fm3m)Cubic (Fm3m)VNVN
61.9161.912.52.5××1010445.435.43Cubic (Fm3m)Cubic (Fm3m)TiNTiN
12.0012.00< 4< 4××101044< 1< 1--CarbonCarbon
133.07133.0722××1010666.976.97Tetragonal Tetragonal (P4(P422/mnm)/mnm)RuORuO22
M.W.M.W.Electronic ConductivityElectronic Conductivityσ×σ×1010--22ΩΩ--11mm--11
DensityDensity(g/cm(g/cm33))
StructureStructureMaterialMaterial
Ref: 1) J. P. Zheng, P. J. Cygan, and T. R. Jow, J. Electrochem. Soc., 142(8), (1995) p.26992) M. Wixom, L. Owens, J. Parker, J. Lee, I. Song, and L. Thompson, Electrochem. Soc. Proc., 96 (25) (1999)
p. 633) P. T. Shaffer, Handbook of High-Temperature Materials, Vol.1, pp.292-92. Plenum Press, New York, (1964)
VN-400oC
VN500o C
TEM Analysis: Morphology of the Nanocrystalline Nitirdes
-45-40-35-30-25-20-15-10-505
1015202530354045
100mV/s 50mV/s 25mV/s
10mV/s
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
2mV/s
Gra
vim
etric
Cur
rent
(I/g
)
Potential V (vs. Hg/HgO)
1 10 1000
200
400
600
800
1000
1200
1400 0.25mg/cm3
0.28mg/cm3
0.44mg/cm3
0.67mg/cm3
0.99mg/cm3
Gra
vim
etric
Cap
acita
nce
(F/g
)
Scan Rate (mV/s)
Figure 2 The (a) cyclic voltammogram of nanocrystallites synthesized at 400oC and (b) gravimetric capacitance (F/g) versus VN nanocrystallites loading scanned at various rates (2~100mV/s) in 1M KOH electrolyte.
Electrochemical Response of the Nanocrystalline Nitrides
4000 3500 3000 2500 2000 1500 1000 500
V=O
-OH stretching
V-O
3535
3047
3423
798
970
VN 400oC cycled 10times at 2mV/s
Wavenumber (cm-1)
(a)
(b)
VN 400oC
(c)
VN 400oC in 1M KOH for 24h
Tran
smitt
ance
(%)
1
x 103
5
10
15
20
25
Cou
nts
540 535 530 525 520 515 510 505Binding Energy (eV)
O 1s
V 2p1
V 2p3
(a)
1
x 103
4
6
8
10
12
14
16
18
20
22
Cou
nts
540 535 530 525 520 515 510 505Binding Energy (eV)
O 1s
V 2p1
V 2p3
(b)
The FTIR spectra of (a) VN powder, immersed in 1M KOH solution for 24h and cycled 200 times and XPS spectra of VN powder (b) before and (c) after electrochemically cycled for 200 times.
Controlled oxidation is the keyminimal reduction in electronicconductivity
XPS: Presence of V2O5before cycling
XPS: Formation of V2O3 after 200 cycles
Major Benefits of Direct Methanol Fuel CellsMajor Benefits of Direct Methanol Fuel Cells
High Efficiency of Energy ConversionHigh Efficiency of Energy Conversion•• Enhanced utilization of fuelEnhanced utilization of fuel•• Lower carbon dioxide emissionsLower carbon dioxide emissions
Direct Generation of Electrical EnergyDirect Generation of Electrical Energy•• Losses in mechanical to electrical energy Losses in mechanical to electrical energy
conversion is avoidedconversion is avoided
Low temperature operationLow temperature operation•• Low emissions of nitrogen oxides, carbon Low emissions of nitrogen oxides, carbon
monoxide and particulatesmonoxide and particulates
Potential solution for portable applicationsPotential solution for portable applications
Near Ambient temperature operationNear Ambient temperature operationHigh energy density required High energy density required Easy to handle fuelEasy to handle fuel
2W 20W 50-100W 500W 1-5kW
DIRECT METHANOL FUEL CELL SYSTEM
METHANOL FUEL CELL
G. Cacciola et al. J. Power Sources 100 (2001) 67-79
CO2 Emissions and Efficiency for Traditional ICE
and methanol or hydrogen fed Fuel Cells
DrawbacksDrawbacks
Expensive materialsExpensive materials•• Platinum catalysts, Platinum catalysts, fluoropolymersfluoropolymersComponents that are expensive to Components that are expensive to manufacturemanufactureLack of fuel flexibilityLack of fuel flexibilityRequires clean fuel; Requires clean fuel; e.g.e.g. sulfur free sulfur free Electrochemical reactions are sensitive to Electrochemical reactions are sensitive to poisons in the environmentpoisons in the environment
PROTON EXCHANGE MEMBRANE (PEM)
CO2
<3% Methanol / water
- Electrode (Anode) + Electrode (Cathode)
LOAD +-
OXIDANT
CO2
3% Methanol / water
FUEL
6H+
+ H20, N2, O2
Air (O2)
3H2O
6H+
+3/2 O2
6e-6e-
H+
H+
H+
H+
H+
H+
H+
H+
H+
H+
H+
H+
H2O+
CH3OH
Direct Methanol Fuel Cell Concept
Cathode (Pt)
6H+ + 1.5 O2 + 6e- 3H2O
Anode (Pt-Ru)
CH3OH + H2O CO2 + 6H+ + 6e-
Synthesis of Catalysts
• Most synthetic approaches in the literature are based on the reduction of Halide precursors of Pt and Ru
• Limitations:
—Need for several washing steps to eliminate unwanted by-products
—Tedious process leading to loss of active material
— Poisoning of the catalyst
• Need for improved catalyst using non-halogen containing precursors
• Objective: Develop novel sol-gel based methods using non-halogen precursors for generating Pt-Ru catalysts— High surface area— Pt to Ru ratio close to unity— High electrochemical activity — (low polarization of the electrode)
Morphology Characterization Transmission Electron Microscopy (TEM)
•TEM micrographs of the powder possessing the highest surface area (120-160 m2/g) with the best electrochemical activity (optimized sample)
—Diffraction pattern indicates single phase Pt-Ru composition
—HRTEM images show 2-4 nm sized crystallites
•Results of electrochemical tests conducted on the powders derived using a large excess of
tetramethylammonium hydroxide [TMAH : (Pt-acac+Ru-acac) = 1.75:1 and Pt:Ru = 1:1]
Electrochemical CharacterizationAnode polarization data
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 2 4 6 8 10
E (25oC, measured)E' (25oC, corrected)E (60oC, measured)E' (60oC, corrected)
y = 0.28913 + 0.014178x R= 0.95483
y = 0.19655 + 0.01602x R= 0.95062 Pote
ntia
l vs
H2/H
+
Ln(mA/g)
SSA = 97.9 m2/g
(a) Two step heat treatment of
400/3h/1%O2 (3 g) (0.5g)300/3h/1%O2
IV-1-1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 2 4 6 8 10
1214.10E (25oC, measured)E' (25oC, corrected)E (60oC, measured)E' (60oC, corrected)
y = 0.26396 + 0.014772x R= 0.97508
y = 0.18419 + 0.013872x R= 0.95196 Pote
ntia
l vs
H2/H
+
Ln(mA/g)
SSA = 139.6 m2/g
(b) Two step heat treatment of
300/2h/1%O2 (3 g) (0/5g)300/4h/1%O2
IV-1-2
Comparison of catalytic activity
Sample Specific
surface area (m2/g)
Intercept on y axis in polarization
curve
Slope in polarization
curve
Cell potential (V) at ln(mA/g)=8
(60°C)
25°C 60°C 25°C 60°C JPL 49.5 0.305 0.182 0.0216 0.0193 0.336
Giner 94.2 0.269 0.177 0.0273 0.0306 0.422 Johnson-Matthey
71.3 0.298 0.173 0.0127 0.0163 0.304
1208.12 94.2 0.214 0.155 0.0284 0.0231 0.340 TMAH:acac=1.25:1 Pt:Ru = 1:1
1212.03 95.9 0.322 0.217 0.0169 0.0194 0.372 TMAH:acac=1.25:1 Pt:Ru = 1:1.25
1214.03 97.9 0.289 0.197 0.0142 0.0160 0.325 TMAH:acac=1.25:1 Pt:Ru = 1:1.5
1214.10 139.6 0.264 0.184 0.0148 0.0139 0.295 TMAH:acac=1.75:1 Pt:Ru = 1:1
330.38590.3859Pt(RuPt(Ru) + C) + C158158Sample BSample B(Sample A: (Sample A:
30030000C/2h in ArC/2h in Ar--1% O2)1% O2)
000.38590.3859Pt(RuPt(Ru))120120Sample CSample C(Sample B: (Sample B:
30030000C/2h in ArC/2h in Ar--1% O1% O22))
63630.38610.3861Pt(RuPt(Ru) + C) + C11Sample ASample A(500(50000C/6h in C/6h in ArAr))
000.38580.3858Pt(RuPt(Ru) +) +RuRu--JM catalystJM catalyst--(600(600ooC/6h in C/6h in ArAr))
000.38660.3866Pt(RuPt(Ru))7070JM catalystJM catalyst
Carbon Carbon content content
(%)(%)
Lattice Lattice parameter parameter
(nm)(nm)
Phase/phases Phase/phases presentpresent
Surface Surface area(marea(m22/g)/g)
Sample Sample identificationidentification
Prospects for FutureProspects for Future
NanomaterialsNanomaterials show potential for energy show potential for energy storage storage NanoscaleNanoscale phenomena in batteries, fuel phenomena in batteries, fuel cells and cells and supercapacitorssupercapacitors still need to be still need to be studiedstudiedConsiderable potential for integration, Considerable potential for integration, theoretical and experimental studiestheoretical and experimental studies