Module B2: Material Substitution
Transcript of Module B2: Material Substitution
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Module B2: MaterialSubstitution
AAE-E3120 CircularEconomy for Energy Storage
Prof. Annukka Santasalo-Aarnio
Valence band
Fermi level
Conduction band
Ener
gy
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Learning outcomes
• Recognize the material choice effect to degradationmechanisms of the system
• What are the frame of active materials we can select?
• Develop new design for recycling approach for energy storageapplication and justify with scientific argumentation
• High activity (how to ensure that with active material selection?)
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Active materials- In electrochemicalsystems
Why have we selected problematicmaterials for the active materials?
H+
H+
ActiveMaterials
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Challenged with active materials
Currentmaterials
Cost
Rareelements Degradation
Dissolution
Corrosion
Stability Low activity
Hazardmaterials
Development for active materials
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Electrochemical cell
Electrode Electrode
Electrolyte
e-e-
e-
e-
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Reaction on two phase boundary
Electrode Electrolyte
SolidLiquid
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Reaction on two phase boundary
Electrode Electrolyte
SolidLiquid Transport
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When voltage is applied
Electrode Electrolyte
Double layer
- Ions in the electrolyte(if liquid) will organize
to the electrodesurface and create a
Double Layer
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Reaction on two phase boundary
Electrode Electrolyte
Diffusionvicinity of the electrode
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Reaction on two phase boundary
Electrode Electrolyte
Adsorptionto the electrode
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Reaction on two phase boundary
Electrode Electrolyte
Reaction:electron transfer
e-
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Reaction on two phase boundary
Electrode Electrolyte
DesorptionFrom the electrode
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Reaction on two phase boundary
Electrode Electrolyte
DiffusionBack to the bulk
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Active materials- Requirement forcatalyst materials
Why have we selected problematicmaterials for the active materials?
Valence band
Fermi level
Conduction band
Ener
gy
EF
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Active materials
Lecture JournalWhat is a catalyst?
Electrocatalyst?
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Active materials
Lecture JournalWhat is a catalyst?
Electrocatalyst?
ElectrocatalystA material working acatalyst in a reactioninvolving an electron
transfer.
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Metal atoms
Me Me
bonding
untibonding
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Metal atoms
Me
Me
bonding
untibonding
Me
Me
e- e-
e- e-
e- e-
If there are more electrons on thebonding orbital – the bond is stable
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Metal Electrode
Valence band
Fermi level
Conduction bandEn
ergy EF
Formed of many metal atoms- > Orbitals incorporate tocontinuous energy bands
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Metal Electrode
MMFE
Valence band
Fermi level
Conduction bandEn
ergy EF
Me~
Formed of many metal atoms- > Orbitals incorporate tocontinuous energy bands
Work function of a unchargedmetal: The electrical work neededto remove an electron from theFermi level of the metal to vacuum
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Electrode potential
MMM
Electrode
M Galvani potential
M surface potential
M outer potential (measurable)
Galvani potential:Energy needed to bring a charged particle fromthe vacuum to the inner part of the metal
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Metal ElectrodeMM
FE Valence band
Fermi level
Conduction band
Ener
gy
Me~
MMe
Me F ~
Uncharged electrodeM
Work function of unchargedelectrode is?
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Metal ElectrodeMM
FE Valence band
Fermi level
Conduction band
Ener
gy
Me~
MMe
Me F ~
Uncharged electrode
Work function of unchargedelectrode is?
Me
MM F
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Metal ElectrodeMM
FE Valence band
Fermi level
Conduction band
Ener
gy
Me~
MMe
Me F ~
Uncharged electrode
Work function of unchargedelectrode is?
Me
MM F
Work function of a metal effects
- Surface potential -> Adsoprtion of molecules on the electrode
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Work Function
Me
MM F
Work function of a metal effects
- Surface potential -> Adsoprtion of molecules on the electrode
Different metals
(eV)Pt 6.351
Au 5.101
Zn 4.31
D. R. Lide (Ed.), CRC Handbook of Chemistry and Physics, 80th ed., CRC Press, Boca Raton 1999/2000.
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Work Function – how that effectsperformance?
J. Zhang et al. Electrochem. Commun. 9 (2007) 1298.
/eV
Pd 5.0
Pt 6.35
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Surface orientationCrystalline structures
(eV)Pt(100) 5.821
Pt(110) 5.852
Pt(111) 6.071
1) M. Salmerón et al. Phys. Ref. B 28 (1983) 6758.2) D. R. Lide (Ed.), CRC Handbook of Chemistry and Physics, 80th ed.,
CRC Press, Boca Raton 1999/2000.
E. Sairanen et al. /Applied Catalysis B:Environmental 148–149(2014) 11
Methanol (solid line), 2-Propanol (dashed line) and 50/50 mixture(thin line) oxidation in 0.1 M HClO4 electrolyte on different surfaceorientations.
A. Santasalo et al. Electrochem. Acta 54 (2009) 6576.
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Work Function – how to modify?• Alloying metals effects the work function of the
electrode
Anna Zielińska-Jurek, Journal of NanomaterialsVolume (2014), http://dx.doi.org/10.1155/2014/208920
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Work Function – performance?
Ethanol oxidation in alkaline media (1 M KOH) on different
catalyst. Au/C is gold nanoparticle catalyst on carbon support.
Lecture Journal
What would be the bestcatalyst for this particular
reaction?
A. Geraldes et al. Electrochimica Acta 111 (2013) 455.
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How to interpret the catalystmaterial data?
In electrochemical cell:25 ºC0.1 M HClO4 + 1 M MeOH
A. Santasalo-Aarnio et al. International Journal of Hydrogen Energy, 37 (2012) 3415-3424.
3 Electrode set up:To study individual electrode reaction
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How to interpret the catalystmaterial data?
In electrochemical cell:25 ºC0.1 M HClO4 + 1 M MeOH
Single cell fuel cell:70 ºC1 M MeOH
A. Santasalo-Aarnio et al. International Journal of Hydrogen Energy, 37 (2012) 3415-3424.
3 Electrode system(anode reaction)
2 Electrode system(anode + cathode)
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Catalyst example:Direct Methanol FuelCell
H+
H+
e–e–
Total: CH3OH + 3/2 O2 CO2 + 2 H2O
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Example: Direct Methanol FuelCell
H+
H+
e–e–
CH3OH + H2O
CO2 + 6 H+ + 6 e–
O2 + 4 H+ + 4 e–
2 H2O
Total: CH3OH + 3/2 O2 CO2 + 2 H2O
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Electro-oxidation of methanolEl
ectro
de P
oten
tial
+
-
LUMO
Organic compound
HOMO
CB
EF
VB
Metal
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0
1
2
3
4
5
6
j / m
A cm
-2
E / V vs. NHE
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Electro-oxidation of methanol
Elec
trode
Pot
entia
l
+
-
LUMO
Organic compound
HOMO
CB
EF
VB
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0
1
2
3
4
5
6
j / m
A c
m-2
E / V vs. NHE
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Electro-oxidation of methanolEl
ectro
de P
oten
tial
+
-
LUMO
Organic compound
HOMOEF
CB
VB
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0
1
2
3
4
5
6
j / m
A c
m-2
E / V vs. NHE
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Electro-oxidation of methanolEl
ectro
de P
oten
tial
+
-
LUMO
Organic compound
HOMOEF
CB
VB0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
0
1
2
3
4
5
6
j / m
A c
m-2
E / V vs. NHE
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Electro-oxidation of methanolEl
ectro
de P
oten
tial
+
-
LUMO
Organic compound
HOMOEF
CB
VB0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0
1
2
3
4
5
6
j / m
A c
m-2
E / V vs. NHE
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Oxygen reductionEl
ectro
de P
oten
tial
+
-
LUMO
Oxygen molecule
HOMO
CB
EF
VB
Metal
0.2 0.4 0.6 0.8 1.0
-20
-15
-10
-5
0
j / m
A c
m-2
E / V vs. NHE
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Oxygen reductionEl
ectro
de P
oten
tial
+
-
LUMO
Oxygen molecule
HOMO
CB
EF
VB
Metal
0.2 0.4 0.6 0.8 1.0
-20
-15
-10
-5
0
j / m
A c
m-2
E / V vs. NHE
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Oxygen reductionEl
ectro
de P
oten
tial
+
-
LUMO
Oxygen molecule
HOMO
CB
EF
VB
Metal
0.2 0.4 0.6 0.8 1.0
-20
-15
-10
-5
0
j / m
A c
m-2
E / V vs. NHE
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Oxygen reductionEl
ectro
de P
oten
tial
+
-
LUMO
Oxygen molecule
HOMO
CBEF
VB
Metal
0.2 0.4 0.6 0.8 1.0
-20
-15
-10
-5
0
j / m
A c
m-2
E / V vs. NHE
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Energy Levels -Batteries
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Different voltages and chemistriesLithium ion battery (LIB)Positive electrode
CoO2 + Li+ + e- <-> LiCoO2 E0 ~ 3.8 V
Negative electrodeLiC6 + <-> C6 + Li+ + e- E0 ~ 0.1 V
Full reactionCoO2 + LiC6 <-> LiCoO2 + C6 E0 ~ 3.7 V
44
Discharge ->
<- Charge
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Different voltages and chemistriesLead (Pb) acid batteryPositive electrodePbO2 + 3H+ + HSO4
- + 2 e- <-> PbSO4 + 2 H2O E0 ~ 1.7 V
Negative electrodePb + HSO4
- <-> PbSO4 + H+ + 2e- E0 ~ 0.4 V
Full reactionPbO2 + Pb + 2H2SO4 <-> 2 PbSO4 + H2O E0 ~ 2.1 V
45
Discharge ->
<- Charge
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How different electrode materials effecton battery voltage
46
A. Manthiram, An Outlook on Lithium Ion Battery Technology – ASC Central ScienceDOI: 10.1021/acscentsci.7b00288
Similarly, the materials ofthe positive and negative
electrodes ->
effect on the batteryvoltage
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Take a home message
From active materials to achieveHIGH performance,
we must understand their impact on theelectrode reaction.
This possess limitations to entirely changethe materials.
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Energy Material –ElectrochemicalPotential(how to derive)
MMM Electrode
M Galvani potential
M surface potential
M outer potential (measurable)
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Electrochemical potential
49
MMM Electrode
M Galvani potential
M surface potential
M outer potential (measurable)
ai
ai
ai Fz ~
Electrochemical potential (ingeneral)
For an electron in a metal phase?
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Electrochemical potential
50
MMM Electrode
M Galvani potential
M surface potential
M outer potential (measurable)
ai
ai
ai Fz ~
Electrochemical potential (ingeneral)
For an electron in a metal phase
MMe
Me F ~
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Electrochemical potential
51
MMM Electrode
M Galvani potential
M surface potential
M outer potential (measurable)
ai
ai
ai Fz ~
Electrochemical potential (ingeneral)
For an electron in a metal phase
MMe
Me F ~
Surface and outer potential?
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Electrochemical potential
52
MMM Electrode
M Galvani potential
M surface potential
M outer potential (measurable)
ai
ai
ai Fz ~
Electrochemical potential (ingeneral)
For an electron in a metal phase
MMe
Me F ~
Surface and outer potential?
MMMe
Me FF ~
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Electrochemical potential
53
MMM Electrode
M Galvani potential
M surface potential
M outer potential (measurable)
ai
ai
ai Fz ~
Electrochemical potential (ingeneral)
For an electron in a metal phase
MMe
Me F ~
Surface and outer potential?
MMMe
Me FF ~
If the electrode is not charged, outer potential of the metal is 0
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Electrochemical potential
54
MMM Electrode
M Galvani potential
M surface potential
M outer potential (measurable)
ai
ai
ai Fz ~
Electrochemical potential (ingeneral)
For an electron in a metal phase
MMe
Me F ~
Surface and outer potential?
MMMe
Me FF ~
If the electrode is not charged, outer potential of the metal is 0MM
eMe F ~