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NTNU - Materials TechnologySustainable Electrolysis
Geir Martin HaarbergNTNU, Trondheim, Norway
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Norwegian University ofScience and Technology (NTNU)
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NTNU key figures (2005)
• 52 departments in 7 faculties• 58 000 student applications
– of which 9000 had NTNU as their first choice
• 20 000 registered students• 3000 degrees awarded• 220 PhD degrees awarded
• 4320 employees• 2600 empl. in education and research; 555
professors• 555 000 m2 owned and rented premises
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Norwegian University ofScience and Technology (NTNU)
Typical study programs
5 years MSc
3 – 4 years PhD
2 years International MSc
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Department of Materials TechnologyElectrochemistry Group
CorrosionCorrosion protection (offshore)Surface treatment (aluminium alloys)
Energy conversionFuel cells (PEM, direct methanol)Water electrolysis (PEM)
ElectrolysisMolten salts electrowinningAqueous solutions electrowinningSustainable electrolysis
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Department of Materials Technology
ElectrolysisMolten salts electrowinningAqueous solution electrowinning
Research projects in electrolysisOxygen supply by water electrolysisKinetics for oxygen evolution in copper electrowinningTi production by deoxidation of TiO2 in molten CaCl2Al production by deoxidation of Al2O3 in molten CaCl2Impurities in electrowinning of aluminiumElectrowinning of iron Electrorefining of silicon in molten salts
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Sustainable electrolysisSustainable development can be achieved by using renewable energy sources for the production of new and advanced materials,metals and chemicals.
Electrolysis can provide efficient use of energy and alternativeways of industrial production with less impact on the environment.
Topics
Aluminium electrowinning – Fundamental electrochemical studies
Anode processes in aqueous solutions – Oxygen evolution for electrowinning
Iron electrowinning – New process with no CO2 emissions
Silicon electrorefining – Solar grade Si by refining of metallurgical Si
Electrolytic titanium production – Develop new industrial process
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Solar cell silicon
Silica (SiO2) Silicon metal ingot for solar cell
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Silicon
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Production of Silicon
MG-Si by carbothermal reduction of silica at ~1900 oC:
SiO2 + C → Si + CO2
Energy requirement: ~12 kWh/kg Si
High purity silicon (Poly-Si) by the Siemens process at ~1150 oC
2 HSiCl3 → Si + 2 HCl + SiCl4Energy requirement: ~145 kWh/kg Si
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Solar cell silicon by electrodeoxidation of SiO2
Ito et al. produce silicon from SiO2 in a molten CaCl2 electrolyte at 850 oC.
SiO2 is a good insulator. Therefore Ito uses a ”SiO2 metal contacting electrode”, in which a Mo wire is directly in contact with SiO2.
Cathode reaction :SiO2 + 4e- (through Mo or Si) → Si + 2O2-
SiO2 contacting electrode
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ScanA/SUN:SOLSILC feedstock
ScanA/SUN:SOLSILC feedstock
SINTEF/Fesil:Recycled Si
WP1: Cleaning & Refining DMR
SINTEF: Small scale purificationFesil: Pilot scale purification
Pillar:Cz
crystallisation
SINTEF:Bridgman crystallisation
(small scale)
WP3: Electrochemical refining
NTNU, SINTEF: Electrochemical
refining
Fesil:MG-Si
production
SINTEF:Bridgman crystallisation
(small scale)
SINTEF: Modelling
Deutsche Solar:Bridgman crystallisation
(large scale)
Deutsche Solar: n-type purificationin pilot equipment
Deutsche Solar:Highly doped n-
type waste
WP2: Cleaning & Refining HDN
WP4: Material Characterisation
SINTEF: SIMS, LECO analysis UKON: lifetimeNTNU: GD-MS, PVScan (particle analysis) UMIB: PL, EBICECN: ICP-AES, IR, lifetime analysis
P-type cell process:UKON: high efficiency baseline, ECN: industrial
baseline, Isofoton: industrial pilot
Characterisation: UKON: lifetime, IV/SPR, IR thermography, UMIB: PL, EBIC, ECN: lifetime,
IV/SPR, FTIR, CoRe
N-type cell process:UKON: high efficiency baseline, ECN: industrial
baseline, Isofoton: industrial pilot
Increased yield:ECN: RPECVD, belt furnace gett., UKON:
mechanical stability, MIRHP, tube furnace gett,
WP5: Cell optimisation
WP6:Modules&Recycling
Isofoton: demo module, n-type module recycling, ECN: LCA
WP
7: Integration
& exp
loitation
ScanA/SUN:SOLSILC feedstock
ScanA/SUN:SOLSILC feedstock
SINTEF/Fesil:Recycled Si
WP1: Cleaning & Refining DMR
SINTEF: Small scale purificationFesil: Pilot scale purification
Pillar:Cz
crystallisation
SINTEF:Bridgman crystallisation
(small scale)
WP3: Electrochemical refining
NTNU, SINTEF: Electrochemical
refining
Fesil:MG-Si
production
SINTEF:Bridgman crystallisation
(small scale)
SINTEF: Modelling
Deutsche Solar:Bridgman crystallisation
(large scale)
Deutsche Solar: n-type purificationin pilot equipment
Deutsche Solar:Highly doped n-
type waste
WP2: Cleaning & Refining HDN
WP4: Material Characterisation
SINTEF: SIMS, LECO analysis UKON: lifetimeNTNU: GD-MS, PVScan (particle analysis) UMIB: PL, EBICECN: ICP-AES, IR, lifetime analysis
P-type cell process:UKON: high efficiency baseline, ECN: industrial
baseline, Isofoton: industrial pilot
Characterisation: UKON: lifetime, IV/SPR, IR thermography, UMIB: PL, EBIC, ECN: lifetime,
IV/SPR, FTIR, CoRe
N-type cell process:UKON: high efficiency baseline, ECN: industrial
baseline, Isofoton: industrial pilot
Increased yield:ECN: RPECVD, belt furnace gett., UKON:
mechanical stability, MIRHP, tube furnace gett,
WP5: Cell optimisation
WP6:Modules&Recycling
Isofoton: demo module, n-type module recycling, ECN: LCA
WP
7: Integration
& exp
loitation
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Electrochemical refining of Si - principlesSource: MG-Si
Potentially low cost
Chloride/fluoride electrolyte
Solid deposit, 800°C
Efficient removal of elements less noble than Si (B,P,Ca) –
will not deposit at the cathode
Efficient removal of elements more noble than Si –
will not dissolve anodically
MG-Si
+
SoG-Si
-
Si4+ Si
alloy substrate
anode cathode
CaCl2
Si (with impurities) → Si4+ + 4e- (anode)
Si4+ +4e- → Si (without impurities) (cathode)
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Solar grade silicon - Experimental
Si counter electrode
W reference electrode
W working electrode
Glassy carbon crucible
Gold film furnace
Electrolyte:CaCl2 + NaCl + CaOat 850 °C
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-0.80
-0.60
-0.40
-0.20
0.00
0.20
0.40
-1.0 -0.5 0.0 0.5
E/ VW
i/ A
cm-2
Pure meltAfter Si addition
Solar grade silicon - Voltammetry
Si can both be deposited and dissolved in the melt
Sweep rate: 200 mVs-1
Electrolyte:85 mol % CaCl25 mol % NaCl
10 mol % CaO
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Voltammetry
Cyclic voltammetry, sweep rate 2 Vs-1 at 800 °C. A): Voltammogram in 65 mol% CaCl2, 35 mol% NaCl, 5 mol% CaO. B): Voltammograms in 62.7 mol % CaCl2, 33.7 mol % NaCl, 4.8 mol % CaO and 3.7mol % SiO2.
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Conclusion
Silicon was electrodeposited successfully.
MG-Si powder dissolved in the melt.
Anode passivation is a problem.
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Lake Biwa -A Water Electrolysis Model
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Restoration of Lake Biwa by deep water electrolysis to supply oxygen
Lake Biwa Seminar, June 27
Main objective: Supply dissolved oxygen by electrolysis
Other aspects: Silicon solar cells- Produce electricity for water electrolysisCapture and handling of hydrogen- Produce additional electricity by on-shore fuel cellsDevelop a general method for oxygen supply in lakes
Background datapH 7 - 9
Dissolved oxygen 2 – 12 mg/l
Suspended solids ~1mg/l
Dissolved total nitrogen ~0.2 – 0.4 mg/l
Dissolved total phosphorus ~0.002 – 0.05 mg/l
Dissolved chloride ~10 mg/l
Spec el conductivity ~135 μS/cm at 25oC
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The Lake Biwa Physical Model
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Electrowinning
Annual production of metals – million tonnes
Aluminium 23Copper 13Zinc 9Nickel 1Magnesium 0.5Cobalt 0.03
Iron 1000
Titanium 0.1
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Letter to Nature – 21 September 2000
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FFC possibilities
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Electrodeposition of iron frommolten salt electrolytes
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Fe ULCOS
ULCOS (Ultra Low CO2 Steelmaking)Purpose: Develop a new process for iron production with reduced CO2 emissions
Iron smelting by carbon reduction of Fe2O3 CO2 emissions
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Electrowinning of iron?
Possibilities Problems/challenges
Aqueous solutions Low current efficiency Low current density? Large space required
Molten salts Low Fe2O3 solubility? No inert anode?
Molten oxides High temperature, corrosive electrolyte Electronic conduction No inert anode
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CV’s of Mo in molten CaCl2-CaF2-Fe2O3 (80-20-0.5 mol%), 827 °C
Reversible cathode reaction
Fe (III) + 3 e- → Fe (s)
Controlled by diffusion Fe(III) towards cathode
DFe(III)= 3.0×10-5 cm2s-1
-0.3 -0.2 -0.1 0.0 0.1 0.2-0.06
-0.04
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
Cyclic voltammetry in molten CaCl2-CaF2
ip c/[Ac
m-2]
E[V] vs Fe reference
0.05V/s 0.1V/s 0.2V/s 0.3V/s 0.4V/s 0.5V/s
0.20 0.25 0.30 0.35 0.40 0.45 0.50-0.035
-0.030
-0.025
-0.020
-0.015
-0.010
-0.005
0.000
i pc /Acm
-2
cFe2O3/mol%
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9-0.060
-0.055
-0.050
-0.045
-0.040
-0.035
-0.030
-0.025
-0.020
-0.015
-0.010
-0.005
ic p/Acm
-2
v1/2/(V/s)1/2
Cathodic peak current density vs square root of sweep rate
Peak current density vs content of Fe2O3
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Reversible cathode reaction
Cyclic voltammetry in molten NaCl - FeCl3, 890oC
Fe (III) + 3 e- → Fe (s)
Controlled by diffusion Fe(III) towards cathode
DFe(III)= 1.4×10-5 cm2s-1
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Bulk electrolysis0.85 Acm-2, molten CaCl2-KF, 1144 K
Changes of cathode potential and cell voltage during galvanostaticelectrolysis at 0.85 Acm-2 in CaCl2-KF-Fe2O3 (1.5 mol% Fe2O3 added) melts at 871 oC
W.E. Fe rod cathode with rotation (260 rpm)
C.E. Magnetite (Fe3O4) anode
R.E. Pt wire
–0.8V is the cathodic limit potential of this melt
1.5 mol% Fe2O3 addition
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
0
0.5
1
1.5
0 500 1000 1500 2000 2500
Cat
hode
pot
entia
l / V
vs.
Pt
Cel
l vol
tage
/ V
Time / sec
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0
500
1000
1500
2000
2500
3000
3500
4000
20 30 40 50 60 70 80
2θ (Cu-Kα )
Inte
nsity
/ cps
0
500
1000
1500
2000
2500
3000
3500
4000
20 30 40 50 60 70 80
2θ (Cu-Kα )
Inte
nsity
/ cps
FeFeO
CaF2
Pure iron
Small amount of impurities
Electrolyte → CaF2
Rinsing the deposit with distilled water → FeO
XRD pattern of the deposit obtained after galvanostatic electrolysis at 0.85 Acm-2 in CaCl2-KF-Fe2O3 (1.5 mol% Fe2O3 added) melt at 1144 K
Galvanostatic electrolysis 0.85 Acm-2 in CaCl2-KF at 1144 K
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Electrowinning of Iron from Molten SaltsEnergy and heat
½Fe2O3(diss) = Fe (s) + ¾ O2 (g)
800ºC: ΔGo = 271 114 J/mol, ΔHo = 403 622 J/mol
Erev = -0.947 V, Eiso = -1.395 V
Current density: 0.5 A/cm2
Cell voltage: 2.2 V Current efficiency: 0.90Energy consumption: 3.5 kWh/kg Fe
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Pure iron can be deposited from molten saltsFe(III) species are stable in mixed fluoride/chloride melts
High current efficiency (> 90 %)
High current density ( 0.85 Acm-2, in CaCl2-KF, rotating cathode )
Conclusions - Fe molten salts
Oxygen evolving anode materials show promising behaviour
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