Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Heli Wang, Postdoc Todd Deutsch, University of Colorado (PhD Student) John Einspahr, Colorado School of Mines (SS Student) Jennifer Leisch, Colorado School of Mines (PhD Student) Ken Menningen, University of Wisconsin (Sabbatical)
Recent Past
Joe Beach, Colorado School of Mines (PhD, Graduated Dec 2001) Lara Kjeldsen, Colorado School of Mines (MS Student - graduated 2003) Scott Warren, Whitman College (SS - now at Cornell) Ken Varner, (SS - North Carolina State)
Others
Vladimir Aroutiounian, University of Yerevan, Armenia (CRDF, ISTC) Arturo Fernndez, Centro de Investigacin en Energa-UNAM, Mexico
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
The goal of this research is to develop a stable, cost effective, photoelectrochemical based system that will split water using sunlight as the only energy input, with a solar-to-hydrogen efficiency of 10% with a 10-year lifetime. Our objectives are: Identify and characterize new semiconductor materials that have appropriate bandgaps and are stable in aqueous solutions. Study multijunction semiconductor systems for higher efficiency water splitting. Develop techniques for the energetic control of the semiconductor electrolyte interphase. Developing techniques for the preparation of transparent catalytic coatings and their application to semiconductor surfaces. Identify environmental factors (e.g., pH, ionic strength, solution composition, etc.) that affect the energetics of the semiconductor, the properties of the catalysts, and the stability of the semiconductor.
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Band Edges of p- and n-Type Semiconductors Immersed in Aqueous Electrolytes to Form Liquid Junctions
E conduction O2 p-type E valence 2H2O + 2e = 2OH + H
P158-A199107
H2O/H2
Band Gap (Eg) must be at least 1.6-1.7 eV Band Edges must straddle H2O redox potentials
Eg
1.23 eV 1.6-1.7 eV Counter Electrode Fast charge transfer Stable in aqueous solution
H2O/O2
p-type Semiconductor
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Project Status
Current status:
12.4% efficiency multijunction system, 20 hour lifetime. H2 Cost: >$13/kg
Targets:
10% solar-to-hydrogen efficiency, 10-year lifetime H2 Cost: $3/kg
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Eg = 1.83 eV
Energy
p-GaInP2
H2O/H2
EF E VB
(+)
H2O/O2
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Experimental Cell
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
-40
-80
-120
Voltage versus Pt
The GaAs integrated PV cell compensates for the energetic mismatch but expensive
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
A p-GaInP
2
-2.0
-2.0
e
-1.0 E (H /H O)
2 2
0
CB
-1.0
0.0
e CB
E (H O/O )
0
0.0
VB
2 2
1.0
1.0
2.0
VB h
2.0
.While the System splits water, the efficiency is very low. The photocurrent is limited by response of the iron oxide. Work is continuing in collaboration with other researchers (as part of our IEA efforts) to discover better materials.
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
The goal is to shift the band edges by surface modification to provide the proper energetic overlap.
CB
Modification
CB
H2O/H2
E
VB VB H2O/O2
Tetra(N-Methyl-4-Pyridyl)porphyrin ~TMPyP(4)~
Transition metal in center of porphyrin may combine favorable properties of band edge shifting and charge transfer.
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
The band edges here should be able to split water..but no water splitting observed.
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Band edge migration is due to negative charges accumulating at the surface catalysis is not sufficient work continues.. (-) e-
H2/H2O
H2/H2O
H2/H2O
O2/H2O
O2/H2O
O2/H2O
h+ (+) Dark
Increasing Light Intensity
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
The soluble porphyrins show large band edge shifts, but why 1 the large /C2 change in slopeindicates a higher doping density?
Untreated Vfb = 0.221 R2 = 0.9996 Treated with FeTMPyP(2) Vfb = 1.195 R2 = 0.9953
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
This phenomenon is not unique to the iron system. Electron density is being drawn from the near surface of the semiconductor, but the mechanism is unclear
3.E+14 3.E+14
1
/C2
Untreated Vfb = 0.220 2 R = 0.9996 Treated with VOTMPyP(4) Vfb = 1.076 2 R = 0.9966
0.5
1.0
1.5
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Photocurrent time profile for PEC/PV Water-Splitting device, showing current decay due to corrosion.
-40
-50
CD, mA/cm
-100
-80
10 Time, hours
15
20
-100
-120
-140 0
500
1000
1500
Time, sec Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
1.0
p -G a N 0 .1 M K O H
E (V) vs SCE
0.5
i a n o d ic
0.0
i c a th o d ic
d a rk
-0.5
-1.0
-8 -7 -6
i ca tho d ic
10 10 10 10
-5
9.0x10
10
2
-4
-5
10
-3
lo g i(lo g (A /c m ))
8.0x10
-5
-5
-5
-5
-5
-5
-5
-5
1000
2000
3000
4000
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Time (s)
These materials are also interesting for high efficiency Solar Cells Lighting
Calculated efficiencies (ideal) 500X AM1.5D: 36% one sun AM0: 31%
1.8 eV
GaInP
GaAs 1.4 eV
6 7 8 9
Energy (eV)
New materials - Preliminary Investigation of GaAsPN for PEC Water Splitting Systems
with Professor Carl Koval University of Colorado at Boulder
Indirect Photoresponse ME087-2
0.014
0.012
0.000000025
0.00000002
0.01
0.008
0.000000015
0.006
0.00000001
0.004
0.000000005
0.002
0 1.5E+00
1.6E+00
1.7E+00
1.8E+00
1.9E+00
2.0E+00
2.1E+00
2.2E+00
2.3E+00
Energy (eV)
0 1.5E+00
1.6E+00
1.7E+00
1.8E+00
1.9E+00
2.0E+00
2.1E+00
2.2E+00
2.3E+00
Energy (eV)
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
e-
Eg
-SiC
-Si Cell #3 p-i-n
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
GaInP2 - NREL (fundamental understanding) GaPN - NREL (high efficiency, stability) InGaN - SVT Associates, NREL, (high efficiency, stability) CuInGaSeS - UNAM (Mexico), NREL (Low cost) Multi-junction Amorphous Silicon - University of Toledo and ECD (Low cost) Energetics
Band edge control Catalysis Surface studies
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Energetics
Band-edge engineering
Development fundamental understanding of surface interaction. Try treatment on other materials
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel
Plans
Band-edge engineering
Development fundamental understanding of surface interaction. Try treatment on other materials
Operated for the U.S. Department of Energy by Midwest Research Institute Battelle Bechtel