National Renewable Energy Laboratory

Photoelectrochemical Water Splitting

NREL Principal Investigator: John A. Turner Current staff

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
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National Renewable Energy Laboratory

Photoelectrochemical Conversion Goals and Objectives

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.
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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

E conduction H2 n-type E valence H2O + 2h+ = 2H+ + 1/2 O2

P158-A199107

National Renewable Energy Laboratory

Material and Energetic Criteria

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

All must be satisfied simultaneously

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Timeline: 1991 to present

Cumulative Federal Funding: $4500K (~0.75 FTE + postdoc, average)

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National Renewable Energy Laboratory

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

Gallium Indium Phosphide/Electrolyte System

National Renewable Energy Laboratory

Used to gain a fundamental understanding of semiconductor/electrolyte junctions (-)

E CB

Eg = 1.83 eV

Energy

p-GaInP2
H2O/H2

Band edges are 0.2-0.4 V too negative

EF E VB

(+)
H2O/O2

Band edges are pH sensitive

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National Renewable Energy Laboratory

World Record Photoelectrolysis Device

Science, April 17 1998.

Direct water electrolysis. Unique tandem (PV/PEC) design. 12.4% Solar-to-hydrogen

Experimental Cell
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National Renewable Energy Laboratory

Comparison of p-GaInP2 and PEC/PV device

0 3 M H 2 SO4 , ~ 11.6 suns 1 : p-GaInP (Pt)/TJ/GaAs 2 2 : p-GaInP2 (Pt) 2 1

Current Density, mA/cm

-40

-80

-120

-160 -1.5 -1.0 -0.5 0.0 0.5

Voltage versus Pt

The GaAs integrated PV cell compensates for the energetic mismatch but expensive
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National Renewable Energy Laboratory

Additional Approaches for Bandedge Mismatch and Stability Issues

b
-Fe O
2 3

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

Lower cost Fe2O3 electrode is a possibility, but..

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National Renewable Energy Laboratory

.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.

Hematite nanorods in 0.5 M KNO3 ~1 W/cm2

GaInP2 in 0.5 M KNO3 ~1 W/cm2

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National Renewable Energy Laboratory

The goal is to shift the band edges by surface modification to provide the proper energetic overlap.

Band Edge Engineering

CB
Modification

Negative charges move the bandedges negative.

CB

H2O/H2

E
VB VB H2O/O2

Positive charges move the bandedges positive.

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The work involved two series of MetalloPorphyrins

Insoluble Soluble

Octaethyl Porphyrin ~OEP~

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.
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National Renewable Energy Laboratory

Band Edge Engineering - GaInP2

VFB vs. pH for RuCl3 + RuOEP Treated GaInP2 Electrode

H2O Oxidation Potential

The band edges here should be able to split water..but no water splitting observed.
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Metal Ion Catalysis

All show bandedge migration

Current Density, mA/cm2

Flatband Potential Migration, V

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Band edge migration is due to negative charges accumulating at the surface catalysis is not sufficient work continues.. (-) e-

National Renewable Energy Laboratory

H2/H2O

H2/H2O

H2/H2O

O2/H2O

O2/H2O

O2/H2O

h+ (+) Dark
Increasing Light Intensity
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National Renewable Energy Laboratory

Mott-Schottky Plot of Fe(III)TMPyP(2), pH 7

3.E+14 2.E+14 2.E+14 1.E+14 5.E+13 0.E+00 -5.E+13 -2.0 -1.5 -1.0 -0.5 0.0 Potential, V vs. SCE 0.5 1.0 1.5

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

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National Renewable Energy Laboratory

pH testing shows even more interesting behavior

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Mott-Schottky Plot for VO(IV)TMPyP(4), pH 7

National Renewable Energy Laboratory

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

2.E+14 2.E+14 1.E+14 5.E+13 0.E+00 -5.E+13 -2.0 -1.5 -1.0

Untreated Vfb = 0.220 2 R = 0.9996 Treated with VOTMPyP(4) Vfb = 1.076 2 R = 0.9966

-0.5 0.0 Potential, V vs. SCE

0.5

1.0

1.5

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National Renewable Energy Laboratory

Photocurrent time profile for PEC/PV Water-Splitting device, showing current decay due to corrosion.

-40
-50

CD, mA/cm

-60 Current Density, mA/cm

2

-100

We are looking for materials with inherently greater stability.

-80

10 Time, hours

15

20

-100

-120

-140 0

Efficiency(%) = (120mA/cm *1.23v/1190 mW/cm )*100 = 12.4%

500

1000

1500

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National Renewable Energy Laboratory

One possibility is nitride materials, an example of which is p-GaN

i a n o d ic
u n d e r illu m in a tio n

1.0

p -G a N 0 .1 M K O H

It shows excellent stability

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

Current density (A/cm )

7.0x10 6.0x10 5.0x10 4.0x10 3.0x10 2.0x10 1.0x10

-5

1 M KOH pH 7 buffer 3 M H 2SO4

and water splitting capability But3.0eV bandgap

-5

-5

-5

-5

-5

-5

1000

2000

3000

4000

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Time (s)

Adding indium lowers the bandgap

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

47% 38% GaInP 1.8 eV GaAs 1.4 eV New 1.0 eV

52% 41% GaInP 1.8 eV GaAs 1.4 eV New 1.0 eV Ge 0.7 eV

GaInP

GaAs 1.4 eV

6 7 8 9

Energy (eV)

In Future generation production

Other material possibilities include..

National Renewable Energy Laboratory

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

Direct Photoresponse ME087-2

0.00000003

0.012
0.000000025

0.00000002

y = 9E-08x - 2E-07 R2 = 0.9926 Eg=1.88 eV

0.01

y = 0.0439x - 0.0772 R = 0.9843 Eg=1.76 eV

2

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)

Electrode ME085-2 ME085-3 ME086-1 ME086-2 ME087-1 ME087-2

Direct Eg 1.74 eV 1.75 eV 1.66 eV 1.69 eV 1.88 eV 1.88 eV

Indirect Eg 1.69 eV 1.67 eV 1.59 eV 1.58 eV 1.75 eV 1.76 eV

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A long shot, but could be low cost.

National Renewable Energy Laboratory

New Materials - Band Gap Requirements for Electrodeposited CIGSSe

Dependence on sulfur content noted. However, this is convoluted by varying concentrations of other elements

Possible low-cost thin-film material

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Results for a-Si samples with Metal-ion Catalysts.

Another possible low-cost thin-film material

e-

Eg
-SiC
-Si Cell #3 p-i-n

1.8 eV 1.6 eV 1.4 eV

-Si Cell #2 p-i-n

-Si Cell #1 p-i-n

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Summary of ongoing work for FY2003 in blue

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

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Plans for future work

Continue materials research, discovery and development.

InxGa1-xN GaPN a-Si CuInGaSSe a-SiN (coating for stability) Others

Energetics
Band-edge engineering
Development fundamental understanding of surface interaction. Try treatment on other materials

Catalysis Surface studies

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Collaborations and Interactions

In the US Colorado School of Mines University of Colorado University of Wisconsin (Whitewater) GM, Astropower (proposed) Others working in this area: FSEC, Duquesne Outside of the US Switzerland, Mexico, Armenia, Sweden, Japan

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Plans

Continue materials development.

Nitrides CuGaInSSe a-Si

Band-edge engineering
Development fundamental understanding of surface interaction. Try treatment on other materials

Increase industry interactions

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