skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes

Abstract

Photoelectrochemical (PEC) water-splitting is an elegant method of converting sunlight and water into H2 fuel. To be commercially advantageous, PEC devices must become cheaper, more efficient and much more durable. This work examines low-cost polycrystalline chalcopyrite films, which are successful as photovoltaic absorbers, for application as PEC absorbers. In particular, Cu-Ga-Se films with wide band gaps can be employed as top cell photocathodes in tandem devices as a realistic route to high efficiencies. In this report, we demonstrate that decreasing Cu/Ga composition from 0.66 to 0.31 in Cu-Ga-Se films increased the band gap from 1.67 to 1.86 eV and decreased saturated photocurrent density from 18 to 8 mA/cm2 as measured by chopped-light current-voltage (CLIV) measurements in 0.5 M sulfuric acid electrolyte. Buffer and catalyst surface treatments were not applied to the Cu-Ga-Se films, and they exhibited promising stability, evidenced by unchanged CLIV after 9 months of storage in air. Finally, films with Cu/Ga = 0.36 (approximately stoichiometric CuGa3Se5) and 1.86 eV band gaps had exceptional durability, and continuously split water for 17 days (~12 mA/cm2 at -1 V vs. RHE). This is equivalent to ~17200 C/cm2, which is a world record for any polycrystalline PEC absorber. These results indicate thatmore » CuGa3Se5 films are prime candidates for cheaply achieving efficient and durable PEC water splitting.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [2]; ORCiD logo [1];  [2]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Univ. of Hawaii, Honolulu, HI (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Hawaii, Honolulu, HI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1456867
Alternate Identifier(s):
OSTI ID: 1570462
Report Number(s):
NREL/JA-5K00-71606
Journal ID: ISSN 1944-8244
Grant/Contract Number:  
AC36-08GO28308; EE0006670
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 23; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; chalcopyrite; hydrogen; photoelectrochemical; polycrystalline; water splitting

Citation Formats

Muzzillo, Christopher P., Klein, W. Ellis, Li, Zhen, DeAngelis, Alexander Daniel, Horsley, Kimberly, Zhu, Kai, and Gaillard, Nicolas. Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes. United States: N. p., 2018. Web. https://doi.org/10.1021/acsami.8b01447.
Muzzillo, Christopher P., Klein, W. Ellis, Li, Zhen, DeAngelis, Alexander Daniel, Horsley, Kimberly, Zhu, Kai, & Gaillard, Nicolas. Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes. United States. https://doi.org/10.1021/acsami.8b01447
Muzzillo, Christopher P., Klein, W. Ellis, Li, Zhen, DeAngelis, Alexander Daniel, Horsley, Kimberly, Zhu, Kai, and Gaillard, Nicolas. Wed . "Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes". United States. https://doi.org/10.1021/acsami.8b01447. https://www.osti.gov/servlets/purl/1456867.
@article{osti_1456867,
title = {Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes},
author = {Muzzillo, Christopher P. and Klein, W. Ellis and Li, Zhen and DeAngelis, Alexander Daniel and Horsley, Kimberly and Zhu, Kai and Gaillard, Nicolas},
abstractNote = {Photoelectrochemical (PEC) water-splitting is an elegant method of converting sunlight and water into H2 fuel. To be commercially advantageous, PEC devices must become cheaper, more efficient and much more durable. This work examines low-cost polycrystalline chalcopyrite films, which are successful as photovoltaic absorbers, for application as PEC absorbers. In particular, Cu-Ga-Se films with wide band gaps can be employed as top cell photocathodes in tandem devices as a realistic route to high efficiencies. In this report, we demonstrate that decreasing Cu/Ga composition from 0.66 to 0.31 in Cu-Ga-Se films increased the band gap from 1.67 to 1.86 eV and decreased saturated photocurrent density from 18 to 8 mA/cm2 as measured by chopped-light current-voltage (CLIV) measurements in 0.5 M sulfuric acid electrolyte. Buffer and catalyst surface treatments were not applied to the Cu-Ga-Se films, and they exhibited promising stability, evidenced by unchanged CLIV after 9 months of storage in air. Finally, films with Cu/Ga = 0.36 (approximately stoichiometric CuGa3Se5) and 1.86 eV band gaps had exceptional durability, and continuously split water for 17 days (~12 mA/cm2 at -1 V vs. RHE). This is equivalent to ~17200 C/cm2, which is a world record for any polycrystalline PEC absorber. These results indicate that CuGa3Se5 films are prime candidates for cheaply achieving efficient and durable PEC water splitting.},
doi = {10.1021/acsami.8b01447},
journal = {ACS Applied Materials and Interfaces},
number = 23,
volume = 10,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: XRD data for Cu-Ga-Se films with Cu/Ga compositions of 0.66 (top black), 0.52 (middle red), and 0.36 (bottom blue). Standard diffraction pattern peak positions for CuGaSe2 (green triangles) and CuGa3Se5 (purple circles) are included for reference.

Save / Share:

Works referenced in this record:

Hydrogen and fuel cells: Towards a sustainable energy future
journal, December 2008


Experimental demonstrations of spontaneous, solar-driven photoelectrochemical water splitting
journal, January 2015

  • Ager, Joel W.; Shaner, Matthew R.; Walczak, Karl A.
  • Energy & Environmental Science, Vol. 8, Issue 10
  • DOI: 10.1039/c5ee00457h

Efficient solar hydrogen production from neutral electrolytes using surface-modified Cu(In,Ga)Se 2 photocathodes
journal, January 2015

  • Kumagai, Hiromu; Minegishi, Tsutomu; Sato, Naotoshi
  • Journal of Materials Chemistry A, Vol. 3, Issue 16
  • DOI: 10.1039/c5ta01058f

Effects of heavy alkali elements in Cu(In,Ga)Se 2 solar cells with efficiencies up to 22.6%
journal, July 2016

  • Jackson, Philip; Wuerz, Roland; Hariskos, Dimitrios
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 10, Issue 8
  • DOI: 10.1002/pssr.201600199

Enhanced Efficiency of Cd-Free Cu(In,Ga)(Se,S)2 Minimodule Via (Zn,Mg)O Second Buffer Layer and Alkali Metal Post-Treatment
journal, November 2017


Development of Chalcogenide Thin Film Materials for Photoelectrochemical Hydrogen Production
journal, January 2013

  • Gaillard, Nicolas; Prasher, Dixit; Kaneshiro, Jess
  • MRS Proceedings, Vol. 1558
  • DOI: 10.1557/opl.2013.1084

A monolithic device for solar water splitting based on series interconnected thin film absorbers reaching over 10% solar-to-hydrogen efficiency
journal, January 2013

  • Jacobsson, T. Jesper; Fjällström, Viktor; Sahlberg, Martin
  • Energy & Environmental Science, Vol. 6, Issue 12
  • DOI: 10.1039/c3ee42519c

Durable hydrogen evolution from water driven by sunlight using (Ag,Cu)GaSe 2 photocathodes modified with CdS and CuGa 3 Se 5
journal, January 2015

  • Zhang, Li; Minegishi, Tsutomu; Nakabayashi, Mamiko
  • Chemical Science, Vol. 6, Issue 2
  • DOI: 10.1039/c4sc02346c

Towards efficient solar-to-hydrogen conversion: Fundamentals and recent progress in copper-based chalcogenide photocathodes
journal, September 2016


Investigation of Cu-Deficient Copper Gallium Selenide Thin Film as a Photocathode for Photoelectrochemical Water Splitting
journal, January 2012

  • Kim, Jaehong; Minegishi, Tsutomu; Kobota, Jun
  • Japanese Journal of Applied Physics, Vol. 51, Issue 1R
  • DOI: 10.7567/jjap.51.015802

Enhanced photoelectrochemical properties of CuGa 3 Se 5 thin films for water splitting by the hydrogen mediated co-evaporation method
journal, January 2012

  • Kim, Jaehong; Minegishi, Tsutomu; Kobota, Jun
  • Energy Environ. Sci., Vol. 5, Issue 4
  • DOI: 10.1039/c1ee02280f

Photoelectrochemical Hydrogen Evolution from Water Using Copper Gallium Selenide Electrodes Prepared by a Particle Transfer Method
journal, January 2014

  • Kumagai, Hiromu; Minegishi, Tsutomu; Moriya, Yosuke
  • The Journal of Physical Chemistry C, Vol. 118, Issue 30
  • DOI: 10.1021/jp409921f

Strategies for stable water splitting via protected photoelectrodes
journal, January 2017

  • Bae, Dowon; Seger, Brian; Vesborg, Peter C. K.
  • Chemical Society Reviews, Vol. 46, Issue 7
  • DOI: 10.1039/c6cs00918b

Photoelectrolysis of water using thin copper gallium diselenide electrodes
journal, September 2008


Studies on the electrochemical stability of CIGS in H2SO4
journal, November 2004

  • Valderrama, R. C.; Sebastián, P. J.; Miranda-Hernandez, M.
  • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 168, Issue 1-2
  • DOI: 10.1016/j.jphotochem.2004.04.006

Cu–Ga–In thermodynamics: experimental study, modeling, and implications for photovoltaics
journal, December 2015

  • Muzzillo, Christopher P.; Campbell, Carelyn E.; Anderson, Timothy J.
  • Journal of Materials Science, Vol. 51, Issue 7
  • DOI: 10.1007/s10853-015-9651-3

Ternary phase relations of the chalcopyrite compound CuGaSe2
journal, May 1981

  • Mikkelsen, J. C.
  • Journal of Electronic Materials, Vol. 10, Issue 3
  • DOI: 10.1007/bf02654590

Long-range structure of Cu(InxGa1−x)3Se5: A complementary neutron and anomalous x-ray diffraction study
journal, January 2011

  • Lehmann, S.; Marrón, D. Fuertes; León, M.
  • Journal of Applied Physics, Vol. 109, Issue 1
  • DOI: 10.1063/1.3524183

What is the bandgap of kesterite?
journal, December 2016


Accelerating materials development for photoelectrochemical hydrogen production: Standards for methods, definitions, and reporting protocols
journal, January 2010

  • Chen, Zhebo; Jaramillo, Thomas F.; Deutsch, Todd G.
  • Journal of Materials Research, Vol. 25, Issue 1
  • DOI: 10.1557/jmr.2010.0020

CuGaSe2–CuGa3Se5 phase transition in CCSVT-grown thin films
journal, July 2006


Preparation and Characterization of Cu-Ga-Se Films of Ordered Vacancy Compound
journal, January 2003


Electrical properties of Na-incorporated Cu(In1−xGax)3Se5 thin films
journal, August 1997

  • Kohara, Naoki; Negami, Takayuki; Nishitani, Mikihiko
  • Applied Physics Letters, Vol. 71, Issue 6
  • DOI: 10.1063/1.119661

Anion displacements and the band-gap anomaly in ternary AB C 2 chalcopyrite semiconductors
journal, April 1983


Preparation and characterization of Cu(In 1− x Ga x ) 3 Se 5 thin films
journal, August 1995

  • Negami, Takayuki; Kohara, Naoki; Nishitani, Mikihiko
  • Applied Physics Letters, Vol. 67, Issue 6
  • DOI: 10.1063/1.115456

Optical functions and electronic structure of CuInSe 2 , CuGaSe 2 , CuInS 2 , and CuGaS 2
journal, January 2001


Technical and economic feasibility of centralized facilities for solar hydrogen production via photocatalysis and photoelectrochemistry
journal, January 2013

  • Pinaud, Blaise A.; Benck, Jesse D.; Seitz, Linsey C.
  • Energy & Environmental Science, Vol. 6, Issue 7
  • DOI: 10.1039/c3ee40831k

Recombination kinetics and stability in polycrystalline Cu(In,Ga)Se2 solar cells
journal, February 2009


Growth Mechanisms and Diffusion in Multinary and Multilayer Chalcopyrite Thin Films
journal, January 1993

  • Klenk, R.; Walter, T.; Schmid, D.
  • Japanese Journal of Applied Physics, Vol. 32, Issue S3
  • DOI: 10.7567/jjaps.32S3.57

    Works referencing / citing this record:

    Efficiency and stability of narrow-gap semiconductor-based photoelectrodes
    journal, January 2019

    • Zheng, Jianyun; Zhou, Huaijuan; Zou, Yuqin
    • Energy & Environmental Science, Vol. 12, Issue 8
    • DOI: 10.1039/c9ee00524b

    Recent Advances and Emerging Trends in Photo-Electrochemical Solar Energy Conversion
    journal, November 2018


    Metal selenide photocatalysts for visible-light-driven Z -scheme pure water splitting
    journal, January 2019

    • Chen, Shanshan; Ma, Guijun; Wang, Qian
    • Journal of Materials Chemistry A, Vol. 7, Issue 13
    • DOI: 10.1039/c9ta00768g