DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Corrosion resistance of functionally graded TiN/Ti coatings for proton exchange membrane fuel cells

Abstract

Bipolar Plates (BPP) are important components of proton exchange membrane fuel cell (PEMFC) stacks. In the development of innovative fuel cell designs, it is advantageous to use aluminum for these applications, however, this material lacks the necessary corrosion resistance. Since the performance of PEMFC stacks depends on BPP properties, in particular, corrosion resistance, depositing titanium nitride (TiN) thin films onto aluminum substrates may improve their efficiency and durability. Present work focuses on improving corrosion resistance and hydrophobicity of TiN/Ti by using N graded films deposited onto aluminum substrates (AA-1100) by grid-assisted magnetron sputtering (GAMS). Electrochemical impedance spectroscopy (EIS) with potentiodynamic and potentiostatic polarization are used to investigate the performance of the substrate/film system at room temperature and 70 oC, thus simulating a prototypic PEMFC electrolyte environment. Electrochemical test results showed that graded TiN films improved corrosion resistance when compared with both the homogeneous films and the AA1100 uncoated substrate. Furthermore, contact angle results reveal improved hydrophobicity for both homogeneous and graded TiN coatings when compared with the AA1100 substrate.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [5]; ORCiD logo [5];  [2]; ORCiD logo [2]
  1. Univ. of Sao Paulo (Brazil). Escola Politecnica. Dept. de Engenharia Metalurgica e de Materiais; Centro Estadual de Educacao Tecnologica “Paula Souza”, Sao Paulo (Brazil). Faculdade de Tecnologia de Cotia
  2. Univ. of Sao Paulo (Brazil). Escola Politecnica. Dept. de Engenharia Metalurgica e de Materiais
  3. Montanuniversitaet Leoben (Austria)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  5. Universidade do Estado de Santa Catarina, Joinville-SC (Brazil). Lab. of Plasmas, Films and Surfaces
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Foundation of Support for Research and Innovation of the Santa Catarina State (FAPESC); Brazilian National Research, Technology and Innovation Council
OSTI Identifier:
1787009
Alternate Identifier(s):
OSTI ID: 1809563
Grant/Contract Number:  
AC05-00OR22725; AC05-06OR23100; 308565/2018-5; PAP-TR-781
Resource Type:
Accepted Manuscript
Journal Name:
International Journal of Hydrogen Energy
Additional Journal Information:
Journal Volume: 45; Journal Issue: 58; Journal ID: ISSN 0360-3199
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; PEMFC; Titanium Nitride; Bipolar Plates; Graded Coatings; Functionally Graded Materials; Corrosion Resistance

Citation Formats

Silva, F. C., Prada Ramirez, O. M., Tunes, M. A., Edmondson, P. D., Sagás, J. C., Fontana, L. C., de Melo, H. G., and Schön, C. G. Corrosion resistance of functionally graded TiN/Ti coatings for proton exchange membrane fuel cells. United States: N. p., 2020. Web. doi:10.1016/j.ijhydene.2020.09.037.
Silva, F. C., Prada Ramirez, O. M., Tunes, M. A., Edmondson, P. D., Sagás, J. C., Fontana, L. C., de Melo, H. G., & Schön, C. G. Corrosion resistance of functionally graded TiN/Ti coatings for proton exchange membrane fuel cells. United States. https://doi.org/10.1016/j.ijhydene.2020.09.037
Silva, F. C., Prada Ramirez, O. M., Tunes, M. A., Edmondson, P. D., Sagás, J. C., Fontana, L. C., de Melo, H. G., and Schön, C. G. Thu . "Corrosion resistance of functionally graded TiN/Ti coatings for proton exchange membrane fuel cells". United States. https://doi.org/10.1016/j.ijhydene.2020.09.037. https://www.osti.gov/servlets/purl/1787009.
@article{osti_1787009,
title = {Corrosion resistance of functionally graded TiN/Ti coatings for proton exchange membrane fuel cells},
author = {Silva, F. C. and Prada Ramirez, O. M. and Tunes, M. A. and Edmondson, P. D. and Sagás, J. C. and Fontana, L. C. and de Melo, H. G. and Schön, C. G.},
abstractNote = {Bipolar Plates (BPP) are important components of proton exchange membrane fuel cell (PEMFC) stacks. In the development of innovative fuel cell designs, it is advantageous to use aluminum for these applications, however, this material lacks the necessary corrosion resistance. Since the performance of PEMFC stacks depends on BPP properties, in particular, corrosion resistance, depositing titanium nitride (TiN) thin films onto aluminum substrates may improve their efficiency and durability. Present work focuses on improving corrosion resistance and hydrophobicity of TiN/Ti by using N graded films deposited onto aluminum substrates (AA-1100) by grid-assisted magnetron sputtering (GAMS). Electrochemical impedance spectroscopy (EIS) with potentiodynamic and potentiostatic polarization are used to investigate the performance of the substrate/film system at room temperature and 70 oC, thus simulating a prototypic PEMFC electrolyte environment. Electrochemical test results showed that graded TiN films improved corrosion resistance when compared with both the homogeneous films and the AA1100 uncoated substrate. Furthermore, contact angle results reveal improved hydrophobicity for both homogeneous and graded TiN coatings when compared with the AA1100 substrate.},
doi = {10.1016/j.ijhydene.2020.09.037},
journal = {International Journal of Hydrogen Energy},
number = 58,
volume = 45,
place = {United States},
year = {Thu Oct 01 00:00:00 EDT 2020},
month = {Thu Oct 01 00:00:00 EDT 2020}
}

Works referenced in this record:

Mechanical behavior of TiN/CrN nano-multilayer thin film deposited by unbalanced magnetron sputter process
journal, February 2011


Fabrication and nanoindentation properties of TiN/NiTi thin films and their applications in electrochemical sensing
journal, May 2009


Enhanced corrosion resistance and fuel cell performance of Al1050 bipolar plate coated with TiN/Ti double layer
journal, November 2013


On the Growth of Highly Ordered Pores in Anodized Aluminum Oxide
journal, September 1998

  • Li, Feiyue; Zhang, Lan; Metzger, Robert M.
  • Chemistry of Materials, Vol. 10, Issue 9
  • DOI: 10.1021/cm980163a

Trends in research and development of protonic ceramic electrolysis cells
journal, October 2019


Age-hardening of high pressure die casting AlMg alloys with Zn and combined Zn and Cu additions
journal, November 2019


Testing and evaluation of aluminum coated bipolar plates of pem fuel cells operating at 70°C
journal, December 2006


Electron energy-loss spectroscopy: A versatile tool for the investigations of plasmonic excitations
journal, August 2014

  • Roth, Friedrich; König, Andreas; Fink, Jörg
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 195
  • DOI: 10.1016/j.elspec.2014.05.007

Biaxial alignment in sputter deposited thin films
journal, December 2006


Investigation on electrochemical behavior and surface conductivity of titanium carbide modified Ti bipolar plate of PEMFC
journal, March 2020


Investigation of single-layer and multilayer coatings for aluminum bipolar plate in polymer electrolyte membrane fuel cell
journal, May 2014


Design and manufacturing of stainless steel bipolar plates for proton exchange membrane fuel cells
journal, December 2014


Ni–P and Ni–Co–P coated aluminum alloy 5251 substrates as metallic bipolar plates for PEM fuel cell applications
journal, May 2012

  • Fetohi, Amani E.; Abdel Hameed, R. M.; El-Khatib, K. M.
  • International Journal of Hydrogen Energy, Vol. 37, Issue 9
  • DOI: 10.1016/j.ijhydene.2012.01.145

On the electrochemical behaviour of aluminium in acidic chloride solution
journal, February 1992


The anodizing of aluminium in sulphate solutions
journal, December 1970


Electrochemical impedance spectroscopy as a tool to obtain mechanistic information on the passive behaviour of aluminium
journal, May 1996


Revised structure zone model for thin film physical structure
journal, April 1984

  • Messier, R.; Giri, A. P.; Roy, R. A.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 2, Issue 2
  • DOI: 10.1116/1.572604

Wear behavior and thermal stability of HPPMS (Al,Ti,Cr,Si)ON, (Al,Ti,Cr,Si)N and (Ti,Al,Cr,Si)N coatings for cutting tools
journal, March 2020


Investigation of PVD coating on corrosion resistance of metallic bipolar plates in PEM fuel cell
journal, September 2003

  • Lee, Shuo-Jen; Huang, Ching-Han; Chen, Yu-Pang
  • Journal of Materials Processing Technology, Vol. 140, Issue 1-3
  • DOI: 10.1016/S0924-0136(03)00743-X

Grid-assisted magnetron sputtering deposition of nitrogen graded TiN thin films
journal, April 2020


Titanium nitride nanopowders produced via sodium reductionin liquid ammonia
journal, February 2009

  • Yuan, Boyan; Yang, Mei; Zhu, Hongmin
  • Journal of Materials Research, Vol. 24, Issue 2
  • DOI: 10.1557/JMR.2009.0050

Electrochemical capacitance performance of titanium nitride nanoarray
journal, December 2013


Fe2Ti interlayer for improved adhesion strength and corrosion resistance of TiN coating on stainless steel 316L
journal, February 2020


An EIS study of aluminium barrier-type oxide films formed in different media
journal, September 1992


Improving performance in PEMFC by applying different coatings to metallic bipolar plates
journal, December 2019


Durability and characterization studies of chromium carbide coated aluminum fuel cell stack
journal, July 2016


Tribological behaviours of PVD TiN and TiCN coatings in artificial seawater
journal, July 2013


Fabrication of multi-filler thermoset-based composite bipolar plates for PEMFCs applications: Molding defects and properties characterizations
journal, May 2020

  • Simaafrookhteh, Sepehr; Khorshidian, Majid; Momenifar, Mohammad
  • International Journal of Hydrogen Energy, Vol. 45, Issue 27
  • DOI: 10.1016/j.ijhydene.2020.03.105

Investigation on physical and electrochemical properties of TiN-coated Monel alloy used for bipolar plates of proton exchange membrane fuel cell
journal, December 2019


Corrosion behavior and adhesion of ion-plated TiN films on AISI 304 steel
journal, August 2000


Corrosion Investigation of Chromium Nitride and Chromium Carbide Coatings for PEM Fuel Cell Bipolar Plates in Simulated Cathode Condition
journal, June 2016

  • Haghighat Ghahfarokhi, H.; Saatchi, A.; Monirvaghefi, S. M.
  • Fuel Cells, Vol. 16, Issue 3
  • DOI: 10.1002/fuce.201600005

Proton exchange membrane fuel cells
journal, August 2006


CPE analysis by local electrochemical impedance spectroscopy
journal, January 2006


Electrically conductive polymer composite coating on aluminum for PEM fuel cells bipolar plate
journal, June 2013


Assessment of the durability of low-cost Al bipolar plates for High Temperature PEM fuel cells
journal, May 2019

  • Alegre, Cinthia; Álvarez-Manuel, Laura; Mustata, Radu
  • International Journal of Hydrogen Energy, Vol. 44, Issue 25
  • DOI: 10.1016/j.ijhydene.2018.07.070

Corrosion behavior of TiN coated type 316 stainless steel in simulated PEMFC environments
journal, June 2004


Electrochemical and electrical resistance behavior of cathodic arc PVD TiN, CrN, AlCrN, and AlTiN coatings in simulated proton exchange membrane fuel cell environment
journal, September 2018

  • Khan, M. Faizan; Adesina, Akeem Y.; Gasem, Zuhair M.
  • Materials and Corrosion, Vol. 70, Issue 2
  • DOI: 10.1002/maco.201810377

Reactive sputter deposition of TiN layers: modelling the growth by characterization of particle fluxes towards the substrate
journal, February 2009


Site specific dependencies of hydrogen concentrations in zirconium hydrides
journal, January 2019


Silver implanted 316L stainless steel as bipolar plates in polymer electrolyte membrane fuel cells
journal, March 2011


Synthesis and localized inhibition behaviour of new triazine-methionine corrosion inhibitor in 1 M HCl for 2024-T3 aluminium alloy
journal, November 2019


New electroplated aluminum bipolar plate for PEM fuel cell
journal, February 2008


Self-assembled graphene film to enable highly conductive and corrosion resistant aluminum bipolar plates in fuel cells
journal, April 2017


Comparison of TiN and CN coatings on orthodontic stainless steel: Tribological and biological evaluation
journal, March 2019


A graded nano-TiN coating on biomedical Ti alloy: Low friction coefficient, good bonding and biocompatibility
journal, February 2017


Influence of apparatus geometry and deposition conditions on the structure and topography of thick sputtered coatings
journal, July 1974

  • Thornton, John A.
  • Journal of Vacuum Science and Technology, Vol. 11, Issue 4
  • DOI: 10.1116/1.1312732

The domestication of fire: The relationship between biomass fuel, fossil fuel and burns
journal, September 2012


Nano mechanical and wear properties of multi-layer Ti/TiN coatings deposited on Al 7075 by high-vacuum magnetron sputtering
journal, September 2017


On the corrosion behavior of TiN-coated AISI D2 steel
journal, January 1999


Influence of the substrate hardness on the cavitation erosion resistance of TiN coating
journal, September 2007


Stress-related effects in thin films
journal, April 1989


Investigation of incorporating oxygen into TiN coating to resist high potential effects on PEMFC bipolar plates in vehicle applications
journal, September 2020


A review of focused ion beam milling techniques for TEM specimen preparation
journal, June 1999


Corrosion of metal bipolar plates for PEM fuel cells: A review
journal, April 2010

  • Antunes, Renato A.; Oliveira, Mara Cristina L.; Ett, Gerhard
  • International Journal of Hydrogen Energy, Vol. 35, Issue 8
  • DOI: 10.1016/j.ijhydene.2010.01.059

Surface modifications of aluminum alloy 5052 for bipolar plates using an electroless deposition process
journal, August 2008


Wear performance of different PVD coatings during hard wet end milling of H13 tool steel
journal, October 2015


Formable chromium nitride coatings for proton exchange membrane fuel cell stainless steel bipolar plates
journal, May 2020

  • Haye, Emile; Deschamps, Fabien; Caldarella, Giuseppe
  • International Journal of Hydrogen Energy, Vol. 45, Issue 30
  • DOI: 10.1016/j.ijhydene.2020.03.248

Corrosion behavior of tantalum coatings on AISI 316L stainless steel substrate for bipolar plates of PEM fuel cells
journal, August 2020


Porous anodic alumina: fabrication, characterization and applications
journal, April 1997


Nitrogen effect on corrosion resistance of ion beam sputtered nanocrystalline zirconium nitride films
journal, June 2009


Technical evaluation of proton exchange membrane (PEM) fuel cell performance – A review of the effects of bipolar plates coating
journal, October 2019

  • Wilberforce, Tabbi; Ijaodola, O.; Ogungbemi, Emmanuel
  • Renewable and Sustainable Energy Reviews, Vol. 113
  • DOI: 10.1016/j.rser.2019.109286

Anodic oxide films on aluminum
journal, June 1969

  • Diggle, J. W.; Downie, Thomas C.; Goulding, C. W.
  • Chemical Reviews, Vol. 69, Issue 3
  • DOI: 10.1021/cr60259a005

Evaluation of the corrosion resistance of Ni(P)Cr coatings for bipolar plates by electrochemical impedance spectroscopy
journal, August 2020


Mechanical properties of TiNx/Cr1−xN thin films on plasma nitriding-assisted AISI H13 steel
journal, April 2005


Ac-impedance and Raman spectroscopy study of the electrochemical behaviour of pure aluminium in citric acid media
journal, March 2001


Improvement of the corrosion resistance of CrN coated steel by an interlayer
journal, September 1998


Conducting polymer-coated stainless steel bipolar plates for proton exchange membrane fuel cells (PEMFC)
journal, September 2005


The use of the electrochemical micro-cell for the investigation of corrosion phenomena
journal, June 2016


Investigating the fretting fatigue life of thin film titanium nitride coated aerospace Al7075-T6 alloy
journal, January 2013


Carbon-based coatings for metallic bipolar plates used in proton exchange membrane fuel cells
journal, March 2019


Thermal stability of nitride thin films
journal, April 2000


Study and Assessment of the Efficiency of the Cocoa Bark Extracted from the Theobroma Cacao as an Inhibitor of the Corrosion of Carbon Steel in Substitution of Benzotriazole
journal, November 2017


Exfoliation corrosion of aluminum alloy AA7075 examined by electrochemical impedance spectroscopy
journal, January 2004


Research on titanium nitride thin films deposited by reactive magnetron sputtering for MEMS applications
journal, December 2015


TiN-coated titanium as the bipolar plate for PEMFC by multi-arc ion plating
journal, July 2011


Initial growth and epitaxy of PVD TiN layers on austenitic steel
journal, June 1989


Reviewing Metallic PEMFC Bipolar Plates
journal, April 2010


Polyaniline and polypyrrole coatings on aluminum for PEM fuel cell bipolar plates
journal, February 2008


Porous Anodic Aluminum Oxide: Anodization and Templated Synthesis of Functional Nanostructures
journal, June 2014

  • Lee, Woo; Park, Sang-Joon
  • Chemical Reviews, Vol. 114, Issue 15
  • DOI: 10.1021/cr500002z

Influence of CrN-coating thickness on the corrosion resistance behaviour of aluminium-based bipolar plates
journal, May 2011


A Review of Finite Element Method Models for Nuclear Graphite Applications
journal, December 2018

  • Arregui-Mena, José David; Worth, Robert N.; Hall, Graham
  • Archives of Computational Methods in Engineering, Vol. 27, Issue 1
  • DOI: 10.1007/s11831-018-09310-y

Effects of pretreatment by ion implantation and interlayer on adhesion between aluminum substrate and TiN film
journal, December 2005


Electrochemical impedance spectroscopy as a tool for investigating underpaint corrosion
journal, May 1996


Electrical resistivity of titanium nitride thin films prepared by ion beam-assisted deposition
journal, December 2001


Molybdenum carbide coated 316L stainless steel for bipolar plates of proton exchange membrane fuel cells
journal, February 2019


An investigation of coated aluminium bipolar plates for PEMFC
journal, December 2012


Effect of film thickness and Ti interlayer on the structure and properties of nanocrystalline TiN thin films on AISI D2 steel
journal, May 2007


Characterizing the Structural Degradation in a PEMFC Cathode Catalyst Layer: Carbon Corrosion
journal, January 2009

  • Young, A. P.; Stumper, J.; Gyenge, E.
  • Journal of The Electrochemical Society, Vol. 156, Issue 8
  • DOI: 10.1149/1.3139963

Microstructure and hydrogen impermeability of titanium nitride thin films deposited by direct current reactive magnetron sputtering
journal, December 2016


Tribological and corrosion behavior of CrN coatings: Roles of substrate and deposition defects
journal, November 2014


A review of PEM hydrogen fuel cell contamination: Impacts, mechanisms, and mitigation
journal, March 2007


An investigation into polypyrrole-coated 316L stainless steel as a bipolar plate material for PEM fuel cells
journal, December 2006


Mechanical properties of homogeneous and nitrogen graded TiN thin films
journal, September 2020


Composite-coated aluminum bipolar plates for PEM fuel cells
journal, June 2013


Electronic currents and the formation of nanopores in porous anodic alumina
journal, October 2009


Age-hardening response of AlMgZn alloys with Cu and Ag additions
journal, August 2020