High-performance anion-exchange membrane water electrolysers using NiX (X = Fe,Co,Mn) catalyst-coated membranes with redox-active Ni–O ligands | Nature Catalysis

Nature Catalysis (2024)Cite this article

Metrics details

Recent efforts in anion-exchange membrane water electrolysis (AEMWE) focus on developing superior catalysts and membrane electrode assemblies to narrow the performance gaps compared with proton-exchange membrane water electrolysis (PEMWE). Here we present and characterize Ir-free AEMWE cells with NiX (X = Fe, Co or Mn) layered double hydroxide (LDH) catalyst-coated membranes with polarization characteristics and hydrogen productivities approaching those of acidic PEMWE cells, achieving >5 A cm−2 at <2.2 V. Operando spectroscopy revealed a correlation between Ni4+ centres and redox-active O ligands with an O K-edge feature, attributed to µ3-O ligands in the γ-LDH catalytic phase via density functional theory calculations. This computational–experimental study challenges the previously assumed correlation between spectral O K-edge features and oxygen evolution reaction performance in Ni-based LDH catalysts and provides insights from the molecular to the technological level demonstrating how redox-active Ni–O species and innovative catalyst-coated membrane preparation boost AEMWE performance to values rivalling state-of-the-art PEMWE cell technology.

This is a preview of subscription content, access via your institution

Access Nature and 54 other Nature Portfolio journals

Get Nature+, our best-value online-access subscription

$29.99 / 30 days

cancel any time

Subscribe to this journal

Receive 12 digital issues and online access to articles

$119.00 per year

only $9.92 per issue

Buy this article

Prices may be subject to local taxes which are calculated during checkout

The data supporting the findings of this study are provided within the Article. Source data are provided with this paper.

Khataee, A., Shirole, A., Jannasch, P., Krüger, A. & Cornell, A. Anion exchange membrane water electrolysis using Aemion™ membranes and nickel electrodes. J. Mater. Chem. A 10, 16061–16070 (2022).

Article CAS Google Scholar

Henkensmeier, D. et al. Overview: state-of-the art commercial membranes for anion exchange membrane water electrolysis. J. Electrochem. Energy Convers. Storage 18, 024001 (2021).

Article CAS Google Scholar

Falcao, D. S. Green hydrogen production by anion exchange membrane water electrolysis: status and future perspectives. Energies 16, 943 (2023).

Article CAS Google Scholar

Minke, C., Suermann, M., Bensmann, B. & Hanke-Rauschenbach, R. Is iridium demand a potential bottleneck in the realization of large-scale PEM water electrolysis? Int. J. Hydrog. Energy 46, 23581–23590 (2021).

Article CAS Google Scholar

Setzler, B. P., Zhuang, Z., Wittkopf, J. A. & Yan, Y. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells. Nat. Nanotechnol. 11, 1020–1025 (2016).

Article CAS PubMed Google Scholar

Kiemel, S. et al. Critical materials for water electrolysers at the example of the energy transition in Germany. Int. J. Energy Res. 45, 9914–9935 (2021).

Article CAS Google Scholar

Vincent, I. & Bessarabov, D. Low cost hydrogen production by anion exchange membrane electrolysis: a review. Renew. Sustain. Energy Rev. 81, 1690–1704 (2018).

Article CAS Google Scholar

Du, N. et al. Anion-exchange membrane water electrolyzers. Chem. Rev. 122, 11830–11895 (2022).

Article CAS PubMed PubMed Central Google Scholar

Fortin, P. et al. High-performance alkaline water electrolysis using Aemion™ anion exchange membranes. J. Power Sources 451, 227814 (2020).

Article CAS Google Scholar

Koch, S. et al. The effect of ionomer content in catalyst layers in anion-exchange membrane water electrolyzers prepared with reinforced membranes (Aemion+™). J. Mater. Chem. A 9, 15744–15754 (2021).

Article CAS Google Scholar

Motealleh, B. et al. Next-generation anion exchange membrane water electrolyzers operating for commercially relevant lifetimes. Int. J. Hydrog. Energy 46, 3379–3386 (2021).

Article CAS Google Scholar

Moreno-González, M. et al. One year operation of an anion exchange membrane water electrolyzer utilizing Aemion+® membrane: minimal degradation, low H2 crossover and high efficiency. J. Power Sources Adv. 19, 100109 (2023).

Article Google Scholar

Chen, N. et al. High-performance anion exchange membrane water electrolyzers with a current density of 7.68 A cm−2 and a durability of 1000 hours. Energy Environ. Sci. 14, 6338–6348 (2021).

Article CAS Google Scholar

Park, D. H. et al. Development of Ni–Ir oxide composites as oxygen catalysts for an anion-exchange membrane water electrolyzer. Adv. Mater. Interfaces 9, 2102063 (2022).

Article CAS Google Scholar

Koch, S. et al. Toward scalable production: catalyst-coated membranes (CCMs) for anion-exchange membrane water electrolysis via direct bar coating. Adv. Sustain. Syst. 7, 2200332 (2022).

Article Google Scholar

Wartner, G. et al. Insights into the electronic structure of Fe–Ni thin-film catalysts during the oxygen evolution reaction using operando resonant photoelectron spectroscopy. J. Mater. Chem. A 11, 8066–8080 (2023).

Article CAS Google Scholar

Drevon, D. et al. Uncovering the role of oxygen in Ni–Fe(OxHy) electrocatalysts using in situ soft X-ray absorption spectroscopy during the oxygen evolution reaction. Sci. Rep. 9, 1532 (2019).

Article PubMed PubMed Central Google Scholar

Lee, Y., Suntivich, J., May, K. J., Perry, E. E. & Shao-Horn, Y. Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J. Phys. Chem. Lett. 3, 399–404 (2012).

Article CAS PubMed Google Scholar

Burke, L. D. & O'Meara, T. O. Oxygen electrode reaction. Part 2.—Behaviour at ruthenium black electrodes. J. Chem. Soc. Faraday Trans. 1 68, 839–848 (1971).

Article Google Scholar

Qi, J. et al. Understanding the stabilization effect of the hydrous IrOx layer formed on the iridium oxide surface during the oxygen evolution reaction in acid. Inorg. Chem. Front. 10, 776–786 (2023).

Article CAS Google Scholar

Dionigi, F. et al. Intrinsic electrocatalytic activity for oxygen evolution of crystalline 3d-transition metal layered double hydroxides. Angew. Chem. Int. Ed. 60, 14446–14457 (2021).

Article CAS Google Scholar

Dionigi, F. et al. In-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution. Nat. Commun. 11, 2522 (2020).

Article CAS PubMed PubMed Central Google Scholar

El-Sayed, H. A., Weiß, A., Olbrich, L. F., Putro, G. P. & Gasteiger, H. A. OER catalyst stability investigation using RDE technique: a stability measure or an artifact? J. Electrochem. Soc. 166, F458–F464 (2019).

Article CAS Google Scholar

Fathi Tovini, M., Hartig-Weiß, A., Gasteiger, H. A. & El-Sayed, H. A. The discrepancy in oxygen evolution reaction catalyst lifetime explained: RDE vs MEA-dynamicity within the catalyst layer matters. J. Electrochem. Soc. 168, 014512 (2021).

Article Google Scholar

Hartig-Weiss, A., Tovini, M. F., Gasteiger, H. A. & El-Sayed, H. A. OER catalyst durability tests using the rotating disk electrode technique: the reason why this leads to erroneous conclusions. ACS Appl. Energy Mater. 3, 10323–10327 (2020).

Article CAS Google Scholar

Trotochaud, L., Young, S. L., Ranney, J. K. & Boettcher, S. W. Nickel–iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation. J. Am. Chem. Soc. 136, 6744–6753 (2014).

Article CAS PubMed Google Scholar

Jeon, S. S. et al. Active surface area and intrinsic catalytic oxygen evolution reactivity of NiFe LDH at reactive electrode potentials using capacitances. ACS Catal. 13, 1186–1196 (2023).

Article CAS Google Scholar

Watzele, S. et al. Determination of electroactive surface area of Ni-, Co-, Fe-, and Ir-based oxide electrocatalysts. ACS Catal. 9, 9222–9230 (2019).

Article CAS Google Scholar

Watzele, S. & Bandarenka, A. S. Quick determination of electroactive surface area of some oxide electrode materials. Electroanalysis 28, 2394–2399 (2016).

Article CAS Google Scholar

Pfeifer, V. et al. In situ observation of reactive oxygen species forming on oxygen-evolving iridium surfaces. Chem. Sci. 8, 2143–2149 (2017).

Article CAS PubMed Google Scholar

Nong, H. N. et al. The role of surface hydroxylation, lattice vacancies and bond covalency in the electrochemical oxidation of water (OER) on Ni-depleted iridium oxide catalysts. Z. Phys. Chem. 234, 787–812 (2020).

Article CAS Google Scholar

Nong, H. N. et al. Key role of chemistry versus bias in electrocatalytic oxygen evolution. Nature 587, 408–413 (2020).

Article CAS PubMed Google Scholar

Frevel, L. J. et al. In situ X-ray spectroscopy of the electrochemical development of iridium nanoparticles in confined electrolyte. J. Phys. Chem. C 123, 9146–9152 (2019).

Article CAS Google Scholar

Pfeifer, V. et al. Reactive oxygen species in iridium-based OER catalysts. Chem. Sci. 7, 6791–6795 (2016).

Article CAS PubMed PubMed Central Google Scholar

Pfeifer, V. et al. The electronic structure of iridium oxide electrodes active in water splitting. Phys. Chem. Chem. Phys. 18, 2292–2296 (2016).

Article CAS PubMed Google Scholar

Massue, C. et al. Reactive electrophilic OI− species evidenced in high-performance iridium oxohydroxide water oxidation electrocatalysts. ChemSusChem 10, 4786–4798 (2017).

Article CAS PubMed PubMed Central Google Scholar

Nong, H. N. et al. A unique oxygen ligand environment facilitates water oxidation in hole-doped IrNiOx core–shell electrocatalysts. Nat. Catal. 1, 841–851 (2018).

Article CAS Google Scholar

Reier, T. et al. Molecular insight in structure and activity of highly efficient, low-Ir Ir–Ni oxide catalysts for electrochemical water splitting (OER). J. Am. Chem. Soc. 137, 13031–13040 (2015).

Article CAS PubMed Google Scholar

Suntivich, J. et al. Estimating hybridization of transition metal and oxygen states in perovskites from O K-edge X-ray absorption spectroscopy. J. Phys. Chem. C 118, 1856–1863 (2014).

Article CAS Google Scholar

Lafuerza, S. et al. Origin of the pre-peak features in the oxygen K-edge X-ray absorption spectra of LaFeO3 and LaMnO3 studied by Ga substitution of the transition metal ion. J. Phys. Condens. Matter 23, 325601 (2011).

Article CAS PubMed Google Scholar

Magnussen, O. M. et al. In situ and operando X-ray scattering methods in electrochemistry and electrocatalysis. Chem. Rev. 124, 629–721 (2024).

Article CAS PubMed Google Scholar

Chatenet, M. et al. Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments. Chem. Soc. Rev. 51, 4583–4762 (2022).

Article CAS PubMed PubMed Central Google Scholar

Ding, H., Liu, H., Chu, W., Wu, C. & Xie, Y. Structural transformation of heterogeneous materials for electrocatalytic oxygen evolution reaction. Chem. Rev. 121, 13174–13212 (2021).

Article CAS PubMed Google Scholar

van Oversteeg, C. H. M., Doan, H. Q., de Groot, F. M. F. & Cuk, T. In situ X-ray absorption spectroscopy of transition metal based water oxidation catalysts. Chem. Soc. Rev. 46, 102–125 (2017).

Article PubMed Google Scholar

Bernt, M., Siebel, A. & Gasteiger, H. A. Analysis of voltage losses in PEM water electrolyzers with low platinum group metal loadings. J. Electrochem. Soc. 165, F305–F314 (2018).

Article CAS Google Scholar

Klingenhof, M. et al. Modular design of highly active unitized reversible fuel cell electrocatalysts. ACS Energy Lett. 6, 177–183 (2020).

Article Google Scholar

Tesch, M. F. et al. Vacuum compatible flow-cell for high-quality in situ and operando soft X-ray photon-in-photon-out spectroelectrochemical studies of energy materials. Electrochem. Sci. Adv. 2, e2100141 (2021).

Article Google Scholar

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

Article Google Scholar

Kresse, G. J. D. et al. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

Article CAS Google Scholar

Kresse, G. F. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

Article CAS Google Scholar

Zeng, Z. et al. Towards first principles-based prediction of highly accurate electrochemical Pourbaix diagrams. J. Phys. Chem. C 119, 18177–18187 (2015).

Article CAS Google Scholar

Dudarev, S., Botton, G., Savrasov, S., Humphreys, C. & Sutton, A. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA.U study. Phys. Rev. B 57, 1505–1509 (1998).

Article CAS Google Scholar

Klimes, J., Bowler, D. R. & Michaelides, A. Van der Waals density functionals applied to solids. Phys. Rev. B 83, 195131 (2011).

Article Google Scholar

Download references

Financial support by the federal ministry for education and research (Bundesministerium für Bildung und Forschung, BMBF) under grant numbers 03SF0613D ‘AEMready’ (P.S.), 03HY130B ‘AEM-Direkt’ (P.S.), 03SF0611E ‘H2Meer’ (P.S.) and 03SF0630C ‘ZnH2’ (P.S.) and the Project ‘ANEMEL’ (Project 101071111) (P.S.) funded by the EISMEA (European Innovation Council and SMES Executive Agency) are gratefully acknowledged. Furthermore, H.T. acknowledges support from the German Federal Ministry of Education and Research in the framework of the project Catlab (grant 03EW0015A/B). We thank S. K. Kilian for support and assistance for the single-cell measurements. We acknowledge the Helmholtz-Zentrum Berlin (HZB) for providing access to the beamline U49-2_PGM-1 at the synchrotron-radiation facility BESSY II, Berlin, Germany. We express our sincere gratitude to R. Golnak and J. Xiao for their invaluable support and assistance during the beamtime.

These authors contributed equally: M. Klingenhof, H. Trzesniowski.

Technische Universität Berlin, Berlin, Germany

M. Klingenhof, F. Lehmann, P. W. Buchheister, F. Dionigi & P. Strasser

Department of Atomic-Scale Dynamics in Light-Energy Conversion, Helmholtz-Zentrum Berlin für Materialien und Energie, Berlin, Germany

H. Trzesniowski

Laboratory for MEMS Applications, IMTEK Department of Microsystems Engineering, University of Freiburg, Freiburg, Germany

S. Koch, L. Metzler, M. Elshamy & S. Vierrath

Hahn-Schickard, Freiburg, Germany

S. Koch & L. Metzler

Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore

J. Zhu

Davidson School of Chemical Engineering, Tarpo Department of Chemistry, Purdue University, West Lafayette, IN, USA

Z. Zeng

Siemens Energy Global GmbH & Co. KG, SE TI SES PRM, Erlangen, Germany

A. Klinger & G. Schmid

Nanoscale Solid–Liquid Interfaces, Helmholtz-Zentrum Berlin für Materialien und Energie, Berlin, Germany

A. Weisser

You can also search for this author in PubMed Google Scholar

M.K., H.T., F.D. and P.S. conceived and designed the experiments. M.K. and F.L. synthesized the NiX LDHs and performed the electrochemistry experiments. P.W.B. assisted in the electrochemistry experiments. H.T. performed the operando XAS measurements and analysed the data. A.W. assisted in the operando spectroscopy measurements. S.K., M.E. and L.M. fabricated and assembled the single cells and conducted the AEMWE single-cell measurements. J.Z. performed the DFT calculations and analysis with support from Z.Z. M.K., H.T., J.Z., Z.Z., F.D. and P.S. wrote and revised the paper. G.S., S.V., A.K., M.K. and P.S. contributed to funding acquisition, project administration and supervision. All of the authors discussed the results and commented on the paper.

Correspondence to P. Strasser.

The authors declare no competing interests.

Nature Catalysis thanks Meital Shviro and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Figs. 1–20, Tables 1–6 and Notes 1–8.

Atomic coordinates of the computational models of the catalyst structures.

Statistical source data.

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

Klingenhof, M., Trzesniowski, H., Koch, S. et al. High-performance anion-exchange membrane water electrolysers using NiX (X = Fe,Co,Mn) catalyst-coated membranes with redox-active Ni–O ligands. Nat Catal (2024). https://doi.org/10.1038/s41929-024-01238-w

Download citation

Received: 14 December 2023

Accepted: 20 September 2024

Published: 28 October 2024

DOI: https://doi.org/10.1038/s41929-024-01238-w

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

News

High-performance anion-exchange membrane water electrolysers using NiX (X = Fe,Co,Mn) catalyst-coated membranes with redox-active Ni–O ligands | Nature Catalysis