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

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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.

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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

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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.

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

Atomic coordinates of the computational models of the catalyst structures.

Statistical source data.

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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

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Received: 14 December 2023

Accepted: 20 September 2024

Published: 28 October 2024

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

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