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Additive-enhanced hydrogen- and hydroxide-based magneto-ionic control in Ni films

M. Kutuzau1,2,3, M. Gößler1,4, S. Topolovec4, S. Schiemenz2, D. Wolf2, M. Richter2,5, K. Nielsch2,6, and K. Leistner1,2

Phys. Rev. Materials 9, 114408 – Published 12 November, 2025

DOI: https://doi.org/10.1103/29bv-d9j4

Abstract

Magneto-ionic control of metals is a promising approach for energy-efficient and voltage-programmable magnetic devices. In this work, we demonstrate a dual hydrogen- and hydroxide-ion-based mechanism to control the magnetic properties of nickel films in an alkaline electrolyte. Upon application of reduction potentials, reversible electrochemical hydrogen absorption into a nickel film electrode is found to decrease its overall magnetic moment, while an increase in the overall magnetic moment at more negative potentials can be explained by the reduction of nickel hydroxide on the surface. Furthermore, coercivity is also decreased in the reduced state. This effect is reversible over 50 reduction-oxidation cycles and reaches up to 30% change at maximum. The addition of thiourea to the electrolyte amplifies the magnitude of the magneto-ionic control of the magnetic moment by a factor of 2 and promotes the energy efficiency of the magneto-ionic effect by decreasing the required overpotentials by ∼0.25V. In situ Raman spectroscopy reveals the formation of an α−Ni(OH)2 layer on the Ni surface in the presence of thiourea, which may be the cause for the improved magneto-ionic effect. Our study not only introduces Ni as a versatile magneto-ionic material, but also demonstrates how electrolyte additives can be used to boost magneto-ionic effects in terms of effect strength and energy efficiency.

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Functional Materials Through Electrochemical Ion Insertion

The Editors of Physical Review Materials are pleased to present the Collection on Functional Materials Through Electrochemical Ion Insertion, highlighting cutting-edge advances in the theory, synthesis, and structural and physical characterization of dynamic property modulation (e.g. optical, electrical, mechanical, chemical) using electrochemical ion insertion into solid state hosts. The Collection is being guest-edited by Veronica Augustyn and Nina Balke of North Carolina State University (USA). Every article published in this collection underwent a rigorous peer review process, adhering to the same high standards applied to all papers. The Physical Review Materials editorial team managed the peer review and made all editorial decisions.

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References (88)

  1. L. Herrera Diez, D. Chiba, D. A. Gilbert, S. Granville, and K. Leistner, Magneto-ionic and electrostatic gating of magnetism: Phenomena and devices, Appl. Phys. Lett. 123, 130401 (2023).
  2. C. Leighton, Electrolyte-based ionic control of functional oxides, Nat. Mater. 18, 13 (2019).
  3. K. Leistner, Electrochemical approaches to room temperature magnetoelectric materials, Curr. Opin. Electrochem. 25, 100636 (2021).
  4. Y. Gu, C. Song, Q. Wang, W. Hu, F. Pan, and Z. Zhang, Emerging opportunities for voltage-driven magneto-ionic control in ferroic heterostructures, APL Mater. 9, 040904 (2021).
  5. Y. Liu and G. Yu, MRAM gets closer to the core, Nat. Electron. 2, 555 (2019).
  6. X. Z. Yu, D. Morikawa, K. Nakajima, K. Shibata, N. Kanazawa, T. Arima, N. Nagaosa, and Y. Tokura, Motion tracking of 80-nm-size skyrmions upon directional current injections, Sci. Adv. 6, eaaz9744 (2020).
  7. S. Bhatti, R. Sbiaa, A. Hirohata, H. Ohno, S. Fukami, and S. N. Piramanayagam, Spintronics based random access memory: A review, Mater. Today 20, 530 (2017).
  8. A. Molinari, H. Hahn, and R. Kruk, Voltage-control of magnetism in all-solid-state and solid/liquid magnetoelectric composites, Adv. Mater. 31, 1806662 (2019).
  9. C. Song, B. Cui, F. Li, X. Zhou, and F. Pan, Recent progress in voltage control of magnetism: Materials, mechanisms, and performance, Progr. Mater. Sci. 87, 33 (2017).
  10. M. Nichterwitz, S. Honnali, M. Kutuzau, S. Guo, J. Zehner, K. Nielsch, and K. Leistner, Advances in magneto-ionic materials and perspectives for their application, APL Mater. 9, 030903 (2021).
  11. P. Monalisha, M. Ameziane, I. Spasojevic, E. Pellicer, R. Mansell, E. Menéndez, S. van Dijken, and J. Sort, Magnetoionics for synaptic devices and neuromorphic computing: Recent advances, challenges, and future perspectives, Small Sci. 4, 2400133 (2024).
  12. M. Nichterwitz, K. Hiekel, D. Wolf, A. Eychmüller, and K. Leistner, Voltage-controlled ON–OFF-switching of magnetoresistance in FeOx/Fe/Au aerogel networks, ACS Mater. Au 4, 55 (2024).
  13. N. Lu, P. Zhang, Q. Zhang, R. Qiao, Q. He, H.-B. Li, Y. Wang, J. Guo, D. Zhang, Z. Duan et al., Electric-field control of tri-state phase transformation with a selective dual-ion switch, Nature (London) 546, 124 (2017).
  14. S. Dasgupta, B. Das, Q. Li, D. Wang, T. T. Baby, S. Indris, M. Knapp, H. Ehrenberg, K. Fink, R. Kruk, and H. Hahn, Toward on-and-off magnetism: Reversible electrochemistry to control magnetic phase transitions in spinel ferrites, Adv. Funct. Mater. 26, 7507 (2016).
  15. S. Robbennolt, P. Yu, A. Nicolenco, P. Mercier Fernandez, M. Coll, and J. Sort, Magneto-ionic control of magnetism in two-oxide nanocomposite thin films comprising mesoporous cobalt ferrite conformally nanocoated with HfO2, Nanoscale 12, 5987 (2020).
  16. M. Nichterwitz, S. Honnali, J. Zehner, S. Schneider, D. Pohl, S. Schiemenz, S. T. B. Goennenwein, K. Nielsch, and K. Leistner, Control of positive and negative magnetoresistance in iron oxide–iron nanocomposite thin films for tunable magnetoelectric nanodevices, ACS Appl. Electron. Mater. 2, 2543 (2020).
  17. K. Duschek, A. Petr, J. Zehner, K. Nielsch, and K. Leistner, All-electrochemical voltage-control of magnetization in metal oxide/metal nanoislands, J. Mater. Chem. C 6, 8411 (2018).
  18. X. Ye, H. K. Singh, H. Zhang, H. Geßwein, M. R. Chellali, R. Witte, A. Molinari, K. Skokov, O. Gutfleisch, H. Hahn, and R. Kruk, Giant voltage-induced modification of magnetism in micron-scale ferromagnetic metals by hydrogen charging, Nat. Comm. 11, 4849 (2020).
  19. M. Prasch, R. Würschum, and S. Topolovec, Indirect magneto-ionic effect in FeSi2/Si nanocomposite induced by electrochemical lithiation and delithiation, J. Phys. Mater. 7, 03LT03 (2024).
  20. U. Bauer, L. Yao, A. J. Tan, P. Agrawal, S. Emori, H. L. Tuller, S. van Dijken, and G. S. D. Beach, Magneto-ionic control of interfacial magnetism, Nat. Mater. 14, 174 (2015).
  21. D. A. Gilbert, J. Olamit, R. K. Dumas, B. J. Kirby, A. J. Grutter, B. B. Maranville, E. Aarenholz, J. A. Borchers, and K. Liu, Controllable positive exchange bias via redox-driven oxygen migration, Nat. Commun. 7, 11050 (2016).
  22. J. Zehner, R. Huhnstock, S. Oswald, U. Wolff, I. Soldatov, A. Ehresmann, K. Nielsch, D. Holzinger, and K. Leistner, Nonvolatile electric control of exchange bias by a redox transformation of the ferromagnetic layer, Adv. Electron. Mater. 5, 1900296 (2019).
  23. S. Robbennolt, E. Menendez, A. Quintana, A. Gomez, S. Auffret, V. Baltz, E. Pellicer, and J. Sort, Reversible, electric-field induced magneto-ionic control of magnetism in mesoporous cobalt ferrite thin films, Sci. Rep. 9, 10804 (2019).
  24. M. Nichterwitz, S. Neitsch, S. Röher, D. Wolf, K. Nielsch, and K. Leistner, Voltage-controlled ON switching and manipulation of magnetization via the redox transformation of β -FeOOH nanoplatelets, J. Phys. D Appl. Phys. 53, 084001 (2020).
  25. A. Quintana, A. A. Firme, C. J. Jensen, D. Zheng, C. Liu, X. Zhang, and K. Liu, Hydroxide-based magneto-ionics: Electric-field control of a reversible paramagnetic-to-ferromagnetic switch in α-Co(OH)2 films, J. Mater. Chem. C 10, 17145 (2022).
  26. A. J. Tan, M. Huang, C. O. Avci, F. Büttner, M. Mann, W. Hu, C. Mazzoli, S. Wilkins, H. L. Tuller, and G. S. D. Beach, Magneto-ionic control of magnetism using a solid-state proton pump, Nat. Mater. 18, 35 (2019).
  27. F. Maroun, F. Reikowski, N. Di, T. Wiegmann, J. Stettner, O. M. Magnussen, and P. Allongue, Potential dependence of the structure and magnetism of electrodeposited Pd/Co/Au(111) layers, J. Electroanal. Chem. 819, 322 (2018).
  28. A. Quintana, E. Menéndez, M. O. Liedke, M. Butterling, A. Wagner, V. Sireus, P. Torruella, S. Estradé, F. Peiró, J. Dendooven et al., Voltage-controlled on–off ferromagnetism at room temperature in a single metal oxide film, ACS Nano 12, 10291 (2018).
  29. J. Zehner, I. Soldatov, S. Schneider, R. Heller, N. B. Khojasteh, S. Schiemenz, S. Fähler, K. Nielsch, R. Schäfer, and K. Leistner, Voltage-controlled deblocking of magnetization reversal in thin films by tunable domain wall interactions and pinning sites, Adv. Electron. Mater. 6, 2000406 (2020).
  30. D. A. Gilbert, A. J. Grutter, E. Aarenholz, K. Liu, B. J. Kirby, J. A. Borchers, and B. B. Maranville, Structural and magnetic depth profiles of magneto-ionic heterostructures beyond the interface limit, Nat. Commun. 7, 12264 (2016).
  31. N. N. Di, J. Kubal, Z. Zeng, J. Greeley, F. Maroun, and P. Allongue, Influence of controlled surface oxidation on the magnetic anisotropy of Co ultrathin films, Appl. Phys. Lett. 106, 122405 (2015).
  32. C. Navarro-Senent, J. Fornell, E. Isarain-Chávez, A. Quintana, E. Menéndez, M. Foerster, L. Aballe, E. Weschke, J. Nogués, E. Pellicer, and J. Sort, Large magnetoelectric effects in electrodeposited nanoporous microdisks driven by effective surface charging and magneto-ionics, ACS Appl. Mater. Interfaces 10, 44897 (2018).
  33. N. Tournerie, A. P. Engelhardt, F. Maroun, and P. Allongue, Influence of the surface chemistry on the electric-field control of the magnetization of ultrathin films, Phys. Rev. B 86, 104434 (2012).
  34. A. E. Kossak, D. Wolf, and G. S. D. Beach, Magneto-ionic enhancement and control of perpendicular magnetic anisotropy, Appl. Phys. Lett. 121, 222402 (2022).
  35. M. Bischoff, R. Ehrler, F. Engelhardt, O. Hellwig, K. Leistner, and M. Gößler, Magneto-ionic control of coercivity and domain-wall velocity in Co/Pd multilayers by electrochemical hydrogen loading, Adv. Funct. Mater. 34, 2405323 (2024).
  36. M. Gößler, M. Albu, G. Klinser, E. Steyskal, H. Krenn, and R. Würschum, Magneto-ionic switching of superparamagnetism, Small 15, 1904523 (2019).
  37. X. Ye, X. Zhu, H. Yang, J. Duan, S. Gao, C. Sun, X. Liu and R.-W. Li, Selective dual-ion modulation in solid-state magnetoelectric heterojunctions for in-memory encryption, Small 19, 2206824 (2023).
  38. H.-B. Li, N. Lu, Q. Zhang, Y. Wang, D. Feng, T. Chen, S. Yang, Z. Duan, Z. Li, Y. Shi et al., Electric-field control of ferromagnetism through oxygen ion gating, Nat. Commun. 8, 2156 (2017).
  39. H. J. Bauer and E. Schmidbauer, Über den Einfluss elektrolytischer Wasserstoffbeladung auf die Magnetisierung von Nickel, Z. Physik 164, 367 (1961).
  40. J.-Z. Yu, Q. Sun, Q. Wang. and Y. Kawazoe, Effect of hydrogen on the magnetism and its solubility in ferromagnetic nickel, Mater. Trans. JIM 40, 1244 (1999).
  41. A. León, E. A. Velásquez, J. Mazo-Zuluaga, J. Mejía-López, J. M. Florez. and P. Vargas, Magnetic effects of interstitial hydrogen in nickel, J. Magn. Magn. Mater. 421, 7 (2017).
  42. V. Vij, S. Sultan, A. M. Harzandi, A. Meena, J. N. Tiwari, W.-G. Lee, T. Yoon and K. S. Kim, Nickel-based electrocatalysts for energy-related applications: Oxygen reduction, oxygen evolution, and hydrogen evolution reactions, ACS Catal. 7, 7196 (2017).
  43. T. Shinagawa and K. Takanabe, Towards versatile and sustainable hydrogen production through electrocatalytic water splitting: Electrolyte engineering, Chem. Sus. Chem. 10, 1318 (2017).
  44. J. Tan and J. Liu, Electrolyte engineering toward high-voltage aqueous energy storage devices, Energy Environ. Mater. 4, 302 (2021).
  45. S. Martins, Z. Ma, X. Solans-Monfort, M. Sodupe, L. Rodriguez-Santiago, E. Menendez, E. Pellicer and J. Sort, Enhancing magneto-ionic effects in cobalt oxide films by electrolyte engineering, Nanoscale Horiz. 8, 118 (2023).
  46. J. Zehner, O. Vaerst, I. Soldatov, K. Nielsch, R. Schafer and K. Leistner, Robust magneto-ionic effect in Fe/FeOx thin films in electrolytes with different cations, IEEE Trans. Magn. 58, 6000108 (2022).
  47. A. Mituya, K. Sekine and G. Toda, Determination of diffusion coefficient of hydrogen through nickel foil, J. Res. Instit. Catalys. Hokkaido Univ. 15, 21 (1967).
  48. G. A. Di Bari, Electrodeposition of Nickel, in Modern Electroplating, edited by M. Schlesinger and M. Paunovic, (Wiley, Hoboken, NJ, 2010), pp. 79–114.
  49. See Supplemental Material at http://link.aps.org/supplemental/10.1103/29bv-d9j4 for Auger electron spectroscopy depth profile (S1), Scheme of in situ SQUID and MOKE cells (S2), Magnetic hysteresis (S3), first in situ SQUID cycle for KOH (S4), in situ Raman spectra (S5), DFT calculations (S6), in situ SQUID for KOH with thiourea (S7), in situ MOKE for 1000 Red-Ox cycles (S8), Calculation of the influence of adsorbed H (Note S1), Estimation of Ni layer thickness using the moment change (Note S2), which also includes Refs.  [50, 51, 52, 53, 54, 55].
  50. B. P. Payne, A. P. Grosvenor, M. C. Biesinger, B. A. Kobe and N. S. McIntyre, Structure and growth of oxides on polycrystalline nickel surfaces, Surf. Interf. Anal. 39, 582 (2007).
  51. S. Ghosh, B. Dasgupta, S. Kalra, M. L. P. Ashton, R. Yang, C. J. Kueppers, S. Gok, E. G. Alonso, J. Schmidt, K. Laun, I. Zebger et al., Evolution of carbonate-intercalated γ-NiOOH from a molecularly derived nickel sulfide (pre)catalyst for efficient water and selective organic oxidation, Small 19, 2206679 (2023).
  52. Z. Qiu, C.-W. Tai, G. A. Niklasson, and T. Edvinsson, Direct observation of active catalyst surface phases and the effect of dynamic self-optimization in NiFe-layered double hydroxides for alkaline water splitting, Energy Environ. Sci. 12, 572 (2019).
  53. L. E. Kalichkina, P. K. Krivolapenko, and V. P. Tuguldurova, Quantitative Raman spectroscopy of urea and thiourea in the reaction mixtures of allantoin and 4,5-dihydroxyimidazolidine-2-Tione formation, J. Raman Spectrosc. 55, 1165 (2024).
  54. K. Christmann, O. Schober, G. Ertl, and M. Neumann, Adsorption of hydrogen on nickel single crystal surfaces, J. Chem. Phys. 60, 4528 (1974).
  55. M. Oshitani, T. Takayama, K. Takashima, and S. Tsuji, A study on the swelling of a sintered nickel hydroxide electrode, J. Appl. Electrochem. 16, 403 (1986).
  56. D. S. Hall, C. Bock, and B. R. MacDougall, The electrochemistry of metallic nickel: Oxides, hydroxides, hydrides and alkaline hydrogen evolution, J. Electrochem. Soc. 160, F235 (2013).
  57. S. Topolovec, H. Krenn, and R. Würschum, Electrochemical cell for in situ electrodeposition of magnetic thin films in a superconducting quantum interference device magnetometer, Rev. Sci. Instr. 86, 063903 (2015).
  58. I. V. Soldatov and R. Schäfer, Selective sensitivity in Kerr microscopy, Rev. Sci. Instr. 88, 073701 (2017).
  59. I. V. Soldatov and R. Schäfer, Advanced MOKE magnetometry in wide-field Kerr-microscopy, J. Appl. Phys. 122, 153906 (2017).
  60. K. Koepernik and H. Eschrig, Full-potential nonorthogonal local-orbital minimum-basis band-structure scheme, Phys. Rev. B 59, 1743 (1999).
  61. https://www.fplo.de/.
  62. J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996).
  63. S. L. Medway, C. A. Lucas, A. Kowal, R. J. Nichols, and D. Johnson, In situ studies of the oxidation of nickel electrodes in alkaline solution, J. Electroanal. Chem. 587, 172 (2006).
  64. J. Proost and A. Delvaux, In-situ monitoring of hydrogen absorption into Ni thin film electrodes during alkaline water electrolysis, Electrochim. Acta 322, 134752 (2019).
  65. D. S. Hall, D. J. Lockwood, S. Poirier, C. Bock, and B. R. MacDougall, Applications of in situ Raman spectroscopy for identifying nickel hydroxide materials and surface layers during chemical aging, ACS Appl. Mater. Interf. 6, 3141 (2014).
  66. D. S. Hall, D. J. Lockwood, C. Bock, and B. R. MacDougall, Nickel hydroxides and related materials: A review of their structures, synthesis and properties, Proc. R. Soc. A. 471, 20140792 (2015).
  67. R. Kostecki and F. McLarnon, Electrochemical and in situ raman spectroscopic characterization of nickel hydroxide electrodes: I. Pure nickel hydroxide, J. Electrochem. Soc. 144, 485 (1997).
  68. J. D. Rall, M. S. Seehra, N. Shah, and G. P. Huffman, Comparison of the nature of magnetism in and β-Ni(OH)2, J. Appl. Phys. 107, 09B511 (2010).
  69. P. W. Selwood, Magnetic saturation results for H2/Ni, H2/Ni–Cu, H2/Co, and H2/Fe, in Chemisorption and Magnetization (Elsevier, Amsterdam, 1975), p. 55–65.
  70. E. B. Ferreira and G. Jerkiewicz, On the electrochemical reduction of β-Ni(OH)2 to metallic nickel, Electrocatal. 12, 199 (2021).
  71. K. Duschek, D. Pohl, S. Fähler, K. Nielsch, and K. Leistner, Research Update: Magnetoionic control of magnetization and anisotropy in layered oxide/metal heterostructures, APL Mater. 4, 032301 (2016).
  72. A. Ramesh, M. R. Govindaraju, D. C. Jiles, S. B. Biner, and J. M. Roderick, Hydrogen charging in nickel and iron and its effect on their magnetic properties, J. Appl. Phys. 79, 5453 (1996).
  73. J. K. Blum and W. Göpel, Influence of hydrogen chemisorption on the magnetism of thin nickel films, Thin. Solid. Films 42, 7 (1977).
  74. L. Mirkova, G. Maurin, M. Monev, and C. Tsvetkova, Hydrogen coevolution and permeation in nickel electroplating, J. Appl. Electrochem. 33, 93 (2003).
  75. T. M. Harris and M. Latanision, Grain boundary diffusion of hydrogen in nickel, Metall. Trans. A 22, 351 (1991).
  76. A. Y. Faid, A. O. Barnett, F. Seland, and S. Sunde, Ni/NiO nanosheets for alkaline hydrogen evolution reaction: In situ electrochemical-Raman study, Electrochim. Acta 361, 137040 (2020).
  77. D. S. Hall, D. J. Lockwood, S. Poirier, C. Bock, and B. R. MacDougall, Raman and infrared spectroscopy of α and β phases of thin nickel hydroxide films electrochemically formed on nickel, J. Phys. Chem. A 116, 6771 (2012).
  78. M. W. Louie and A. T. Bell, An investigation of thin-film Ni–Fe oxide catalysts for the electrochemical evolution of oxygen, J. Am. Chem. Soc. 135, 12329 (2013).
  79. M. Jayalakshmi, P. Radhika, K. P. Raja, and M. M. Rao, Solvent and thiourea adsorption/intercalation effects on the solid-state electrochemistry of α-phase nickel hydroxide nanoparticles, J. Solid State Electrochem. 11, 165 (2006).
  80. B. Baranowski and Z. Szklarska-Smialowska, A galvanostatic and potentiostatic study of the nickel-hydrogen system, Electrochim. Acta 9, 1497 (1964).
  81. Y. Oren, E. Elish, A. Tamir, and Z. Gavra, A dilatometric study of nickel wire electrode electrochemically charged by hydrogen, J. Alloys Comp. 235, 30 (1996).
  82. W. Visscher and E. Barendrecht, Absorption of hydrogen in reduced nickel oxide, J. Appl. Electrochem. 10, 269 (1980).
  83. L. Wang, C. Lin, D. Huang, J. Chen, L. Jiang, M. Wang, L. Chi, L. Shi, and J. Jin, Optimizing the volmer step by single-layer nickel hydroxide nanosheets in hydrogen evolution reaction of platinum, ACS Catal. 5, 3801 (2015).
  84. W. Lai, L. Ge, H. Li, Y. Deng, B. Xu, B. Ouyang, and E. Kan, In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure, Int. J. Hydrogen Energy 46, 26861 (2021).
  85. S. Xue, Y. Liang, S. Hou, Y. Zhang, and H. Jiang, Alpha-nickel hydroxide coating of metallic nickel for enhanced alkaline hydrogen evolution, Chem. Sus. Chem 15, e202201072 (2022).
  86. E. Protopopoff and P. Marcus, Surface effects on hydrogen entry into metals, in Corrosion Mechanisms in Theory and Practice, edited by P. Marcus, (CRC Press, Boca Raton, FL, 2002), Vol. 17, p. 53–96.
  87. M. Guan, L. Wang, S. Zhao, B. Peng, W. Su, Z. He, G. Dong, T. Min, J. Ma, Z. Hu et al., Ionic modulation of interfacial magnetism in light metal/ferromagnetic insulator layered nanostructures, Adv. Funct. Mater. 29, 1805592 (2019).
  88. M. Kutuzau, M. Gößler, S. Topolovec, S. Schiemenz, D. Wolf, M. Richter, K. Nielsch, and K. Leistner, Dataset for the manuscript “Additive-enhanced hydrogen- and hydroxide-based magneto-ionic control in Ni films,” Zenodo (2025), doi:10.5281/zenodo.17417586.

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