Electrodeposition of near-equiatomic CoCuFeNi multi-principal element alloys from an acidic glycine-citrate-triton X100 aqueous electrolyte

Sun, Yunkai; Gao, Yuanchen; Zhou, Bicheng; Yang, Zhenzhen; Ingram, Brian J.; Zangari, Giovanni

doi:10.1016/j.electacta.2025.146879

Title: Electrodeposition of near-equiatomic CoCuFeNi multi-principal element alloys from an acidic glycine-citrate-triton X100 aqueous electrolyte

Journal Article · Wed Jul 09 00:00:00 UTC 2025 · Electrochimica Acta

DOI: https://doi.org/10.1016/j.electacta.2025.146879 · OSTI ID:3006346

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^[1]; Ingram, Brian J. ^[1];

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Argonne National Laboratory (ANL), Argonne, IL (United States)
Univ. of Virginia, Charlottesville, VA (United States)

Understanding the composition and morphology control of electrodeposited CoCuFeNi is the first step to finding a general strategy for developing electrodeposition processes of unconventional alloys with large redox potential differences and complicated deposition mechanisms. Here, in this work, we have successfully synthesized the near-equiatomic (<5 at% error) CoCuFeNi films with ~200nm thickness by electrodeposition from glycine-citrate-Triton X-100 acidic electrolytes. This system generally follows the Principle II in Brenner’s paradigm on alloy composition control in electrodeposition. X-ray diffraction (XRD) profiles show that the films only consist of one crystalline phase, different from the deposit from ammonia-citrate-boric acid electrolytes and the equilibrium phases predicted by CALPHAD. The near-equiatomic deposits at Ru substrates were successfully annealed at 400 ° C without significant intermixing between the substrate and the deposit, in which no phase separation of the crystalline phase was observed in its XRD profile. Xray photoelectron spectroscopy (XPS) reveals that some depositing elements (mainly Fe) exist as metal oxides. Cu is dissolved in the crystalline phases, stabilized by small crystalline domain size and the amorphous metal oxides inside the CoCuFeNi deposits.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 3006346

Journal Information:: Electrochimica Acta, Journal Name: Electrochimica Acta Vol. 537; ISSN 0013-4686

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Surface Oxidation and Reduction of CuO and Cu2O Studied Using XPS and XAES Poulston, S.; Parlett, P. M.; Stone, P. Surface and Interface Analysis, Vol. 24, Issue 12 https://doi.org/10.1002/(SICI)1096-9918(199611)24:12<811::AID-SIA191>3.0.CO;2-Z	journal	November 1996
Hierarchical Nanospheres with Polycrystalline Ir&Cu and Amorphous Cu₂O toward Energy‐Efficient Nitrate Electrolysis to Ammonia Akram, Muhammad Awais; Zhu, Botao; Cai, Jiahao Small, Vol. 19, Issue 15 https://doi.org/10.1002/smll.202206966	journal	January 2023
Influence of surfactants as additives to electrolyte solutions on zinc electrodeposition and potential oscillation behavior Miyazaki, Kohei; Nakata, Akiyoshi; Lee, You-Shin Journal of Applied Electrochemistry, Vol. 46, Issue 10 https://doi.org/10.1007/s10800-016-0987-4	journal	July 2016
Review of electrodeposition methods for the preparation of high-entropy alloys Shojaei, Zahra; Khayati, Gholam Reza; Darezereshki, Esmaeel International Journal of Minerals, Metallurgy and Materials, Vol. 29, Issue 9 https://doi.org/10.1007/s12613-022-2439-y	journal	July 2022
The kinetics of deposition and dissolution of iron: Effect of alloying impurities Bockris, J. O'M.; Drazic, D. Electrochimica Acta, Vol. 7, Issue 3 https://doi.org/10.1016/0013-4686(62)87007-8	journal	May 1962
The stability of CuO and Cu2O surfaces during argon sputtering studied by XPS and AES Panzner, G.; Egert, B.; Schmidt, H. P. Surface Science, Vol. 151, Issue 2-3 https://doi.org/10.1016/0039-6028(85)90383-8	journal	March 1985
Magnetic properties of oxide-coated iron nanoparticles synthesized by electrodeposition Banerjee, S.; Roy, S.; Chen, J. W. Journal of Magnetism and Magnetic Materials, Vol. 219, Issue 1 https://doi.org/10.1016/S0304-8853(00)00417-0	journal	August 2000
Thermo-Calc & DICTRA, computational tools for materials science Andersson, J-O; Helander, Thomas; Höglund, Lars Calphad, Vol. 26, Issue 2 https://doi.org/10.1016/S0364-5916(02)00037-8	journal	June 2002
A critical review of high entropy alloys and related concepts Miracle, D. B.; Senkov, O. N. Acta Materialia, Vol. 122 https://doi.org/10.1016/j.actamat.2016.08.081	journal	January 2017
Superior wear resistance in a TaMoNb compositionally complex alloy film via in-situ formation of the amorphous-crystalline nanocomposite layer and gradient nanostructure Luo, Jiasi; Sun, Wanting; Liang, Dingshan Acta Materialia, Vol. 243 https://doi.org/10.1016/j.actamat.2022.118503	journal	January 2023
XPS investigation of monatomic and cluster argon ion sputtering of tantalum pentoxide Simpson, Robin; White, Richard G.; Watts, John F. Applied Surface Science, Vol. 405 https://doi.org/10.1016/j.apsusc.2017.02.006	journal	May 2017
Using sputtering parameters to mitigate argon ion sputtering induced reduction of nickel in XPS Moore, Craig; Moon, Jeremy; Chidambaram, Dev Applied Surface Science, Vol. 659 https://doi.org/10.1016/j.apsusc.2024.159876	journal	June 2024
XPS study of the effects of long-term Ar+ ion and Ar cluster sputtering on the chemical degradation of hydrozincite and iron oxide Steinberger, R.; Walter, J.; Greunz, T. Corrosion Science, Vol. 99 https://doi.org/10.1016/j.corsci.2015.06.019	journal	October 2015
Influence of glycine on Co electrodeposition: IR spectroscopy and near-surface pH investigations Critelli, Renan A. J.; Sumodjo, Paulo T. A.; Bertotti, Mauro Electrochimica Acta, Vol. 260 https://doi.org/10.1016/j.electacta.2017.12.032	journal	January 2018
The role of glycine in the iron-phosphorous alloy electrodeposition Kovalska, Natalia; Pfaffeneder-Kmen, Martin; Tsyntsaru, Natalia Electrochimica Acta, Vol. 309 https://doi.org/10.1016/j.electacta.2019.03.203	journal	June 2019
Strategies to engineer FeCoNiCuZn high entropy alloy composition through aqueous electrochemical deposition Reddy, Kunda Siri Kiran Janardhana; Chokkakula, L. P. Pavithra; Dey, Suhash Ranjan Electrochimica Acta, Vol. 453 https://doi.org/10.1016/j.electacta.2023.142350	journal	June 2023
Electrodeposited NiFeCo-(Mo,W) high-entropy alloys with nanocrystalline and amorphous structures Haché, Michel J. R.; Tam, Jason; Erb, Uwe Journal of Alloys and Compounds, Vol. 952 https://doi.org/10.1016/j.jallcom.2023.170026	journal	August 2023
A comprehensive review on advances in high entropy alloys: Fabrication and surface modification methods, properties, applications, and future prospects Krishna, S. Aravind; Noble, Niveditha; Radhika, N. Journal of Manufacturing Processes, Vol. 109 https://doi.org/10.1016/j.jmapro.2023.12.039	journal	January 2024
Microstructure and the properties of FeCoCuNiSnx high entropy alloys Liu, L.; Zhu, J. B.; Zhang, C. Materials Science and Engineering: A, Vol. 548 https://doi.org/10.1016/j.msea.2012.03.080	journal	June 2012
Effect of Fe content upon the microstructures and mechanical properties of FexCoNiCu high entropy alloys Qiu, Huan; Zhu, Heguo; Zhang, Jifeng Materials Science and Engineering: A, Vol. 769 https://doi.org/10.1016/j.msea.2019.138514	journal	January 2020
Effect of surfactant on the bath stability and electrodeposition of Sn–Ag–Cu films Joseph, Shany; Phatak, Girish J. Surface and Coatings Technology, Vol. 202, Issue 13 https://doi.org/10.1016/j.surfcoat.2007.11.002	journal	March 2008
Facile electrodeposition synthesis and super performance of nano-porous Ni-Fe-Cu-Co-W high entropy alloy electrocatalyst Bian, Haowei; Wang, Rui; Zhang, Kuizhao Surface and Coatings Technology, Vol. 459 https://doi.org/10.1016/j.surfcoat.2023.129407	journal	April 2023
Rational Compositional Control of Electrodeposited Ag–Fe films Sun, Yunkai; Zangari, Giovanni Inorganic Chemistry, Vol. 59, Issue 8 https://doi.org/10.1021/acs.inorgchem.9b03600	journal	April 2020
Platinum Electrodeposited onto MoS_x for Hydrogen Evolution Reaction: A Kinetic Model under Diffusive-Convective Transport Influence Ferreira, Bianca Tainá; González-Gil, Rosa Maria; Gómez-Romero, Pedro The Journal of Physical Chemistry C, Vol. 128, Issue 18 https://doi.org/10.1021/acs.jpcc.4c00071	journal	April 2024
CTAB-Assisted Synthesis of FeNi Alloy Nanoparticles: Effective and Stable Electrocatalysts for Urea Oxidation Reactions Dhawale, Somnath C.; Munde, Ajay V.; Mulik, Balaji B. Langmuir, Vol. 40, Issue 5 https://doi.org/10.1021/acs.langmuir.3c03205	journal	January 2024
Electrodeposited NiFeCoMoW High-Entropy Alloys with Nanoscale Amorphous Structure as Effective Hydrogen Evolution Electrocatalysts Carroll, Zachary Liam; Haché, Michel J. R.; Wang, Bowen ACS Applied Energy Materials, Vol. 7, Issue 19 https://doi.org/10.1021/acsaem.4c01316	journal	October 2024
Finite Element Analysis of Local pH Variations in Electrolysis with Porous Electrodes, Considering Water Self-Ionization Nagita, Kaito; Nakanishi, Shuji; Mukouyama, Yoshiharu ACS Applied Materials & Interfaces, Vol. 16, Issue 43 https://doi.org/10.1021/acsami.4c09328	journal	October 2024
A perspective on corrosion of multi-principal element alloys Birbilis, N.; Choudhary, S.; Scully, J. R. npj Materials Degradation, Vol. 5, Issue 1 https://doi.org/10.1038/s41529-021-00163-8	journal	April 2021
Revisiting trends in the exchange current for hydrogen evolution Yang, Timothy T.; Patil, Rituja B.; McKone, James R. Catalysis Science & Technology, Vol. 11, Issue 20 https://doi.org/10.1039/D1CY01170G	journal	January 2021
Additive manufacturing of multiscale NiFeMn multi-principal element alloys with tailored composition Mooraj, Shahryar; Fu, Jintao; Feng, Shuai Materials Futures, Vol. 3, Issue 4 https://doi.org/10.1088/2752-5724/ad89e1	journal	November 2024
Recent developments in the Inorganic Crystal Structure Database: theoretical crystal structure data and related features Zagorac, D.; Müller, H.; Ruehl, S. Journal of Applied Crystallography, Vol. 52, Issue 5 https://doi.org/10.1107/S160057671900997X	journal	September 2019
The Scherrer equation and the dynamical theory of X-ray diffraction Muniz, Francisco Tiago Leitão; Miranda, Marcus Aurélio Ribeiro; Morilla dos Santos, Cássio Acta Crystallographica Section A Foundations and Advances, Vol. 72, Issue 3 https://doi.org/10.1107/S205327331600365X	journal	April 2016
Practical guides for x-ray photoelectron spectroscopy: Use of argon ion beams for sputter depth profiling and cleaning Shard, Alexander G.; Baker, Mark A. Journal of Vacuum Science & Technology A, Vol. 42, Issue 5 https://doi.org/10.1116/6.0003681	journal	July 2024
Au–Cu Phase Diagram Fedorov, P. P.; Volkov, S. N. Russian Journal of Inorganic Chemistry, Vol. 61, Issue 6 https://doi.org/10.1134/S0036023616060061	journal	June 2016
Effect of Surfactants on Electrodeposition of the Sn–Ni Alloy from Oxalate Solutions Shekhanov, R. F.; Kuz’min, S. M.; Balmasov, A. V. Russian Journal of Electrochemistry, Vol. 53, Issue 11 https://doi.org/10.1134/S1023193517110131	journal	November 2017
Anomalous Codeposition of Iron Group Metals: I. Experimental Results Zech, N. Journal of The Electrochemical Society, Vol. 146, Issue 8 https://doi.org/10.1149/1.1392024	journal	January 1999
Induced Codeposition: I. An Experimental Investigation of Ni‐Mo Alloys Podlaha, E. J.; Landolt, D. Journal of The Electrochemical Society, Vol. 143, Issue 3 https://doi.org/10.1149/1.1836553	journal	March 1996
The Effect of Some Addition Agents on the Kinetics of Copper Electrodeposition from a Sulfate Solution Turner, D. R.; Johnson, G. R. Journal of The Electrochemical Society, Vol. 109, Issue 9 https://doi.org/10.1149/1.2425558	journal	January 1962
Electrodeposition of Alloys, 1930 to 1940 Faust, Charles L. Transactions of The Electrochemical Society, Vol. 78, Issue 1 https://doi.org/10.1149/1.3071314	journal	October 1940
An Interpretation of the Mechanism of Bright Electroplating Henricks, John A. Transactions of The Electrochemical Society, Vol. 82, Issue 1 https://doi.org/10.1149/1.3071403	journal	October 1942
The Electrodeposition of Indium from Cyanide Solutions Gray, Daniel Transactions of The Electrochemical Society, Vol. 65, Issue 1 https://doi.org/10.1149/1.3498045	journal	January 1934
Electrodeposition of High Entropy Alloy of Ni-Co-Cu-Mo-W from an Aqueous Bath Ahmadkhaniha, D.; Kruemmling, J.; Zanella, C. Journal of The Electrochemical Society, Vol. 169, Issue 8 https://doi.org/10.1149/1945-7111/ac87d5	journal	August 2022
Facile Preparation of Fe-Co-Ni-Mo-W High Entropy Alloy Coatings from An Aqueous Bath by Direct Current Electrodeposition: Microstructure and Performance Zhang, Yifan; Zhong, Yiwei; Yu, Yu Journal of The Electrochemical Society, Vol. 171, Issue 6 https://doi.org/10.1149/1945-7111/ad52f3	journal	June 2024
Suppressing Dendrite Growth during Zinc Electrodeposition by PEG-200 Additive Banik, Stephen J.; Akolkar, Rohan Journal of The Electrochemical Society, Vol. 160, Issue 11 https://doi.org/10.1149/2.040311jes	journal	January 2013
Critical survey of stability constants of complexes of glycine Kiss, T.; Sovago, I.; Gergely, A. Pure and Applied Chemistry, Vol. 63, Issue 4 https://doi.org/10.1351/pac199163040597	journal	January 1991
Experimental determination of (BCC + FCC) phase fields in the quaternary isotherm of Fe–Ni–Co–Cu at 950°C Samantaray, Biswarupa; Kulkarni, Kaustubh N. Journal of Materials Research, Vol. 38, Issue 17 https://doi.org/10.1557/s43578-023-01124-4	journal	August 2023
Comparative Analysis of Metal Electrodeposition Rates towards Formation of High-Entropy WFeCoNiCu Alloy Ratajczyk, Tomasz; Donten, Mikołaj Materials, Vol. 17, Issue 7 https://doi.org/10.3390/ma17071513	journal	March 2024
Combinatorial Design of an Electroplated Multi-Principal Element Alloy: A Case Study in the Co-Fe-Ni-Zn Alloy System Nagy, Péter; Péter, László; Kolonits, Tamás Metals, Vol. 14, Issue 6 https://doi.org/10.3390/met14060700	journal	June 2024

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Title: Electrodeposition of near-equiatomic CoCuFeNi multi-principal element alloys from an acidic glycine-citrate-triton X100 aqueous electrolyte

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