Abstract
Seawater electrolysis powered by renewable electricity provides an attractive strategy for producing green hydrogen1,2,3,4,5. However, direct seawater electrolysis faces many challenges, primarily arising from corrosion and competing reactions at the anode caused by the abundance of halide ions (Cl−, Br−) in seawater6. Previous studies3,6,7,8,9,10,11,12,13,14 on seawater electrolysis have mainly focused on the anode development, because the cathode operates at reducing potentials, which is not subject to electrode dissolution or chloride corrosion reactions during seawater electrolysis11,15. However, renewable energy sources are intermittent, variable and random, which cause frequent start–shutdown operations if renewable electricity is used to drive seawater electrolysis. Here we first unveil dynamic evolution and degradation of seawater splitting cathode in intermittent electrolysis and, accordingly, propose construction of a catalyst’s passivation layer to maintain the hydrogen evolution performance during operation. An in situ-formed phosphate passivation layer on the surface of NiCoP–Cr2O3 cathode can effectively protect metal active sites against oxidation during frequent discharge processes and repel halide ion adsorption on the cathode during shutdown conditions. We demonstrate that electrodes optimized using this design strategy can withstand fluctuating operation at 0.5 A cm−2 for 10,000 h in alkaline seawater, with a voltage increase rate of only 0.5% khr−1. The newly discovered challenge and our proposed strategy herein offer new insights to facilitate the development of practical seawater splitting technologies powered by renewable electricity.
This is a preview of subscription content, access via your institution
Access options
Access through your institution
Change institution
Buy or subscribe
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Learn more
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Learn more
Buy this article
Purchase on SpringerLink
Instant access to full article PDF
Buy now
Prices may be subject to local taxes which are calculated during checkout
Additional access options:
Log in
Learn about institutional subscriptions
Read our FAQs
Contact customer support
Fig. 1: Cathode oxidation and corrosion under start–shutdown water electrolysis cycles.
Fig. 2: HER performance and intermittent electrolysis stability.
Fig. 3: Reaction mechanism.
Fig. 4: Structural evolution during intermittent electrolysis.
Fig. 5: Theoretical calculation.
Similar content being viewed by others
A membrane-based seawater electrolyser for hydrogen generation
Article 30 November 2022
Efficient bubble/precipitate traffic enables stable seawater reduction electrocatalysis at industrial-level current densities
Article Open access 05 April 2024
Direct seawater electrolysis by adjusting the local reaction environment of a catalyst
Article 30 January 2023
Data availability
The data that support the findings of this study have been included in the main text and the Supplementary Information.
References
Xie, H. et al. A membrane-based seawater electrolyser for hydrogen generation. Nature 612, 673–678 (2022).
ArticleADSCASPubMedMATHGoogle Scholar
Tong, W. et al. Electrolysis of low-grade and saline surface water. Nat. Energy 5, 367–377 (2020).
ArticleADSCASMATHGoogle Scholar
Kuang, Y. et al. Solar-driven, highly sustained splitting of seawater into hydrogen and oxygen fuels. Proc. Natl Acad. Sci. USA 116, 6624–6629 (2019).
ArticleADSCASPubMedPubMed CentralMATHGoogle Scholar
Kosmala, T. et al. Operando visualization of the hydrogen evolution reaction with atomic-scale precision at different metal–graphene interfaces. Nat. Catal. 4, 850–859 (2021).
ArticleCASMATHGoogle Scholar
Lu, S.-Y. et al. Synthetic tuning stabilizes a high-valence Ru single site for efficient electrolysis. Nat. Synth. 3, 576–585 (2024).
ArticleADSCASMATHGoogle Scholar
Zhang, S. et al. Concerning the stability of seawater electrolysis: a corrosion mechanism study of halide on Ni-based anode. Nat. Commun. 14, 4822 (2023).
ArticleADSCASPubMedPubMed CentralMATHGoogle Scholar
Shi, H. et al. A sodium-ion-conducted asymmetric electrolyzer to lower the operation voltage for direct seawater electrolysis. Nat. Commun. 14, 3934 (2023).
ArticleADSCASPubMedPubMed CentralMATHGoogle Scholar
Hu, H., Wang, X., Attfield, J. P. & Yang, M. Metal nitrides for seawater electrolysis. Chem. Soc. Rev. 53, 163–203 (2024).
ArticleCASPubMedMATHGoogle Scholar
Duan, X. et al. Dynamic chloride ion adsorption on single iridium atom boosts seawater oxidation catalysis. Nat. Commun. 15, 1973 (2024).
ArticleADSCASPubMedPubMed CentralMATHGoogle Scholar
Xu, W. et al. Ag nanoparticle-induced surface chloride immobilization strategy enables stable seawater electrolysis. Adv. Mater. 36, 2306062 (2024).
ArticleCASGoogle Scholar
Kang, X. et al. A corrosion-resistant RuMoNi catalyst for efficient and long-lasting seawater oxidation and anion exchange membrane electrolyzer. Nat. Commun. 14, 3607 (2023).
ArticleADSCASPubMedPubMed CentralMATHGoogle Scholar
Fan, R. et al. Ultrastable electrocatalytic seawater splitting at ampere-level current density. Nat. Sustain. 7, 158–167 (2024).
ArticleGoogle Scholar
Xu, X. et al. Corrosion-resistant cobalt phosphide electrocatalysts for salinity tolerance hydrogen evolution. Nat. Commun. 14, 7708 (2023).
ArticleADSCASPubMedPubMed CentralMATHGoogle Scholar
Liu, W. et al. Ferricyanide armed anodes enable stable water oxidation in saturated saline water at 2 A/cm2. Angew. Chem. Int. Ed. 62, e202309882 (2023).
ArticleADSCASGoogle Scholar
Yang, F. et al. A durable and efficient electrocatalyst for saline water splitting with current density exceeding 2000 mA cm−2. Adv. Funct. Mater. 31, 2010367 (2021).
ArticleCASGoogle Scholar
Beverskog, B. & Puigdomenech, I. Revised Pourbaix diagrams for chromium at 25–300 °C. Corros. Sci. 39, 43–57 (1997).
ArticleCASGoogle Scholar
Dinh, C.-T. et al. Multi-site electrocatalysts for hydrogen evolution in neutral media by destabilization of water molecules. Nat. Energy 4, 107–114 (2019).
ArticleCASMATHGoogle Scholar
Gong, M. et al. Blending Cr2O3 into a NiO–Ni electrocatalyst for sustained water splitting. Angew. Chem. Int. Ed. 54, 11989–11993 (2015).
ArticleCASMATHGoogle Scholar
Peng, L. et al. Stabilizing the unstable: chromium coating on NiMo electrode for enhanced stability in intermittent water electrolysis. ACS Appl. Mater. Interfaces 14, 40822–40833 (2022).
ArticleCASPubMedGoogle Scholar
Cherevko, S. et al. Dissolution of noble metals during oxygen evolution in acidic media. ChemCatChem 6, 2219–2223 (2014).
ArticleCASMATHGoogle Scholar
Li, T. et al. Atomic-scale insights into surface species of electrocatalysts in three dimensions. Nat. Catal. 1, 300–305 (2018).
ArticleMATHGoogle Scholar
Yu, K. et al. A sequential dual-passivation strategy for designing stainless steel used above water oxidation. Mater. Today 70, 8–16 (2023).
ArticleCASGoogle Scholar
Li, T. et al. Phosphate-decorated Ni3Fe-LDHs@CoPx nanoarray for near-neutral seawater splitting. Chem. Eng. J. 460, 141413 (2023).
ArticleADSCASGoogle Scholar
Hu, Y. et al. Understanding the sulphur-oxygen exchange process of metal sulphides prior to oxygen evolution reaction. Nat. Commun. 14, 1949 (2023).
ArticleADSCASPubMedPubMed CentralMATHGoogle Scholar
Li, P. et al. Common-ion effect triggered highly sustained seawater electrolysis with additional NaCl production. Research 2020, 2872141 (2020).
ArticleADSCASPubMedPubMed CentralGoogle Scholar
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
ArticleCASMATHGoogle Scholar
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
ArticleADSCASMATHGoogle Scholar
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
ArticleADSCASMATHGoogle Scholar
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
ArticleADSGoogle Scholar
Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).
ArticleADSCASMATHGoogle Scholar
Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
ArticleADSCASMATHGoogle Scholar
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996); erratum 78, 1396 (1997).
ArticleADSCASPubMedGoogle Scholar
Download references
Acknowledgements
We acknowledge H. Dai and Y. Kuang for the helpful guidance, L. Gu, T. Zhang and Y. Lu for the help on HAADF-STEM characterization and D. Lu for the help on TOF-SIMS characterization. X.S. and D.Z. acknowledge financial support from the National Key Research and Development Project (2022YFA1504000), the National Natural Science Foundation of China (21935001), Beijing Natural Science Foundation (Z210016), a long-term subsidy from China’s Ministry of Finance and the Ministry of Education. D.Z. acknowledges financial support from the Young Elite Scientists Sponsorship Program by CAST (2022QNRC001). B.L. acknowledges financial support from the City University of Hong Kong startup fund (9020003), ITF-RTH-Global STEM Professorship (9446006) and JC STEM lab of Advanced CO2 Upcycling (9228005).
Author information
Author notes
These authors contributed equally: Qihao Sha, Shiyuan Wang
Authors and Affiliations
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, People’s Republic of China
Qihao Sha, Shiyuan Wang, Li Yan, Zhuang Zhang, Shihang Li, Xinlong Guo, Tianshui Li, Daojin Zhou & Xiaoming Sun
State Power Investment Corporation Hydrogen Energy Tech Co., Ltd., Beijing, People’s Republic of China
Shiyuan Wang
Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, People’s Republic of China
Yisui Feng & Hui Li
State Key Laboratory of Organic–Inorganic Composites, Beijing University of Chemical Technology, Beijing, People’s Republic of China
Zhongbin Zhuang
Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong SAR, People’s Republic of China
Bin Liu
Department of Chemistry, Hong Kong Institute of Clean Energy (HKICE) & Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong SAR, People’s Republic of China
Bin Liu
Authors
Qihao Sha
View author publications
You can also search for this author in PubMedGoogle Scholar
2. Shiyuan Wang
View author publications
You can also search for this author in PubMedGoogle Scholar
3. Li Yan
View author publications
You can also search for this author in PubMedGoogle Scholar
4. Yisui Feng
View author publications
You can also search for this author in PubMedGoogle Scholar
5. Zhuang Zhang
View author publications
You can also search for this author in PubMedGoogle Scholar
6. Shihang Li
View author publications
You can also search for this author in PubMedGoogle Scholar
7. Xinlong Guo
View author publications
You can also search for this author in PubMedGoogle Scholar
8. Tianshui Li
View author publications
You can also search for this author in PubMedGoogle Scholar
9. Hui Li
View author publications
You can also search for this author in PubMedGoogle Scholar
10. Zhongbin Zhuang
View author publications
You can also search for this author in PubMedGoogle Scholar
11. Daojin Zhou
View author publications
You can also search for this author in PubMedGoogle Scholar
12. Bin Liu
View author publications
You can also search for this author in PubMedGoogle Scholar
13. Xiaoming Sun
View author publications
You can also search for this author in PubMedGoogle Scholar
Contributions
X.S., B.L. and D.Z. supervised the project. Q.S. and S.W. conceived the idea and carried out the experiments and also conducted materials synthesis and electrochemical measurements. Q.S. wrote the paper. X.G., T.L. and Z. Zhuang helped with the anion exchange membrane test. L.Y., S.L. and X.G. helped with the stability test. H.L., Y.F. and Z. Zhang performed the density functional theory calculations.
Corresponding authors
Correspondence to Daojin Zhou, Bin Liu or Xiaoming Sun.
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature thanks Xiaoqiang Du and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Rights and permissions
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
About this article
Check for updates. Verify currency and authenticity via CrossMark
Cite this article
Sha, Q., Wang, S., Yan, L. et al. 10,000-h-stable intermittent alkaline seawater electrolysis. Nature (2025). https://doi.org/10.1038/s41586-025-08610-1
Download citation
Received:14 August 2024
Accepted:07 January 2025
Published:05 March 2025
DOI:https://doi.org/10.1038/s41586-025-08610-1
Share this article
Anyone you share the following link with will be able to read this content:
Get shareable link
Sorry, a shareable link is not currently available for this article.
Copy to clipboard
Provided by the Springer Nature SharedIt content-sharing initiative