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Review

Graphenes for Corrosion Protection in Electrochemical Energy Technology

by
Dan Liu
1,
Xuan Xie
2,
Xuecheng Chen
3 and
Rudolf Holze
4,5,6,*
1
Institute of Corrosion Science and Technology, Guangzhou 510641, China
2
Key Laboratory for Anisotropy and Texture of Materials (MoE), School of Materials Science and Engineering, Northeastern University, Shenyang 110819, China
3
Faculty of Chemical Technology and Engineering, West Pomeranian University of Technology in Szczecin, Piastow Ave. 45, 71-311 Szczecin, Poland
4
Confucius Energy Storage Lab, School of Energy and Environment, Southeast University, Nanjing 210096, China
5
State Key Laboratory of Materials-Oriented Chemical Engineering, School of Energy Science and Engineering, Nanjing Tech University, Nanjing 211816, China
6
Chemnitz University of Technology, D-09107 Chemnitz, Germany
*
Author to whom correspondence should be addressed.
Corros. Mater. Degrad. 2025, 6(3), 33; https://doi.org/10.3390/cmd6030033
Submission received: 22 April 2025 / Revised: 4 July 2025 / Accepted: 8 July 2025 / Published: 17 July 2025
(This article belongs to the Special Issue Corrosion in Electrochemical Energy Technology: Causes and Effects, Investigations and Remediation)
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Abstract

Graphene, graphene oxide, reduced graphene oxide, and few-layer graphene as functional coating materials for corrosion protection in devices for electrochemical energy conversion and storage are reviewed. Reported applications are briefly described, enabling the reader to make an informed decision about the protective options based on the reported achievements.

1. Introduction

A literature survey on the use of graphene (GR) and its chemical relatives graphene oxide (GO), reduced graphene oxide (rGO), and few-layer graphene (flG) (see Figure 1) as coatings in devices for electrochemical energy technology (EET) yields more than 1400 reports on their use primarily for corrosion protection or for some other specific function. Both aspects appear to be in need of a current review as support for ongoing research as well as guidance towards the usage of these materials as coatings in EET. The latter aspect has been thoroughly reviewed recently elsewhere [1], while the former one is the subject of this report. An attempt is made to distinguish between these various graphene-related materials; the sometimes encountered (but mostly not stated and only implied) assumption that rGO and GR are the same (presumably based on the assumption that, e.g., reduced copper oxide and copper are the same) as found in, e.g., Ref. [2], is not correct as discussed in detail elsewhere [3]. Further possibly relevant details, like electronic conductivity, have been reviewed before [1].
The options and practical approaches to meet the vast technical and economic challenges posed by the corrosion of all forms, but particularly of metals, their alloys, and composites, by corrosion protection are numerous and well-developed into many different approaches, as described in several monographs and extended reviews [4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20] and as frequently highlighted in contributions to this journal. The term corrosion is—different from the common and popular perception—not limited to the corrosion of metals. By definition, it covers all deterioration of materials by chemical, even biochemical, attack from the environment. Thus, the corrosion of an electrode (material) is not limited to metals like zinc or lithium; it might also affect SnS2, proposed as a negative electrode material in metal-ion batteries [21].
Among the protection options, the coatings of materials possibly exposed to corrosive attack from the environment with protective layers are prominent. The carbon materials mentioned above have been suggested repeatedly; overviews and examples are available for GR coatings [22,23,24]; for an example for flG, see [25]; for examples dealing with selected metals to be protected, see [26,27]. Functionalized carbon allotropes, including the members of the graphene family, as corrosion protection coating have been surveyed [28].
The mode of operation is straightforward: A defect-free coating GR keeps away any ionically conducting phase (electrolyte solution) as well as oxygen as the most frequent reactant of the cathodic reaction in corrosion because of the almost perfect impermeability for species except protons [29]. The high electronic conductivity of GR (for an overview, see [1]) will nevertheless enable the transfer of electrons when the coating is applied, e.g., to a bipolar plate, or even charge transfer in electrode reactions—this is a major difference from practically all other nonmetallic and more or less insulating coatings. Basically, the same reasoning applies to GO, rGO, and flG. The protection effect can be further enhanced by combining, e.g., an rGO coating with, e.g., silane, to increase hydrophobicity [30]. Another option towards enhancement is the functionalization of GR [31]. Given a primarily protective purpose, some coatings are not suitable for application in devices for EET when the coating inhibits or slows down electrode reactions by inhibiting charge transfer or creating at least an unwelcome Ohmic potential drop. In the case of only corrosion protection and no other function being desired, composites containing one of the coating materials reviewed in this report, and, in most cases, a vast excess of polymer material, are applied. Because the protective properties of a dense and defect-free coating with, e.g., GR cannot be achieved in such compounds, the function of graphenes in such compounds is different from the protective one: As pointed out in reports on protective composites containing metallic zinc, the function of added GR is frequently just the provision of electronic conduction between zinc particles [32,33,34].
Parts of the field mentioned above have attracted attention and are covered in reviews [35,36,37,38]. The corrosion protection of components in EET devices needs to enable charge transfer and electrode reactions typical of a battery, supercapacitor, or fuel cell electrode—different from the more general corrosion protection briefly outlined above. First of all, a high electronic conductivity is required. GR and its relatives meet this requirement [1]. Thus, some composites containing significant fractions of basically non-conducting polymers are presented below because optimized addition of GR, etc., provides sufficient electronic conduction.
In several cases of multi-functional coatings, corrosion suppression is only one of several tasks. Accordingly, such reports can be found in a report on functional coatings without attention to corrosion protection (see [1]). The reasons for choosing a particular material from the group of materials reviewed in this paper are rarely mentioned, if reported arguments are provided below.
A fundamental problem of GR as a corrosion protection coating is the fact known from corrosion studies with coatings by materials electrochemically more noble (e.g., chromium plating) than the metal to be protected: Once there is a defect in the coating, the coated substrate and the coating (e.g., GR) will form an electrochemical cell with a severe corrosive attack of the substrate. This is schematically illustrated in Figure 2. Corrosion will be most severe at the pit-like imperfection (defect) of the GR topcoat.
This has been addressed in a study of copper conformally coated with GR [29]. The authors noticed differences between different crystallographic faces of the copper substrate and concluded that a good coupling of GR to the substrate (i.e., adhesion) and the absence of wrinkles or other indicators of imperfect coupling are required. The direct formation of GR on stainless steel surfaces aiming at a practically “perfect” coating has been described [39]. In the studied samples, a substantial reduction in the electric resistance was noticed as an added benefit. Serious doubts on the long-term protective performance at least when GR is coated on copper or silicon have been raised, although short-term protection was confirmed [40]. Subtle differences between CVD-coated GR have been suggested as possible reasons for both the different protective performance and long-term stability [24] as well as vast differences in protection efficiencies [31]. Similar considerations have been made regarding flG [25]. A very straightforward explanation can be based on the claimed very noble character of graphite [41], which was not verified in this report. Instead, it is based on a claimed listing in [42], where graphite can be found between gold and titanium. The listing is based on experimental measurements with galvanic cells in seawater reported elsewhere [43] and not on the electrochemical series. Presumably, the preferred dioxygen reduction as the cathodic reaction on graphite and—in the present context—graphene is the reason for this placement. This conclusion is in line with the observations discussed in [24,25,29,40].
In what follows, all available reported examples of coatings with the materials presented above are described and briefly characterized. The specific advantages as well as the limitations and flaws as reported by the authors are included. When provided, details of the protective effects are discussed. Thus, the present text will provide a complete and comprehensive overview, hopefully helping researchers looking for a suitable corrosion protection for EET and researchers looking for a challenging application of their coating material based on GR and its chemical relatives.

2. The Applications

Coatings with the materials reviewed in this paper can be applied in various ways. The selected mode can affect the properties of the coating, in particular the corrosion inhibition efficiency. The mode may also affect costs and, thus, the economic viability of a coating. The mentioned methods in the examined research reports include the following:
  • Chemical vapor deposition from gaseous precursors [22,23,25,27,29,39]. This seems to be currently the only option to obtain more or less perfect, defect-free coatings.
  • Deposition or adsorption from dispersions of the coating material [26,44].
  • Hydrothermal reduction of GO to rGO (not GR) deposited from rGO dispersion [2].
  • Mechanical blade coating [45].
  • Electrophoretic deposition [46,47].
  • Inkjet printing [48].

2.1. In Secondary Batteries

A separator modified with a composite of graphite fluoride nanosheets and poly(vinylidene difluoride) (PVDF) restricts dendrite growth on a lithium electrode [42]. LiF and GR nanosheets formed by the chemical reaction between lithium and the separator provide fast lithium ion transport channels and suppress lithium corrosion [45]. The corrosion of a lithium metal electrode by Mn ions crossing the cell from the positive electrode after dissolution could be prevented by coating the separator with GR, which traps (presumably the intended meaning of “obstructed”) the ions [49].
Coating particles of nickel-rich positive electrode material for lithium-ion batteries with a dual layer of polydimethyldiallyl ammonium chloride/GO have been suggested [50]. A similar approach with GO modified with p-phenylenediamine has been tested successfully with LiFePO4, with significantly improved capacitance retention and better rate capability [43]. The protection of the active mass against corrosion by the electrolyte solution was proposed as a major reason for the improved performance.
Coating the separator for a lithium/sulfur battery on its side towards the negative electrode with a colloid of Nb2O5/rGO retards lithium metal corrosion, in addition to preventing dendrite formation and the suppression of the polysulfide shuttle [51]. Another coating with iron tetraaminophthalocyanine physisorbed on rGO on the separator hindered polysulfide migration and lithium electrode corrosion [52].
Nanocrystals of SnS2 studied as negative electrode material for sodium- and lithium-ion batteries were protected against the corrosive attack of the electrolyte solution by coating with a carbon shell anchored on rGO [21]. A stable capacity along 200 cycles and increased rate capability prove the beneficial effects of the coating.
In lithium-ion batteries, the positive electrode is mostly supported by aluminum foil, also serving as the current collector. For the improved mechanical adhesion of the active mass on the metal foil and a better electronic contact, surface modifications of the metal by roughening or other means have been considered. For improved corrosion protection, which becomes more challenging when moving to ever higher cell voltages and higher positive electrode potentials, conformal coating with GR has been studied [53]. Moreover, corrosion protection established as increased capacitance retention during cycling (in comparison to cells with uncoated current collectors) improved rate capability points at a better contact between the active mass and current collector. A similar effect was achieved by coating aluminum foil with rGO [54]. A lower self-discharge was claimed as evidence of less corrosion; in addition, a greater capacity and longer cycling life suggested protective effects and further benefits. The barrier function of a coating against the pitting-corrosion-inducing anion PF 6 - was highlighted. A similar approach with similar benefits has been reported elsewhere [55]. This time, the protection against a corrosive attack by HF was highlighted. The ink-jet coating of aluminum foil with GR has been examined as a further practical option of applying a corrosion protection layer, also improving performance in terms of higher stability and rate capability [45]. The coating of aluminum foil used as a positive-electrode current collector with GR was also found to protect against corrosion with deep-eutectic electrolyte lithium-ion batteries [56]. The designation of this electrolyte as “aqueous” may suggest a fundamental misunderstanding.
The corrosion of magnesium negatively affects its use as a negative electrode in batteries. A gadolinium nanorod-decorated coating of the magnesium alloy AZ13 was claimed to be helpful in preventing corrosion in a magnesium battery [57]. In the absence of major experimental details, and with a line of reasoning very difficult to follow, it is hard to understand how the claimed electron transfer from the magnesium alloy to the gadolinum ions should afford corrosion protection.
A zincophilic molecular brush of polyacrylamide on rGO coated on a zinc electrode inhibits hydrogen evolution and promotes a homogeneous zinc deposition [58]. In cycling tests, a capacitance retention of 96.7% after 3500 cycles was obtained, without the coating; only 82.3% after 1000 cycles was obtained. A GR coating on the negative zinc electrode induced a reversible behavior [59]. The suppression of corrosion and associated hydrogen evolution was also noticed. The options for the surface treatment of zinc electrodes for the suppression of dendrite formation, including those presented in this paper, have been reviewed [60]. A coating of the negative zinc electrode with a hydrotalcite (a layered double hydroxide of magnesium and aluminum) and GR quantum dots has been suggested as an option to improve zinc electrode performance [61]. The possible cycle numbers were almost doubled. The addition of chlorinated GR quantum dots to the electrolyte solution was proposed as another option [62]. Without the addition, the cell capacity collapsed after about 220 cycles, whereas, with the addition, the capacitance was maintained at least for 350 cycles.

2.2. In Other Storage Systems

In addition to secondary batteries (primary batteries are less relevant because the coatings discussed in this report are most likely hardly attractive for economic reasons), supercapacitors and other storage systems, like metal–air batteries, may also face corrosion problems as discussed for the former case in [35,36,38]. Coatings with the materials reviewed in this paper have not been reported to date, except for the two examples presented in what follows.
Hydrogen storage materials to be used in the negative electrodes of Ni-MH batteries are currently based on AB5 alloys. Attractive Mg-based alloys of the AB2 type, like Mg2Ni, suffer from corrosion. A coating with rGO provides corrosion protection, and it also accelerates charge transfer reactions and the hydrogen diffusion rate [63].
Nanoparticles of FeNi confined within Co, N-co-doped GR have been examined successfully as a bifunctional catalyst for the oxygen electrode in a zinc–air cell [64].

2.3. In Fuel Cells and Electrolyzers

GO was deposited thermally from a gas phase of methanol and water on nickel foam, yielding a “collaborative” “carbocatalyst” for hydrogen evolution [65]. GO also offered corrosion protection.
GR deposited on stainless steel used for bipolar plates has shown enhanced corrosion resistance; in addition, the formation of an unwelcome, poorly conducting passivation layer was suppressed [66]. A coating procedure for stainless-steel bipolar plates based on water-dispersed GR (instead of gas-phase processes), yielding a sufficiently dense and compact protective coating, has been described [67]. Multilayer GR has been found to offer efficient corrosion protection on stainless-steel bipolar plates [68]. rGO has been found to be an efficient corrosion prevention coating for a stainless-steel 316L bipolar plate [41].
The improvement in degradation and corrosion resistance of graphene-coated nickel and Monel (Ni-Cu alloy) bipolar plates has been reported [69]. Electronic conductivity was not negatively affected. The corrosion of bipolar plates and other auxiliary components in fuel cells, mostly of the PEM type, poses a serious problem in the long-term operation of these EET devices. A coating of bipolar plates made of stainless-steel 304SS with a bilayer of polypyrrole-GO/PPy-camphorsulfonic acid by electropolymerization from pyrrole-containing solutions provided better corrosion protection than coating with only PPy-GO [70]; see also [71]. The electronic conductivity and mechanical adhesion of the composite coating were found to be sufficient during 696 h of immersion in a corrosive solution (not an actual cell). The authors designate their coating obviously and appropriately as a “bilayer coating”; why they also call it a “composite” remains unexplained. A superhydrophobic coating of copper bipolar plates with a cobalt/GR composite has been suggested; experimental results in fuel cell environment revealed enhanced stability against corrosion [72]. A hydrophobic octadecylamine-functionalized GR/TiO2 hybrid coating applied to copper-based bipolar plates has shown high efficiency in keeping aqueous sulfuric acid away from the protected metal [73]. The electrophoretic deposition of p-phenylenediamine-functionalized rGO on titanium bipolar plates avoids the surface oxide formation encountered in some other coating processes [74]. The reduction in the corrosion current by about two orders of magnitude and a decrease in the interfacial contact resistance to 1/30 of the value found with uncoated titanium were observed. In an overview of materials for bipolar plates in PEM fuel cells, carbon materials, possibly suitable as corrosion protection coatings, have been considered.
GR coating grown on nickel foam (used as a flow distributor or flow field) for corrosion protection has shown significant corrosion inhibition [75]. The electronic conductivity was found to be similar to that of TiN and Au coatings. A nickel foam used as a flow field was coated with a composite of tin and GR for corrosion protection [76]. The addition of GR increased the corrosion protection when compared with a simple tin coating. Elsewhere, a nickel/GR coating provided better corrosion protection than a plain nickel coating on metal foam used as flow field in a PEM fuel cell [77].
The coating of fuel cell components with rGO as an option towards cost-efficient corrosion protection, applicable to copper as a construction material requiring such protection, has been reviewed [78]. In a survey of nanomaterials for fuel cells, GR was mentioned in passing as a possible coating material [79].

3. Conclusions

GR and its chemical relatives are frequently employed as corrosion protection coatings. The reported applications closely focus on a few applications where the corrosion of a substrate, an active mass, or an auxiliary material is particularly relevant: Aluminum foils for positive electrodes and other metals are used as current collectors and support of the negative electrodes of metal and metal-ion batteries, flow fields, and bipolar plates in fuel cells.
Further research and development should aim at improving the protective properties, including more quantitative data on protection efficiency, in particular in comparison to established coatings and in advanced processes for coatings, meeting technical as well as commercial aspects. In addition to cost considerations and a balance between economics and protection efficiency, details of the properties of the coatings, in terms of close and perfect coverage, should be carefully considered when selecting a particular material from the ones discussed in this paper and the method of application. Given the infrequently raised doubts regarding the long-term performance of these coatings, such studies over extended time appear to be necessary.

Author Contributions

Writing, review, and editing, all authors. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Acknowledgments

The preparation of this communication was supported in various ways by the Alexander von Humboldt-Foundation, Deutscher Akademischer Austauschdienst, Fonds der Chemischen Industrie, Deutsche Forschungsgemeinschaft, National Basic Research Program of China, and Natural Science Foundation of China. The support provided within a research project at St. Petersburg State University grants Nos. 26455158 and 70037840 is appreciated.

Conflicts of Interest

The authors declare no conflicts of interest.

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Cmd 06 00033 g001
Figure 1. Chemical structures of graphite, GR, GO, and rGO. flG is not shown because its sketch would be highly similar to that of graphite (see also [1]).
Figure 1. Chemical structures of graphite, GR, GO, and rGO. flG is not shown because its sketch would be highly similar to that of graphite (see also [1]).
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Figure 2. Corrosion on an imperfectly coated surface.
Figure 2. Corrosion on an imperfectly coated surface.
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Liu, D.; Xie, X.; Chen, X.; Holze, R. Graphenes for Corrosion Protection in Electrochemical Energy Technology. Corros. Mater. Degrad. 2025, 6, 33. https://doi.org/10.3390/cmd6030033

AMA Style

Liu D, Xie X, Chen X, Holze R. Graphenes for Corrosion Protection in Electrochemical Energy Technology. Corrosion and Materials Degradation. 2025; 6(3):33. https://doi.org/10.3390/cmd6030033

Chicago/Turabian Style

Liu, Dan, Xuan Xie, Xuecheng Chen, and Rudolf Holze. 2025. "Graphenes for Corrosion Protection in Electrochemical Energy Technology" Corrosion and Materials Degradation 6, no. 3: 33. https://doi.org/10.3390/cmd6030033

APA Style

Liu, D., Xie, X., Chen, X., & Holze, R. (2025). Graphenes for Corrosion Protection in Electrochemical Energy Technology. Corrosion and Materials Degradation, 6(3), 33. https://doi.org/10.3390/cmd6030033

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