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Review

Progress in Surface Engineering Techniques for Magnesium–Lithium-Based Alloys

by
Ningning Li
1,2,
Zhenjie Hao
1,2,
Yaya Feng
3,
Yan Shang
4,
Yuping Tong
1,2,
Fan Lu
5,
Lei Xu
1,2,*,
Xi Chen
1,2,
Shuai Li
4 and
Jin Peng
1,2,*
1
School of Materials Science and Engineering, North China University of Water Resources and Electric Power, Zhengzhou 450045, China
2
Henan Engineering Research Center on Special Materials and Applications of Water Conservancy and Hydropower Engineering, Zhengzhou 450045, China
3
National Key Laboratory of Aerospace Chemical Power, Inner Mongolia Research Institute of Synthetic Chemical Industry, Hohhot 010010, China
4
School of Mechanical Engineering, North China University of Water Resources and Electric Power, Zhengzhou 450045, China
5
School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
*
Authors to whom correspondence should be addressed.
Coatings 2025, 15(5), 502; https://doi.org/10.3390/coatings15050502
Submission received: 16 March 2025 / Revised: 17 April 2025 / Accepted: 21 April 2025 / Published: 23 April 2025
(This article belongs to the Special Issue Advanced Corrosion Protection through Coatings and Surface Rebuilding)

Abstract

:
Magnesium–lithium alloys, currently the lightest metallic structural materials, exhibit exceptional specific strength, superior damping capacity, and remarkable electromagnetic shielding properties. These characteristics endow them with significant potential for engineering applications in automotive, aerospace, satellite, and military industries. However, their poor corrosion resistance severely restricts practical implementation. This review systematically examines recent advances in surface engineering techniques for magnesium–lithium alloys, with a focus on corrosion protection strategies. Key approaches are critically analyzed, including chemical conversion coatings, electroless plating, anodization, and advanced coating technologies. Furthermore, emerging hybrid methods combining multiple surface treatments are highlighted. Finally, future research directions are proposed to address existing challenges in surface protection of magnesium–lithium alloys.

Graphical Abstract

1. Introduction

Magnesium–lithium (Mg–Li) alloys exhibit exceptional properties, including high specific strength (the ratio of a material’s strength to its density), superior specific stiffness, excellent thermal conductivity, remarkable electromagnetic shielding and damping performance. These characteristics offer broad application prospects in aerospace, defense equipment, electronic information, and automotive industries [1,2,3]. Recognized as “green engineering materials of the 21st century” [4,5], Mg–Li alloys are among the most promising lightweight materials for sustainable development, addressing the growing demand for weight reduction, energy efficiency, and high integration. Figure 1 illustrates the research and applications of Mg–Li alloys, mainly in aeronautics and astronautics, biomedicine, weaponry, battery anodes, automotives, electronic information and so on [6,7].
The phase structure of Mg–Li alloys is primarily determined by their Li content. When the Li content is below 5.7 wt.%, the alloy consists of an α-Mg phase with a hexagonal close-packed (hcp) structure, where Li is dissolved in the Mg matrix. When the Li content exceeds 10.3 wt.%, the alloy is dominated by a β-Li phase with a body-centered cubic (bcc) structure, where Mg is dissolved in the Li matrix. For Li contents between 5.7 wt.% and 10.3 wt.%, the alloy exhibits a typical dual-phase structure composed of both α-Mg and β-Li phases [8].
However, the wider application of Mg–Li alloys is hindered by their intrinsic limitations, including low strength (due to the excessive Li content, grain coarsening, or insufficient alloying elements), poor stability, and weak corrosion resistance. Particularly, the galvanic corrosion caused by the potential difference between the α-Mg and β-Li phases in biphasic Mg–Li alloys significantly compromises their performance in service environments, thereby restricting their engineering applications [9,10]. Based on the search results for “Mg–Li alloys” in the Web of Science database from 2010 to 2025, as illustrated in Figure 2, the data analysis reveals the main research areas on Mg–Li alloys are remarkably extensive, with materials science [11], physics [12], and engineering [13] being the top three predominant fields.
Therefore, the development of surface engineering technologies aimed at enhancing the strength and corrosion resistance of magnesium–lithium alloys is of paramount importance. These technologies include chemical conversion [14,15,16], electroless plating [17,18,19], anodizing [20,21,22], coating techniques [23,24,25], and various surface modification methods [26,27,28]. This article comprehensively reviews the fundamental principles and practical applications of these approaches, while also identifying their current limitations and potential development directions. The findings presented herein aim to provide valuable insights for the fabrication of high-performance magnesium–lithium alloys.

2. Different Surface Engineering of Mg–Li Alloys

Surface modification involves altering the chemical composition of the substrate surface to achieve desired changes in surface structure and properties [29,30,31]. In contrast, surface treatment refers to the process of enhancing surface characteristics through microstructural modifications of the substrate material while maintaining its original chemical composition, as exemplified by surface heat treatment techniques [31,32,33,34]. Surface coating, on the other hand, entails the deposition of a distinct film layer onto the substrate surface, where both the chemical composition and microstructure of the coating may significantly differ from those of the underlying substrate material [35,36,37].
The limited corrosion resistance of Mg–Li alloys primarily stems from two factors: the low-density oxide film naturally formed on their surface and the localized galvanic corrosion induced by the presence of secondary phases and alloying elements within the matrix [38,39,40]. In response to these challenges, significant research efforts have been directed toward developing effective surface protection strategies in recent years, resulting in substantial advancements in this field.

2.1. Chemical Conversion

Chemical conversion involves the formation of oxide or metallic compound passivation films on metal surfaces through chemical treatment solutions [41,42]. This process offers several advantages, including minimal instrumentation requirements, operational simplicity, and the ability to be completed through straightforward immersion. However, the resulting conversion films are typically thin and exhibit limited adhesion strength, which primarily serves to reduce rather than effectively prevent corrosion. Consequently, additional coating processes are often required to achieve comprehensive protection.
Currently, several surface chemical treatment techniques have been developed for Mg–Li alloys, including phytic acid conversion [43], phosphate conversion [44], stannate conversion [45], and rare earth-based conversion coatings [46].
Phytic acid (C6H18O24P6), a novel metal surface treatment agent, forms protective films on substrate surfaces through chemical adsorption. These films effectively inhibit the penetration of corrosive anions to the metal surface, demonstrating significant corrosion protection properties [47]. However, the quality of phytic acid conversion films is influenced by multiple parameters, including pH value, concentration, and treatment duration, making quality control challenging. Gao et al. [48] investigated chromium-free phytic acid conversion on Mg-11Li alloy. Figure 3 showed the surface morphology of Mg–Li alloy after the conversion coating treatment. Figure 3a demonstrated nearly full surface coverage of the membrane on the specimen, while Figure 3b revealed localized micro-crack formation within the coating. Electrochemical corrosion testing was subsequently conducted, the results demonstrating enhanced corrosion resistance through increased corrosion potential and reduced current density compared to conventional chromic acid conversion.
Phosphate conversion films are formed through chemical reactions between metal surfaces and phosphoric acid-based conversion solutions [49]. Song et al. [50] systematically analyzed the formation mechanism of phosphate conversion films on biphasic magnesium–lithium alloys using XPS and SEM. Their findings revealed a three-stage process: initial dissolution of Mg(OH)2 and MgO from the alloy surface, subsequent dissolution of the β-phase, and finally, the establishment of dynamic equilibrium between film formation and dissolution. The phosphate conversion coating formation on Mg-8.8Li alloy substrates progressed through three characteristic phases, as schematically illustrated in Figure 4. Stage I (Figure 4a,b) was characterized by selective dissolution of the native oxide layer and subsequent surface activation. During Stage II (Figure 4c–e), heterogeneous nucleation and epitaxial growth of crystalline phosphate compounds occurred, establishing a continuous protective film. Stage III (Figure 4f) showed the improvement of the phosphate conversion film, yielding a defect-mitigated coating architecture with enhanced barrier properties.
Stannate conversion, recognized for its environmental compatibility, offers several advantages including cost-effectiveness, rapid film formation, and uniform thickness distribution [51,52]. Yang et al. [51] researched the stannate conversion coatings (SnCC), which were fabricated on Mg-8Li alloy substrates via the immersion deposition technique at 45 °C for 30 min. Comprehensive microstructural characterization was performed using SEM and is systematically documented in Figure 5. Figure 5a reveals incomplete particle coalescence at 30 min, characterized by coexisting small and large particles due to ongoing nucleation and growth processes. The 60 min-treated coating (Figure 5b) achieves optimal integrity with minimal defects, driven by efficient Mg2+-assisted surface reactions that promote uniform particle deposition. Prolonged treatment to 90 min degrades coating (Figure 5c) quality through non-uniform overgrowth, conclusively demonstrating the 60 min SnCC as the most homogeneous and compact morphology. The reaction between rare earth salt solutions and magnesium–lithium alloy surfaces occurs rapidly. When combined with other salt solutions, these reactions produce protective films with enhanced corrosion resistance. Moreover, the conversion process is environmentally benign and biocompatible [53,54].
Rare earth-based conversion coatings are formed by mixing rare earth salt solutions with other salt solutions, resulting in a protective film that exhibits enhanced corrosion resistance [46]. Silane coupling agents (SCA) feature hydrophilic/hydrophobic groups that enhance metal–inorganic/organic interface bonding, offering a novel strategy to optimize rare earth (RE) conversion coatings. Xu et al. [55] systematically investigated key parameters for rare earth (RE)–silane (Si) composite conversion coatings, including immersion time, temperature, pH value of the conversion solution, and curing duration. Through comprehensive optimization, they established the optimal technological parameters for RE–Si composite coating preparation; the metallographic morphology of the samples prepared under different conditions is shown in Figure 6. The substrate surface displays numerous potholes and scratches (Figure 6a). The silane coating, while relatively compact, contains multiple gaps and exhibits minimal thickness (Figure 6b). The RE–Si composite coating demonstrates significantly improved compactness and uniformity compared to the silane coating, accompanied by a substantial thickness increase (Figure 6c). The incorporation of nano-zirconium dioxide particles markedly enhances the compactness of the RE–Si composite coating while significantly reducing crack formation (Figure 6d). These findings demonstrate that nanoparticle addition not only improves coating morphology and quality but also positively influences the conversion coating formation process.

2.2. Electroless Plating

Electroless plating is an autocatalytic deposition process that utilizes redox reactions to deposit metallic elements from solution onto substrate surfaces without external current application. This well-established technique produces coatings with excellent comprehensive performance, particularly when employing high-density nanocrystalline nickel plating, which exhibits superior wear resistance [56,57,58].
However, the inherent challenge lies in the negative standard electrode potentials of Mg and Li in magnesium–lithium alloys, which renders them susceptible to corrosion by conventional Ni–P plating solutions [59,60]. To address this issue, researchers have developed specialized pretreatment processes. Pei et al. [59] studied the electroless Ni–P coating on Mg–Li alloy; the electroless plating setup is schematically illustrated in Figure 7a, while the adhesion evaluation of the Ni–P coating was conducted via automatic scratch tester, as shown in Figure 7b. The optimized coating has a good adhesion force of 55.6 N. It indicated good adhesion between the coating and the substrate.
Yue et al. [61] investigated the electroless deposition of zinc on Mg–Li alloy surfaces, as illustrated in Figure 8. The study included a schematic representation of the electroless plating galvanic cell (Figure 8a), open-circuit potential measurements (Figure 8b), and tafel polarization curve analyses under various conditions (Figure 8c,d). The experimental results demonstrated a significant positive shift in the corrosion potential of the Mg–Li alloy, reaching −1.38 V, accompanied by a substantial reduction in corrosion current density to 2.78 × 10−6 A/cm2. These findings indicate that the electroless zinc deposition process significantly enhances the corrosion resistance of Mg–Li alloys.

2.3. Anodic Oxidation

Anodizing represents an electrochemical process that generates a robust oxide layer on alloy surfaces through the application of specialized electrolytes and controlled electric currents [62]. Compared to chemical conversion coatings, anodic films exhibit superior durability, enhanced wear resistance, and improved corrosion protection [63,64]. Furthermore, these films demonstrate exceptional characteristics, including strong adhesion, effective electrical insulation, and remarkable thermal shock resistance [6]. Consequently, anodizing has emerged as one of the most prevalent surface treatment techniques for Mg–Li alloys [65].
The formation of porous oxide layers during anodization primarily results from hydrogen evolution at the cathode, combined with inherent chemical and electrochemical heterogeneities on Mg–Li alloy surfaces. To address these structural limitations, the incorporation of process additives has become crucial for enhancing oxide film compactness and structural integrity. In a significant study, Li et al. [66] systematically investigated ordinary anodic oxidation coatings on Mg–Li alloys using galvanic anodizing, and the potentiodynamic scanning curves of the anodizing coatings obtained at different pH values is presented in Table 1. The results demonstrate enhanced corrosion resistance compared to the Mg–Li alloy base material. However, varying pH levels significantly affect the coating’s corrosion resistance.
Micro-arc oxidation (MAO), alternatively referred to as plasma electrolytic oxidation or anodic spark deposition, represents an advanced surface modification technology. This process involves the formation of dense, wear-resistant, and corrosion-resistant ceramic coatings predominantly composed of metal oxides through controlled arc discharge phenomena [67,68,69]. MAO technology offers numerous advantages, including operational simplicity and environmental compatibility, making it particularly suitable for applications in aerospace, electronic equipment, and marine engineering. Furthermore, its implementation on Mg–Li alloy surfaces has demonstrated significant potential [70,71,72]. Shi et al. [71] studied the additives on the structure and corrosion resistance of ceramic coatings on Mg–Li alloy by micro-arc oxidation; Figure 9 displays the surface part morphologies of the ceramic coating on Mg–Li samples, revealing micrometer-sized near-circular pores. Sample a exhibits a coarser structure compared to samples b and c, with oxide nodules approximately 10 μm in size. In contrast, sample b demonstrates a more homogeneous surface structure with finer nodules, while sample c shows a significant reduction in nodule quantity. These observations suggest that additive doping suppresses nodule formation. Cross-sectional analysis further indicates uniform coating thickness in samples a and b, whereas sample c lacks uniformity.
The MAO coating formation process is inherently complex, with multiple influencing factors that determine coating performance. These parameters include substrate composition, electrolyte formulation, additive selection, power supply configuration, voltage, current density, frequency, and duty cycle [70,73]. In a comprehensive study, Qian et al. [74] investigated calcium phosphate (CaP) coatings on Mg-8Li-2Ca alloy prepared through MAO in an alkaline Na3PO4-Ca[C3H7O6P] solution at varying applied voltages, as partially illustrated in Figure 10. The researchers employed X-ray diffraction to analyze the coating microstructure and phase composition (Figure 10a). Electrochemical performance was evaluated through hydrogen evolution measurements and tafel plots in simulated body fluid solution (Figure 10b,c), while tribological properties were assessed using a friction and wear testing machine (Figure 10d). The experimental results revealed that the MAO coatings exhibited a porous structure primarily composed of MgO, Ca5(PO4)3(OH), and CaH2P2O5. Notably, increasing applied voltage significantly enhanced both corrosion and wear resistance properties. The corrosion current density of MAO coatings demonstrated approximately two orders of magnitude reduction compared to the untreated substrate.

2.4. Coating Technology

Surface engineering technologies for Mg–Li alloys encompass a diverse array of advanced methodologies, including vapor deposition, thermal spraying, and the development of superhydrophobic coatings through organic-inorganic hybridization. Vapor deposition techniques are primarily classified into physical vapor deposition (PVD) [75] and chemical vapor deposition (CVD) [76,77], with plasma-enhanced chemical vapor deposition (PECVD) emerging as a particularly noteworthy technique [78]. PECVD employs plasma to activate reactive gases, thereby facilitating chemical reactions on or near the substrate surface to form durable solid films. As shown in Figure 11, the maganic spurring coating system (a: PVD, studied by Chen et al. [75]) and potentiodynamic polarization curves of atomic layer-deposited (b: CVD, investigated by Wang et al. [76]) coatings fabricated on Mg–Li substrates were systematically investigated in a 3.5 wt.% NaCl solution. The results demonstrate that coating methodologies significantly lead to enhanced performance of the base material.
Thermal spraying techniques, including plasma spraying [79,80] and cold spraying [81,82,83], involve the deposition of metallic or ceramic particles onto alloy surfaces to create protective coatings. These coatings reduce the impact of the corrosive environment on the substrate, significantly enhancing both corrosion and wear resistance. The plasma thermal-spraying of pure aluminum coating onto Mg–Li alloy plates was investigated by Tsujikawa et al. [79], as shown in Figure 12. The corrosion resistance of plasma-sprayed plates, as assessed via salt spray testing, was enhanced (Figure 12a). Additionally, a slightly cold-rolled surface following thermal spraying demonstrated superior corrosion resistance owing to the closure of surface-to-substrate microchannels (Figure 12b).
In addition, the Al2O3 ceramic coatings have demonstrated substantial improvements in the surface hardness and corrosion resistance of Mg–Li alloys [83]. However, challenges persist in optimizing interfacial bonding strength and coating uniformity.
Superhydrophobic coatings represent an innovative approach through the construction of micro-nano structured surfaces that induce high water contact angles, thereby minimizing corrosive media adhesion [84,85,86]. These coatings not only enhance corrosion resistance but also impart self-cleaning properties to Mg–Li alloys [87,88,89]. Significant progress has been made in this field, with researchers achieving promising results through chemical modification and laser processing techniques for superhydrophobic coating preparation on Mg–Li alloys, the corrosion current density of the superhydrophobic coating on the rhombic, rectangular and cylindrical microstructure surfaces decreased to 4.261 × 10−6 A/cm2, 1.124 × 10−6 A/cm2 and 9.676 × 10−7 A/cm2, respectively [90]. These advancements demonstrate considerable potential for expanding the practical applications of Mg–Li alloys in demanding environments.
In a pioneering study, He et al. [91] developed a novel approach combining screen-printed mask electroplating with electrodeposition to fabricate dense micro/nanoscale papillary-structured superhydrophobic surfaces on Mg–Li alloys. The research revealed that extended deposition times induced copper anode dissolution, resulting in the formation of copper compounds within the superhydrophobic coating. This process generated dense, needle-like structures on the papillae, as illustrated in Figure 13. Notably, the armor-like nickel columns effectively maintained high contact angles despite structural wear, demonstrating remarkable surface properties including low adhesion, self-cleaning capability, chemical stability, and exceptional corrosion resistance.

2.5. Other Surface Modification Techniques

In addition to the aforementioned methods, surface engineering for Mg–Li alloys also encompasses surface nanocrystallization and composite surface engineering technologies, which provide advanced performance enhancements [28,92]. Surface nanocrystallization represents an innovative approach that significantly improves surface properties through grain refinement at the nanoscale [93]. Composite surface engineering, defined as the strategic integration of two or more surface treatment techniques, creates composite-modified layers with gradient or multilayer structures on material surfaces, thereby enhancing their functional characteristics [94].
Surface nanocrystallization of Mg–Li alloys can be accomplished through advanced techniques such as surface mechanical attrition treatment (SMAT) [95] and ultrasonic nanocrystal surface modification (UNSM) [29]. Zhang et al. [95] conducted a comprehensive investigation of Mg-3 wt.% Li-6 wt.% Al alloy using SMAT. Their findings revealed that grain refinement primarily occurs through dislocation slip, with twinning playing a significant role during the initial stages when grain sizes are larger. This process resulted in substantial surface hardness enhancement. Figure 14 presents the schematic diagram of the UNSM instrument, based on research by Zou et al. [96]. UNSM achieves surface nanocrystallization by utilizing high-frequency ultrasonic waves (20–40 kHz) to drive a hardened spherical tip (tungsten carbide) to deliver repeated micro-impacts on the material surface, inducing severe plastic deformation. Their systematic study examined the effects of UNSM treatment on hot-rolled Mg–Li alloys (LAE361 and LA106), focusing on microstructure evolution, mechanical properties, deformation mechanisms, and corrosion resistance. The treatment demonstrated remarkable improvements in surface hardness and significant reductions in surface roughness. Notably, UNSM treatment achieved simultaneous enhancements in both strength and plasticity [96]. However, the underlying mechanisms responsible for these improvements warrant further in-depth investigation.
Composite coating technologies for Mg–Li alloys have evolved to include various innovative combinations, such as plasma electrolysis with chemical conversion [92], sol–gel methods [97], superhydrophobic coatings integrated with electroless plating [98], micro-arc oxidation [99,100], and micro-arc oxidation combined with chitosan (CS) [101].
Li et al. [98] successfully developed an innovative superhydrophobic composite coating system consisting of nickel-based metal coupled with layered double hydroxides (LDHs) on Mg–Li alloy substrates. Figure 15 illustrates the schematic diagram of the preparation process and underlying mechanisms, which primarily involve three sequential steps: (1) deposition of Ni–P coating, (2) in situ growth of MgAl LDHs, and (3) surface modification with stearic acid. The study also presented a comprehensive analysis of the corrosion mechanisms for different coating systems. Experimental results demonstrated that MgAl LDHs uniformly grew in situ on the electroless-plated Ni–P coating through hydrothermal treatment. The resulting MgAl LDHs exhibited a complex honeycomb-like micro-nano structure, increasing the composite coating’s surface roughness to 126 nm. This superhydrophobic composite coating represents a significant advancement in corrosion protection for Mg–Li alloys, substantially enhancing their durability and performance in demanding environments [98].
Figure 16 presents the schematic illustration of the self-degradation mechanism of MAO/CS composite coatings on Mg-4Li-1Ca alloys in Hank’s solution [101]. The degradation process of CS on the Mg-4Li-1Ca alloy proceeds through five distinct stages: (1) water diffusion through the CS film onto the MAO coating (Figure 16a); (2) release of R-NH3+ through CS self-degradation (Figure 16b); (3) chemical corrosion of the MAO coating through existing cracks and pores; (4) electrochemical corrosion of the substrate; and (5) eventual peeling of the CS film (Figure 16c).

3. Innovation and Further Perspectives

With the rapid advancement of materials science, nanotechnology, and intelligent manufacturing, surface treatment technologies for magnesium–lithium alloys are undergoing transformative developments. Future research in this field will concentrate on four key dimensions: performance enhancement, environmental sustainability, intelligent innovation, and multi-scenario adaptability:
(1) Collaborative Design of High-Precision Multifunctional Composite Coatings
Future research will emphasize the development of intelligent coatings that integrate multiple functionalities, including corrosion resistance, wear resistance, and thermal/electrical conductivity. By incorporating nanomaterials into ceramic or polymer matrices, gradient structures can be engineered at the micro-scale to achieve a balance between mechanical performance and environmental responsiveness. For instance, self-healing coatings utilizing micro-capsule technology or dynamic chemical bonds can autonomously repair surface damage, significantly extending service life. Furthermore, bio-inspired coatings, fabricated with precision, will enhance the stability of magnesium–lithium alloys in humid or corrosive environments. Computational materials science simulations will play a critical role in optimizing composition distribution and interfacial bonding strength, ensuring long-term compatibility with the substrate.
(2) Iterative Upgrading of Green and Low-Carbon Surface Treatment Processes
Chromium-free conversion coatings, low-temperature plasma deposition, and bio-based coating technologies are poised to replace traditional electroplating and chemical oxidation methods. For example, micro-arc oxidation employing water-soluble ionic liquid electrolytes can substantially reduce toxic byproducts while improving coating density. Energy-efficient technologies, such as photo-curing and laser-induced deposition, will streamline processing steps and minimize carbon emissions. Under the principles of the circular economy, recyclable coating designs and regeneration techniques will emerge as key research areas, fostering sustainable development across the industry chain.
(3) Full-Chain Integration of Intelligent and Digital Surface Engineering
Artificial intelligence and digital twin technologies will revolutionize coating development and application. Machine learning-driven high-throughput experimental platforms will enable rapid screening of optimal coating formulations and process parameters, significantly reducing trial-and-error costs. The integration of 3D printing with topology optimization algorithms will facilitate the creation of customized functional surface structures for complex components. Online monitoring systems will provide real-time tracking of coating deposition processes, ensuring consistent quality. Digital twin models will simulate coating failure mechanisms under extreme conditions, offering theoretical support for lifespan prediction. This integration will drive a paradigm shift from “experience-driven” to “data-driven” approaches.
(4) Innovative Breakthroughs in Extreme Environment-Adaptive Coatings
For applications in extreme environments—such as aerospace cryogenic conditions, deep-sea high-pressure zones, or nuclear radiation settings—coatings must demonstrate exceptional environmental tolerance. High-temperature oxidation-resistant coatings could unlock new applications for magnesium–lithium alloys in engine components. Nanoscale oxide protective layers, fabricated via atomic layer deposition (ALD), can effectively mitigate hydrogen permeation, addressing hydrogen embrittlement in acidic or irradiated environments. Additionally, adaptive color-changing coatings (e.g., thermochromic or mechanochromic materials) may incorporate sensing capabilities to provide real-time structural health monitoring. The successful development of such coatings will enable breakthrough applications of magnesium–lithium alloys in defense, energy, and other high-tech sectors.

4. Conclusions

As an ultra-lightweight structural material, the optimization of surface treatment technologies for Mg–Li alloys is critical to enhancing their corrosion resistance, wear resistance, and engineering applicability. This review summarizes four widely used methods: chemical conversion, electroless plating, anodic oxidation, and coating technologies, with their advantages and limitations summarized in Table 2. Current research trends focus on hybrid modification strategies and eco-friendly processes to synergistically improve protective efficiency and environmental compatibility. Future advancements will rely on innovative approaches, such as high-precision composite coatings, low-carbon surface treatments, digital surface engineering, and environmentally adaptive coatings, which will further promote the reliable application of Mg–Li alloys in extreme environments, including aerospace and biomedical fields.

Author Contributions

Writing—original draft preparation, N.L.; conceptualization, N.L., Z.H., L.X. and Y.T.; methodology, N.L., Z.H., Y.S., F.L., Y.T. and S.L.; writing—review and editing, L.X. and J.P.; investigation, N.L., Z.H., Y.F., Y.S., F.L., X.C. and J.P.; formal analysis, N.L., Z.H., Y.F., Y.T., X.C. and S.L.; data curation, Y.F., S.L., F.L., L.X. and J.P.; resources, Y.F., Y.S., F.L., X.C., S.L. and Y.T.; supervision L.X. and J.P. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the Key R & D and Promotion Project of the Henan Province (Science and Technology Research) (Nos. 252102220078, 252102231064, and 252102220064), the fund of Henan Province Science and Technology Research Project (Nos. 232102220055 and 242102220072).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding authors.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Research progress and application areas of Mg–Li alloys.
Figure 1. Research progress and application areas of Mg–Li alloys.
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Figure 2. The main research areas were analyzed by searching the keywords “Mg–Li alloys” in the Web of Science database from 2010 to 2025.
Figure 2. The main research areas were analyzed by searching the keywords “Mg–Li alloys” in the Web of Science database from 2010 to 2025.
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Figure 3. SEM morphology of phytic acid conversion coating on Mg–Li alloy: (a) 500×; (b) 5000× [48].
Figure 3. SEM morphology of phytic acid conversion coating on Mg–Li alloy: (a) 500×; (b) 5000× [48].
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Figure 4. The sketch map of deposition conversion film on Mg-8.8Li alloy [50]. (a,b) the dissolution of loose surface film; (ce) the initiation and growth of phosphate conversion film; (f) the improvement of phosphate conversion film.
Figure 4. The sketch map of deposition conversion film on Mg-8.8Li alloy [50]. (a,b) the dissolution of loose surface film; (ce) the initiation and growth of phosphate conversion film; (f) the improvement of phosphate conversion film.
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Figure 5. SEM images of stannate coatings treated for different times: (a) 30 min, (b) 60 min, and (c) 90 min [51].
Figure 5. SEM images of stannate coatings treated for different times: (a) 30 min, (b) 60 min, and (c) 90 min [51].
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Figure 6. OM images of (a) substrate; (b) silane coatings; (c) RE–Si composite conversion coatings; and (d) RE–Si composite conversion coatings doping with zirconium dioxide nanoparticles [55].
Figure 6. OM images of (a) substrate; (b) silane coatings; (c) RE–Si composite conversion coatings; and (d) RE–Si composite conversion coatings doping with zirconium dioxide nanoparticles [55].
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Figure 7. Electroless Ni–P coating on magnesium–lithium alloy. (a) the status of the sample during electroless plating; (b) the adhesion test [59].
Figure 7. Electroless Ni–P coating on magnesium–lithium alloy. (a) the status of the sample during electroless plating; (b) the adhesion test [59].
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Figure 8. Electroless-deposited Zn on the surface of Mg–Li Alloy and electrochemical testing. (a) schematic diagram of the galvanic cell, (b) open-circuit potential vs. immersion time curves, (c) tafel polarization curves affected by the time in 3.5%NaCl, (d) tafel polarization curves affected by Zn content in 3.5%NaCl [61].
Figure 8. Electroless-deposited Zn on the surface of Mg–Li Alloy and electrochemical testing. (a) schematic diagram of the galvanic cell, (b) open-circuit potential vs. immersion time curves, (c) tafel polarization curves affected by the time in 3.5%NaCl, (d) tafel polarization curves affected by Zn content in 3.5%NaCl [61].
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Figure 9. The surface part SEM photographs of the ceramic coatings of sample (ac) [71].
Figure 9. The surface part SEM photographs of the ceramic coatings of sample (ac) [71].
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Figure 10. Calcium phosphate (CaP) coatings prepared on Mg-8Li-2Ca alloy by MAO, (a) XRD pattern of MAO coatings on Mg–8Li–2Ca alloy prepared at different voltages, (b) hydrogen content of MAO coating at different voltages in different immersion time, (c) tafel curve of MAO coating at different voltages and matrix, (d) coefficient of friction of MAO coatings at different voltages [74].
Figure 10. Calcium phosphate (CaP) coatings prepared on Mg-8Li-2Ca alloy by MAO, (a) XRD pattern of MAO coatings on Mg–8Li–2Ca alloy prepared at different voltages, (b) hydrogen content of MAO coating at different voltages in different immersion time, (c) tafel curve of MAO coating at different voltages and matrix, (d) coefficient of friction of MAO coatings at different voltages [74].
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Figure 11. Coatings technology of magnesium–lithium alloys. (a) Maganic spurring coating system (PVD) [75]; (b) Potentiodynamic polarization curves in a 3.5% NaCl solution for the substrate and with LiAlxOy films (CVD) of various thicknesses [76].
Figure 11. Coatings technology of magnesium–lithium alloys. (a) Maganic spurring coating system (PVD) [75]; (b) Potentiodynamic polarization curves in a 3.5% NaCl solution for the substrate and with LiAlxOy films (CVD) of various thicknesses [76].
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Figure 12. Features of surface: (a) as sprayed, (b) cold-rolled 3% [79].
Figure 12. Features of surface: (a) as sprayed, (b) cold-rolled 3% [79].
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Figure 13. Attempt to improve the robustness of superhydrophobic coatings prepared by electrodeposition using armor-like nickel patterns [91].
Figure 13. Attempt to improve the robustness of superhydrophobic coatings prepared by electrodeposition using armor-like nickel patterns [91].
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Figure 14. Schematic diagram of the UNSM instrument [96].
Figure 14. Schematic diagram of the UNSM instrument [96].
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Figure 15. Schematic diagram of the research process of superhydrophobic coatings paired with electroless plating [98].
Figure 15. Schematic diagram of the research process of superhydrophobic coatings paired with electroless plating [98].
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Figure 16. (ac) Schematic illustration of the self-degradation mechanism of the MAO/CS composite coating [101].
Figure 16. (ac) Schematic illustration of the self-degradation mechanism of the MAO/CS composite coating [101].
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Table 1. Corrosion parameters of the coating [66].
Table 1. Corrosion parameters of the coating [66].
Anodizing ConditionEcorr (VSCE)I0 (A/cm2)RP (Ω cm2)
Mg–Li alloy base−1.5470.0012421.1
pH 2.5, room temperature−1.3567.915 × 10−63296
pH 3.5, room temperature−1.3671.76 × 10−51483
pH 4.5, room temperature−1.3953.45 × 10−67551
pH 5.5, room temperature−1.4816.21 × 10−64200
pH 4.5, 40 °C−1.4172.95 × 10−5885.5
pH 4.5, 50 °C−1.0910.00011236.5
Table 2. Summary of different surface engineering techniques of Mg–Li alloys.
Table 2. Summary of different surface engineering techniques of Mg–Li alloys.
MethodsTypesAdvantagesLimitationsRefs.
Chemical ConversionPhytic acid
-
Eco-friendly, non-toxic.
-
Self-healing potential.
-
Simple process.
-
Thin film (1–3 µm).
-
pH-sensitive.
-
Weak adhesion to coatings.
[47,48]
Phosphate conversion
-
Low cost.
-
Porous structure for secondary coatings.
-
Fast processing.
-
Contains heavy metals.
-
Brittle film.
-
Moderate corrosion resistance.
[49,50]
Stannate conversion
-
Dense SnO2/Mg(OH)2 film (high corrosion resistance).
-
Stable process.
-
Expensive stannate salts.
-
Brittle film.
-
High temperature required.
[51,52,53,54]
Rare earth-based conversion coatings
-
Eco-friendly (Cr-free).
-
Self-healing (Ce3+/La3+).
-
High stability.
-
Slow film growth.
-
Sensitive to pH/ionic concentration.
-
Costly.
[46,55]
Electroless PlatingNi–P
-
Uniform coating on complex shapes.
-
High hardness/wear resistance.
-
Toxic bath (Ni, hypophosphite).
-
Poor adhesion on Mg–Li alloys.
[59,60]
Zinc
-
Low cost.
-
Sacrificial protection.
-
Requires cyanide baths (toxic).
-
Short-term corrosion resistance.
[61]
Anodic OxidationOrdinary anodizing
-
Forms thick oxide layers.
-
Improves adhesion for top coatings.
-
High energy consumption.
-
Brittle oxide layer.
[66]
Micro-arc oxidation
-
Ceramic-like oxide layer (high hardness).
-
Excellent corrosion resistance.
-
High voltage/energy use.
-
Porous surface requires sealing.
[67,68,69,70,71,72,73,74]
Coating TechnologiesVapor deposition
-
Ultra-thin, dense films.
-
Tailored functional properties.
-
High equipment cost.
-
Limited scalability for large parts.
[75,76,77,78]
Thermal spraying
-
Thick coatings for severe wear.
-
Wide material choices.
-
Poor adhesion on Mg–Li.
-
High porosity/thermal stress.
[79,80,81,82,83]
Superhydrophobic coatings
-
Water-repellent surface.
-
Anti-icing/anti-fouling properties.
-
Low mechanical durability.
-
Complex preparation.
[84,85,86,87,88,89,90,91]
Other Surface Modification TechniquesSMAT
-
Deep nanocrystalline layer (100–500 µm).
-
Residual compressive stress.
-
High surface roughness.
-
Limited to simple geometries.
[95]
UNSM
-
Nanocrystalline surface (50–200 nm).
-
Suitable for complex shapes.
-
High equipment cost.
-
Slow processing speed.
[29,96]
superhydrophobic composite coating
-
Dual protection (barrier + water repellent).
-
Synergistic performance.
-
Multi-step process.
-
Risk of coating delamination.
[98]
MAO/CS composite coatings
-
Bioactive/antibacterial properties.
-
Seals MAO pores effectively.
-
Chitosan degrades in humid environments.
-
Multi-step process.
[101]
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MDPI and ACS Style

Li, N.; Hao, Z.; Feng, Y.; Shang, Y.; Tong, Y.; Lu, F.; Xu, L.; Chen, X.; Li, S.; Peng, J. Progress in Surface Engineering Techniques for Magnesium–Lithium-Based Alloys. Coatings 2025, 15, 502. https://doi.org/10.3390/coatings15050502

AMA Style

Li N, Hao Z, Feng Y, Shang Y, Tong Y, Lu F, Xu L, Chen X, Li S, Peng J. Progress in Surface Engineering Techniques for Magnesium–Lithium-Based Alloys. Coatings. 2025; 15(5):502. https://doi.org/10.3390/coatings15050502

Chicago/Turabian Style

Li, Ningning, Zhenjie Hao, Yaya Feng, Yan Shang, Yuping Tong, Fan Lu, Lei Xu, Xi Chen, Shuai Li, and Jin Peng. 2025. "Progress in Surface Engineering Techniques for Magnesium–Lithium-Based Alloys" Coatings 15, no. 5: 502. https://doi.org/10.3390/coatings15050502

APA Style

Li, N., Hao, Z., Feng, Y., Shang, Y., Tong, Y., Lu, F., Xu, L., Chen, X., Li, S., & Peng, J. (2025). Progress in Surface Engineering Techniques for Magnesium–Lithium-Based Alloys. Coatings, 15(5), 502. https://doi.org/10.3390/coatings15050502

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