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Review

Modification of Cu-Based Current Collectors and Their Application in High-Performance Zn Metal Anode: A Review

by
Xiujie Gao
1,
Fei Wang
2,
Yibo Xing
1,
Chunyang Kong
1,
Yumeng Gao
1,
Zhihui Jia
1,
Guangbin Wang
1,
Yifei Pei
1 and
Yong Liu
1,3,*
1
Henan Key Laboratory of Non-Ferrous Materials Science & Processing Technology, School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471023, China
2
Faculty of Engineering, Huanghe Science & Technology University, Zhengzhou 450063, China
3
Provincial and Ministerial Co-Construction of Collaborative Innovation Center for Non-Ferrous Metal New Materials and Advanced Processing Technology, Henan University of Science and Technology, Luoyang 471023, China
*
Author to whom correspondence should be addressed.
Coatings 2024, 14(10), 1300; https://doi.org/10.3390/coatings14101300
Submission received: 31 August 2024 / Revised: 7 October 2024 / Accepted: 9 October 2024 / Published: 11 October 2024
(This article belongs to the Special Issue Surface Modification of Advanced Transition Metal-Based Materials for Electrochemical Energy Storage)
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Abstract

:
Zinc-based batteries (ZBBs) have proven to be tremendously plausible for large-scale electrochemical energy storage applications due to their merits of desirable safety, low-cost, and low environmental impact. Nevertheless, the zinc metal anodes in ZBBs still suffer from many issues, including dendrite growth, hydrogen evolution reactions (HERs), corrosion, passivation, and other types of undesirable side reactions, which severely hinder practical application. The modification of Cu-based current collectors (CCs) has proven to be an efficient method to regulate zinc deposition and prevent dendritic growth, thereby improving the Coulombic efficiency (CE) and lifespan of batteries (e.g., up to 99.977% of CE over 6900 cycles after modification), which is an emerging research topic in recent years. In this review, we provide a systematic overview of the modification of copper-based CCs and their application in zinc metal anodes. The relationships between their modification strategies, nano-micro-structures, and electrochemical performance are systematically reviewed. Ultimately, their promising prospects for future development are also proposed. We hope that this review could contribute to the design of copper-based CCs for zinc-based batteries and facilitate their practical application.

1. Introduction

Nowadays, with the overuse of fossil fuel resources and the need for environmental protection, the exploitation of new, clean, and renewable energy sources has come to be the hotspot due to their low environmental impact [1,2,3,4,5,6,7,8,9,10]. Recently, clean and renewable energy sources, such as wind, solar, tidal, and geothermal energies have been extensively developed and could alleviate energy shortages to some extent [11,12,13,14,15]. Nevertheless, their intrinsic intermittence and fluctuation severely limit their widespread utilization [16,17,18,19,20]. Fortunately, electrochemical energy storage devices can effectively solve this problem [21,22,23,24]. Among them, lithium-ion batteries (LIBs) have been intensively investigated and developed over the last few decades, which is attributed to their high energy density and long-term sustainability [25,26,27,28]. Nevertheless, LIBs are also severely affected by limited lithium resources, expensive price and toxicity, as well as a flammable organic electrolyte, which have seriously hindered its further development and practical application [29,30,31,32,33]. Therefore, it is urgent to develop high-safety, cost-effective, and environmentally friendly new rechargeable battery systems to replace LIBs [34,35,36,37,38,39,40].
Recently, zinc-based batteries (ZBBs) have received considerable attention from researchers because of their high safety, cost-effectiveness, and environmental friendliness [41,42,43,44]. Moreover, Zn has many appealing merits as an anode material, such as low redox potential, high theoretical capacity, and low cost [45,46,47,48]. Currently, a great amount of effort has been made in research and innovations to develop and design ZBBs, mainly including zinc-ion batteries, zinc–air batteries, and static zinc–iodine batteries [49,50,51]. However, the Zn anodes are associated with various problems, including the short circuit of devices caused by serious dendrite growth, the low utilization of Zn caused by “dead Zn” and chemical corrosion, the production of by-products, and electrolyte consumption on the zinc anode caused by a hydrogen evolution reaction. These disadvantages severely restrict the further development of zinc–metal anodes in the energy storage sector [52,53,54,55,56]. Hence, for the further development of ZBBs, it is requisite to explore novel materials and strategies to protect the zinc anode, optimize the electrochemical microenvironment, and enhance battery performance. To address the problem of dendritic growth, researchers have exerted considerable effort and suggested numerous strategies, mainly including surface modification [57], electrolyte optimization [58], 3D host structure design, and modification of the separator [59,60,61]. In addition to the above methods, the application of the current collector (CC) is also crucial in Zn plating/stripping processes.
For the application of the current collectors in a high-performance Zn metal anode, selecting the suitable substrate material is important for improving battery performance. These substrate materials not only affect the conductivity but are also related to their safety and stability. Among the many substrate materials for current collectors, copper has suitable Zn affinity, has stable chemical/electrochemical properties in aqueous systems, and exhibits excellent cycling performance compared with other substrates (Al, Ti, Sn, Ag, Pb, Ni, carbon cloth, and stainless steel) [3,62]. Additionally, copper has many other advantages, such as being an abundant natural resource, ease of extraction, good ductility, electronic conductivity, and corrosion resistance. Moreover, copper can be recycled many times without loss of its mechanical properties, which is conducive to environmental protection [63]. Based on the above advantages, a Cu-based current collector (Cu CC) has become an essential component of ZBBs, mainly being used in the anode. It provides support to the active materials of the anode and, additionally, gathers electrons produced by the electrochemical process, directing them to the peripheral circuit and achieving an energy conversion between chemical and electrical energy [64]. In addition, the high chemical inertness of Cu CC properties maintains complex electrochemical stability, and its high robustness effectively stabilizes electrodes during charging and discharging processes [65]. More importantly, the application of Cu CC regulates zinc deposition and mitigates dendritic growth. Benefiting from the above advantages, many researchers have also studied the modification of Cu-based CCs and their application in a zinc metal anode, and the counts of annual publications have been rising steadily each year (Figure 1). For instance, in 2019, Shi et al. plated a layer of metallic zinc onto a copper foam surface by simple electrodeposition to direct the zinc to be uniformly deposited [66]. Later, Fang et al. constructed a Cu foam decorated by nanowire, which was characterized by excellent hydrophilicity and zincophilicity, improving the reversible nature of electro-deposition and electro-stripping through an in situ modification and heat-reduction approach [67]. This strategy of constructing a 3D Cu CC not only reduces the generation of zinc dendrites but also minimizes the volume change of the ZBBs. It is noteworthy that, in recent times, there have been several outstanding review articles that have emphasized tactics for stabilizing Zn anodes. For instance, in 2022, Yang et al. summarized the strategies for addressing the issues of Zn anodes in mild aqueous zinc-ion batteries [68]. Very recently, Nie et al. reviewed recent advancements related to the strategies for high-performance Zn anodes [69]. In addition, a few reviews on the Cu CCs for zinc anodes, which enhance the performance of zinc anodes, have emerged in recent years [70,71]. To our knowledge, however, there has been a scarcity of critical reviews that thoroughly concentrate on the modifications and uses of Cu-based CCs in Zn anodes, especially those that exclusively focus on various methods and materials, which have been rarely reported.
Herein, we review the recent advancements in Cu-based current collectors aimed at protecting the Zn anode. As shown in Scheme 1, we systematically categorized them into chemical modifications and structural modifications. Furthermore, they are further categorized into distinct groups based on the particular modifying methods and material characteristics employed by researchers. Furthermore, the modification of Cu-based CCs and their application in a Zn anode are concluded. Finally, several reasoned proposals for their design and next-phase research endeavors are also provided. It is hoped that this review will generate increased interest in the modification of copper-based CCs for Zn anodes and promote their practical applications.

2. Chemical Modification of Cu-Based CCs

As discussed in Section 1, the Cu-based current collector holds a significant position in the zinc-deposition process. Its properties can influence the morphology and homogeneity of the zinc-deposition layer. However, commercially unmodified Cu CCs contain a large number of breaks and holes in the micron to nanometer length range. These defect sites exhibit low charge-transfer resistance compared to other surface locations, making them ‘hot spots’ for rapid zinc nucleation and growth, severely affecting battery performance [72,73]. Fortunately, this problem can be attenuated by the chemical modification of Cu CC. Chemical modification refers to the introduction of chemical components other than copper, which includes physical–chemical techniques to alter the chemical composition of the ultimate Cu-based CCs. In this part, we categorize the chemical-modifying methods of Cu CCs, focusing primarily on the mechanism, benefits, and shortcomings of diverse modifying approaches, organized under the following two aspects: protective-layer modification and alloying modification.

2.1. Protective-Layer Modification

Currently, the protective-layer modification of Cu-based CCs can extend the cycle life of ZBBs by introducing zincophilic sites to lower the nuclear overpotential of zinc and lead to uniform zinc deposition. During the subsequent discussion, we classify and review this research based on the component materials of the protective layer, including metal/alloy protective layers, inorganic protective layers, and organic protective layers.

2.1.1. Metal/Alloy Protective Layers

Metals like Sn, Ag, Zn, and their alloys are coated on Cu substrates to form a protective layer that subsequently transforms into a Zn-M (M for metal) alloy during galvanization [74]. In this instance, the alloy performs the role of an “electric glue”, enhancing the zincophilicity, establishing an electrical connection between zinc and the copper substrate, and optimizing the adhesion. Some layers are coated on planar copper-based CCs and some on 3D copper-based CCs (e.g., 1D copper pillars and nanowires, 2D copper mesh, and 3D copper foam) to guide the distribution of zinc ion fluence and minimize the volumetric fluctuations during cycling. In addition, various plating processes have been employed, including the electrodeposition method [75], the electroless plating method [76], etc., depending on the materials used.
Within the plated metals, Sn and Ag have been extensively studied and are highly regarded. For instance, Jian et al. plated a copper mesh with a conformal nanoporous tin (Sn) layer, which served as a host (NSH) for the zinc anode [76] (Figure 2a). As demonstrated in Figure 2b, the symmetric cell utilizing Zn foil as its counter electrode exhibited consistent voltage profiles during plating and stripping for over 200 cycles at 2 mA cm−2 and 1 mAh cm−2. When assembled into the Zn||MnO2 battery, the cell with the Zn@NSH anode displayed specific capacities of 280 and 145 mAh g−1 at 0.2 and 2 A g−1, respectively (Figure 2c). Moreover, the battery displayed a high capacity of 164 mAh g⁻1 and retained 86.2% of its initial capacity after 1200 cycles at 1 A g−1 (Figure 2d). This is because of the fact that the newly introduced NSH provides a significant number of zinc nucleation sites, uniformizes the ion fluence and electrical field across the electrode surface, and inhibits the side effects occurring at high hydrogen release reaction overpotentials with Sn, resulting in zinc deposition without dendrites and a process of electroplating/stripping that is highly reversible. Additionally, akin to the research conducted by Jian et al., Wang and coworkers plated tin on copper foam to form a stable Sn@Cu foam as the substrate of zinc anodes [77]. This Sn@Cu foam not only inherits the advantages of copper foams but also inhibits the hydrogen evolution reaction (HER) and reduces the original barrier to heterogeneous nucleation of zinc deposition.
In addition to Sn and Ag, it is of interest to point out that zinc itself has also been employed in alloying the Cu current-collector surfaces. For instance, Zhang et al. fabricated a three-dimensional dendrite-free zinc anode by uniting a copper–zinc solid-solution interface and a Zn-oriented polyacrylamide electrolyte additive [78]. The symmetric cell can be cycled stably for 280 h at a high capacity of 4 mAh cm−2, with a voltage hysteresis as low as 93.1 mV, and when assembled as a Zn/MnO2 cell, the full cell achieves a long cycle life (600 cycles), with 98.5% capacity retention at 1000 mA g−1. This strategy produced a cost-effective Zn anode and electrolyte, making them ideal for commercial applications in Zn ion batteries. The above approaches primarily modulate the preliminary nucleation stage of zinc by introducing zincophilic metals or their alloys onto the copper foil, thereby introducing many nucleation sites and efficiently guiding the zinc deposit.

2.1.2. Inorganic Protective Layers

The inorganic protective layer, as the term implies, consists of a light coating of inorganic components that covers the CC. Depending on its composition, it is generally classified into two categories, namely (i) metal oxides-based inorganic protective layers and (ii) non-metal-based inorganic protective layers.
Currently, the modification of copper-based current collectors with metal oxides has gained much focus. For example, Zhang et al. developed a versatile bio-scaffold by synergistically utilizing a fractal copper branch array arranged in parallel in combination with a CTO-based coating layer (Figure 3a,b) [79]. The Zn@Bio-scaffold||Zn@Bio-scaffold symmetric cells showed a significantly higher average CEs ≈ 99.83% and cyclability of 4000 cycles at 5 mA cm−2 (Figure 3c). As shown in Figure 3d, when assembled into Zn||VOH full cells, the cell with the Zn@Bio-scaffold anode demonstrated capacity retention of approximately 48.2% after 500 cycles, accompanied by an average Coulombic efficiency of about 99.44%. It is because of the excellent conductivity and open structure of fractal copper arrays that not only did it promote electrolyte wetting and the diffusion of multivalent ions but it also significantly lowered the local current density during the plating of multivalent metals. In addition, the CTO-based coating effectively prevented interfacial side reactions and achieved uniform ion flux.
In addition to metal oxides, inorganic non-metallic materials have been investigated to modify copper-based current collectors. Within all non-metallic materials, carbon-based materials are primarily utilized for preparing Cu CC protective layers owing to their high strength, flexibility, excellent electric conductivity, and tunable morphological properties, including porosity and specific surface area (SSA) [80,81]. For example, An et al. designed N/O dual-doped three-dimensional porous carbon architectures on Cu foam CC (NOCA@CF). NOCA@CF is prepared from metal–organic framework precursors via an easy binary solvent method, followed by green vacuum distillation [82]. As displayed in Figure 4c, the average Coulombic efficiency of NOCA@CF remained approximately 95.7% for 350 cycles at a rate of 1 mA cm−2. Figure 4d shows the rate performance of Zn||LiMn2O4 batteries with Zn@NOCA@CF anodes at current densities ranging from 100 to 1000 mA g−1. Owing to its outstanding hydrophilicity, excellent conductivity, and large surface area, the NOCA@CF electrode achieves a uniform distribution of electric fields. This distribution reduces the local current density, thereby promoting homogeneous zinc deposition (Figure 4a). Figure 4b is the scanning electron microscope images of primitive NOCA@CF. Similarly, Liu et al. utilized a mechanically coated layer of nitrogen-doped porous carbon nanocages on copper foil. This approach realized a novel anode-free zinc energy storage system that does not require a Zn-rich anode [83]. The system achieved consistently high CE (99.6%) and low average hysteresis over more than 100 cycles, even at high current densities. Moreover, Li et al. developed a stable hydrophobic layer on the Cu foil, which consisted of repolymerized tetrafluoroethylene and carbonized ingredients (marked as (C2F4)n-C@Cu) using vacuum evaporation in order to guide even Zn2+ deposition without dendrites and side reactions (Figure 4e,f) [84]. The (C2F4)n-C@Cu electrode exhibited a low nucleation overpotential of 33.8 mV (Figure 4g). When assembled into symmetric cells, the (C2F4)n-C@Cu@Zn battery exhibited a small voltage hysteresis of 30.9 mV in the first cycle (Figure 4h). Also, the (C2F4)nC@Cu@Zn||V2O5 showed a discharge capacity of 140 mAh g−1 in the first cycle, and the discharge-capacity retention reached 88.35% after 2500 cycles at 3 A g−1(Figure 4i).

2.1.3. Organic Protective Layers

Various organic materials have also been extensively studied as protective layers for Cu-based CCs due to their structural flexibility, which allows them to accommodate volume changes during the cycling of metallic zinc anode-based batteries [85]. For instance, Yuan and coworkers coated a thick layer of epoxy resin on a pure copper rod as a copper substrate for the in situ observation of heterogeneous concentration changes caused by early-stage Zn nucleation and growth on copper substrates [86]. Jian et al. proposed and developed a new electrode using a polybenzimidazole (PBI) nanofiber framework on a copper substrate by way of a convenient electrospinning method [87]. The PBI nanofibers provided homogeneous nucleation sites for depositing zinc, and the polar functional groups on the surface of the nanofibers facilitated a homogeneous transport of Zn2⁺ (Figure 5a,b). When assembled into a Zn||MnO2 cell, the cell with the newly developed Zn anode showed an exceptional rate capability (120 mA h g−1 at 2 A g−1) (Figure 5c) and a capacity retention of nearly 100% after 1000 cycles at 1A g−1 (Figure 5d). Moreover, Kumar et al. fabricated a PAN copper (PAN@Cu) through the method of electrospinning to act as a CC for the zinc anode [88]. The corresponding symmetrical battery with this methodology showed 270 reliable cycles at 2 mA cm−2, realizing compact, flat, and dendrite-free Zn plating. This organic protective-layer-modified Cu CC’s structure can offer homogeneous nucleation sites for Zn2+ deposition, promoting uniform Zn2+ migration.

2.2. Alloying-Method Modification

The alloying method involves physically or chemically alloying copper with other metals to regulate the nucleation overpotential of zinc and optimize the zinc deposition. Li et al. developed a Cu2−xTe alloy (Cu1.8125Te) with a typical synthetic route (Figure 6a) [89]. After in situ electrochemical activation, Cu2−xTe was subsequently employed as the electrode in aqueous Zn-ion batteries. More impressively, when a Cu2−xTe//Na3V2(PO4)3 full cell is assembled and when tested in the C/2 range of 0.1–1.7 V, the Cu2−xTe alloy electrode demonstrated a 92% capacity retention after 1000 cycles (Figure 6b). Additionally, the charge–discharge curves over the 1000 cycles exhibited consistent characteristics, with an average discharge voltage of 0.94 V (depicted in Figure 6c). In addition, because of the high CE of Cu2−xTe of up to 100% and the slightly higher zinc storage potential of Cu2−xTe than that of Zn deposition and H2 evolution, the utilization of Cu2−xTe also avoids zinc dendrite formation and the degradation of water, thereby contributing to enhanced cycling stability. Similarly, Liu et al. developed a three-dimensional nanoporous Cu-Zn alloy current collector using primary brass (60 Cu–40 Zn) as the precursor, followed by the processes of thermal annealing, in situ electrochemical reduction, and dealloying (Figure 6d) [90]. For the purpose of generating an ordered porous structure, these nanowires pre-obtained by annealing typically have widths ranging from 50 to 80 nm and lengths of several microns (Figure 6e). The scanning electron microscopy images of the three-dimensional nanoporous Zn–Cu alloy reveal the representative nanoporous structure with a characteristic length of approximately 10 nm (Figure 6f,g). The symmetric cells with the 3D nanoporous Zn–Cu electrode exhibit ultra-stable charging and discharging capabilities for a duration of up to 300 h at 2 mA cm−2 (Figure 6h). Figure 6i presents the charge–discharge capacity and the corresponding CE at 4 mA cm−2. The three-dimensional nanoporous Zn–Cu alloy electrode maintained a discharge capacity of 1.58 mAh cm−2 at the 5000th cycle, which is 95.2% of the initial discharge capacity, displaying excellent cycle stability.

2.3. Summary

As discussed in Section 2, various chemical modification methods have been suggested that employ a range of chemicals and production processes to alter the performance of Cu-based CCs, mainly including protective-layer modification and alloying-method modification. Among these two strategies, protective-layer modification can enhance zincophilicity. The interaction between the substrate and Zn atoms can reduce the nucleation obstacles for Zn, increase nucleation sites, and lower the nucleation overpotential of Zn, achieving a uniform distribution of Zn nuclei on the surface of Cu-based current collectors, thus realizing uniform zinc deposition and extending the cycle life of ZBBs [91]. In addition, it also decreases the local current density by increasing the SSA during zinc plating–stripping, which is the most commonly used method. The composite ZBBs that utilize Cu-based current collectors with a protective-layer modification exhibit diminished nucleation barriers and enhanced Coulombic efficiency over extended cycling periods [71]. Modifying the Cu-based current-collector surface with protective-layer methods is straightforward to execute and conducive to large-scale production. In addition to the protective-layer modification, it is worth proposing that the Zn alloy anode formed by alloying-method modification can simultaneously serve as a zinc source to compensate for the irreversible loss of active zinc and as a zinc nucleus to ensure uniform zinc growth during the deposition process [92]. Based on the results above, chemical modification methods can efficiently improve the stability and the electrochemical performance of the zinc metal anode. Currently, although significant advancements have been made in Cu-based current collectors, the electrochemical properties, preparation methods, costs, and environmental impacts also should be carefully considered when designing the CC modification process.

3. Structural Modification of Cu-Based CCs

For applications in batteries, Cu CCs must exhibit several crucial characteristics, such as excellent chemical and mechanical stability, high electronic conductivity, and lightweight design, among others [93]. Ideal Cu CCs for a Zn anode should have a large SSA and display minimized volume changes in the process of zinc plating–stripping. Nevertheless, the planar Cu CCs cannot meet these requirements, which ultimately leads to an increase in inner pressure and interfacial roughness. To address these issues, some structural modifications, such as reduction methods and some other methods, are widely used. It is worth noting that the structural modifications incorporate both physical and chemical methods, finally resulting in changes to the morphology and structure of Cu-based CCs, yet maintaining their original chemical composition. The electrochemical performances of various Cu-based CCs-modified Zn anodes are shown in Table 1.
The reduction method involves oxidizing copper in a solution and then reducing it to copper, building a 3D structure in the process, and leaving only copper in the final 3D CC. The 3D structure serves to decrease the local current density and offers an additional zone for zinc deposition, thereby contributing to a slower growth of dendrites. Reduction methods generally involve several steps, such as oxidation, dehydration, and reduction, among others. For example, Zhang et al. in situ formed zincophilic copper nanoclusters on copper foil with the I3− electrolyte additive through an easy in situ electrochemical reduction approach [94]. First, a small quantity of I3− ion (10 mM) was introduced into the 2 M ZnSO4 electrolyte. Owing to the powerful oxidizing nature of I3−, the copper foil reacts rapidly with I3− to form CuI on its surface. Upon the electrochemical reduction of CuI to a potential of 0.1 V, the micron-scale particulates of CuI were converted into porous Cu nanoclusters (CuNCs) (Figure 7a). Figure 7b shows the SEM images of CuNCs. Simultaneously, Figure 7c illustrates that the zinc flakes did not merely coat the surface of the Cu nanoclusters. Instead, copper nano-particulates were interspersed among the zinc flakes, causing the development of a horizontally arranged zinc–copper composite structure. When assembled to the anode-free Zn-iodine battery (AFZIB) with a CuNC@Cu anode and a G/PVP@ZnI2 cathode, the AFZIB showed a specific capacity of 125.7 mAh g−1 at 1 A g−1(Figure 7d) and also achieved a gravimetric energy density of 162 Wh kg−1 (Figure 7e). Moreover, Fang et al. fabricated a nanowire-decorated copper foam with excellent hydrophilicity and zincophilicity to improve the reversibility of the plating and stripping processes via in situ modification and the thermal reduction strategy (Figure 7f) [67]. The Zn || MnO2 full battery with the Zn@Cu NW@Cu foam anode not only demonstrated a preliminary capacity of 179.6 mAh g−1 but also stabilized at 181.8 mAh g−1 after 3000 cycles, with a satisfactory average CE of ~99.7% at 2 A g−1 (Figure 7g). The excellent electrochemical performances of the Zn@Cu NW@Cu foam anode can be ascribed to the Cu NW@Cu foam substrate, which not only enhances the surface area to offer additional zincophilic nucleation sites but also promotes a uniform distribution of ions due to the capillary-like effect generated by the configuration of numerous copper nanowires.
In addition to the reduction methods, modulating the dominant crystal orientation upon the surface of copper-based collectors is also an efficient method for constructing a uniform deposition morphology and has been successfully used in the process of zinc deposition [71,95,96,97,98,99]. For instance, Hao et al. prepared a (111)-textured Cu current collector via a room-temperature electrodeposition strategy based on an optimized rate relationship between the diffusion and consumption of Cu2+ [100]. Attributed to the high lattice match between the (002) facet of Zn with the (111) facet of Cu, the deposition of Zn along its [001] orientation is achieved on the (111)-textured Cu. The mechanism of zinc deposited on the 111-Cu is described in Figure 8a. Figure 8b demonstrates the SEM images of Zn deposited on 111-Cu with a capacity of 4 mAh cm−2 at 1 mA cm−2. In addition, the cyclic voltammetry (CV) curve of the 111-Cu@Zn||111Cu cell displays the lowest overpotential and the highest peak current density, suggesting rapid reaction kinetics (Figure 8c). When assembled to the Cu||Zn cells, the batteries exhibited a long life span of over 2186 cycles (Figure 8d). Similarly, Wang et al. explored native planar copper foils with different dominant crystal facets. The symmetric cells using the Zn anodes with Cu-100 or Cu-110 exhibited the first cycle CE of 95% with plate-like deposition morphology and a life of 1000 h [101]. While these results clearly indicate that differences exist among various crystal facets, additional research is necessary to eliminate the current ambiguity regarding the selection of optimal facets. In addition, Çamurcu et al. developed a three-dimensional porous copper foam CC via the dynamic hydrogen bubble template (DHBT) method [102]. The outstanding electronic conductivity and open pore structure of the 3D porous copper scaffold facilitated the homogeneous deposition and stripping of zinc during cycling. The resulting electrochemical properties further demonstrate that the three-dimensional porous Cu foam CC can inhibit Zn dendrite growth, reduce polarization, enhance CE, and alleviate volume changes, highlighting the significant potential of the DHBT method for preparing a 3D porous current collector.
As outlined above, the electrochemical performance of Cu-based current collectors can be enhanced through the structural modification of Cu-based CCs. Among the structural modifying methods, the reduction method and the DHBT method can effectively reduce the local current density because of their high specific surface area and interstitial volume. Unlike the previous, the selected crystal plane orientation can be further used to regulate zinc deposition by the different deposition behaviors of zinc on different crystal planes. Based on the results obtained above, in general, some of the characteristics of structural modifications can be summarized as follows. (1) The large SSA prevents the growth of zinc dendrites. (2) The pore morphology achieves small volume changes. (3) They can control the diffusion flux of Zn ions and curtail the mass diffusion distance during Zn plating–stripping. (4) Modulating the dominant crystal orientation of Cu-based CCs can effectively construct a homogeneous zinc-deposition morphology. Currently, reducing the fabrication cost of the 3D CC and improving the overall stability are important to note.
Table 1. Cycling performance of symmetrical cells with modified Cu-based CCs.
Table 1. Cycling performance of symmetrical cells with modified Cu-based CCs.
Current CollectorsModification MethodsVoltage Hysteresis V a (V) (C1 c (mA cm−2))Lifespan T b h [C1 c (mA cm−2),
C2 c (mAh cm−2)]		Ref.
Modification strategy: Chemical modification
SCF Metal/alloy protective layers~0.04 (1)270 (1, 0.5)[75]
NSHMetal/alloy protective layers 0.0395 (2)300 (1, 1)[76]
Sn@Cu foam Metal/alloy protective layers 0.025 (1)1800 (1, 1)[77]
Cu-Zn@Cu meshMetal/alloy protective layers 0.0931 (2)280 (2, 4)[78]
Cu-AgMetal/alloy protective layers /400 (0.5, 0.125)[103]
Zn-Cu@Cu foilMetal/alloy protective layers ~0.0625 (0.5)400 (0.5 0.25)[104]
R-CF@SnMetal/alloy protective layers0.105 (5)700 (5, 1)[105]
Bio-scaffoldInorganic protective layer 0.026 (1)800 (1, 1)[79]
CF-CuInorganic protective layer 0.0146 (0.5)2200 (0.5, 0.25)[80]
Cu NBs@NCFsInorganic protective layer 0.0346 (2)450 (2, 1)[81]
NOCA@CFInorganic protective layer 0.045 (1)240 (1, 0.5)[82]
(C2F4)n-C@CuInorganic protective layer 0.0309 (1)1200 (1, 1)[84]
3DP-Cu@GrInorganic protective layer0.083 (5)300 (10, 2)[106]
BN-ZnCuInorganic protective layer0.041 (2)800 (1, 1)[107]
Cu5Zn8@NC NRAsInorganic protective layer0.0186 (1)7000 (1, 1)[108]
PBI-Cu Organic protective layer 0.035 (10)300 (10, 1)[87]
PAN-CuOrganic protective layer ~0.035 (2)~270 (2, 1)[88]
SA-Cu@ZnOrganic protective layer0.026 (1)2000 (1, 1)[109]
TNGsOrganic protective layer0.0335 (5)2800 (2, 1)[110]
Cu@Zn@CMC-ZnF2Organic protective layer/210 (10, 5)[111]
3D NP Zn-CuAlloying method~0.02 (2)300 (2, /)[90]
Cu/Al2CuAlloying method0.020 (0.5)4000 (0.5, 0.5)[112]
Sb/Sb2Zn3-HI@CuAlloying method0.020 (5)700 (5, 5)[113]
Modification strategy: Structural modification
Cu NW@Cu foamReduction method~0.0339 (1)3000 (1, 1)[67]
Cu (220)Other methods0.03 (5)~360 (/, 4)[95]
Cu (111)Other methods0.1467 (20)400 (10, 4)[100]
Cu (100) or Cu (110)Other methods~0.025 (2)1000 (2, 1)[101]
3D porous copper foam Other methods 0.178 (5)200 (5, 1)[102]
a voltage (V). b time (h). c C1: current density (mA cm−2); C2: specific area capacity (mAh cm−2).

4. Conclusions and Outlook

In summary, this review summarizes the modification of Cu-based CCs for zinc anodes and the recent advancements in their application for high-performance Zn metal anodes. The electrochemical performance of various Cu-based CCs-modified Zn anodes are presented in Table 1. A number of modification methods for Cu CCs were described, such as protective-layer modification, alloying-method modification, reduction-method modification, and other methods of modification. Among them, the protective-layer modification is the most widely used to modify Cu-based CCs, as it is versatile and simple. The modification of Cu CCs can deliver multiple benefits, which include (1) increasing the SSA, (2) decreasing the local current density, (3) reducing the nucleation overpotential, and (4) controlling the morphology of zinc deposition. Although some progress has been made on Cu CC modification, there are still several obstacles to overcome. In order to further promote the wide application of Cu-based current collectors in a high-performance Zn metal anode, suggestions for development can be put forward from the following aspects (Figure 9).
  • Mechanism exploration
Although there are many previous works examining the advantages of Cu-based CCs ZBBs, there are few studies on their mechanism of action. As a result, the mechanisms of modulation of zinc-ion deposition behavior by copper-based current collectors are not clear enough and still need to be studied in depth. In situ techniques, including in situ X-ray diffraction (XRD), in situ scanning electron microscopy (SEM), and in situ transmission electron microscopy (TEM), as well as in situ nuclear magnetic resonance (NMR), are highly beneficial for acquiring time-dependent information. Thus, more research using in situ techniques is needed to gain insight into Cu-based CCs for Zn anodes. For instance, Yin et al. characterized zinc deposition on different current collectors using an in situ super depth surface profile measurement microscope (SDM), which is conducive to further exploration of its regulatory mechanisms [115]. Additionally, the necessary theoretical simulation calculations (e.g., molecular dynamics (MD) simulation, DFT calculations, etc.) may also assist in clarifying the changes in surface–interface chemistry and physics during repeated charging and discharging. For instance, Ji et al. applied the finite-element analysis to simulate the deposition of zinc on copper with different crystal surfaces and found that, due to the different exchange current densities of different crystalline surfaces, the electrical field distribution on the surface of the current collector in the initial state is not uniform, resulting in the selective deposition of zinc in the region of high electric field strength and exacerbation of the inhomogeneity of the electrical field in the subsequent deposition process [71]. Very importantly, by exploring the role of Cu CCs in the zinc nucleation process and the improvement of battery performance, we are more likely to find more efficient structural and chemical ways to modify them and enhance the performance of the battery to a higher degree.
2.
New Composites
Currently, the main materials used for the chemical modification of Cu-based CCs are metal materials and their alloys or oxides and inorganic non-metallic materials, and some organic materials such as porous polybenzimidazole (PBI) nanofiber frameworks are also employed [87]. Among them, inorganic materials usually have high ionic conductivity, excellent mechanical strength, and thermal stability. However, they are often too fragile to control volume fluctuations during battery cycling. In contrast, organic materials generally possess a flexible structure but tend to have low ionic conductivity and inadequate mechanical strength. This indicates that additional efforts are necessary to develop inorganic–organic composites (e.g., ZIF), and there is a need to explore new types of modifying materials to tackle the aforementioned issues [42,72]. Additionally, the further exploration of the use of novel composites for well-designed 3D Cu-based CCs can not only improve the SSA but also provide multiple zincophilic sites to maximize the role of copper-based collectors in zinc metal anodes [25]. Therefore, the development of new types of CCs will offer more possibilities for the application of zinc metal anodes.
3.
Novel synthesis process
To date, the most frequently employed technique for modifying Cu-based CCs is electrodeposition. The electrodeposition process can be adjusted through the current, voltage, temperature, and other parameters to manage the thickness and nature of the cover layer in order to form a uniform, dense, and high-quality metal cover layer on the surface of the copper substrate and can be used for different shapes of the substrate, deposition speed, high productivity, and controllability [79,116]. However, the extensive practical implementation of this method is limited by the lack of comprehensive studies on the nucleation process and the regulation of the factors affecting crystal growth. In addition, electrodeposition methods consume large amounts of electricity in practice. Therefore, optimized electrodeposition process parameters need to be explored in the future to better modify Cu-based CCs.
In addition, many other technical methodologies have also been employed to modify the Cu-based CCs, such as the electrospinning method, the mechanical coating strategy, and the green vacuum distillation method. However, some of them remain in the initial phase and have seldom been employed. For example, the electrospinning method is an efficient method to prepare uniform pore structure and size distribution on the surface of Cu-based CCs, but it is rarely reported [87,88]. Thus, focusing more on rarely used synthesis methods may assist in the fabrication of new Cu-based CCs.
4.
Large-scale practical applications
Currently, some research on the application of Cu-based current collectors in Zn anodes has made significant progress. Nevertheless, some modifying materials (e.g., Ag) and production processes (e.g., vacuum evaporation) for Cu-based collectors are expensive and not suitable for practical production applications. In addition to this, another key issue is the lack of uniform test standards for ZBBs, such as the cycling test pact (current density, voltage limits, and C-rate) and the format of data presentation, among others. It is widely recognized that all of these factors can greatly influence battery performance, and consequently, variations in these factors may result in ambiguity when evaluating material performance. In addition, the battery system is an integrated whole. Thus, other factors must also be taken into consideration to further enhance the performance of zinc anodes [117,118,119,120], such as electrode design, electrolyte optimization, the creation of a new separator, etc. With the progress of science and technology, Cu CCs will offer significant application possibilities in practical applications.
We hope that this review can provide background and research progress on Cu-based CCs in a high-performance Zn anode. We also expect this review to promote the application of copper-based CCs in a high-performance Zn metal anode.

Author Contributions

Conceptualization, Y.L.; methodology, X.G., Y.X. and C.K.; validation, X.G., Y.G. and Z.J.; investigation, X.G., G.W. and Y.P.; writing—original draft preparation, Y.L. and X.G.; writing—review and editing, F.W., Y.L. and X.G.; funding acquisition, Y.L. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the Natural Science Foundation of Henan Province (242300420021), the Open Fund of State Key Laboratory of Advanced Refractories (SKLAR202210), the Student Research Training Plan of Henan University of Science and Technology (2022040, 2022044, 2023040), and the Undergraduate Innovation and Entrepreneurship Training Program of Henan Province (S202110464005).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. (a) The Pourbaix diagram of Cu (25 °C, the activity of Cu2+ is 1 and 10−3). (b) Pie diagram of the proportion of diverse modification methods for Cu-based CCs. (c) Bar diagram of the major Cu-based CCs for Zn anodes in recent years. Statistics from the Web of Science. (a) is adapted with permission [62]. Copyright 2018, Beijing: Science Press.
Figure 1. (a) The Pourbaix diagram of Cu (25 °C, the activity of Cu2+ is 1 and 10−3). (b) Pie diagram of the proportion of diverse modification methods for Cu-based CCs. (c) Bar diagram of the major Cu-based CCs for Zn anodes in recent years. Statistics from the Web of Science. (a) is adapted with permission [62]. Copyright 2018, Beijing: Science Press.
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Scheme 1. The advantages and modification methods of the Cu CC for Zn anode.
Scheme 1. The advantages and modification methods of the Cu CC for Zn anode.
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Figure 2. (a) Schematic diagram of the fabrication process for NSH. (b) Voltage profiles for charge–discharge cycles of zinc plating/stripping on PCH and NSH substrates. (c) Rate capability and (d) cycling stability of the MnO2 full batteries paired with various three-dimensional zinc anodes at a current density of 1 A g−1. (a–d) are adapted with permission [76]. Copyright 2021, Elsevier B.V.
Figure 2. (a) Schematic diagram of the fabrication process for NSH. (b) Voltage profiles for charge–discharge cycles of zinc plating/stripping on PCH and NSH substrates. (c) Rate capability and (d) cycling stability of the MnO2 full batteries paired with various three-dimensional zinc anodes at a current density of 1 A g−1. (a–d) are adapted with permission [76]. Copyright 2021, Elsevier B.V.
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Figure 3. (a) Optical image of a pinned honeybee, with an SEM image of bee hairiness shown in the inset. (b) Schematic demonstration depicting the multivalent metal plating–stripping process on the Bio-scaffold. (c) CEs of Zn plating–stripping on Cu foil and bio-scaffold at 5 mA cm−2 with a capacity of 1 mAh cm−2. The reversible behavior of zinc plating–stripping on the bio-scaffold is shown schematically in the inset. (d) Cycling stability of the Zn@Cu||VOH and Zn@Bio-scaffold||VOH cells at a current density of 2 A g−1. The corresponding DRT profiles of the cells after 1 cycle and 50 cycles are shown in the inset. (a–d) are adapted with permission [79]. Copyright 2022, Wiley-VCH.
Figure 3. (a) Optical image of a pinned honeybee, with an SEM image of bee hairiness shown in the inset. (b) Schematic demonstration depicting the multivalent metal plating–stripping process on the Bio-scaffold. (c) CEs of Zn plating–stripping on Cu foil and bio-scaffold at 5 mA cm−2 with a capacity of 1 mAh cm−2. The reversible behavior of zinc plating–stripping on the bio-scaffold is shown schematically in the inset. (d) Cycling stability of the Zn@Cu||VOH and Zn@Bio-scaffold||VOH cells at a current density of 2 A g−1. The corresponding DRT profiles of the cells after 1 cycle and 50 cycles are shown in the inset. (a–d) are adapted with permission [79]. Copyright 2022, Wiley-VCH.
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Figure 4. (a) Schematic illustrating the zinc deposition behavior on CF and NOCA@CF surfaces. (b) SEM images of primitive NOCA@CF. (c) CEs were tested at rates of 1 mA cm−2. (d) Rate performances of Zn||LiMn2O4 batteries with Zn@CF or Zn@NOCA@CF anodes. (e) The schematic illustrations on the preparation of the (C2F4)n-C@Cu substrate. (f) Schematic illustration of zinc plating on (C2F4)n-C@Cu and copper foil. (g) Nuclear overpotentials of (C2F4)nA-C@Cu and Cu foil. (h) The enlarged voltage profiles of the symmetrical cells during the first cycle are shown. (i) Long-term cycling performance of the (C2F4)n-C@Cu@Zn||V2O5 and 20 μm-Zn||V2O5 full cells at 3 A g−1. (a–d) are adapted with permission [82]. Copyright 2020, Elsevier B.V. (e–i) are adapted with permission [84]. Copyright 2023, Wiley-VCH.
Figure 4. (a) Schematic illustrating the zinc deposition behavior on CF and NOCA@CF surfaces. (b) SEM images of primitive NOCA@CF. (c) CEs were tested at rates of 1 mA cm−2. (d) Rate performances of Zn||LiMn2O4 batteries with Zn@CF or Zn@NOCA@CF anodes. (e) The schematic illustrations on the preparation of the (C2F4)n-C@Cu substrate. (f) Schematic illustration of zinc plating on (C2F4)n-C@Cu and copper foil. (g) Nuclear overpotentials of (C2F4)nA-C@Cu and Cu foil. (h) The enlarged voltage profiles of the symmetrical cells during the first cycle are shown. (i) Long-term cycling performance of the (C2F4)n-C@Cu@Zn||V2O5 and 20 μm-Zn||V2O5 full cells at 3 A g−1. (a–d) are adapted with permission [82]. Copyright 2020, Elsevier B.V. (e–i) are adapted with permission [84]. Copyright 2023, Wiley-VCH.
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Figure 5. Schematic demonstrations of zinc deposition (a) on a bare Cu electrode and (b) on a copper electrode modified with a PBI nanofiber framework. (c) Rate performance and (d) cycling performance at 1000 mA g−1 of Zn–MnO2 full battery. (a–d) are adapted with permission [87]. Copyright 2020, The Royal Society of Chemistry.
Figure 5. Schematic demonstrations of zinc deposition (a) on a bare Cu electrode and (b) on a copper electrode modified with a PBI nanofiber framework. (c) Rate performance and (d) cycling performance at 1000 mA g−1 of Zn–MnO2 full battery. (a–d) are adapted with permission [87]. Copyright 2020, The Royal Society of Chemistry.
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Figure 6. (a) Synthetic illustration of Cu2−xTe. (b) Cycling performance of Cu2−xTe at a rate of C/2. (c) charge–discharge profiles of selected cycles. (d) The fabrication process of three-dimensional nanoporous Zn–Cu alloy electrode. (e) The SEM image of zinc nanowire array. (f) Top-view and (g) cross-sectional SEM images of three-dimensional nanoporous Zn–Cu alloy electrode. (h) Discharge–charge voltage profiles of the three-dimensional nanoporous Zn–Cu alloy and zinc anodes with 2 mA cm−2. (i) Capacity retention as a function of cycle number for the three-dimensional Zn-Cu alloy anode at a galvanostatic charge–discharge current density of 4 mA cm−2. The inset displays representative voltage-time profiles during these charge–discharge cycles. (a–c) are adapted with permission [89]. Copyright 2021, Wiley-VCH. (d–i) are adapted with permission [90]. Copyright 2020, Wiley-VCH.
Figure 6. (a) Synthetic illustration of Cu2−xTe. (b) Cycling performance of Cu2−xTe at a rate of C/2. (c) charge–discharge profiles of selected cycles. (d) The fabrication process of three-dimensional nanoporous Zn–Cu alloy electrode. (e) The SEM image of zinc nanowire array. (f) Top-view and (g) cross-sectional SEM images of three-dimensional nanoporous Zn–Cu alloy electrode. (h) Discharge–charge voltage profiles of the three-dimensional nanoporous Zn–Cu alloy and zinc anodes with 2 mA cm−2. (i) Capacity retention as a function of cycle number for the three-dimensional Zn-Cu alloy anode at a galvanostatic charge–discharge current density of 4 mA cm−2. The inset displays representative voltage-time profiles during these charge–discharge cycles. (a–c) are adapted with permission [89]. Copyright 2021, Wiley-VCH. (d–i) are adapted with permission [90]. Copyright 2020, Wiley-VCH.
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Figure 7. (a) The CuNC@Cu anode. (b) The SEM images of CuNC@Cu. (c) SEM images and elemental mapping of zinc-deposition morphology on CuNC@Cu electrode at 1 mAh cm−2. (d) Galvanostatic discharge-capacity curves at 1 A g−1 of AFZIB with G/PVP@ZnI2 cathode || CuNC@Cu anode. (e) Cycling performance of AFZIB at 1 A g−1 with different batteries. (f) Preparation of Cu NW@Cu foam current collector. (g) Long-term cycling stability of Zn || MnO2 batteries with Zn@Cu NW@Cu foam and Zn foil at 2 A g−1. (a–e) are adapted with permission [94]. Copyright 2022, The Author(s). (f,g) are adapted with permission [67]. Copyright 2023, The Royal Society of Chemistry.
Figure 7. (a) The CuNC@Cu anode. (b) The SEM images of CuNC@Cu. (c) SEM images and elemental mapping of zinc-deposition morphology on CuNC@Cu electrode at 1 mAh cm−2. (d) Galvanostatic discharge-capacity curves at 1 A g−1 of AFZIB with G/PVP@ZnI2 cathode || CuNC@Cu anode. (e) Cycling performance of AFZIB at 1 A g−1 with different batteries. (f) Preparation of Cu NW@Cu foam current collector. (g) Long-term cycling stability of Zn || MnO2 batteries with Zn@Cu NW@Cu foam and Zn foil at 2 A g−1. (a–e) are adapted with permission [94]. Copyright 2022, The Author(s). (f,g) are adapted with permission [67]. Copyright 2023, The Royal Society of Chemistry.
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Figure 8. (a) Schematic diagram of the Zn nucleation and deposition process on the different Cu foils. (b) SEM images of Zn deposited on 111-Cu with a capacity of 4 mAh cm−2 at 1 mA cm−2. (c) CV curves of Zn plating–stripping on Cu foils at a scan rate of 1 mV s−1. (d) Long-term CE tested at 20 mA cm−2. Inset is charge–discharge curves of cells at selected cycles. (a–d) are adapted with permission [100]. Copyright 2024, Wiley-VCH.
Figure 8. (a) Schematic diagram of the Zn nucleation and deposition process on the different Cu foils. (b) SEM images of Zn deposited on 111-Cu with a capacity of 4 mAh cm−2 at 1 mA cm−2. (c) CV curves of Zn plating–stripping on Cu foils at a scan rate of 1 mV s−1. (d) Long-term CE tested at 20 mA cm−2. Inset is charge–discharge curves of cells at selected cycles. (a–d) are adapted with permission [100]. Copyright 2024, Wiley-VCH.
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Figure 9. Outlook and perspective study directions of the Cu CC for high-performance Zn metal anode. Top left: reproduced with permission from Ref. [87]. Copyright 2020, The Royal Society of Chemistry. Top right—reproduced with permission from Ref. [114] Copyright 2019, Elsevier B.V. Bottom left—reproduced with permission from Ref. [76]. Copyright 2021, Elsevier B.V. Bottom right—reproduced with permission from Ref. [84]. Copyright 2023, Wiley-VCH.
Figure 9. Outlook and perspective study directions of the Cu CC for high-performance Zn metal anode. Top left: reproduced with permission from Ref. [87]. Copyright 2020, The Royal Society of Chemistry. Top right—reproduced with permission from Ref. [114] Copyright 2019, Elsevier B.V. Bottom left—reproduced with permission from Ref. [76]. Copyright 2021, Elsevier B.V. Bottom right—reproduced with permission from Ref. [84]. Copyright 2023, Wiley-VCH.
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Gao, X.; Wang, F.; Xing, Y.; Kong, C.; Gao, Y.; Jia, Z.; Wang, G.; Pei, Y.; Liu, Y. Modification of Cu-Based Current Collectors and Their Application in High-Performance Zn Metal Anode: A Review. Coatings 2024, 14, 1300. https://doi.org/10.3390/coatings14101300

AMA Style

Gao X, Wang F, Xing Y, Kong C, Gao Y, Jia Z, Wang G, Pei Y, Liu Y. Modification of Cu-Based Current Collectors and Their Application in High-Performance Zn Metal Anode: A Review. Coatings. 2024; 14(10):1300. https://doi.org/10.3390/coatings14101300

Chicago/Turabian Style

Gao, Xiujie, Fei Wang, Yibo Xing, Chunyang Kong, Yumeng Gao, Zhihui Jia, Guangbin Wang, Yifei Pei, and Yong Liu. 2024. "Modification of Cu-Based Current Collectors and Their Application in High-Performance Zn Metal Anode: A Review" Coatings 14, no. 10: 1300. https://doi.org/10.3390/coatings14101300

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