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Construction of 3D Copper-Based Collector and Its Application in Lithium Metal Batteries

Chi Guo , Wang Zhang , Ji Tu , Shengrui Chen , Jiyuan Liang , Xiangke Guo

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 370 -383.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 370-383 DOI: 10.7536/PC210107
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Construction of 3D Copper-Based Collector and Its Application in Lithium Metal Batteries
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Abstract

Lithium metal is considered as an ideal anode for next generation high energy density secondary batteries due to its high specific capacity (3860 mAh·g-1) and low redox potential (-3.04 V vs standard hydrogen electrode). However, the "hostless" lithium metal is plated/stripped at the metal/electrolyte interface layer, inevitably growing dendrites and resulting in uneven distribution of current on the surface of lithium metal, which may puncture the battery separator and cause short circuit of the battery. In practical applications, by constructing three-dimensional current collector/lithium metal composite anode, the lithium deposition behavior can be effectively regulated and the dendrite can be suppressed, which further enhances the Coulombic efficiency, cycling life and rate performance. The research on this aspect has become a hot topic in recent years. In this review, firstly, the related principles and models of the suppression of lithium dendrite based on 3D current collector are summarized. Secondly, for the copper-based current collector, the preparation methods of 3D current collectors and their application in the protection of lithium metal anode are systematically summarized according to the dimension of substrate units. Finally, we summarize and outlook on the composite lithium anode constructed by 3D current collectors.

Contents

1 Introduction

2 Mechanisms of regulating action of 3D collector on inhibition of lithium dendrite

2.1 Surface nucleation growth model

2.2 Classical nucleation theory

2.3 Heterogeneous nucleation model

2.4 Space charge model

2.5 Deposition-dissolution model

2.6 Phase field model

3 Preparation of 3D current collector based on copper powder(0D)

4 Preparation of 3D current collector based on copper nanowire(1D)

5 Preparation of 3D current collector based on copper foil(2D)

5.1 Construction of a porous copper-based collector by alloying/dealloying

5.2 Modification of copper foil by metal/metal compounds

5.3 Modification of copper foil by inorganic nonmetallic materials

6 Modification of 3D current collector based on copper foam and copper mesh

6.1 Modification of copper foam and copper mesh by metal/metal compounds

6.2 Modification of copper foam and copper mesh by inorganic nonmetallic materials

7 Conclusion and outlook

Graphical abstract

Keywords

lithium metal / 3D copper based current collectors / dendrite / Coulombic efficiency

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Chi Guo, Wang Zhang, Ji Tu, Shengrui Chen, Jiyuan Liang, Xiangke Guo. Construction of 3D Copper-Based Collector and Its Application in Lithium Metal Batteries. Progress in Chemistry, 2022, 34(2): 370-383 DOI:10.7536/PC210107

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1 Introduction

Under the background of the rapid rise of high technology and the trend of information, the energy crisis has caused great challenges. In the field of electrochemical energy storage, people have been committed to seeking green, high energy density energy storage devices to meet the needs of high-end electronic devices with long endurance[1⇓~3]. Choosing appropriate anode and cathode materials is one of the methods to improve the energy density of batteries. Compared with traditional anode materials for lithium-ion batteries (such as graphite), lithium metal has a unique advantage in energy storage, and its ultra-high theoretical capacity (3860 mAh·g-1, about 10 times that of graphite 372 mAh·g-1) and mass energy density (5928 Wh·kg-1) are considered to be the most promising anode materials for the next generation of high-energy metal-based lithium-ion batteries, such as lithium-air and lithium-sulfur[4⇓~6][7,8].
However, due to the inherent high reactivity, infinite volume expansion and difficult control of dendrite growth of lithium metal, lithium metal batteries are hindered by low Coulombic Efficiency (CE), short cycle life and potential safety problems in practical use (Figure 1), and their commercial application has been limited[9,10]. In order to inhibit the growth of lithium dendrites, researchers have taken a series of measures from the origin of lithium dendrites, mainly including two aspects: (1) to construct a stable Solid Electrolyte Interface (SEI), such as using Electrolyte additives (such as Solid Electrolyte Interface, CsNO3 and Li2S8) to stabilize the structure and composition of SEI or using Solid electrolytes with high Young's modulus to buffer the growth of dendrites[11⇓~13][14,15]; (2) By constructing a "host" structure, such as a three-dimensional (3D) current collector structure and a nano-electrode structure, the surface effective current density of the electrode can be reduced, the electric field distribution can be stabilized, the volume expansion of lithium can be alleviated, and finally the dendrite growth can be inhibited[16⇓~18]. Because lithium dendrites may still grow in the gap of the interface layer during the infinite expansion of the volume of lithium metal anode, the construction of a stable solid electrolyte interface layer can not fundamentally solve the problem of lithium dendrite growth[19]. Therefore, the method of suppressing lithium dendrite growth by constructing "host" structures has attracted the interest of researchers in recent years.
The copper-based current collector has a wide range of applications in the traditional lithium-ion battery anode, because it has the following advantages: from the characteristics of the current collector itself, the copper-based current collector can effectively support the active material, connect the external circuit and transfer electrons[21]; The high chemical inertness of the copper-based current collector can maintain complex electrochemical stability; The high robustness effectively stabilizes the electrode during the charge and discharge process. For other negative current collectors, such as nickel-based current collectors and carbon-based current collectors, the advantages of copper-based current collectors are their high thermal conductivity (to dissipate ohmic heat and reaction heat), high conductivity (to maintain rapid charge transfer), and low cost (to achieve large-scale commercial production). The traditional current collector is a two-dimensional planar structure, which can not restrict the infinite volume expansion of lithium metal to homogenize the lithium ion flow and reduce the surface effective current density. Therefore, there is a need to construct a current collector with a three-dimensional structure of appropriate channels and use it for a lithium metal anode. Copper-based composite current collectors with three-dimensional structure can be divided into four categories according to the dimensions of their constituent substrate units: (1) 3D current collectors based on copper powder (0D); (2) construct a 3D current collector by taking a cop nanowire (1D) as a substrate; (3) construct a 3D current collector by taking a cop foil (2D) as a substrate; And (4) taking the foam copper or the copper mesh (3D) as a substrate to carry out surface modification to construct the 3D current collector. In this paper, the low-cost, simple and feasible preparation methods and modification approaches of copper-based three-dimensional current collectors in recent years will be summarized and analyzed from the perspective of different dimensional copper-based materials, and the application, research and status of copper-based three-dimensional current collectors in lithium metal anode will be summarized. In addition, in order to better understand the reasons for the suppression of lithium dendrites by three-dimensional current collector pairs, we also introduce the related lithium nucleation and growth models.

2 Regulating mechanism of three-dimensional current collector on lithium dendrite inhibition

A large number of experiments have confirmed that the reasonable design of three-dimensional current collector can effectively improve the cycle stability of composite lithium anode, but the mechanism has been rarely explored. Therefore, starting from the theoretical model of lithium nucleation and growth, we will reveal the control mechanism of dendrite growth by constructing three-dimensional current collectors.

2.1 Nucleation and Growth Model of Lithium Surface

As far as the characteristics of lithium metal itself are concerned, due to the relatively low binding energy between lithium atoms, the low surface energy and self-diffusion coefficient of lithium metal, and the lattice defects on the surface of metal, the free energy difference of lithium metal in different dimensions will be greater.This will cause the deposition and aggregation of lithium ions on the surface of lithium metal to form an unstable one-dimensional dendritic structure (rather than two-dimensional or three-dimensional) during the charging and discharging process of the battery[22⇓⇓~25].

2.2 Classical nucleation theory

To understand the nucleation process of lithium from the point of view of energy, the total free energy of lithium metal will change with the nucleation process of lithium, which directly affects the stability of lithium nucleus and the uniformity of lithium ion deposition after initial nucleation. The classical nucleation equation can reveal the relationship between lithium nucleus size, overpotential and current density, as shown in formulas (1), (2) and (3): Δ G n u c l e a t i o n is the Gibbs free energy of forming a spherical lithium nucleus with radius r, which is the sum of the volume free energy G v and the surface free energy γ[26⇓⇓~29]. γ N E refers to the surface free energy of the lithium core/electrolyte interface, V m refers to the molar volume of lithium, η refers to the nucleation overpotential of lithium, F is the Faraday constant, and r c r i t i c a l is the critical radius (in the thermodynamically and dynamically stable state). From these formulas, it can be concluded that the free energy change and interfacial energy change caused by the nucleation process of metal lithium can produce overpotential η (nucleation overpotential), which includes: (1) the initial nucleation overpotential produced by overcoming the nucleation barrier, which is caused by charge transfer[26,30]; (2) After the initial nucleation, lithium ions reach the surface of the current collector through the SEI film and preferentially deposit on the sites where lithium nuclei have been formed (lower energy barrier), which includes the overpotential caused by the diffusion of lithium ions and the overpotential caused by the interface formed between lithium ions and other substances (mainly electrolyte and SEI) during the deposition process. It can be seen from the formula (3) that since the surface free energy of lithium is constant under steady-state conditions, the change of overpotential η will directly affect the size of nucleation, that is, the nucleation volume of lithium is larger and sparsely distributed at low current density, and the nucleation overpotential is smaller; The lithium nuclei formed at high current densities are smaller, more densely distributed and have larger nucleation overpotentials (Fig. 2a, B). However, the classical nucleation theory does not explain other factors in the lithium nucleation process, such as the characteristics of the support substrate and the ion concentration of the solution, as well as the lithium deposition behavior after the initial lithium nucleation. In order to further study the mechanism of lithium nucleation and deposition process, the heterogeneous nucleation model and the space charge model have been proposed, which will be further elaborated in the following two sections.
Δ G n u c l e a t i o n = - 4 3 π r 3 Δ G v + 4 π r 3 γ N E V m
Δ G v = F | η | V m
r c r i t i c a l = 2 γ V m F | η |

2.3 Heterogeneous nucleation model

The heterogeneous nucleation model points out that the characteristics of the support (such as the structure and orientation of the crystal plane, as well as the current collector parameters such as impurity defects) will affect the nucleation behavior of lithium, and the process is controlled by both thermodynamics and kinetics: in equilibrium, lithium nuclei will grow to a critical size (corresponding to a critical radius r c r i t i c a l[25,29,31]; Under non-equilibrium conditions, the fast lithium deposition process will lead to the uneven morphology of lithium nuclei. In addition, the stress of the heterointerface will also induce the growth of dendrites. The theory also summarizes the relationship between the contact angle θ of lithium core/electrolyte and the critical free energy Δ G e q * as shown in formulas (4) and (5), where γ S E 、 γ S N and γ N E represent the interfacial free energy of substrate/electrolyte, substrate/lithium core and lithium core/electrolyte, respectively (Fig. 2 C), and the smaller the contact angle is, the better the wettability of substrate to lithium core is[4]. It can be seen from the formula (5) that the critical free energy Δ G e q * required for lithium nucleation is 0 under a special θ = 0 ° value condition, and the substrate (with superior lithium wettability) under this condition can greatly reduce the lithium nucleation barrier and induce a uniform nucleation process.
c o s θ = γ S E - γ S N γ N E
Δ G e q * = 1 3 ( 4 π r e q * 2 ) γ N E 2 - 3 c o s θ + c o s 3 θ 4

2.4 Space charge model

In order to explore the deposition behavior of lithium after the initial nucleation, Chazalviel proposed a space charge model to explain the influence of the ion concentration on the electrode surface on the structure and morphology of lithium deposition: under the influence of the electric field, the anions in the low concentration electrolyte will move to the positive electrode.Cations (mainly lithium ions) will move towards the negative electrode, and the result of continuous directional movement of ions is that there are too many cations and too few anions near the negative electrode (until the number of anions in the micro-area of the electrode surface is zero), which will produce local electronegative space charge areas and corresponding electric fields near the electrode surface (electrode/electrolyte interface layer)[31]. The unstable electric field will inevitably affect the diffusion, migration and subsequent deposition of lithium ions on the SEI film. In addition, the unstable SEI film will aggravate the consumption of lithium ions in the process of rupture and repair.Therefore, the problems of uneven lithium deposition, increased polarization voltage and dendrite growth are unavoidable under the condition of large deviation of ion concentration. Since then, it has been found that the growth of dendrites will occur when the current density exceeds a certain value (limiting current density), and the ion distribution in the solution is more uniform at low current density than at high current density, which can alleviate the instability of lithium anode and the growth of dendrites[27]. Therefore, reducing the effective current density can indirectly control the electric field distribution and achieve a stable lithium deposition process.

2.5 Deposition-dissolution model

The model combines the surface growth model of lithium and the classical nucleation theory to discuss the effect of interfacial stress on the dendrite growth in the process of lithium ion deposition. The detailed description is as follows: (1) Lithium ions migrate through the SEI film with ionic conductivity to the surface of lithium metal for deposition, and the SEI film is not damaged during the deposition process in a short time[25]; (2) After the initial nucleation, lithium tends to deposit at the nucleated sites, and the mechanical stress (Li metal/SEI film interface) generated by the continuous deposition process will lead to higher lithium ion conductivity at these sites (with more lithium deposition), which will further lead to the "tip effect" and the rupture of the SEI film; (3) In order to alleviate the stress, the inherent defects of lithium (lattice defects, low surface energy and low diffusion coefficient, etc.) And other factors will drive the deposited lithium to deform; (4) When the growth stress of lithium cannot be relaxed, the SEI film may be damaged. According to the surface nucleation and growth model of lithium, lithium will further grow into whisker-like (one-dimensional) lithium in the SEI cracks. (5) Under the action of stress, whisker-like lithium is easy to bend, break and dissolve, thus forming granular lithium and dead lithium.

2.6 Phase-field model

It is difficult to quantitatively describe the phase transition and interface movement during lithium deposition.All the physical and chemical parameters (such as barrier function, barrier height, electrostatic potential and lithium ion concentration, etc.) In the time-varying Li/SEI interface can be expressed by the functions of the phase-field order parameter ( ξ), and the phase transition problem can be indirectly transformed into the solving process of various equations for the order parameter ( ξ). Zhang Qiang et al. Of Tsinghua University analyzed the dendrite growth of structured metal lithium anode by using phase field model[32]. It Is found that at the initial stage of the kinetic process, the lithium ion deposition is not limited by the ionic/electronic conductivity of the solution due to the uniform distribution of the solution concentration.The composite anode with high specific surface area provides more electrochemical reaction sites, so the structural specific surface area SA (local total surface area of current collector/cross-sectional area of current collector) of the three-dimensional composite metal lithium anode has a linear relationship with the lithium deposition rate in the early kinetic stage. In the later stage of kinetics, the deposition of lithium ions is affected by the rapid consumption of lithium ions in the micro-area (near the nucleation point) of the electrode surface ( "tip effect"). At the same time, the non-uniform deposition of lithium and the growth of dendrites in the interstices will lead to the decrease of the pore (d) value, at this time, the composite anode with high specific surface area will bring smaller pore diameter.As a result, lithium ion diffusion and migration are hindered (especially at high current density and high charge capacity), resulting in the pore specific surface area SV (total current collector surface area/electrode pore volume) of the composite anode being inversely proportional to the lithium deposition rate at the late kinetic stage. Therefore, by controlling the specific surface area and pores of the three-dimensional framework, the three-dimensional framework can play its role to maximize the uniform deposition of lithium metal and avoid dendritic growth.
Of course, in order to truly understand the nucleation and dendrite growth of lithium, it is far from enough to rely on the above six models and theories. In addition, some models and theories, such as charge-induced growth model and SEI diffusion control model, also have an important impact on deepening the understanding of lithium deposition process[11].
Through the summary of the above models and theories, in order to inhibit lithium dendrite, the measures we can take from the perspective of various models are as follows: (1) The lithium surface nucleation and growth model proposes the characteristics and defects of lithium metal itself, and it is necessary to construct high diffusion coefficient and high surface energy components on the lithium surface to overcome the inherent shortcomings of lithium. (2) The classical nucleation theory points out that the η of overpotential produced in the nucleation process will directly affect the size and distribution density of lithium nuclei, and how to reduce the nucleation overpotential is a problem that needs to be considered. (3) The heterogeneous nucleation model suggests that the substrate wettability has a great influence on the deposition behavior of lithium, and it is necessary to construct a lithiophilic substrate to reduce the free energy required for lithium nucleation and achieve a stable and efficient nucleation process. (4) The space charge model explores the influence of ion concentration in the electrode surface micro-region on the lithium deposition behavior and dendrite growth. The dendrite growth is easier under the condition of high current density, and how to reduce the local current density needs to be studied. (5) The deposition-dissolution model illustrates the effect of stress on the dendrite during lithium deposition, and how to solve the problems such as the increase of interfacial stress caused by the volume expansion of lithium and the loss of lithium capacity and the growth of lithium dendrite caused by the "tip effect" caused by the increase of local current density, which need to be considered. (6) The phase field model quantitatively analyzes the influence of the specific surface area of the three-dimensional conductive framework on the dendrite. It is of great significance to construct a current collector with appropriate specific surface area and pore size for stabilizing the composite lithium anode. From the above six points of view, these problems will be solved by constructing a stable lithiophilic three-dimensional current collector with suitable pores. Therefore, in the following, we will summarize and analyze the construction methods of different three-dimensional copper-based current collectors in recent years and their applications in lithium metal anodes, and further deepen the understanding of these models for the construction of high-stability composite lithium anodes.

3 Preparation of Current Collector with Copper Powder (0D) as Substrate

Copper powder has large specific surface area and good formability and sinterability, which creates favorable conditions for the construction of three-dimensional current collector. Wang et al. used sodium chloride as a template to sinter copper powder in a simple and low-cost method, and then fully mixed the sintered powder with the binder polyethersulfone (PES) and the solvent N-methyl-2-pyrrolidone (NMP) to form a slurry, further prepared a thin film and subjected to heat treatment, and finally removed the template to obtain a 3D copper skeleton with an open porous micron size (Figure 3A)[33]. In order to evaluate the performance of the current collector and whether the battery assembled by combining it with lithium metal group can meet the standards of the actual industrial field, the researchers assembled the current collector and lithium sheet into a half-cell for coulombic efficiency test to evaluate the stability of lithium metal. Benefiting from the unique open porous conductive network structure, the current collector was stably cycled for 700 cycles at a current density of 0.5 mA·cm-2 and 400 cycles at a current density of 1.0 mA·cm-2, and the Coulombic efficiency of lithium deposition/exfoliation on the 3D copper skeleton was maintained above 95% (Figure 3 B).

4 Preparation of Current Collector Based on Copper Nanowire (1D)

Three-dimensional nanonetwork current collector based on copper nanowires can effectively control the deposition behavior of lithium due to its short ion transmission path, high conductivity and large specific surface area[34,35]. Due to the uniform distribution of lithium ions and electron transport, lithium metal can be uniformly deposited on the surface of copper nanowires and gradually confined to the three-dimensional framework, thus greatly inhibiting the growth of lithium dendrites. Lu et al. Used hydrazine to reduce copper nitrate in sodium hydroxide solution to prepare copper nanowires (CuNWs). The ethanol-hydrazine solution of CuNWs was poured into a mold and evaporated into a film to obtain a current collector with a self-supporting structure[36]. The current collector was subjected to half-cell testing and was able to cycle 200 cycles with an average Coulombic efficiency of 98.6% at current densities up to 7.5 mA·cm-2, and no dendritic lithium formation was observed by scanning electron microscopy characterization after cycling. Yan et al. prepared copper nanowires (CuNWs) by a simple aqueous solution reduction method, formed a membrane by simple suction filtration, and then uniformly coated graphene oxide solution on the membrane to obtain a composite current collector CuNWs @ GE[37]. The thus-obtained copper nanowire framework and its internal interstitial space facilitate the conduction process of electrons and can effectively accommodate lithium deposition. At the same time, the graphene layer wrapped around the framework of CuNWs acts as a flexible interface layer to protect the excess lithium deposition. The coulombic efficiency of lithium deposited on the CuNWs @ GE current collector can be maintained at more than 97% and more than 200 cycles, which is much higher than that of the unmodified two-dimensional copper foil current collector. In addition, Hong et al. prepared a heterogeneous fiber scaffold with conductivity gradient (CG) by using copper nanowires (high conductivity) and cellulose nanofibers (insulation). The CG system consists of a bottom layer with high conductivity, a top layer with electrical insulation and a middle layer with moderate conductivity[38]. The COMSOL multi-physics simulation data show (Figure 4) that the local reaction of lithium ion flux is more concentrated at the bottom where the conductivity is high, while the transport of electrons is fixed at the top. In addition, the intermediate layer with good conductivity exhibits an appropriate lithium ion reaction flux, and thus the system can provide dense lithium metal deposition through efficient electron and ion transfer. Thanks to the distributed lithium ion flux generated by this controllable conductivity, the CG host exhibits better lithium deposition/stripping behavior than the traditional copper foil and copper mesh current collector composed of copper nanowires. The half cell can be cycled stably for 120 cycles with a high coulombic efficiency of 96% at a current density of 0.5 mA·cm-2; In order to further evaluate the cycling stability of the current collector and the lithium metal composite anode, the deposition/delamination behavior of lithium on the current collector was investigated.The current collector was assembled with lithium sheets to form a symmetrical battery for testing, and the results showed that the current collector could operate stably for 250 cycles (500 H) under cycling conditions of 1.0 mA·cm-2 and 1.0 mAh·cm-2. In addition to the above modification approaches, three-dimensional nano-network structure current collectors can also be prepared by simply rolling copper nanowires: Chu et al. Prepared copper nanowire foils by rolling copper nanowire fabrics.When the thickness is reduced to ~ 1.5 μm, the surface quality can reach ~1.2 mg·cm-2, while the porous structure and rough surface can provide good wettability and adhesion for lithium metal, achieve uniform lithium deposition and alleviate the volume expansion of lithium metal[39]. There is no doubt that the application of this simple and low-cost three-dimensional current collector in lithium metal batteries will be brilliant.

5 Preparation of Current Collector Based on Copper Foil (2D)

The two-dimensional planar structure of copper foil can not provide enough space for lithium deposition. In the process of lithium deposition, metal lithium will be stacked unevenly directly on the surface of copper foil, which is easy to form dead lithium and lithium dendrites. By etching the copper foil (brass) or modifying some lithiophilic nanoarrays on its surface, the copper foil can be constructed into a three-dimensional conductive framework to provide accommodation space for lithium deposition and alleviate the interface stress in the process of lithium deposition. In addition, the lithiophilic nanoarray can further improve the specific surface area of the current collector, improve the wettability of the current collector to lithium, and reduce the nucleation barrier and nucleation overpotential of lithium. Lithiophilic materials can react with lithium to generate SEI film components with high diffusion coefficient and high surface energy during the battery cycle process, and the stable SEI film components can effectively regulate the distribution of space charge and reduce the local current on the surface of the composite lithium anode, so that the growth of dendrites can be alleviated to a certain extent. These methods are summarized below.

5.1 Porous copper-based current collector constructed by alloying/dealloying

A simple one-step hot-melt method provides a route for the preparation of alloyed 3D current collectors. For example, Jia et al. Treated copper foil with molten lithium metal at 500 ℃ in vacuum, and the lithium-copper alloy obtained was divided into two phases: lithium metal and lithium solid solution (Li-CuNWs network), in which the atomic ratio of lithium to copper in the lithium solid solution was 60:1[40]. The alloyed current collector forms a 3D framework in situ during cooling due to phase separation and solute distribution,Therefore, the current collector can provide built-in inert scaffolds (CuNWs) for lithium exfoliation and deposition to mitigate the volume change of lithium to achieve efficient lithium deposition behavior with good battery performance: it can be cycled stably for 500 cycles with high Coulombic efficiency (~ 98%) under half-cell test conditions of 1.0 mA·cm-2 and 1.0 mAh·cm-2, while exhibiting an ultra-high theoretical specific capacity of 3353 mAh·g-1, comparable to that of pure lithium anode.
Metal dealloying is the selective dissolution of a component of the alloy, which often produces a porous structure, which is also one of the ways to build 3D current collectors[41,42]. Zhang et al. used hydrochloric acid to corrode commercial brass to obtain a Cu-Zn porous framework, and obtained current collectors with different degrees of dealloying by controlling the corrosion time (Fig. 5a-e)[43]. Through the EDX cross section image, it can be observed that the Zn atoms gradually decrease with the increase of corrosion time (Fig. 5 f ~ H). It was found that the current collector treated with hydrochloric acid for 2 H had the best performance, and uniform lithium deposition could be obtained (Fig. 5 I ~ l), which could be stably cycled for 220 and 150 cycles at the current densities of 0.5 mA·cm-2 and 1.0 mA·cm-2, respectively. Coincidentally, Yun et al. Used a mixed solution of HCl and NH4Cl to treat the commercial copper-zinc alloy Cu0.64Zn0.36,12 h, and Zn was completely dissolved to obtain an interconnected 3D porous copper skeleton, which could be used as a current collector to circulate 250 times at a current density of 0.5 mA·cm-2.It was cycled more than 140 cycles at 1.0 mA·cm-2 current density and showed a high coulombic efficiency of 97%, and a long life of 1000 H was obtained in a symmetrical cell, which also showed great potential for practical application in the performance test of the whole cell[44].

5.2 Modification of Copper Foil by Metal/Metal Compound

Compared with dealloying to construct a 3D porous copper skeleton, it is simpler to construct a 3D porous skeleton current collector on the surface of a copper foil through a coating technology. For example, Liu et al. Coated micron copper powder, nano-copper powder, sodium chloride, carbon nanotubes and polyacrylonitrile (PAN) on copper foil, and then heat treated and removed sodium chloride to obtain 3D mixed structure Cu skeleton[12]. The micron cop powder in that structure can play a role in support the skeleton and inhibiting the agglomeration of the nano copper powder, and the nano cop powder can be used as a sintering additive to improve the mechanical strength of the skeleton. Based on the structural advantages, the coulombic efficiency of the current collector was maintained above 98. 8% after 500 cycles at 1.0 mA·cm-2 current density and 1.0 mAh·cm-2 surface capacity. The coulombic efficiency is 91.6% for 100 cycles when the surface capacity reaches the 4 mAh·cm-2. In addition, according to the heterogeneous nucleation theory, improving the wettability of the current collector to lithium metal can reduce the interfacial contact angle, which in turn can reduce the nucleation free energy of lithium[29]. The results show that the LixM alloy layer can be In-situ formed during the battery cycle when the copper foil is modified by the metal M (Ge, Sn, Al, Zn, Mg, Ca, Bi, As, In, etc.) Which can form an alloy with lithium. The strong bond cooperation between the lithium alloys can make the alloy layer have good lithium wettability, thus guiding the nucleation of lithium to achieve the purpose of promoting the uniform deposition of lithium ions and inhibiting the growth of lithium dendrites[45⇓⇓~48]. Ye et Al. First constructed a copper fiber array on the copper foil to obtain a 3D framework, and then attached an Al metal layer on the surface of the current collector framework by magnetron sputtering technology, benefiting from the two advantages of the high conductivity 3D framework and the alloying effect of Al and Li in the battery cycle process.The current collector can stably cycle more than 80 cycles (0.5 mA·cm-2, 2.0 mAh·cm-2) with high coulombic efficiency in the half-cell test, and the symmetrical cell can stably cycle 1700 h(0.5 mA·cm-2, 2.0 mAh·cm-2), and these performances are much higher than those of the unmodified copper foil current collector[49].
Limited by the "lithium-phobic" characteristics of copper foil, the deposition of lithium on copper foil usually shows a large nucleation barrier, which is easy to form lithium dendrites[50,51]. The results show that the ordered arrays of metal compounds (nanoneedles, nanowires, nanosheets, nanotubes, etc.) with high electron conductivity, short ion transmission path and good lithiophilic properties are constructed on the copper foil to act as the nucleation sites of lithium, which enables lithium metal to preferentially deposit at the interface between the electrode and the separator in a "top growth mode"[52]. Meanwhile, metal compounds on the surface of the current collector can react with lithium to generate compounds for stabilizing the SEI film in situ, and the uniform SEI film components can enable lithium ion flux and current density distribution to be uniform, thereby realizing a high-efficiency lithium deposition/stripping process[53⇓~55]. The modification of copper foil by metal oxides is the most studied direction at present. For example, Zhang et al. treated a copper foil with ammonia water to obtain a lithiophilic layer of copper oxide nanosheets growing perpendicular to the copper foil, and the current collector can ensure good electron transfer and rapid ion diffusion.Stable cycling of 180 cycles with a Coulombic efficiency of more than 94% was achieved at a current density of 1.0 mA·cm-2, and the symmetric battery was able to cycle stably for 700 H at a current density of 0.5 mA·cm-2. The stabilization of the lithium metal anode was achieved simply and effectively by this method[56]. Wang et al. Immersed the copper foil in the mixed solution of zinc nitrate and ammonia water, and obtained the copper foil with uniformly distributed ZnO array through vacuum heating and dehydration, and the current collector realized the uniform lithium deposition process.The Cu @ ZnO | Li half cell still showed a high Coulombic efficiency of 93.3% after 200 cycles at a current density of 5 mA·cm-2, cycling for more than 800 H with a current density of 1.0 mA·cm-2, a cycling capacity of 1.0 mAh·cm-2 and a low and stable overpotential of about 56.4 mV in a Li | Li symmetric cell[57].
However, oxides on the surface of the current collector tend to reduce the overall conductivity of the current collector. In order to balance high lithium ion conductivity and good lithiophilic characteristics, while obtaining faster lithium ion diffusion and more stable SEI film composition, researchers have shifted their attention to modifying the current collector with metal nitrides, fluorides and phosphides[58]. Lee et al. Treated the copper foil with ammonium persulfate and sodium hydroxide to obtain copper hydroxide nanosheets, and then treated them with nitrogen/ammonia mixture to obtain copper foil loaded with copper nitride nanocrystals. This 3D current collector can react with lithium metal to form a Li3N with high ionic conductivity to achieve uniform lithium ion flux and lithium deposition[35]. In the symmetrical cell test, the current collector was cycled stably for 100 H at a current density of 5.0 mA·cm-2 and a capacity of 5.0 mAh·cm-2. Chang et al. Used electrochemical corrosion method to turn brass into porous copper foil, and then used zinc acetate solution to obtain porous copper foil, which was dried to obtain ZnO @ Cu composite current collector, and then used ammonium fluoride solution to fluorinate ZnO @ Cu composite current collector.A 3D Cu @ ZnO/F current collector is obtained, the current collector can generate LiF which is an SEI film component with high ionic conductivity in situ during the lithium deposition process, and the mixed MIEC can effectively inhibit the growth of lithium dendrites[59]. The Li | Cu @ ZnO/F half cell was cycled stably for 300 cycles with a high Coulombic efficiency of 98% at 0.5 mA·cm-2, 1 mAh·cm-2, and the performance of the symmetrical cell was also better than that of pure copper foil. Zhang et al. Used glucose as a reducing agent to treat the copper foil to obtain a copper foil with uniformly grown copper nanowires, and then used phosphine gas generated by decomposition of sodium hypophosphite to phosphorize the copper foil at low temperature (100oC) to obtain a copper foil with a gradient of copper phosphide (Cu3P) along the cross section of the current collector[60]. In the cycle process of the battery, the Li3P generated by the in-situ reaction of lithium ions and Cu3P can be distributed on the surface of the copper foil current collector, and the Li3P has lower ion migration potential barrier and lower electron transfer potential barrier compared with Li2S and Li2O.This current collector possesses a high average Coulombic efficiency of 97.3% under cycling conditions with a lithium deposition capacity of 3 mAh·cm-2, and the symmetrical cell has a cycle life of 300 H at a current density of 2 mA·cm-2. In addition, the current collector with the modified gradient effect can provide a lithiophilic gradient and an ion/electron conductivity gradient, so that lithium metal is uniformly deposited at the electrode in a bottom growth mode, which also provides a feasible scheme for obtaining uniform high lithium ion flux on the surface of the electrode[38,53,61].
Table 1 summarizes some of the studies on the modification of copper foils with metal compounds and their performance in half cells. It can be seen that lithium nucleation and deposition can be more uniform and stable by introducing lithiophilic materials to the surface of copper foil, and the coulombic efficiency of the half-cell can be improved, which is of great significance for the design of electrodes that can induce lithium deposition to the main skeleton.

5.3 Modification of copper foil by inorganic non-metallic materials

Many non-metallic elements (such as Si, C) with high capacity can be used as anode active materials, but the influence of the internal microstructure and surface function of these materials on the deposition behavior of lithium has not received enough attention. At present, some research work has made progress, for example, Chen et al. Have vertically grown carbon nanofibers on copper foil as the main body of lithium metal anode, and the unique conical stacked graphite structure inside the nanofibers has improved the specific surface area and surface electrochemical activity of the electrode.The current collector can effectively mitigate the volume expansion of lithium metal during lithium deposition/exfoliation to maintain a stable electrode thickness (Figure 6a), showing a low overpotential (35 mV, 500 H) and high Coulombic efficiency (1 mA·cm-2, 2 mAh·cm-2, CE of 93% after 100 cycles) during long-term cycling[64]. Ren et al. Prepared cuprous oxide microspheres by solvothermal method using ethylenediamine as reducing agent. During the preparation process, nano-silicon powder was added into the solution, and Si and Cu2O were uniformly distributed on the copper foil by radio frequency magnetron sputtering method[65]. Due to the lithiophilicity of the Cu2O, the intercalation and deintercalation process of lithium and the alloying effect of silicon, the 3D current collector can still maintain a high coulombic efficiency of 98% after 100 cycles, and the average specific capacity loss is only 0. 24%. Non-metallic simple substance also has other functions: in order to obtain the porous copper skeleton, Lin et al. dropped the mixed slurry of nano-sulfur powder, carbon black and polyvinylidene fluoride on the surface of copper foil, and realized the conversion process of copper intermetallic compounds through annealing, hydrogen reduction and other treatments, and finally obtained the binder-free porous copper skeleton (Fig. 6B).As a current collector, it exhibits high coulombic efficiency (300 cycles, CE > 97.3%) and long life (> 880 H) at a current density of 1.0 mA·cm-2 and a capacity of 1.0 mAh·cm-2, and can cycle stably for 50 cycles even at a high areal capacity of 10 mAh·cm-2[66]. This idea of indirect conversion also provides a new method for researchers to prepare 3D current collectors.
In view of the current research work on 3D structure current collector based on copper foil (2D) current collector, the following points can be summarized: from the point of view of preparation approach, the 3D porous framework constructed by alloying and dealloying of copper foil can provide internal space for lithium deposition.However, the complex process of alloying and dealloying, as well as the pore size and uniformity of the prepared porous structure, will affect its further industrial development. From the performance point of view, the small pore size (< 2 μm) and limited pore volume of the dense porous copper foam made of copper-based alloy make it impossible to provide an effective path for ion migration and store a large amount of deposited lithium.As a result, the ability of lithium deposition will be greatly reduced (<2.0 mAh·cm-2), and the additional lithium layer will cover the porous matrix, which will lead to a series of problems such as volume expansion of lithium metal anode and lithium dendrite growth[36,67,68].
Moreover, three-dimensional structures can be constructed by coating or modifying nanoarrays on the surface of copper foils, and the reaction of surface-modified materials with lithium can generate new SEI components, which will further affect the behavior of lithium deposition. However, it is not difficult to find that the three-dimensional structure of the three-dimensional framework constructed on the basis of copper foil may be destroyed due to the lack of rigidity in the long-term cycle process, at this time, lithium deposition will become a host-free deposition mode again, which will lead to a series of problems of lithium dendrite. Therefore, the construction of copper current collector with more rigid skeleton structure is a direction of future development.

6 Modification of Current Collector Based on Copper Foam and Copper Mesh (3D)

Commercial copper foam and copper mesh have large pore volume and interconnected pores, which are conducive to accommodating a large number of lithium metal and transferring ions. Some works have confirmed that using copper foam and copper mesh as current collectors can effectively alleviate the volume expansion of lithium metal and obtain better battery performance. A typical case is the research of Li et al.: In this work, copper meshes with different pore sizes (pore size of 60 ~ 170 μm) were used, and lithium metal was embedded into the pores through mechanical pressure to manufacture 3D copper/lithium composite electrodes (Fig. 7 a ~ C). It can be clearly seen from the scanning electron microscopy images in Fig. 7 C that the pores of the copper meshes were filled with lithium metal[69]. In the battery test, the performance of the composite anode is much higher than that of the bare lithium metal anode, and the advantages of the composite anode can be reflected by low voltage hysteresis, small interface impedance and long cycle life. However, the large pore size (100 ~ 200 μm) and lithiophobic surface of the copper foam lead to mossy and dendritic lithium loosely accumulated in the pores, which can not provide good electrical contact and sufficient support for lithium in the process of lithium deposition/exfoliation.Lithium metal will be separated from the copper skeleton to form dead lithium. Similarly, these problems will also occur in copper mesh current collector system batteries, so it is necessary to modify the copper foam and copper mesh current collector[70,71][33,67]. Because copper foam and copper mesh have their own 3D structure compared with copper foil, most of the current modification work of copper foam and copper mesh is directed towards the preparation of mixed ionic/electronic conductive scaffolds (MIEC)[72]. The modification of copper foam and copper mesh current collectors can refer to copper foil-based current collectors, but there are still some differences in the way they construct composite lithium anodes: composite lithium anodes with copper foil, copper foam and copper mesh as current collectors can be prepared by electrodeposition.The copper foil-based lithium metal anode can also be obtained by simple rolling or repeated stacking (fig. 7d), while the lithium metal anode of the copper foam and copper mesh-based current collector can be prepared by the hot melt method (molten lithium injection method), which is simpler than the electrodeposition method to prepare the composite lithium anode[73]. In addition, the composite lithium anode prepared by the hot melt method can maintain a stable volume and shape, and the surface wettability of the current collector can be intuitively observed during the preparation process, and the lithiophilic property of the current collector can be quickly judged (fig. 8)[74⇓⇓⇓~78][79].

6.1 Modification of copper foam and copper mesh by metal/metal compound

By modifying a metal capable of forming an alloy with lithium on the copper foam or copper mesh, the current collector can be transformed into a lithiophilic framework, thereby reducing the nucleation barrier of lithium and guiding the uniform deposition of lithium, and finally effectively inhibiting dendrite and dead lithium. For example, Ye et al. Used the electrodeposition method to deposit metal zinc on the foam copper. In order to prove the superiority of the alloy structure, they set the half-cell test conditions as 1.0 mA·cm-2 and 3.0 mAh·cm-2. As a result, the current collector could still cycle 87 times with a high coulombic efficiency of 97.6%, while the foam copper could only cycle 35 times with a coulombic efficiency of less than 90%[80]. When the cycle capacity increases to 5 mAh·cm-2, the 3D Cu-Zn alloy current collector can still be cycled for 70 cycles with an average coulombic efficiency of 98%, while the cell with copper foam fails after only 23 cycles. The research on the modified copper mesh includes the work of Luan et al. In this work, the copper mesh is used as a substrate, and a Sn layer with good lithiophilic property is plated on the copper mesh by an electrodeposition method, and the Sn layer is used as a current collector to uniformly induce lithium nucleation.The deposition and exfoliation processes of lithium ions after nucleation were stabilized, resulting in dendrite-free lithium deposition behavior and excellent stable cycle performance (the nucleation overpotential in the half-cell test was 2.8 mV, which was very close to that of gold and silver[81]; It can be cycled 900 times under 1.0 mA·cm-2, 1.0 mAh·cm-2 cycle conditions, and maintain a high coulombic efficiency of 98.6%).
Lithiophilic metal compounds modified copper foam and copper mesh can not only increase the specific surface area of the current collector to provide enough space for lithium deposition, but also reduce the local current density on the surface of the current collector to achieve uniform charge distribution. Table 2 summarize some examples of cop foam current collectors modified with lithiophilic metal compounds and their performance in symmetric cell. Among them, there are many studies on the modification of oxides, such as modifying Cu2O, CuO, CuO x [ 86 ], ZnO and Al2O3 on the surface of copper foam[82,83][84,85][61,87][61]. These oxides will react with metal lithium in the process of melting lithium (Fig. 8A shows the preparation process of ZnO nanoarrays grown on copper foam and its performance as a current collector in the experiment of melting lithium).Lithium melts into the skeleton of the current collector (as seen in the SEM image of fig. 8A) and generates a lithiophilic conductor Li2O in situ, which can adjust the distribution of lithium ion flow during the battery cycle to achieve uniform lithium deposition[88]. Similarly, using copper mesh as current collector, Huang et al. Used a simple air annealing method to achieve a uniform surface zinc oxide coating on brass (copper-zinc alloy) mesh, and the low stacking fault energy of brass ensures the release of chemical energy to drive the diffusion of surface atoms. The modified brass mesh as current collector can be cycled stably for 1200 H under the symmetrical battery cycling conditions of 1.0 mA·cm-2 and 1.0 mAh·cm-2, which is much longer than that of the copper foil current collector for 300 H under the same test conditions. Because the transfer barriers of lithium ions and electrons in oxides are generally high, researchers are exploring the deposition behavior of metal sulfides (such as Cu2S), metal nitrides (such as Cu3N) and metal phosphides (such as Cu3P) with high conductivity[71,89][79][90]. For example, Park et al. treated the copper foam on which the copper hydroxide nanorods were grown with ammonia (NH3) to obtain a lithiophilic copper nitride film (Cu3N) without significantly changing the structure of the current collector. Compared with the unmodified copper foam, the molten lithium can penetrate into the internal skeleton of the current collector after nitridation treatment more quickly (Fig. 8C)[79]. In addition, since the nitride anion (N3-) has a stronger binding ability with lithium metal, the Cu3N reacts with Li during the lithium melt injection to be converted into a Li3N having a high lithium ion conductivity (around 10-3S·cm-1 at room temperature) and a low conductivity (<10-12S·cm-1),Can effectively stabilize the metallic lithium anode, thereby exhibiting a lower overpotential and a longer cycle life (stable cycling for 400 H at a current density of 1 mA·cm-2 and an areal cycling capacity of 3 mAh·cm-2) during the symmetrical battery cycling test[35,91⇓ ~93].

6.2 Modification of Copper Foam and Copper Mesh by Inorganic Nonmetal Materials

Some inorganic non-metallic materials, such as carbon and silicon, can be used to modify copper foam and copper mesh. Carbon materials can be used as the support of lithium metal anode due to their excellent conductivity, but it is difficult to induce the uniform deposition of lithium due to their lithiophobicity[94]. In recent years, some studies have shown that the introduction of lithiophilic groups into the carbon skeleton can reduce the nucleation barrier of lithium and improve the lithiophilicity of carbon materials. Therefore, many carbon materials rich in lithiophilic organic functional groups, such as nitrogen-doped graphene and redox graphene, have been used to modify copper foam[95,96][97]. Yu et al. treated copper foam with graphene oxide (GO), and the spontaneous redox process allowed CuO and reduced graphene oxide (rGO) to be generated in situ on the surface of the treated copper foam, which could be stably cycled for 350 cycles with a high coulombic efficiency of 98.5% at a current density of 1.0 mA·cm-2 and an areal capacity of 1.0 mAh·cm-2 in a half-cell test[98]. For silicon materials, the transition of the current collector substrate from lithiophobicity to lithiophilicity can be realized by means of the interfacial reaction between lithium and silicon. Liang et al. Introduced silicon coatings on copper foam and porous carbon film respectively, which showed good wettability to metal lithium in the process of lithium melt injection[99].
Based on the research work of composite lithium anode with copper foam and copper mesh current collector, the following conclusions can be drawn: although the three-dimensional rigid skeleton of copper foam and copper mesh can provide space for lithium,However, its low specific surface area and large porosity will lead to the loss of lithium capacity, while the large mass ratio of foam copper and copper mesh will also lead to the loss of energy density of the battery. In order to improve the specific surface area and lithiophilicity of copper foams and copper meshes, it is necessary to construct lithiophilic materials in their frameworks. The modified copper foam and copper mesh can not only be used to construct composite lithium anode by electrodeposition method, but also be used to prepare composite lithium anode by melt lithium injection method. Compared with the electrodeposition method, the operation of the lithium injection method is simpler and the wettability of the current collector can be directly compared in the melting process, so the method has a certain industrial application prospect.

7 Conclusion and prospect

Lithium metal has been regarded as the "holy grail" anode material of lithium batteries because of its high energy density and low reduction potential. However, the problems of lithium dendrite growth and volume expansion in practical applications greatly limit its commercial application, so it is still a challenging task to achieve a stable lithium metal anode. The three-dimensional current collector can effectively inhibit the growth of lithium dendrites and the volume expansion of lithium metal, and has a commercial prospect.
In this paper, the related principles and models of lithium dendrite inhibition based on three-dimensional current collectors are summarized, and then the methods of constructing three-dimensional copper-based current collectors with different dimensions of copper substrates and their applications in lithium metal anodes are summarized. Through the above summary and analysis, we can conclude that the ideal three-dimensional current collector for composite lithium anode should include the following aspects: excellent lithiophilicity, that is, having a nucleation overpotential equal to zero or close to zero with metal lithium; Have continuous ultra-high conductivity; Have a large specific surface area and a uniformly distributed conductive structure; A porou structure having excellent mechanical strength and electrochemical stability. However, how to use a simple method to prepare a current collector material for three-dimensional composite lithium anode with these advantages is still a serious technical and manufacturing challenge in the future.
Although lithium dendrite can be suppressed to some extent by constructing three-dimensional current collector/lithium metal composite anode materials, due to the complexity of electrochemical process, there are other factors, such as electrolyte, SEI components and test conditions (current), which will affect the uniformity of lithium deposition. Therefore, we also need to balance various factors to maximize the elimination of lithium dendrites. If the three-dimensional composite metal lithium anode is combined with the solid electrolyte, not only the advantages of the three-dimensional current collector can be brought into play, but also the cycle life of the battery can be further improved and the safety of the battery can be improved by optimizing the interface between the composite lithium anode and the solid electrolyte. In a word, the construction of three-dimensional composite lithium anode is of great significance to promote the commercialization of lithium metal batteries.

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Funding

National Natural Science Foundation of China(51802122)

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