Ultrafast microwave-induced synthesis of lithiophilic oxides modified 3D porous mesh skeleton for high-stability Li-metal anode
Introduction
Lithium (Li)-ion batteries (LIBs) have been widely used in the field of electric vehicles and large-scale energy storage due to their high energy density, low self-discharge, long service life, strong environmental adaptability, and no memory effect[1], [2], [3], [4], [5], [6]. Nevertheless, the energy density of conventional graphite anode is close to its theoretical capacity (372 mA h g−1), and the space for future improvement is very restricted[7], [8], [9], [10], [11], [12]. Hence, Li metal anode returns to the public with its very high theoretical specific capacity (3860 mA h g−1)[13], [14], [15], [16]. However, the wide application of Li metal anode is still hampered by huge volume change and uneven deposition of Li during charging and discharging. The uneven deposition of Li leads to the generation of “dead Li”, dendrites and the rapid consumption of electrolyte, which reduces the coulombic efficiency (CE) and shortens the service life of the battery[17], [18], [19]. If the dendrites penetrate the diaphragm causing a short circuit, it may lead to thermal runaway of the battery, resulting in fire or even explosion. Therefore, guiding the homogenous deposition of Li is important to improve the electrochemical stability of Li metal anode[20].
The current mainstream solutions can be roughly divided into two categories. Firstly, the uniform solid-electrolyte interphase (SEI) with higher strength and elasticity can be constructed through electrolyte modification[21], [22], [23], [24], interface modification[25], [26], [27], [28] or artificial SEI preparation[29], [30], [31], [32]. It can improve the chemical and mechanical stability of LMB anode interface. The modification of SEI can only inhabit the growth of dendrites to a certain extent, but cannot fundamentally solve the generation of dendrites[33], [34]. Secondly, it is possible to design a 3D skeleton as the current collector for Li deposition, such as 3D Cu[35], [36], Ni foam[37], [38] and porous carbon[39]. The larger specific surface area of 3D skeleton can alleviate the volume change of Li metal anode[40], [41], [42], [43], [44]. According to the Sand’s model, the large specific surface area can reduce the current density on the electrode surface, thus inhibiting the generation of Li dendrites[45], [46], [47], [48]. However, the original 3D skeleton, Cu foam or Ni foam, has a poor affinity for Li metal. In the actual deposition process, Li metal tends to deposit at the top of the current collector due to relatively high nucleation overpotential[49]. Hence, the 3D current collector needs further optimization to better guide the uniform deposition of Li.
Recently, many researchers have focused on introducing lithiophilic matrix into 3D skeleton to improve the lithiophilic properties. 3D current collectors Mo@MoO3 mesh[50], 3D TiO2/ZnO[51], Cu3P/CoP@C/CNT[52] and Canvas Ni-Ag2S[13] exhibit good electrochemical properties. Nevertheless, the existing methods of synthesizing 3D current collector with lithiophilic matrix, such as hydrothermal method[53], chemical sedimentation[54], [55] or electrochemical deposition method[56], [57], are multi-step reactions. These synthetic methods are relatively complex, time-consuming, and high requirement for equipment, so they are not suitable for large-scale application. Therefore, it is urgent to explore a fast and convenient method to synthesize 3D lithiophilic current collector. Compared with traditional synthesis methods, microwave-induced synthesis is fast and convenient. Microwave heating has a unique position in the field of material processing because of its selective heating and instantaneous heating properties[58], [59]. The strong coupling between microwave and polar solvent can effectively control the synthesis of materials in polar liquid phase[60], [61], [62]. The “skin effect” of electrons in a good conductor metal under microwave radiation can be used to construct porous structures on the surface of the conductor[63]. Hence, a reasonable design of microwave-induced synthesis method can achieve rapid synthesis of 3D current collector with lithiophilic matrix.
In this work, a 3D porous mesh skeleton with lithiophilic oxides (FeO and CuO) layer is obtained by microwave-induced synthesis in a short time. The 3D porous structure is controlled by adjusting the microwave-induced reaction time. The 3D porous structure can provide sufficient space for Li deposition and make the electric field distribution uniform. The lithiophilic oxides (FeO and CuO) can greatly improve the Li affinity of skeleton and low the nucleation overpotential of Li. The novel skeleton used as Li metal anode shows favorable cyclic performance with steady CE and cycle stability up to 1000 h (2500 cycles at 5 mA cm−2, 1 mA h cm−2). The full-cell assembled with the lithiophilic skeleton and commercial LiCoO2 (LCD) cathode shows good capacity retention rate. The capacity retention rate of 500 cycles is more than 87.2 % at 0.5C.
Section snippets
Result and discussion
Fig. 1a is the schematic diagram of preparation of 3D porous skeleton. The commercial brass mesh (CBM) was immersed into Fe(NO3)3 solution (0.025 M) under microwave condition. The formation of porous structure is related to the etching of Zn in CBM and follows the reactions: 2Fe3++4e-→Fe2++Fe (1); Zn-2e-→Zn2+ (2) [63] NO3– may decompose into NOx gas under microwave heating, which can act uniformly on the surface of the material and form pores. In the synergistic effect of Fe3+ corrosion and NO3–
Conclusion
In summary, a 3D porous lithiophilic skeleton for Li metal anode is obtained from the commercial brass mesh by microwave-induced methods in a short time. The 3D structure can reduce the local current density and inhibit the growth of dendrites. The lithiophilic oxides (FeO and CuO) can increase the affinity of Li and guide a uniform deposition of Li. The half-cells and symmetrical-cells assembled by MW270-Fe skeleton exhibit high coulombic efficiency and long stable cycle performance (1000 h at
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
The authors are grateful for the financial support from the National Natural Science Foundation of China (No. 51871135). The authors acknowledge the assistance of Shandong University Testing and Manufacturing Center for Advanced Materials. The authors thank shiyanjia lab (www.shiyanjia.com) for the support of HRTEM test.
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