Extraordinary dendrite-free Li deposition on highly uniform facet wrinkled Cu substrates in carbonate electrolytes
Introduction
Li metal has been considered as the most ideal anode material due to its high theoretical specific capacity (3862 mAh g−1), low gravimetric density (0.531 g cm−3) and the lowest reduction potential (−3.04 V vs. SHE) [1], [2], [3], [4], [5], [6]. However, it has a critical limitation for its use as an anode. The non-uniform distribution of Li on the anode side during repeated charge/discharge process generates Li dendrites and dead Li, which causes the low Coulombic efficiency and safety problem [2], [3], [6], [7]. Thus, the control of Li deposition on anode in Li metal battery is the most important factor for realizing their practical application.
To obtain uniform Li deposition, various strategies have been suggested including the interface control [8], [9], adopting a protective layer [10], [11] and structural design of electrode [12], [13]. Among the strategic methods, structural control of current collectors as a key factor of the electrode design could be important role for mitigating the lithium dendrite formation, in which most of the current collectors used in the Li battery system are planar shape and have a number of small grains with randomly oriented planes [14]. This conventional Cu substrate could not guarantee a uniform Li deposition without mossy and needle-like dendritic Li formation. As strategic methods of current collector modification for uniform Li deposition, three dimensional (3D) Cu frameworks and adopting a seed material on current collectors can homogeneously disperse the electric field and Li+ flux [4], [15], [16], [17], [18], [19]. However, there has been not much research on the current collectors for uniform Li deposition thoroughly. In the present study, we designed for the first time a wrinkled copper (Cu) anode with a specific crystal highly uniform [100] plane as Cu substrates for highly uniform lithium deposition in carbonate-based electrolyte. The Cu substrates modified by silver (Ag)-assisted chemical vapor deposition (CVD) graphene growth method exhibited extraordinarily uniform Li nucleation and growth, resulting in the significantly improved battery performance including good cyclability with high Coulombic efficiency (CE).
We show that the deposited lithium is uniformly distributed across the entirety of the Cu substrate surface. This resulted in the elimination of dendritic lithium formation and long-term electrochemical cycle life with 99% CE for more than 250 cycles in a Li/Cu half-cell. Additionally, 90% capacity retention was achieved for more than 200 cycles without noticeable capacity decrease up to 500 cycles in a LiFePO4/Li full-cell, which was obtained in a carbonate-based electrolyte.
Section snippets
Synthesis of wrinkled Cu via chemical vapor deposition graphene growth process
The overall procedure for fabricating a wrinkled copper (Cu) substrate by chemical vapor deposition (CVD) graphene growth process is presented in Fig. 1. It is important to note that Cu is a well-known substrate material for CVD-graphene growth synthesis [20], [21]. During the synthesis, Cu undergoes surface changes due to the thermal energy expansion difference between the grown graphene and Cu [22], [23]. In this study, we utilized the Cu foil obtained after the CVD process by using graphene
Conclusion
We developed a novel Cu substrate with sharp wrinkles and a highly uniform [100] facet for the dendrite-free deposition of Li using a CVD graphene-growth process. The electrochemical results demonstrated the superior cyclic stability of this Cu substrate in both LiFePO4/Li full-cell and Li/Cu half-cell tests, even when a carbonate-based electrolyte was used. The ex situ AFM, SEM, and EBSD analyses clearly showed that the wrinkled surface structure and the uniform [100] facet play an important
wCu synthesis
To obtain a polycrystalline wrinkled Cu foil with graphene, a bare Cu foil (ca. ~ 20 µm thick) was transferred into a 4-in. CVD quartz tube for graphene synthesis and evacuated to ~ 80 mTorr. A furnace was heated up to 1000 °C for 1 h under 8 sccm in a H2 environment (120 mTorr). When a temperature of 1000 °C was achieved, the H2 gas injection was stopped and 50 sccm of CH4 gas was injected. All of the gas injection processes were controlled by a mass-flow controller (MFC, Atovac GMC-1200).
CRediT authorship contribution statement
Ju Ye Kim: Conceptualization, Methodology, Validation, Investigation, Resources, Writing - original draft, review & editing, Visualization. Oh B. Chae: Conceptualization, Validation, Writing - original draft, Writing - review & editing. Mihye Wu: Conceptualization, Validation, Investigation, Writing - original draft, Writing - review & editing, Supervision. Eunsoo Lim: Resources. Gukbo Kim: Investigation. Yu Jin Hong: Investigation. Woo-Bin Jung: Resources. Sungho Choi: Resources. Do Youb Kim:
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.
Acknowledgements
This study was supported by the National Research Foundation of Korea (NRF) grant funded by the Ministry of Science, ICT and Future Planning, Korea (MSIP, NRF-2018R1A2B3008658, NRF-2020M3H4A3081874) and supported by the Technology Innovation Program (20007034) funded By the Ministry of Trade, Industry & Energy (MOTIE, Korea). This research was also supported by KAIST Institute for the NanoCentury and Saudi Aramco-KAIST CO2 Management Center. J.Y.K and O.B.C contributed equally to this work.
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These authors contributed equally to this work.