Construction of Dendrite-free Lithium Metal Electrode Using Three-Dimensional Porous Copper and Zinc Coatings

doi:10.6023/A21110529

Abstract

Metal Li has been considered as one promising anode due to its high theoretical capacity and the lowest redox potential, however its dendrites growth and volumetric changes during cycling easily cause battery failure and safety hazards. Here a three dimensional (3D) porous Cu with pore size of about 5 μm coated with Zn layer is used as current collector for Li deposition to construct dendrite-free metal Li electrode. The suitable pore size and high stability of 3D Cu is beneficial to decrease local current density and buffer volumetric changes, and the Zn layer can decrease the nucleation overpotential of Li, synergistically induce uniform deposition of Li and effectively suppress the growth of Li dendrites. There is no dendrite appears when the 3D Cu@Zn is used as the current collector even the depositing capacity increases to 4 mAh•cm^–2, and displays smooth surface after Li stripping, however, the Li on Cu appears obvious dendrites and non-uniformity, Li on 3D Cu appears local non-uniformity and some dendrites. The semi-cell Li||3D Cu@Zn demonstrates stable coulombic efficiency at 0.5 and 1 mA•cm^–2 with a capacity of 1 mAh•cm^–2, the symmetrical cell Li||3D Cu@Zn@Li stably cycle for above 700 h at high current density of 2 mA•cm^–2 with a capacity of 1 mAh•cm^–2. The full cell with 3D Cu@Zn@Li as anode and LiFePO₄ as cathode remains 88 mAh•g^–1 after 150 cycles, which is much better than those using Cu@Li plate and 3D Cu@Li as the anodes.

Key words: lithium metal, three-dimensional porous copper, zinc, electrodeposition, lithium dendrite

Cite this article

Xiaoyong Fan, Shuai Zhang, Yongqiang Zhu, Maosen Jing, Kaixin Wang, Lulu Zhang, Julong Li, Lei Xu, Lei Gou, Donglin Li. Construction of Dendrite-free Lithium Metal Electrode Using Three-Dimensional Porous Copper and Zinc Coatings[J]. Acta Chimica Sinica, 2022, 80(4): 517-525.

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Fig. & Tab. 11

Figure 1. Schematic of Li plating/stripping behavior on Cu foil (a), 3D Cu (b) and 3D Cu@Zn (c)

Figure 2. Scanning electron microscope (SEM) images of 3D Cu (a, c), 3D Cu@Zn (b, d) and digital photos of 3D Cu (inset in a) and 3D Cu@Zn (inset in b)

Figure 3. SEM and corresponding energy dispersive spectrometer (EDS) mapping images of Cu and Zn of 3D Cu@Zn (a) and X-ray diffraction (XRD) patterns of 3D Cu@Zn (b)

Figure 4. Coulombic efficiency (CE) of Li||3D Cu@Zn, Li||3D Cu and Li||Cu cells at 0.5 mA•cm–2 (a) and 1 mA•cm–2 (b), (c) their voltage profiles of Li plating at 1 mA•cm–2 with a capacity of 1 mAh•cm–2 (inset is nucleation overpotential of lithium on different current collectors) and charge/discharge profiles of the 3D Cu@Zn in the 1st, 5th, 10th, 30th, 50th, 60th cycle at 1 mA•cm–2 with a capacity of 1 mAh•cm–2 (d)

Figure 5. Voltage-time profiles of the Li electrochemical plating/stripping process in symmetric cells at 0.5 mA•cm–2 (a) and 2.0 mA•cm–2 (d) with a capacity of 1 mAh•cm–2, and the magnified voltage-time profiles in the ranges 250~260 h (b) and 500~510 h (c) at 0.5 mA•cm–2, 80~90 h (e) and 290~300 h (f) at 2.0 mA•cm–2

Figure 6. SEM image of the Li plating and stripping behavior on 3D Cu@Zn, 3D Cu and Cu with the capacity increasing from 1 to 4 mAh•cm–2 and stripping 3 mAh•cm–2 at a current density of 0.5 mA•cm–2 SEM images of the Li plating with the capacities of 1, 2 and 4 mAh•cm–2 on 3D Cu@Zn (a~c), 3D Cu (e~g) and Cu (i~k). SEM images of Li stripping with a capacity of 3 mAh•cm–2 on 3D Cu@Zn (d), 3D Cu (h) and Cu (l)

Figure 7. SEM images of Li plating on Cu (a, d), 3D Cu (b, e) and 3D Cu@Zn (c, f) at 0.5 mA•cm–2 with a capacity of 1 mAh•cm–2 after 50 cycles

Figure 8. Cyclability profiles of the full cells using 3D Cu@Zn@Li, 3D Cu@Li and Cu@Li as the anodes, cathode capacity of about 1 mg•cm–2 at 1 C (a) and their charge/discharge profiles (b~d)

Figure 9. Cyclability profiles (a) of the full cells using 3D Cu@Zn@Li, 3D Cu@Li and Cu@Li as the anodes, cathode capacity of about 1 mg•cm–2 at different current densities and their charge/discharge profiles (b~d)

Figure 10. Cyclability profiles of the full cells using 3D Cu@Zn@Li, 3D Cu@Li and Cu@Li as the anodes, cathode capacity of about 3 mg•cm–2 at 2 C (a) and their charge/discharge profiles (b~d)

Figure 11. Cyclability profiles of the full cells using NCM cathode with a capacity of about 10 mg•cm–2, 3D Cu@Zn@Li, 3D Cu@Li and Cu@Li as the anodes (a) and their charge/discharge profiles (b~d) at 1 C

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