图1 铜集流体改性流程及表面物相结构变化

Fig. 1 Copper current collector modification process and surface phase structure change (a) Copper current collector modification process; (b, c) Inverse pole figure coloring diagrams of copper current collector (b) before and (c) after annealing; (d) XRD patterns of copper current collector before and after annealing; (e, f) AFM images of copper current collector (e) before and(f) after annealing. Colorful figures are available on website

图2 铜集流体对锌的剥离性能研究

Fig. 2 Stripping performance of zinc from copper current collector (a, b) Zinc-copper asymmetric battery cycle tests of copper current collector before and after annealing under (a) low current and (b) high depth of discharge conditions; (c) Nucleation overpotential of copper current collector after annealing at low current; (d-f) Surface SEM images of initial copper current collector after (d) one cycle, (e) five cycles and (f) ten cycles; (g-i) Surface SEM images of annealed copper current collector after (g) one cycle, (h) five cycles and (i) ten cycles

图3 铜集流体对锌的沉积性能研究

Fig. 3 Deposition performance of copper current collector to zinc (a, b) In-situ optical microscopy characterization of zinc electrodeposition on copper current collector (a) before and (b) after annealing; (c) XRD patterns of electrodeposited zinc on the surface of copper current collector before and after annealing; (d, e) SEM images of electrodeposited zinc on copper current collector (d) before and (e) after annealing

图4 锌在Cu(111)晶面上的第一性原理计算

Fig. 4 First-principle calculations of zinc on Cu(111) crystal plane (a) Diffusion path diagram of zinc atoms on the Cu(111) crystal plane; (b) Typical diffusion energy barrier profile of zinc atom diffusion on Cu(111) crystal plane; (c) Interface model diagram of Zn(002) crystal plane and Cu(111) crystal plane; (d) Theoretical interfacial energy between three typical zinc crystal planes and Cu(111) crystal plane

图5 在电流密度为5 mA·cm−2条件下, 锌在退火(a)前、(b)后的铜集流体上沉积不同时间的形貌

Fig. 5 Deposition morphologies of zinc on copper current collectors (a) before and (b) after annealing at 5 mA·cm−2 for different time

图6 退火前后铜集流体应用在全电池中的长循环性能对比

Fig. 6 Comparision of long cycle performance of copper current collector before and after annealing in full cell (a) Long cycle performance of annealed copper current collector in full cell; (b) Comparison of cycle performance of copper current collector before and after annealing in full cell; (c, d) Comparison of discharge curves of the first ten cycles of copper current collector (c) before and (d) after annealing in full cell; (e) Discharge curves of the initial copper current collector applied in the full cell at the 2nd, 10th, 50th and 100th cycles; (f) Discharge curves of the annealed copper current collector applied in the full cell at the 2nd, 100th, 400th and 700th cycles. Colorful figures are available on website

图S1 酸洗(a)前、(b)后铜集流体表面的光学显微镜表征

Fig. S1 Optical microscope characterization of copper current collector surface (a) before and (b) after pickling

图S2 退火(a)前、(b)后铜集流体的表面缺陷分布图

Fig. S2 Surface defect distribution of copper current collector (a) before and (b) after annealing

图S3 退火(a)前、(b)后铜集流体的应力-应变曲线

Fig. S3 Stress-strain curves of copper current collector (a) before and (b) after annealing

图S4 退火(a)前、(b)后铜集流体表面的SEM照片

Fig. S4 SEM images of copper current collector surface (a) before and (b) after annealing

图S5 退火(a)前、(b)后铜集流体作为锌铜非对称电池正极经历1、5、10圈循环后的表面XRD图谱

Fig. S5 Surface XRD patterns of copper current collector (a) before and (b) after annealing as positive electrode of zinc-copper asymmetric battery after one cycle, five cycles and ten cycles

图S6 退火(a)前、(b)后铜集流体表面电沉积锌的宏观形貌图

Fig. S6 Macroscopic morphology of electrodeposited zinc on the surface of copper current collector (a) before and (b) after annealing

图S7 锌原子在Cu(100)、(110)和(111)晶面上的扩散能垒

Fig. S7 Diffusion energy barriers of zinc atoms on Cu(100), (110) and (111) planes