Stable Li-metal Depositon on Lithiophilic 3D CuO Nanosheet-decorated Cu Mesh

doi:10.15541/jim20190545

Abstract

Abstract:

Lithium metal anode, due to its highest theoretical specific capacity (3860 mAh·g ^-1) and lowest electrochemical potential (-3.04 V (vs SHE)), has become the first choice of the next generation of electrochemical energy storage devices. It is known as the “holy grail” of the battery industry. However, the disadvantage of lithium metal battery is particularly obvious: during the charge and discharge process, lithium metal battery is easy to deposit unevenly on the anode electrode, resulting in lithium dendrite which causes the continuous rupture and formation of solid electrolyte interface (SEI) film. The unstable SEI film, intensifying the formation of lithium dendrites and then piercing the separator, causes a decline for the battery cycle performance and the safety hazard. Therefore, it is particularly important to take corresponding measures to make lithium metal uniformly deposited on the anode. In this study, the uniform lithiophilic copper oxide nanosheet array formed on the surface of commercial copper mesh through oxidation of alkaline solvent and calcination of air. The 3D structure of copper mesh can effectively reduce the current density, and the lithiophilic nanosheet array can effectively reduce the overpotential of lithium deposition simultaneously. This lithiophilic 3D copper-based current collector makes lithium deposited uniformly and effectively, and inhibits the formation of lithium dendrites. In the half-cell test at a current density of 3 mA·cm ^-2 the battery circulated stably for 230 cycles with Coulombic efficiency remaining above 99%. The lithium iron phosphate (LFP) full battery with the as-prepared material as current collector worked stably for more than 300 cycles at 1C(0.17 mA·mg ^-1) and present a capacity retention of ~95%. This study provides a new design strategy of 3D current collector for stable lithium metal batteries.

Key words: 3D Cu current collector, CuO nanosheet array, surface engineering, lithium metal anode, lithium metal battery

CLC Number:

O646

LI Rui,WANG Hao,FU Qiang,TIAN Ziyu,WANG Jianxu,MA Xiaojian,YANG Jian,QIAN Yitai. Stable Li-metal Depositon on Lithiophilic 3D CuO Nanosheet-decorated Cu Mesh[J]. Journal of Inorganic Materials, 2020, 35(8): 882-888.

Figures/Tables 12

Fig. 1 Schematic illustration for the fabrication of CuO@Cu Mesh

Fig. 2 (a) XRD pattern, (b) XPS spectrum, high-resolution XPS spectra of (c) Cu2p and (d) O1s for CuO@Cu Mesh

Fig. 3 Structure characterizaton of (a-c) SEM, (d) TEM, (e)βHRTEM images, and (f) elements mappings of CuO@Cu Mesh

Fig. 4 (a) Cycling performances, (b) first cyclic charge curves, (c) first cyclic EIS plots for half cells with Cu foil, Cu Mesh, CuO@Cu Mesh as current collectors

Fig. 5 (a) Cycling performances, (b) rate performances and(c)first cyclic EIS plots of LFP full cells with CuO@Cu Mesh, Cu mesh and Cu foil as current collectors (1C=0.17 mA?mg-1)

Fig. 6 (a) Cycling performances, (b) rate performances and (c) first cyclic EIS plots for LiNi0.6Co0.2Mn0.2O2 full cells with CuO@Cu Mesh, Cu mesh and Cu foil as current collectors (1C=0.18 mA?mg-1)

Fig. 7 Current density distribution simulation for Comsol with CuO@Cu Mesh, Cu mesh and Cu foil as current collectors in presence of lithium dendrite (a,b) 3D model diagram; (c,d) 2D simplified simulation

Fig. S1 Photographs of (a) Cu mesh, (b) CuOx mesh, (c) CuO@Cu Mesh

Fig. S2 Magnified XRD pattern of CuO@Cu Mesh

Fig. S3 SEM images of Cu foil, Cu mesh and CuO@Cu Mesh in half cells after different cycles at 3 mA?cm-2 & 1 mAh?cm-2

Fig. S4 Magnified first cyclic charge curves for half cells with Cu foil, Cu Mesh, CuO@Cu Mesh as current collectors

Fig. S5 (a) Voltage profiles of CuO@Cu Mesh half-cell at the first cycle, (b) XRD patterns of CuO@Cu Mesh current collector at corresponding potentials

References 15

[1]	TARASCON, ARMAND J M. Issues and challenges facing rechargeable lithium batteries. Nature, 2001,414(6861):359-367. DOI URL PMID
[2]	LIN D, LIU Y, CUI Y, et al. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol., 2017,12:194-206. DOI URL PMID
[3]	XU W, ZHANG J G, DING F, et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci., 2014,10:513-537.
[4]	REHNLUND D, LINDGREN F, BÖHME S, et al. Lithium trapping in alloy forming electrodes and current collectors for lithium based batteries. Energy Environ. Sci., 2017,10:1350-1357. DOI URL
[5]	XU K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev., 2014,114(23):11503-11618. DOI URL PMID
[6]	TARASCON J M, GOZDZ A S, SCHMUTZ C, et al. Performance of bellcore’s plastic rechargeable Li-ion batteries. Solid State Ionics, 1996, 86-88:49-54. DOI URL
[7]	CHEN K H, SANCHEZ A J, KAZYAK E, et al. Synergistic effect of 3D current collectors and ALD surface modification for high Coulombic efficiency lithium metal anodes. Adv. Energy Mater., 2019,9(4):1802534.
[8]	LIU S, ZHANG X, LI R, et al. Dendrite-free Li metal anode by lowering deposition interface energy with Cu₉₉Zn alloy coating. Energy Storage Mater., 2018,14:143-148.
[9]	CHENG Y, KE X, CHEN Y, et al. Lithiophobic-lithiophilic composite architecture through co-deposition technology toward high- performance lithium metal batteries. Nano Energy, 2019,63:103854. DOI URL
[10]	LIU T, HU J, LI C, et al. Unusual conformal Li plating on alloyable nanofiber frameworks to enable dendrite suppression of Li metal anode. ACS Appl. Energy Mater., 2019,2(6):4379-4388. DOI URL
[11]	HOU Z, YU Y, WANG W, et al. Lithiophilic Ag nanoparticle layer on Cu current collector toward stable Li metal anode. ACS Appl. Mater. Interfaces, 2019,11(8):8148-8154.
[12]	ZHU J, CHEN J, SUN Z, et al. Lithiophilic metallic nitrides modified nickel foam by plasma for stable lithium metal anode. Energy Storage Mater., 2019,23:539-546.
[13]	KE X, LIANG Y, SHI Z, et al. Surface engineering of commercial Ni foams for stable Li metal anodes. Energy Storage Mater., 2019,23:547-555.
[14]	LIANG F, LIN L, FENG Z, et al. Spatial separation of lithiophilic surface and superior conductivity for advanced Li metal anode: the case of acetylene black and N-doped carbon spheres. J. Mater. Chem. A, 2019,7(15):8765-8770. DOI URL
[15]	LIANG Z, LIN D, ZHAO J, et al. Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating. Proc. Natl. Acad. Sci., 2016,113(11):2862-2867. DOI URL PMID