In-situ Modification of Carbon Nanotubes with Metallic Bismuth Nanoparticles for Uniform Lithium Deposition

doi:10.15541/jim20220208

Abstract

Abstract:

Lithium (Li) metal is one of the most attractive anode materials for the development of high energy density batteries due to its high theoretical specific capacity and low electrochemical potential. However, during the repeated deposition/stripping of Li metal anode, irregular Li dendrite growth inevitably takes place, which seriously affects the cycle life and safety of Li metal batteries. In this study, a simple and mild strategy was developed to in-situ modify the carbon nanotubes with bismuth (Bi) nanoparticles, followed by coating the as-prepared materials on the surface of commercial copper foil as current collector for Li metal anode. It is demonstrated that the in-situ modified Bi nanoparticles promotes the uniform Li deposition, thereby inhibiting the growth of Li dendrites and improving the electrochemical performance of Li metal batteries. Under the current density of 1 mA·cm^-2, Coulombic efficiency of Li|Cu cell based on the Bi@CNT/Cu current collector maintains 98% after 300 cycles. Meanwhile, the symmetric cell based on the Li@Bi@CNT/Cu anode can maintain the stable cycling for 1000 h. When it is applied in LiFePO₄ (LFP) full cell, the Bi@CNT/Cu current collector also exhibits excellent electrochemical performance, which can retain the stable cycling for 700 cycles at the rate of 1C (170 mA·g^-1). This study provides a new strategy for suppressing dendrite growth of Li metal anodes.

Key words: Li metal battery, Li dendrite, bismuth nanoparticle, current collector

CLC Number:

O646

CAI Jia, HUANG Gaoxu, JIN Xiaopan, WEI Chi, MAO Jiayi, LI Yongsheng. In-situ Modification of Carbon Nanotubes with Metallic Bismuth Nanoparticles for Uniform Lithium Deposition[J]. Journal of Inorganic Materials, 2022, 37(12): 1337-1343.

Figures/Tables 6

Fig. 1 Schematic diagram for the synthesis of Bi@CNT

Fig. 2 Microstructure characterization of samples (a) XRD patterns of CNT and Bi@CNT; (b) Total survey and (c) high-resolution Bi4f XPS spectra of Bi@CNT; (d, e) TEM images and (f) EDS elemental mapping of Bi@CNT

Fig. 3 Coulombic efficiencies of Li|Cu cells based on Bi@CNT/Cu, CNT/Cu and Cu current collectors at (a) 1 mA·cm-2, 1 mAh·cm-2 and (b) 3 mA·cm-2, 1 mAh·cm-2; Capacity-voltage curves of Li|Cu cells based on (c) Bi@CNT/Cu, (d) CNT/Cu, and (e) Cu current collectors at 1 mA·cm-2, 1 mAh·cm-2Colorful figures are available on website

Fig. 4 SEM images of (a) Bi@CNT/Cu, (b) CNT/Cu, and (c) Cu current collectors in Li|Cu cells after 50 cycles; (d) First cyclic EIS plots of Li|Cu cells based on Bi@CNT/Cu, CNT/Cu and Cu current collectors, and voltage-time curves of symmetric cells based on Li@Bi@CNT/Cu, Li@CNT/Cu and Li@Cu anodes at (e) 1 mA·cm-2, 1 mAh·cm-2 and (f) 2 mA·cm-2, 1 mAh·cm-2 Colorful figures are available on website

Table 1 Comparison of electrochemical properties of copper foils modified by different materials

Symmetric cell				Li\|Cu cell
Current collector	Current density/ (mA·cm^-2)	Planting/ strippingcapacity/ (mAh·cm^-2)	Cycling time/h	Current density/ (mA·cm^-2)	Planting capacity/ (mAh·cm^-2)	Cycle number, n	Coulombic efficiency/%	Ref.
Bi@CNT	1	1	1000	1	1	300	98	This work
Bi@CNT	2	1	260	3	1	100	96	This work
SMC-2	1	1	220	0.5	1	210	97	[21]
PDA	0.1	0.2	800	1	1	100	96	[22]
3D-CuZn	1	1	450	1	1	150	95	[23]
Li-MMT	3	1	70	2	0.25	100	97.9	[24]
LHCE	1	1	700	1	1	200	99.1	[25]
NMPC	0.5	0.5	400	1	1	200	98	[26]
Duplex Cu	1	1	880	1	1	300	97.3	[27]
Ti₃C₂T_x	1	1	500	1	1	250	98.4	[28]
q-PET	3	1	100	1	1	100	98	[29]
SF	3	3	350	1	1	200	96	[30]

Fig.5 (a) Cycling performances and (b) rate performances of LFP full cells based on Li@Bi@CNT/Cu, Li@CNT/Cu, and Li@Cu anodes, and (c-e) capacity-voltage profiles of LFP full cells based on (c) Li@Bi@CNT/Cu, (d) Li@CNT/Cu, and (e) Li@Cu anodes at 1C Colorful figures are available on website

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