金属铋纳米颗粒原位修饰碳纳米管促进锂均匀沉积

doi:10.15541/jim20220208

摘要/Abstract

摘要：

锂金属具有高理论比容量和低电化学电位, 是发展高能量密度电池最有吸引力的负极材料之一。然而, 锂金属负极在反复的沉积/剥离过程中, 不可避免地会出现不规则的锂枝晶生长, 这将严重影响锂金属电池的循环寿命和使用安全性。本研究发展了一种简单温和的策略, 在碳纳米管上原位修饰铋纳米颗粒, 并涂覆在商业铜箔表面用作锂金属负极的集流体。研究表明, 原位修饰的铋纳米颗粒可显著促进锂均匀沉积, 抑制锂枝晶生长, 从而提高锂金属电池的电化学性能。在电流密度为1 mA·cm^-2的条件下, 基于Bi@CNT/Cu集流体的锂铜电池循环300圈后库仑效率可稳定在98%。基于Li@Bi@CNT/Cu负极的对称电池可稳定循环1000 h。基于Bi@CNT/Cu集流体的磷酸铁锂(LFP)全电池也获得了优异的电化学性能, 在1C(170 mA·g^-1)倍率下可稳定循环700圈。本研究为抑制锂金属负极枝晶生长提供了新的思路。

关键词: 锂金属电池, 锂枝晶, 铋纳米颗粒, 集流体

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

中图分类号:

O646

蔡佳, 黄高旭, 金晓盼, 魏驰, 毛嘉毅, 李永生. 金属铋纳米颗粒原位修饰碳纳米管促进锂均匀沉积[J]. 无机材料学报, 2022, 37(12): 1337-1343.

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.

图/表 6

图1 Bi@CNT样品的制备示意图

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

图2 样品的微观结构表征

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

图3 基于Bi@CNT/Cu、CNT/Cu和Cu集流体的锂铜电池在(a)1 mA·cm-2, 1 mAh·cm-2和(b)3 mA·cm-2, 1 mAh·cm-2条件下的库仑效率, 基于(c)Bi@CNT/Cu、(d)CNT/Cu和(e)Cu集流体的锂铜电池在1 mA·cm-2, 1 mAh·cm-2条件下的容量-电压曲线

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

图4 锂铜电池循环50次后(a) Bi@CNT/Cu、(b) CNT/Cu和(c) Cu集流体的SEM照片, (d)基于Bi@CNT/Cu、CNT/Cu和Cu集流体的锂铜电池的首圈EIS图谱, 基于Li@Bi@CNT/Cu、Li@CNT/Cu和Li@Cu负极的对称电池在(e)1 mA·cm-2, 1 mAh·cm-2和(f)2 mA·cm-2, 1 mAh·cm-2的电压-时间曲线

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

表1 使用不同材料修饰铜箔后的电化学性能对比

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]

图5 基于Li@Bi@CNT/Cu, Li@CNT/Cu和Li@Cu负极的LFP全电池的(a)长循环性能, (b)倍率性能, 基于(c)Li@Bi@CNT/Cu, (d)Li@CNT/Cu, (e)Li@Cu负极的LFP全电池在1C下的容量-电压曲线

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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