无机材料学报 ›› 2022, Vol. 37 ›› Issue (12): 1337-1343.DOI: 10.15541/jim20220208
蔡佳(), 黄高旭, 金晓盼, 魏驰, 毛嘉毅, 李永生(
)
收稿日期:
2022-04-12
修回日期:
2022-07-13
出版日期:
2022-12-20
网络出版日期:
2022-10-19
通讯作者:
李永生, 教授. E-mail: ysli@ecust.edu.cn作者简介:
蔡 佳(1996-), 女, 硕士研究生. E-mail: caijia0902@163.com
基金资助:
CAI Jia(), HUANG Gaoxu, JIN Xiaopan, WEI Chi, MAO Jiayi, LI Yongsheng(
)
Received:
2022-04-12
Revised:
2022-07-13
Published:
2022-12-20
Online:
2022-10-19
Contact:
LI Yongsheng, professor. E-mail: ysli@ecust.edu.cnAbout author:
CAI Jia (1996-), female, Master candidate. E-mail: caijia0902@163.com
Supported by:
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。
中图分类号:
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
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 |
2 | 1 | 260 | 3 | 1 | 100 | 96 | ||
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] |
Ti3C2Tx | 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] |
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 |
2 | 1 | 260 | 3 | 1 | 100 | 96 | ||
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] |
Ti3C2Tx | 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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