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

无机材料学报 ›› 2022, Vol. 37 ›› Issue (12): 1337-1343.DOI: 10.15541/jim20220208 CSTR: 32189.14.10.15541/jim20220208

所属专题：【能源环境】超级电容器,锂金属电池,钠离子电池和水系电池(202409)

金属铋纳米颗粒原位修饰碳纳米管促进锂均匀沉积

蔡佳(), 黄高旭, 金晓盼, 魏驰, 毛嘉毅, 李永生()

华东理工大学材料科学与工程学院, 上海 200237

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:
国家自然科学基金(51672083)

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

CAI Jia(), HUANG Gaoxu, JIN Xiaopan, WEI Chi, MAO Jiayi, LI Yongsheng()

School of Materials Science and Engineering, East China University of Science & Technology, Shanghai 200237, China

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.cn
About author:CAI Jia (1996-), female, Master candidate. E-mail: caijia0902@163.com
Supported by:
National Natural Science Foundation of China(51672083)

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

参考文献 30

[1]	DUNN B, KAMATH H, TARASCON J M. Electrical energy storage for the grid: a battery of choices. Science, 2011, 334(6058): 928-935. DOI PMID
[2]	QIAN J, HENDERSON W A, XU W, et al. High rate and stable cycling of lithium metal anode. Nature Communications, 2015, 6: 6362. DOI PMID
[3]	HE B, RAO Z, CHENG Z, et al. Rationally design a sulfur cathode with solid-phase conversion mechanism for high cycle-stable Li-S batteries. Advanced Energy Materials, 2021, 11(14): 2003690. DOI URL
[4]	JUNG W B, PARK H, JANG J S, et al. Polyelemental nanoparticles as catalysts for a Li-O₂ battery. ACS nano, 2021, 15(3): 4235-4244. DOI URL
[5]	WOOD K N, KAZYAK E, CHADWICK A F, et al. Dendrites and pits: untangling the complex behavior of lithium metal anodes through operando video microscopy. ACS Central Science, 2016, 2(11): 790-801. PMID
[6]	SANCHEZ A J, KAZYAK E, CHEN Y, et al. Plan-view operando video microscopy of Li metal anodes: identifying the coupled relationships among nucleation, morphology, and reversibility. ACS Energy Letters, 2020, 5(3): 994-1004. DOI URL
[7]	AURBACH D. Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteries. Journal of Power Sources, 2000, 89(2): 206-218. DOI URL
[8]	CHENG X B, ZHANG R, ZHAO C Z, et al. A review of solid electrolyte interphases on lithium metal anode. Advanced Science, 2016, 3(3): 1500213. DOI URL
[9]	SHEN X, LI Y, QIAN T, et al. Lithium anode stable in air for low-cost fabrication of a dendrite-free lithium battery. Nature Communications, 2019, 10: 900. DOI PMID
[10]	XU R, ZHANG X Q, CHENG X B, et al. Artificial soft-rigid protective layer for dendrite-free lithium metal anode. Advanced Functional Materials, 2018, 28(8): 1705838. DOI URL
[11]	LIU Y, LIU Q, XIN L, et al. Making Li-metal electrodes rechargeable by controlling the dendrite growth direction. Nature Energy, 2017, 2: 17083. DOI URL
[12]	XU K. Electrolytes and interphases in Li-ion batteries and beyond. Chemical Reviews, 2014, 114(23): 11503-11618. DOI PMID
[13]	HUANG S, ZHANG W, MING H, et al. Chemical energy release driven lithiophilic layer on 1 m² commercial brass mesh toward highly stable lithium metal batteries. Nano Letters, 2019, 19(3): 1832-1837. DOI URL
[14]	PEI F, FU A, YE W, et al. Robust lithium metal anodes realized by lithiophilic 3D porous current collectors for constructing high-energy lithium-sulfur batteries. ACS Nano, 2019, 13(7): 8337-8346. DOI PMID
[15]	YAN K, LU Z, LEE H W, et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nature Energy, 2016, 1: 16010. DOI URL
[16]	PEI A, ZHENG G, SHI F, et al. Nanoscale nucleation and growth of electrodeposited lithium metal. Nano Letters, 2017, 17(2): 1132-1139. DOI PMID
[17]	ZHANG Y, LUO W, WANG C, et al. High-capacity, low-tortuosity, and channel-guided lithium metal anode. Proceedings of the National Academy of Sciences, 2017, 114(14): 3584-3589. DOI URL
[18]	QIU H, TANG T, ASIF M, et al. 3D porous Cu current collectors derived by hydrogen bubble dynamic template for enhanced Li metal anode performance. Advanced Functional Materials, 2019, 29(19): 1808468. DOI URL
[19]	HU Z, LI Z, XIA Z, et al. PECVD-derived graphene nanowall/ lithium composite anodes towards highly stable lithium metal batteries. Energy Storage Materials, 2019, 22: 29-39. DOI URL
[20]	HOU G, SUN Q, AI Q, et al. Growth direction control of lithium dendrites in a heterogeneous lithiophilic host for ultra-safe lithium metal batteries. Journal of Power Sources, 2019, 416: 141-147. DOI URL
[21]	ZHANG F, LIU X, YANG M, et al. Novel S-doped ordered mesoporous carbon nanospheres toward advanced lithium metal anodes. Nano Energy, 2020, 69: 104443. DOI URL
[22]	HE Y, XU H, SHI J, et al. Polydopamine coating layer modified current collector for dendrite-free Li metal anode. Energy Storage Materials, 2019, 23: 418-426. DOI URL
[23]	ZHANG D, DAI A, WU M, et al. Lithiophilic 3D porous CuZn current collector for stable lithium metal batteries. ACS Energy Letters, 2019, 5(1): 180-186. DOI URL
[24]	NAN Y, LI S, HAN C, et al. Interlamellar lithium-ion conductor reformed interface for high performance lithium metal anode. Advanced Functional Materials, 2021, 31(25): 2102336. DOI URL
[25]	LIU Y, WU X, NIU C, et al. Systematic evaluation of carbon hosts for high-energy rechargeable lithium-metal batteries. ACS Energy Letters, 2021, 6(4): 1550-1559.
[26]	LIU H, WANG E, ZHANG Q, et al. Unique 3D nanoporous/ macroporous structure Cu current collector for dendrite-free lithium deposition. Energy Storage Materials, 2019, 17: 253-259. DOI URL
[27]	LIN K, LI T, CHIANG S W, et al. Facile synthesis of ant-nest-like porous duplex copper as deeply cycling host for lithium metal anodes. Small, 2020, 16(37): 2001784. DOI URL
[28]	YANG D, ZHAO C, LIAN R, et al. Mechanisms of the planar growth of lithium metal enabled by the 2D lattice confinement from a Ti₃C₂T_x MXene intermediate layer. Advanced Functional Materials, 2021, 31(24): 2010987. DOI URL
[29]	ZHANG W, ZHUANG H L, FAN L, et al. A “cation-anion regulation” synergistic anode host for dendrite-free lithium metal batteries. Science Advances, 2018, 4(2): eaar4410. DOI URL
[30]	FU A, WANG C, PENG J, et al. Lithiophilic and antioxidative copper current collectors for highly stable lithium metal batteries. Advanced Functional Materials, 2021, 31(15): 2009805. DOI URL

金属铋纳米颗粒原位修饰碳纳米管促进锂均匀沉积

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

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