新型高能量密度锂离子电池负极Li21Si5/石墨烯复合材料的合成与性能研究

doi:10.15541/jim20180097

摘要/Abstract

摘要：

本研究利用放电等离子烧结技术同时实现热化学锂化与致密化, 制备得到Li₂₁Si₅与石墨烯两相分布均匀、高致密度的纳米结构复合材料。石墨烯的二维结构、优异的电导率以及大量结合紧密的两相界面能够有效地限制活性颗粒在脱锂过程中的体积收缩并促进电荷在活性颗粒内部的传输, 促使该复合材料表现出优异的电化学性能。预脱锂和首次嵌锂比容量分别为968和1007 mAh∙g^-1, 达到商业化应用锂-碳体系的3倍, 首次库伦效率达到94.5%。循环100圈后比容量仍然可保持在590 mAh∙g^-1, 循环稳定性相比于采用碳颗粒制备的复合材料提升了1倍。即使在1 A∙g^-1的高电流密度下循环, 比容量仍可保持在540 mAh∙g^-1。本研究为设计开发应用于锂离子硫、锂离子氧等高能量密度电池体系中的富锂合金负极材料提供了新的途径。

关键词: 锂化, 负极, 石墨烯, 复合材料, 锂离子电池

Abstract:

Taking advantage of simultaneous thermochemical lithiation and densification of spark plasma sintering, the Li₂₁Si₅/graphene nanocomposites with uniform distribution and high density were prepared. Due to the two-dimensional structure and excellent electrical conductivity of graphene, and the presence of a high proportion of tightly bonded interfaces of Li₂₁Si₅/graphene, the volume shrinkage of the active particles during the delithiation process was limited effectively, and the charge transport inside the active particles was enhanced dramatically. Therefore, the composite exhibits excellent electrochemical performance. The specific capacities of pre-delithiation and the first lithiation were 968 mAh∙g^-1 and 1007 mAh∙g^-1, respectively, which are 3 times as high as those of the commercial lithium-carbon compound. Its first Coulomb efficiency was 94.5% at the same time. Moreover, the specific capacity remained 590 mAh∙g^-1 after 100 cycles, and the cyclic stability doubled compared to the composites prepared by carbon particles. Even at a high current density of 1 A∙g^-1, the specific capacity can be maintained at 540 mAh∙g^-1. This work provides a new approach for the development of lithium-rich alloy anode materials, which are promising in high energy density batteries, such as lithium ion-sulfur and lithium ion-oxygen systems.

Key words: lithiation, anode, graphene, nanocomposite, lithium-ion batteries

中图分类号:

TQ152

杨科, 侯超, 宋晓艳. 新型高能量密度锂离子电池负极Li₂₁Si₅/石墨烯复合材料的合成与性能研究[J]. 无机材料学报, 2018, 33(10): 1065-1069.

YANG Ke, HOU Chao, SONG Xiao-Yan. Synthesis and Property of Novel Li₂₁Si₅/Graphene Composites Anode for High Energy Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2018, 33(10): 1065-1069.

图/表 7

图1 Li21Si5、Li21Si5@AB、Li21Si5@rGP的XRD图谱

Fig. 1 XRD patterns of Li21Si5, Li21Si5@AB and Li21Si5@rGP

图2 Si+rGP的扫描电镜照片(a)、透射电镜照片(b)

Fig. 2 SEM (a) and TEM (b) images of Si+rGP

图3 Li21Si5@rGP电极在首次充电测试条件下的充放电曲线

Fig. 3 Charge/discharge curves of Li21Si5@rGP electrode wnder the test condition of pre-delithiation

图4 Li21Si5、Li21Si5@AB和Li21Si5@rGP电极的循环性能和库伦效率

Fig. 4 Cycling performances and Coulombic efficiencies of Li21Si5, Li21Si5@AB and Li21Si5@rGP electrodes

图5 Li21Si5@rGP电极循环100圈后脱锂态电极的SEM照片(a), Li21Si5@rGP电极循环不同圈数处于脱锂态的阻抗谱以及与Li21Si5@AB电极首次脱锂后阻抗的对比(b)

Fig. 5 SEM image of Li21Si5@rGP electrode at delithiation state after 100 circles (a), and Nyquist plots of Li21Si5@rGP electrode at delithiation state after different cycles and the comparison with Li21Si5@AB electrode after the first cycles (b)

图6 Li21Si5@AB和Li21Si5@rGP电极的倍率性能和库伦效率对比

Fig. 6 Comparison of rate performance and Coulombic efficiency of Li21Si5@AB and Li21Si5@rGP electrodes

图7 Li21Si5@rGP(a)和Li21Si5@AB(b)电极的循环伏安曲线

Fig. 7 CV curves of Li21Si5@rGP (a) and Li21Si5@AB (b) electrodes

参考文献 22

[1]	TARASCON J M, ARMAND M.Issues and challenges facing rechargeable lithium batteries.Nature, 2001, 414(6861): 359-367.
[2]	ARICO A S, BRUCE P, SCROSATI B,et al. Nanostructured materials for advanced energy conversion and storage devices. Nature Materials, 2005, 4(5): 366-377.
[3]	PALACIN M R.Recent advances in rechargeable battery materials: a chemist’s perspective.Chemical Society Reviews, 2009, 38(9): 2565-2575.
[4]	NISHIHARA H, KYOTANI T.Templated nanocarbons for energy storage.Advanced Materials, 2012, 24(33): 4473-4498.
[5]	SU X, WU Q, LI J, et al. Silicon-based nanomaterials for lithium- ion batteries: a review. Advanced Energy Materials, 2014, 4(1): 1300882-1-23.
[6]	LIU N, LU Z, ZHAO J,et al. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nature Nanotechnology, 2014, 9(3): 187-192.
[7]	WU H, CUI Y.Designing nanostructured Si anodes for high energy lithium ion batteries.Nano Today, 2012, 7(5): 414-429.
[8]	FERGUS J W.Recent developments in cathode materials for lithium ion batteries.Journal of Power Sources, 2010, 195(4): 939-954.
[9]	HUANG J Q, LIU X F, ZHANG Q,et al. Entrapment of sulfur in hierarchical porous graphene for lithium-sulfur batteries with high rate performance from 40 to 60℃. Nano Energy, 2013, 2(2): 314-321.
[10]	HUANG J Q, ZHANG Q, ZHANG S M,et al. Aligned sulfur- coated carbon nanotubes with a polyethylene glycol barrier at one end for use as a high efficiency sulfur cathode. Carbon, 2013, 58: 99-106.
[11]	ZHAO J, LU Z, LIU N, et al. Dry-air-stable lithium silicide-lithium oxide core-shell nanoparticles as high-capacity prelithiation reagents. Nature Communications, 2014, 5(5): 5088-1-8.
[12]	LI X, KERSEYBRONEC F E, KE J,et al. Study of lithium silicide nanoparticles as anode materials for advanced lithium ion batteries. ACS Applied Materials & Interfaces, 2017, 9(19): 16071.
[13]	ZHAO J, LU Z, WANG H,et al. Artificial solid electrolyte interphase-protected LixSi nanoparticles: an efficient and stable prelithiation reagent for lithium-ion batteries. Journal of the American Chemical Society, 2015, 137(26): 8372-8375.
[14]	LI B, YANG S, LI S,et al. From commercial sponge toward 3D graphene-silicon networks for superior lithium storage. Advanced Energy Materials, 2015, 5(15): 107-114.
[15]	LUO Z, XIAO Q, LEI G,et al. Si nanoparticles/graphene composite membrane for high performance silicon anode in lithium ion batteries. Carbon, 2016, 98: 373-380.
[16]	JIE Z, ZHOU G, KAI Y,et al. Air-stable and freestanding lithium alloy/graphene foil as an alternative to lithium metal anodes. Nature Nanotechnology, 2017, 12(10): 993.
[17]	BUNCH J S, VERBRIDGE S S, ALDEN J S,et al. Impermeable atomic membranes from graphene sheets. Nano letters, 2008, 8(8): 2458-2462.
[18]	ZHANG W, ZUO P, CHEN C,et al. Facile synthesis of binder-free reduced graphene oxide/silicon anode for high-performance lithium ion batteries. Journal of Power Sources, 2016, 312: 216-222.
[19]	HOU G, CHENG B, CAO Y,et al. Scalable production of 3D plum-pudding-like Si/C spheres: towards practical application in Li-ion batteries. Nano Energy, 2016, 24: 111-120.
[20]	IWAMURA S, NISHIHARA H, ONO Y, et al. Li-rich Li-Si alloy as a lithium-containing negative electrode material towards high energy lithium-ion batteries. Scientific Reports, 2015, 5: 8085-1-8.
[21]	DENG H, QIU F, LI X,et al. A Li-ion oxygen battery with Li-Si alloy anode prepared by a mechanical method. Electrochemistry Communications, 2017, 78: 11-15.
[22]	JIANG T, ZHANG S, QIU X,et al. Preparation and characterization of silicon-based three-dimensional cellular anode for lithium ion battery. Electrochemistry Communications, 2007, 9(5): 930-934.

新型高能量密度锂离子电池负极Li₂₁Si₅/石墨烯复合材料的合成与性能研究

Synthesis and Property of Novel Li₂₁Si₅/Graphene Composites Anode for High Energy Lithium-ion Batteries

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