Silicon lithium-ion battery anode with enhanced performance: Multiple effects of silver nanoparticles

doi:10.1016/j.jmst.2018.02.004

Abstract

Abstract:

Silicon has been regarded as one of the most promising next generation lithium-ion battery anode. However, the poor cyclic stability of the Si based anode has severely limited its practical applications, which is even worse with high mass loading density (>1 mg cm^-2). A new concept has been developed to enhance the electrochemical performance of the Si nanoparticle anode. Silver nanoparticles are composited with the silicon nanoparticles in a facile way for the first time. It is found that the mechanical properties of the Si electrode have been significantly improved by the incorporation of the silver nanoparticles, leading to enhanced cyclic performance. With the Si/Ag mass ratio of 4:1, the reversible specific discharge capacity is retained as 1156 mA h g^-1 after 100 cycles at 200 mA g^-1, which is more than three times higher than that of the bare silicon (318 mA h g^-1). The rate performance has been effectively improved as well due to excellent electron conductivity of the silver nanoparticles.

Key words: Silicon, Silver, Nanoparticles, Nanocomposite, Lithium-ion battery, Anode

Shanshan Yin, Qing Ji, Xiuxia Zuo, Shuang Xie, Kai Fang, Yonggao Xia, Jinlong Li, Bao Qiu, Meimei Wang, Jianzhen Ban, Xiaoyan Wang, Yi Zhang, Ying Xiao, Luyao Zheng, Suzhe Liang, Zhaoping Liu, Cundong Wang, Ya-Jun Cheng. Silicon lithium-ion battery anode with enhanced performance: Multiple effects of silver nanoparticles[J]. J. Mater. Sci. Technol., 2018, 34(10): 1902-1911.

Figures/Tables 17

Fig. 1. Schematic of macroscopic visual change of electrodes after cycling test (a), cross-sectional view of newly prepared Si/Ag electrode with Si/Ag ratio of 1:1 (b) and fabrication process of Si/Ag electrode (c).

Table 1 Electrode mass loading densities with respect to Si/Ag nanocomposites.

Electrode	Si/Ag mass ratio
Electrode	1:0	4:1	2:1	1:1	1:2	1:4
Cycling performance test	1.25	1.43	1.43	1.38	1.52	1.55
Rate performance test	1.13	1.45	1.36	1.42	1.55	1.65

Fig. 2. XRD patterns of Si/Ag nanocomposites with Si/Ag mass ratios of 1:0, 4:1, 2:1, 1:1, 1:2, and 1:4.

Fig. 3. Morphologies of Si/Ag nanocomposites with Si/Ag mass ratios of 1:0 (a), 4:1 (b), 2:1 (c), 1:1 (d), 1:2 (e) and 1:4 (f).

Fig. 4. Elemental mapping of Si/Ag nanocomposites with different Si/Ag mass ratios.

Fig. 5. Modulus and hardness of pristine bare silicon and Si/Ag nanocomposite electrodes.

Fig. 6. Discharge/charge curves of bare silicon (a) and Si/Ag nanocomposites with Si/Ag mass ratios of 4:1 (b), 2:1 (c), 1:1 (d), 1:2 (e) and 1:4 (f) under current density of 0.2C.

Fig. 7. Cyclic performance of Si/Ag nanocomposites with different mass ratios of Si/Ag (The specific capacity values in Fig. 7(a) are calculated based on the total mass of silicon and silver, and the specific capacity values in Fig. 7(b) are calculated based on the silicon content only).

Table 2 Cyclic performance of bare Si and Si/Ag nanocomposite anodes depicted in Fig. 7.

Si/Ag ratio	Maximum discharge capacity (mA h g^-1) (against Si/Ag)	Maximum discharge capacity (mA h g^-1) (against Si only)	Capacity retention
1:0	3168	3168	10%
4:1	1594	1993	73%
2:1	1418	2156	63%
1:1	1508	3016	35%
1:2	1234	3704	42%
1:4	665	3323	47%

Table 3 Summarized performance of reported Si/Ag lithium-ion battery anodes.

Ref.	Test condition	Max capacity (mA h g^-1)	Cycle number	Capacity retention	Morphology
					Si	Ag
[37]	CCC method	1300	100	120%	particle	particle
[39]	300 mA g^-1	1225	80	64%	particle	particle
[39]	300 mA g^-1	1244	80	37%	particle	particle
[35]	0.1 mA cm^-2	2800	30	21%	particle	particle
[20]	0.1 mA cm^-2	1750	30	34%	particle	particle
[20]	0.1 mA cm^-2	2050	30	37%	particle	particle
[47]	0.2 mA cm^-2	280	50	90%	particle	particle
[38]	500 mA g^-1	3500	50	51%	porous	particle
[34]	100 mA g^-1	3500	100	66%	porous	particle
[31]	500 mA g^-1	3762	100	93%	porous	particle
[36]	400 mA g^-1	2800	50	28%	porous	particle

Fig. 8. CV curves of bare silicon (a) and Si/Ag nanocomposite electrode with Si/Ag mass ratio of 1:1 at different cycles.

Fig. 9. Rate performance of Si/Ag nanocomposites with different Si/Ag mass ratios calculated based on total mass of silicon and silver (a) and silicon content (b).

Table 4 Rate performance of Si/Ag nanocomposite anodes depicted in Fig. 9(a).

Si/Ag ratio	Current density (mA g^-1)
Si/Ag ratio	100	200	500	1000
1:0	2725	1770	1142	541
4:1	1656	1484	950	381
2:1	1428	1368	1218	919
1:1	1301	1124	856	501
1:2	995	968	876	743
1:4	764	635	513	398

Table 5 Rate performance of Si/Ag nanocomposite anodes depicted in Fig. 9(b).

Si/Ag ratio	Current density (mA g^-1)
Si/Ag ratio	100	200	500	1000
1:0	2725	1770	1142	541
4:1	2070	1855	1188	477
2:1	2164	2073	1845	1392
1:1	2602	2248	1712	1002
1:2	3015	2933	2655	2252
1:4	3820	3175	2565	1990

Fig. 10. Electrochemical impedance spectra (EIS) of bare Si and Si/Ag nanocomposite electrodes after 3 cycles.

Table 6 Resistance (RS + RSEI + RCT) (Ω) values derived from fitting result with different Si/Ag mass ratios.

1:0	4:1	2:1	1:1	1:2	1:4
271.6	78.9	75.6	19.1	18.2	15.2

Fig. 11. Morphologies of electrodes with Si/Ag mass ratios of 1:0 (a, a’, a”), 4:1 (b, b’, b”), 2:1 (c, c’, c”), 1:1 (d, d’, d”), 1:2 (e, e’, e”), 1:4 (f, f’, f”) before (a’-f’) and after (a”-f”) cycling.

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