锑硅纳米复合薄膜作为钠离子电池负极材料的电化学行为研究

doi:10.15541/jim20170326

摘要/Abstract

摘要：

近年来, 合金作为钠离子电池的负极材料具有较高的比容量而受到广泛关注。然而, 硅与钠离子的电化学反应活性很低, 硅基合金型负极材料鲜有报道。本研究通过脉冲激光沉积技术制备了锑硅(Sb-Si)纳米复合薄膜, 并对其作为钠离子电池负极材料的电化学性能和反应机理进行了研究。电化学性能表征发现, 锑硅纳米复合薄膜在10 μA/cm²的电流密度下, 循环100次后能保持约0.011 mAh/cm²(270 mAh/g)的可逆比容量, 远优于同样方法和条件下制备的单质锑和单质硅薄膜电极的电化学性能。进一步的研究表明, 在放电过程中, Sb和Si分别和钠离子发生合金化反应生成了Na₃Sb和NaSi的纳米晶。在充电过程中, Na₃Sb和NaSi纳米晶发生可逆的脱钠反应, 重新形成单质Sb和Si纳米晶粒。大量存在于锑硅纳米复合薄膜中的异质晶界有利于钠离子的扩散和输运, 从而提高了纳米复合薄膜电极的电化学性能。

关键词: 钠离子电池, 负极材料, 锑硅复合材料, 薄膜, 脉冲激光沉积

Abstract:

Recent years, alloy attracted significant research interest as anode materials for room temperature sodium-ion batteries, due to its high specific capacity and low cost. Among them, the study of Si-based alloy anodes are very limited, owing to the low electrochemical reactivity of Si with Na ions. In this study, Sb-Si nanocomposite thin films were successfully prepared by pulsed laser deposition. Their electrochemical performance and reaction mechanism were studied as new anode materials for sodium ion batteries. They exhibited a reversible specific capacity of about 0.011 mAh/cm² (corresponding to 270 mAh/g) over 100 cycles at a rate of 10 μA/cm², which is much higher than those for pure Si or Sb thin films prepared under the same condition. The investigation of electrochemical reaction mechanism reveals that Na₃Sb and NaSi nanocrystallines are formed after discharge, due to the alloying reaction between the Sb-Si films and Na. During the recharge process, Na₃Sb and NaSi phases both decompose and form Sb and Si nanocrystallines again, respectively. It is proposed that heterogeneous grain boundaries existing in the Sb-Si nanocomposite thin films are benefical to Na-ion transportation, thus enhance the electrochemical performance of the nanocomposite thin film electrode.

Key words: sodium-ion battery, anode material, Sb-Si nanocomposite, thin film, pulsed laser deposition

中图分类号:

TQ15

肖娜, 潘洋, 宋云, 吴晓京, 傅正文, 周永宁. 锑硅纳米复合薄膜作为钠离子电池负极材料的电化学行为研究[J]. 无机材料学报, 2018, 33(5): 494-500.

XIAO Na, PANG Yang, SONG Yun, WU Xiao-Jing, FU Zheng-Wen, ZHOU Yong-Ning. Electrochemical Behavior of Sb-Si Nanocomposite Thin Films as Anode Materials for Sodium-ion Batteries[J]. Journal of Inorganic Materials, 2018, 33(5): 494-500.

图/表 7

图1 Sb-Si纳米复合薄膜作为钠离子电池负极在电流密度为10 μA/cm2下的恒电流充放电曲线(a); Sb-Si纳米复合薄膜、Sb薄膜和Si薄膜首次恒电流充放电曲线(b); Sb-Si纳米复合薄膜、Sb薄膜和Si薄膜的循环容量图(c)

Fig. 1 Galvanostatic charge-discharge profiles of the as-deposited Sb-Si nanocomposite thin film at a current density of 10 μA/cm2 (a); The first galvanostatic charge-discharge profiles of the as-deposited Sb-Si nanocomposite thin film, pure Sb film and pure Si film (b); Cycling performance of Sb-Si nanocomposite thin film, pure Sb film and pure Si film (c)

图2 Sb-Si纳米复合薄膜(a)、单质Sb薄膜(b)和单质Si薄膜(c)在0.1~2.0 V之间的循环伏安特性曲线

Fig. 2 First three cyclic voltammograms for Sb-Si nanocomposite thin film (a), Sb thin film (b) and Si thin film (c) between 0.1-2.0 V

图3 Sb-Si纳米复合薄膜在初始态(a)、放电态(b)、充电态(c)状态下的SEM照片以及XRD图谱(d)

Fig. 3 SEM images (a)-(c) and XRD patterns (d) of Sb-Si nanocomposite thin film as-deposited, discharged to 0.1 V, recharged to 2.0 V

图4 初始态、放电态和充电态Sb-Si纳米复合薄膜的高分辨电子显微镜照片(a)~(c)和选区电子衍射图像(d)~(f)

Fig. 4 HRTEM images (a)-(c) and SAED patterns (d)-(f) of Sb-Si nanocomposite thin film as-deposited, discharged to 0.1 V and recharged to 2.0 V, respectively

表1 晶面间距d的实验值与标准值的比较

Table 1 d-spacing (nm) derived from SAED analysis of as-deposited, first discharging to 0.1 V and recharging to 2.0 V of Sb-Si nanocomposite thin film electrode

	Sb (R-3m)	Si (P4₁2₁2)
As-deposited	(No.85-1322)	(No.39-0973)
0.311	0.311 (012)
0.226		0.228 (302)
0.181		0.183 (412)
0.158	0.156 (024)
0.139	0.139 (211)
	Na₃Sb (P6₃/mmc)	NaSi (C2/c)
Discharged	(No.74-1162)	(No.89-2625)
0.320		0.319 (-113)
0.208	0.208 (202)
0.185		0.186 (330)
0.150	0.150 (106)
0.122	0.124 (312)
	Sb (R-3m)	Si (P4₁2₁2)
Recharged	(No.85-1322)	(No.39-0973)
0.313	0.311 (012)
0.225		0.228 (302)
0.183		0.183 (412)
0.158	0.156 (024)

图5 初始态(a)、放电态(b)和充电态(c)Sb-Si纳米复合薄膜、单质Sb薄膜和单质Si薄膜的电化学阻抗(EIS) 图谱。(a)中的插图为该体系的等效模拟电路, (b)和(c)中的插图为Sb-Si薄膜EIS曲线的放大图。

Fig. 5 Electrochemical impedance spectroscopy of Sb-Si nanocomposite thin film, Sb and Sn thin films at (a) as-deposited, (b) discharged and (c) charged states

表2 Sb-Si薄膜、单质Sb薄膜和单质Si薄膜的电化学阻抗比较

Table 2 Impedance of as-deposited Sb-Si film, Sb film and Si film electrodes

R_ct/Ω	As-deposited	Discharged	Charged
Sb-Si	132	762	791
Sb	116	3078	4985
Si	146	12521	N/A

参考文献 35

[1]	KIM S, SEO D, MA X, et al. Electrode materials for rechargeable sodium-ion batteries: potential alternatives to current lithium-ion batteries.Advanced Energy Materials. 2012, 2(7): 710-721.
[2]	PAN H, HU Y, CHEN L.Room-temperature stationary sodium- ion batteries for large-scale electric energy storage.Energy & Environmental Science, 2013, 6(8): 2338-2360.
[3]	ZHOU Y N, MA J, HU E,et al. Tuning charge-discharge induced unit cell breathing in layer-structured cathode materials for lithium- ion batteries. Nature Communications, 2014, 5(5): 5381.
[4]	XIE H.Comprehensive analysis on electrochemical energy storage mode and energy storage materials.Smart Grid, 2014(7): 4-8.
[5]	YABUUCHI N, KUBOTA K, DAHBI M,et al. Research development on sodium-ion batteries. Chemical Reviews, 2014, 114(23): 11636-11682.
[6]	ELLIS B L, NAZAR L F.Sodium and sodium-ion energy storage batteries.Current Opinion in Solid State & Materials Science, 2012, 16(4): 168-177.
[7]	WANG Y S, RONG X H, XU S Y, et al. Recent progress of electrode materials for room-temperature sodium-ion stationary batteries. Energy Storage Science and Technology, 2016, 5(3): 268-284.
[8]	LI Y, LU Y, ZHAO C,et al. Recent advances of electrode materials for low-cost sodium-ion batteries towards practical application for grid energy storage. Energy Storage Materials, 2017, 7: 130-151.
[9]	LI Y, HU Y, QI X,et al. Advanced sodium-ion batteries using superior low cost pyrolyzed anthracite anode: towards practical applications. Energy Storage Materials, 2016, 5: 191-197.
[10]	ZHOU Y N, SINA M, PEREIRA N,et al. FeO0.7F1.3/C nanocomposite as a high-capacity cathode material for sodium-ion batteries. Advanced Functional Materials, 2015, 25(5): 696-703.
[11]	YE F P, WANG L, LIAN F,et al. Advance in Na-ion batteries. Chemical Industry and Engineering Progress, 2013, 32(8): 1789-1795.
[12]	GE P, FOULETIER M.Electrochemical intercalation of sodium in graphite.Solid State Ionics, 1988, 28: 1172-1175.
[13]	SANGSTER J.C-Na (carbon-sodium) system.Journal of Phase Equilibria and Diffusion, 2007, 28(6): 571-579.
[14]	MORTAZAVI M, YE Q, BIRBILIS N,et al. High capacity group- 15 alloy anodes for Na-ion batteries: electrochemical and mechanical insights. Journal of Power Sources, 2015, 285: 29-36.
[15]	WANG M, YANG Z, WANG J,et al. Sb nanoparticles encapsulated in a reticular amorphous carbon network for enhanced sodium storage. Small, 2015, 11(40): 5381-5387.
[16]	WU L, HU X, QIAN J,et al. Sb-C nanofibers with long cycle life as an anode material for high-performance sodium-ion batteries. Energy & Environmental Science, 2013, 7(1): 323-328.
[17]	ZHANG N, LIU Y C, LU Y Y, et al. Spherical nano-Sb@C composite as a high-rate and ultra-stable anode material for sodium-ion batteries. Nano Research, 2015, 8(10): 3384-3393.
[18]	ALLAN P K, GRIFFIN J M, DARWICHE A,et al. Tracking sodium- antimonide phase transformations in sodium-ion anodes: insights from operando pair distribution function analysis and solid-state NMR spectroscopy. Journal of the American Chemical Society, 2016, 138(7): 2352-2365.
[19]	LI S, WANG Z, LIU J,et al. Yolk-shell Sn@C eggette-like nanostructure: application in lithium-ion and sodium-ion batteries. ACS Applied Materials & Interfaces, 2016, 8(30): 19438-19445.
[20]	NITHYADHARSENI P, REDDY M V, NALINI B,et al. Electrochemical studies of CNT/Si-SnSb nanoparticles for lithium ion batteries. Materials Research Bulletin, 2015, 70: 478-485.
[21]	WANG Y, ZHANG P, WANG J,et al. Lithium storage characteristics and electrochemical performance of Si-Sb-Ag composite anode materials. International Journal Electrochemical Science, 2015, 10: 9652-9665.
[22]	SZZECH J R, SONG J.Nanostructured silicon for high capacity lithium battery anodes.Energy & Environmental Science, 2010, 4(1): 56-72.
[23]	WANG J, WANG Y, ZHANG P,et al. Preparation and electrochemical properties of binary SixSb immiscible alloy for lithium ion batteries. Journal of Alloys & Compounds, 2014, 610(30): 308-314.
[24]	GUO H, ZHAO H, YIN C,et al. Si/SnSb alloy composite as high capacity anode materials for Li-ion batteries. Journal of Alloys and Compounds. 2006, 426(1/2): 277-280.
[25]	CHOU C, LEE M, HWANG G S.A comparative first-principles study on sodiation of silicon, germanium, and tin for sodium-ion
	batteries. Journal of Physical Chemistry C, 2015, 119(27): 14843-14850.
[26]	LIM C, HUANG T, SHAO P,et al. Experimental study on sodiation of amorphous silicon for use as sodium-ion battery anode. Electrochimica Acta, 2016, 211: 265-272.
[27]	XU Y, SWAANS E, BASAK S,et al. Reversible Na-ion uptake in Si nanoparticles. Advanced Energy Materials, 2016, 6(2): 1501436.
[28]	GORKA J, BAGGETTO L, KEUM J K,et al. The electrochemical reactions of SnO2 with Li and Na: a study using thin films and mesoporous carbons. Journal of Power Sources, 2015, 284: 1-9.
[29]	ZHOU Y N, ZHANG H, WU C L,et al. Electrochemical properties of GeO2 films fabricated by plused laser deposition. Chinese Journal of Inorganic Chemistry, 2007, 23(8): 1353-1357.
[30]	ELLIS L D, WILKES B N, HATCHARD T D,et al. In situ XRD study of silicon, lead and bismuth negative electrodes in nonaqueous sodium cells. Journal of the Electrochemical Society, 2013, 161(3): A416-A421.
[31]	KOMABA S, MATSUURA Y, ISHIKAWA T,et al. Redox reaction of Sn-polyacrylate electrodes in aprotic Na cell. Electrochemistry Communications, 2012, 21: 65-68.
[32]	LI G, WANG W, YANG W,et al. Epitaxial growth of group III-nitride films by pulsed laser deposition and their use in the development of LED devices. Surface Science Reports, 2015, 70(3): 380-423.
[33]	TANG P, LI B, FENG L, et al. Structural, electrical and optical properties of AlSb thin films deposited by pulsed laser deposition. Journal of Alloys and Compounds, 2017, 692: 22-25.
[34]	MOSCICKI T, RADZIEJEWSKA J, HOFFMAN J,et al. WB2 to WB3 phase change during reactive spark plasma sintering and pulsed laser ablation/deposition processes. Ceramics International, 2015, 41(7): 8273-8281.
[35]	ZHU X, ONG C S, XU X,et al. Direct observation of lithium-ion transport under an electrical field in LixCoO2 nanograins. Scientific Reports, 2013, 3(1): 1084.