Wrinkled Graphene-Reinforced Nickel Sulfide Thin Film as High-Performance Binder-Free Anode for Sodium-Ion Battery

doi:10.1016/j.jmst.2016.09.017

Abstract

Abstract:

Sodium-ion batteries (SIBs) recently have received a worldwide attention due to the resource abundance of sodium and similar battery chemistry with lithium-ion batteries (LIBs). However, search for suitable anodes for SIBs still remains a challenge since graphitized carbon, the anode for commercial LIBs, usually exhibits low electrochemical Na-storage activity. In this work, a unique graphene-reinforced Ni₃S₂ thin film (Ni₃S₂/G) has been constructed and investigated as a promising anode for SIBs. The Ni₃S₂ thin film has a thickness of 200-300 nm and is composed of small sized crystals of around 100 nm. The graphene has a wrinkled surface profile which offers three-dimensional networks for electron conductivity and structural reinforcement. The Ni₃S₂/G thin film exhibits high capacity, excellent cycling stability and good rate capability due to the introduction of wrinkled graphene. Ni₃S₂/G can deliver a high initial capacity of 791 mAh g^-1 at 50 mA g^-1. The capacity can be maintained at 563 mAh g^-1 after 110 cycles. This work provides a unique design for high-performance SIBs anodes.

Key words: Sodium ion battery, Anode, Wrinkled graphene, Nickel sulfide, Thin film

Xia Xueke, Xie Jian, Zhang Shichao, Pan Bin, Cao Gaoshao, Zhao Xinbing. Wrinkled Graphene-Reinforced Nickel Sulfide Thin Film as High-Performance Binder-Free Anode for Sodium-Ion Battery[J]. J. Mater. Sci. Technol., 2017, 33(8): 775-780.

Figures/Tables 7

Fig.1. XRD patterns of Ni3S2/G on Ni substrate.

Fig.2. (a) Low-magnification and (b) high-magnification SEM images of graphene-coated Ni substrate, and (c) Raman spectrum of graphene on Ni substrate.

Fig.3. (a-c) SEM images of Ni3S2/G on Ni substrate and (d) TEM image of Ni3S2 exfoliated from Ni3S2/G.

Fig.4. (a) CV plots of Ni3S2/G at 0.1 mV s-1, (b) the first five charge and discharge curves and (c) cycling stability of Ni3S2/G and Ni3S2 at 50 mA g-1, (d) comparison of rate capability of Ni3S2/G and Ni3S2, and (e) Nyquist plots of Ni3S2/G and Ni3S2 after 5th and 20th cycles.

Table 1 Cycling stability of some typical sulfide/graphene composites

Sample	Current density (mA g^-1)	Initial capacity (mAh g^-1)	Cycle number	Capacity retention	Reference
Ni₃S₂/G	50	791	110	71.1%	This work
MnS/G	100	497	125	62.0%	^[22]
Ni₃S₂ + Ni₇S₆/G	100	419	50	88.4%	^[23]
VS₄/G	100	450.4	50	53.5%	^[25]
WS₂/G	200	359.1	200	93%	^[29]

Table 2 Fitting results of the Nyquist plots using the equivalent circuit

Sample	Cycle number	R_e (Ω)	R_f (Ω)	Q₁		R_ct (Ω)	Q₂
Sample	Cycle number	R_e (Ω)	R_f (Ω)	Y	n	R_ct (Ω)	Y	n
Ni₃S₂/G	5	34	81	8.9 × 10^-6	0.77	1810	2.0 × 10^-5	0.73
Ni₃S₂/G	20	36	86	5.4 × 10^-6	0.82	1959	2.4 × 10^-5	0.67
Ni₃S₂	5	41	83	2.1 × 10^-6	0.97	4303	1.5 × 10^-5	0.64
Ni₃S₂	20	49	112	3.2 × 10^-6	0.83	5331	1.1 × 10^-5	0.67

Fig.5. SEM images of (a, b) Ni3S2/G and (c, d) Ni3S2 on Ni substrate after the first sodiation at 50 mA g-1, and (e) schematic illustration of the sodiation process of Ni3S2/G on Ni substrate.

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