Effect of Nitrogen and Sulfur Co-Doped Graphene on the Electrochemical Hydrogen Storage Performance of Co0.9Cu0.1Si Alloy

doi:10.1007/s40195-023-01532-9

Abstract

Abstract:

Co_0.9Cu_0.1Si alloy was prepared by mechanical alloying method. Nitrogen-doped graphene (NG) and nitrogen-sulfur co-doped graphene (NSG) were prepared by hydrothermal method. 5 wt% graphene oxide, NG and NSG were doped into Co_0.9Cu_0.1Si alloy, respectively, by ball milling to improve the electrochemical hydrogen storage performance of the composite material. X-ray diffraction and scanning electron microscopy were used to characterize the structure and morphology of the composite material, and the LAND battery test system and three-electrode battery system were used to test the electrochemical performance of the composite material. The composite material showed better discharge capacity and better cycle stability than the pristine alloy. In addition, in order to study the optimal ratio of NSG, 3%, 5%, 7% and 10% of NSG were doped into Co_0.9Cu_0.1Si alloy, respectively. Co_0.9Cu_0.1Si alloy doped with 5% NSG had the best performance among all the samples. The best discharge capacity was 580.1 mAh/g, and its highest capacity retention rate was 64.1%. The improvement in electrochemical hydrogen storage performance can be attributed to two aspects. On the one hand, the electrocatalytic performance of graphene is improved by co-doping nitrogen and sulfur, on the other hand, graphene has excellent electrical conductivity.

Key words: Co_0.9Cu_0.1Si alloy, Nitrogen-sulfur co-doped graphene (NSG), Composite material, Electrochemical hydrogen storage

Wenhao Fan, Jianxun Zhao, Dayong Liu, Qingcheng Liang, Wanqiang Liu, Qingshuang Wang, Heng Liu, Peng Chen, Shang Gao, Xinlong Bao, Yong Cheng, Xinwei Wang, Xin Guo. Effect of Nitrogen and Sulfur Co-Doped Graphene on the Electrochemical Hydrogen Storage Performance of Co0.9Cu0.1Si Alloy[J]. Acta Metallurgica Sinica (English Letters), 2023, 36(6): 1023-1037.

Figures/Tables 15

Fig. 1 Diagram of synthesis process of Co0.9Cu0.1Si + NSG composite

Fig. 2 Structural characteristics and SEM images of GO, NG and NSG: a XRD patterns of GO, NG and NSG; b SEM image of GO; c SEM image of NG; d SEM images of NSG

Fig. 3 SEM image and the corresponding elemental mappings of NG and NSG: a NG; b NSG

Fig. 4 SEM images and EDS images of NG a, NSG b

Fig. 5 XRD patterns of Co0.9Cu0.1Si and composite: a Co0.9Cu0.1Si + 5% GO, NG, NSG; b Co0.9Cu0.1Si + x% NSG (x = 3, 5, 7, 10)

Fig. 6 SEM images of Co0.9Cu0.1Si alloy and composites: a, b Co0.9Cu0.1Si; c Co0.9Cu0.1Si + 5% GO; d Co0.9Cu0.1Si + 5% NG; e-h Co0.9Cu0.1Si + x% NSG (x = 3, 5, 7, 10)

Fig. 7 Discharge capacities of Co0.9Cu0.1Si and composite: a Co0.9Cu0.1Si + 5% GO, NG, NSG; b Co0.9Cu0.1Si + x% NSG composite electrodes

Table 1 Electrochemical performance of Co0.9Cu0.1Si alloy and composites

Samples	C_max (mAh/g)	S₅₀ (%)	E_corr (V)	I_corr (mA/cm²)
Co_0.9Cu_0.1Si	524.3	51.3	− 0.94	34.8
Co_0.9Cu_0.1Si + 5% GO	528.4	55.4	− 0.94	31.2
Co_0.9Cu_0.1Si + 5% NG	541.9	58.5	− 0.926	29.6
Co_0.9Cu_0.1Si + 3% NSG	530.6	60.1	− 0.937	30.8
Co_0.9Cu_0.1Si + 5% NSG	580.1	64.1	− 0.894	26.8
Co_0.9Cu_0.1Si + 7% NSG	557.3	62.2	− 0.901	27.3
Co_0.9Cu_0.1Si + 10% NSG	559.4	54.4	− 0.898	28.5

Fig. 8 Charge/discharge curves of Co0.9Cu0.1Si and composite: a Co0.9Cu0.1Si + 5% GO, NG, NSG; b Co0.9Cu0.1Si + x% NSG composite electrodes

Fig. 9 High-rate dischargeability of Co0.9Cu0.1Si and composites: a Co0.9Cu0.1Si + 5% GO, NG, NSG; b Co0.9Cu0.1Si + x% NSG composite electrodes

Table 2 HRD and dynamic performance of Co0.9Cu0.1Si alloy and composites

Samples	HRD₂₀₀ (%)	I₀ (mA/g)	R_ct (Ω)	D (× 10⁻¹¹ cm²/s)
Co_0.9Cu_0.1Si	77.8	86	0.357	7.5
Co_0.9Cu_0.1Si + 5% GO	79.1	99.5	0.344	7.7
Co_0.9Cu_0.1Si + 5% NG	83.3	143.4	0.202	8.2
Co_0.9Cu_0.1Si + 3% NSG	82.7	135.8	0.243	8.7
Co_0.9Cu_0.1Si + 5% NSG	85.8	203.2	0.171	9.6
Co_0.9Cu_0.1Si + 7% NSG	84.6	167.5	0.188	9.1
Co_0.9Cu_0.1Si + 10% NSG	80.4	112.3	0.272	8.1

Fig. 10 Linear polarization curves of Co0.9Cu0.1Si and composites: a Co0.9Cu0.1Si, Co0.9Cu0.1Si + 5% GO, NG, NSG; b Co0.9Cu0.1Si, Co0.9Cu0.1Si + x% NSG composites

Fig. 11 Potentiodynamic polarization curves of Co0.9Cu0.1Si and composites: a Co0.9Cu0.1Si, Co0.9Cu0.1Si + 5% GO, NG, NSG; b Co0.9Cu0.1Si, Co0.9Cu0.1Si + x% NSG composites

Fig. 12 EIS curves of Co0.9Cu0.1Si and composites: a Co0.9Cu0.1Si, Co0.9Cu0.1Si + 5% GO, NG, NSG; b Co0.9Cu0.1Si + x% NSG composites; c equivalent circuit

Fig. 13 Anodic current-time responses of Co0.9Cu0.1Si and composites: a Co0.9Cu0.1Si + 5% GO, NG, NSG; b Co0.9Cu0.1Si + x% NSG composite electrodes

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