V掺杂对Ni-Co-S/细菌纤维素基碳气凝胶电催化性能的影响

doi:10.15541/jim20200011

摘要/Abstract

摘要：

本研究以细菌纤维素基碳气凝胶(CA)为载体材料, 通过水热法制备了Ni-Co-S/CA复合气凝胶, 掺入钒元素调控材料的微观结构和性能。研究结果表明: Ni-Co-S的主要物相为NiCo₂S₄, 次相为NiS₂。随着镍钴盐浓度的增大, 负载量增加, 电催化峰电流密度先升后降。当镍钴盐浓度较低时, 掺微量钒后, Ni-Co-S从结晶度较高的球形颗粒转变成低结晶度的方形微粒, 电催化活性和稳定性都得到改善。在0.01 mol/L镍钴盐溶液中掺入3mol% V, 制备的电极对甲醇具有最优的催化氧化性能, 与不掺V的样品相比, 其峰电流密度(78.18 mA/cm ²)提升了至少45.7%。Ni-Co-S/CA复合气凝胶电极具有轻质、高孔隙率等优点, 有望用于便携式直接甲醇燃料电池。

关键词: 细菌纤维素, 碳气凝胶, 镍钴硫, 钒掺杂, 甲醇氧化

Abstract:

Ni-Co-S/CA composite aerogels were prepared by hydrothermal method using bacterial cellulose-derived carbon aerogels (CA) as support. The microstructure and properties of the composites were adjusted via adding trace vanadium. The characterization results show that the main phase of Ni-Co-S is NiCo₂S₄with the secondary phase of NiS₂. With the increment of the nickel-cobalt salt concentration, the load amount increases, and the peak current density of electrocatalysis firstly upgraded and then degraded. After being doped with a small amount of vanadium at lower nickel-cobalt salt concentration, Ni-Co-S transforms from spherical particles with high crystallinity to square particles with low crystallinity, and its electrocatalytic activity and stability are improved. Under the preparative conditions of 0.01 mol/L total concentration of nickel-cobalt salt and 3mol% vanadium salt, the as-obtained electrode exhibits the optimal catalytic performance for methanol oxidation. Compared with the sample without V doping, its peak current density (78.1 mA/cm ²) enhanced by 45.7% at least. The Ni-Co-S/CA composite aerogel electrodes with the advantages of light weight and high porosity, is expected to be applied in portable direct methanol fuel cell.

Key words: bacterial cellulose, carbon aerogel, Ni-Co-S, vanadium doping, methanol oxidation

中图分类号:

TQ174

吕子夜, 唐谊平, 曹华珍, 郑国渠, 侯广亚. V掺杂对Ni-Co-S/细菌纤维素基碳气凝胶电催化性能的影响[J]. 无机材料学报, 2020, 35(10): 1142-1148.

LYU Ziye, TANG Yiping, CAO Huazhen, ZHENG Guoqu, HOU Guangya. Effect of V Doping on Electrocatalytic Performance of Ni-Co-S on Bacterial Cellulose-derived Carbon Aerogel[J]. Journal of Inorganic Materials, 2020, 35(10): 1142-1148.

图/表 6

图1 (a) CA、NCS-2、NCS-10和V3-NCS-1的XRD图谱; NCS-2的XPS (b)全谱、(c) Ni2p、(d) Co2p和(e) S2p谱图

Fig. 1 (a) XRD patterns of CA, NCS-2, NCS-10 and V3-NCS-1 samples; (b) Total survey, (c) Ni2p, (d) Co2p and (e) S2p XPS spectra of NCS-2

图2 (a)碳气凝胶, (b) NCS-1, (c, d) NCS-2, (e) NCS-5和(f) NCS-10的SEM照片

Fig. 2 SEM images of (a) carbon aerogels, (b) NCS-1, (c, d) NCS-2, (e) NCS-5 and (f) NCS-10

图3 NCS-2的(a~b)高分辨TEM照片, (b) HAADF-STEM照片以及相应(c) EDS元素面分布图

Fig. 3 (a-b) High-resolution TEM image, (b) HAADF-STEM image and (c) EDS element mappings of NCS-2

图4 (a) NCS-1和Vx-NCS-1 (x=3(b), 5(c), 10(d))的SEM照片

Fig. 4 SEM images of (a) NCS-1 and Vx-NCS-1 (x is (b)3, (c)5 or (d)10)

图5 (a) CA、NCS-n (n=1, 2, 10)和V3-NCS-n (n=1,2)的CV曲线; (b) NCS-n (n=1, 2), Vx-NCS-n (x=3, 5, 10; n=1,2)的峰值电流密度和平均负载量对比图; (c) V3-NCS-1在1 mol/L KOH中, 以10、20、30、40、50 mV/s扫描的CV曲线, 插图为峰值电流密度与扫速平方根之间的关系; (d) V3-NCS-1的峰电流密度与甲醇浓度的关系曲线

Fig. 5 (a) CV curves of CA, NCS-n (n=1, 2, 5, 10) and V3-NCS-n (n=1,2); (b) Comparison of the peak current density and the average load amount of NCS-n (n=1, 2), Vx-NCS-n (x=3, 5, 10; n=1,2); (c) CV curves of V3-NCS-1 in 1 mol/L KOH at 10, 20, 30, 40, 50 mV/s sweep speed with inset showing the relationship between the peak current density and the square root of the sweep speed; (d) Relationship between the methanol concentration and the peak current density of V3-NCS-1

图6 NCS-2和V3-NCS-1电极循环1000次的(a)氧化峰电流密度变化曲线、(b)计时电流测试曲线和(c)循环前后的XRD图谱; NCS-2试样中负载的颗粒1000次循环后的(d) TEM照片, (e) HAADF-STEM照片以及相应的EDS元素分布图

Fig. 6 (a) Oxidation peak current densities and (b) I-t curves of NCS-2 and V3-NCS-1 electrodes varied within 1000 CV cycles, and (c) XRD patterns of NCS-2 and V3-NCS-1 before and after 1000 cycles; (d) TEM image, (e) HAADF-STEM image and corresponding EDS element mappings of the particles loaded in NCS-2 after 1000 cycles

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