Ni掺杂黑液木质素基活化木材陶瓷的制备与性能研究

doi:10.15541/jim20180098

摘要/Abstract

摘要：

以造纸黑液木质素和NiCl₂·6H₂O为原料、经1200℃高温烧结制备Ni掺杂木材陶瓷, 并用KOH进行活化处理, 得到呈泡沫状的三维网络结构的Ni掺杂活化石墨化木材陶瓷。采用X射线衍射(XRD)、拉曼光谱(RS)、扫描电镜(SEM)、透射电镜(TEM)、比表面积测试仪及电化学工作站等对其性能进行分析与表征。结果表明: Ni既参与构筑木材陶瓷骨架, 又对无定形碳进行催化石墨化。所制备样品的石墨化倾向明显, 有石墨烯片层结构出现, 部分晶格间距接近理想石墨的点阵参数。同时, 活化处理可以有效地形成多层次孔隙结构, 增加微孔与超微孔数量。800℃活化3 h后, 样品中的孔径主要集中在3.60 nm左右, 比表面积从359 m²·g^-1提高到856 m²·g^-1。活化能够改善Ni掺杂木材陶瓷的电化学性能, 在20 mV·s^-1扫描速率下, 其比电容为153.8 F·g^-1, 是未活化样品的2.2倍。

关键词: 活化木材陶瓷, Ni掺杂, 制备方法, 性能表征

Abstract:

Ni doping woodceramics were prepared from papermaking black liquor lignin and NiCl₂·6H₂O, which sintered at 1200℃ and then activated with KOH. The Ni doping activated graphite woodceramics presents 3-D net structure with foam formation. X-ray diffraction, Raman spectrum, scanning electron microscope, transmission electron microscope, specific surface area tester, and electrochemical workstation were employed to characterize the samples. The results show that Ni constructs the framework of woodceramics, and catalyzes graphitization of amorphous carbon. The sample displays obvious graphitization tendency, and graphene lamellar structure is found. The lattice spacing is close to the lattice parameter of ideal graphite. Meanwhile, activating treatment can effectively form hierarchical porous and increase the quantity of micropores and ultramicropore. The pore diameter mainly concentrats at 3.60 nm, and the specific surface area increases from 359 m²·g^-1 to 856 m²·g^-1, as the sample activated at 800℃ for 3 h. Additionally, activation improves the electrochemical performance of Ni doping woodceramics, whose specific capacitance is 153.8 F·g^-1 at 20 mV·s^-1scanning rate, 2.2 times higher than that of non-activated sample.

Key words: activated woodceramics, Ni doping, preparation method, property characterization

中图分类号:

TQ138

余先纯, 孙德林, 计晓琴. Ni掺杂黑液木质素基活化木材陶瓷的制备与性能研究[J]. 无机材料学报, 2018, 33(12): 1289-1296.

YU Xian-Chun, SUN De-Lin, JI Xiao-Qin. Preparation and Performance of Black Liquor Lignin Basic Activated Woodceramics Doped Ni[J]. Journal of Inorganic Materials, 2018, 33(12): 1289-1296.

图/表 10

图1 AGWC的催化石墨化机理

Fig. 1 Graphitization mechanism of AGWC

图2 AGWC与NAWC的XRD图谱

Fig. 2 XRD patterns of AGWC and NAWC

图3 AGWC和NAWC的拉曼图谱

Fig. 3 Raman spectra of AGWC and NAWC

表1 AGWC与NAWC的峰位、强度和R值

Table 1 Peak positions, intensities and R values of AGWC and NAWC

	Peak position/cm^-1		Intensity/cnt
	D-band	G-band	D-band	G-band
AGWC	1357.71	1581.58	1482.59	1258.97	1.28
NAWC	1354.15	1587.92	759.12	718.03	1.77

图4 AGWC(a, b)、NAWC(c)和普通木材陶瓷(d)的SEM照片

Fig. 4 SEM images of AGWC (a, b), NAWC (c) and ordinary woodceramics (d)

图5 AGWC的TEM照片

Fig. 5 TEM images of AGWC(a) Graphene sheets in AGWC; (b) Crystal structure and lattice spacing size of AGWC with inset showing partial enlarged image

图6 AGWC和NAWC的吸附-脱附和孔径-孔容曲线图

Fig. 6 Adsorption-desorption and pore diameter-volume curves of AGWC and NAWC(a) Adsorption-desorption curves; (b) Pore volume-diameter curves (BJH method) with inset showing its curves of micropore and ultramicropore (HK method)

表2 NAWC与AGWC的孔结构参数

Table 2 Pore structure parameter of NAWC and AGWC

	Specific surface area (BET method)/(m²·g^-1)	Pore diameter /nm		Total pore volume /(mL·g^-1)	Average pore diameter/nm
NAWC	359.068	HK method	0.648	0.1780	1.981
NAWC	359.068	BJH method	3.040	0.1780	1.981
AGWC	856.126	HK method	0.643	0.5417	2.531
AGWC	856.126	BJH method	3.070	0.5417	2.531

图7 AGWC的电化学性能曲线

Fig. 7 Electrochemical performance curves of AGWC(a) CV curves of AGWC; (b) GCD curves of AGWC; (c) Nyquist curves of AGWC with inset showing its local magnification; (d) Specific capacitances of AGWC with different scanning rate

图8 AGWC与NAWC的CV与GCD曲线

Fig. 8 CV and GCD curves of AGWC and NAWC(a) CV curves of AGWC and NAWC; (b) GCD curves of AGWC and NAWC with inset showing the single curve fo NAWC 0.5 A/g

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