基于石墨烯及其复合物电极的电容去离子技术研究进展

doi:10.15541/jim20150231

摘要/Abstract

摘要：

电容去离子技术是一种高效节能、绿色环保的脱盐方法, 通过施加静电场, 强制离子向两侧电极迁移, 使其被电极表面产生的双电层吸附, 从而达到脱盐的目的。电容去离子技术的关键是高性能电极材料的制备, 要求具有较高的比表面积、合理的孔径分布和良好的导电性。石墨烯具有较高的理论比表面积和优异的导电性, 是一种理想的电极材料。然而由于石墨烯的聚集效应, 实际比表面积远远低于理论值, 将石墨烯制备成三维网络结构或将石墨烯与其他材料进行复合可以克服聚集效应, 提高电极的脱盐性能。本文综述了基于石墨烯及其复合物电极的电容去离子技术研究进展、存在的问题及应用前景。

关键词: 石墨烯, 电极, 电容去离子, 综述

Abstract:

Capacitive deionization is an energy-efficient and environment-friendly desalination method, which forces ionic species toward oppositely charged high-surface-area electrodes under an electric field to achieve the purpose of desalination. The key technology is to prepare electrode materials, which require high specific surface area, reasonable pore size distribution and excellent electrical conductivity. Graphene is a desired kind of electrode material used in capacitive deionization for its high specific surface area and wonderful conductivity. However, the actual specific surface area is far below the theoretical value due to the effect of aggregation of graphene. The three-dimensional graphene or the composite materials can overcome aggregation effect to improve the performance of electrode. The research progress of the capacitive deionization technology based on graphene and its composite electrode are reviewed in detail. The existing problems and application prospect are also objectively pointed out in this review.

Key words: graphene, electrodes, capacitive deionization, review

中图分类号:

TB383

冯爱虎, 于云, 宋力昕. 基于石墨烯及其复合物电极的电容去离子技术研究进展[J]. 无机材料学报, 2016, 31(2): 123-134.

FENG Ai-Hu, YU Yun, SONG Li-Xin. Research Progress of Graphene and Its Composites as Electrodes for Capacitive Deionization[J]. Journal of Inorganic Materials, 2016, 31(2): 123-134.

图/表 18

图1 吡啶-热解法制备石墨烯的流程图[27]

Fig. 1 Procedure of the GR preparation by pyridine-thermal strategy[27]

图2 多步还原合成的石墨烯示意图[19]

Fig. 2 Schematic of the multistep reduction synthesis of graphene[19]

图3 3DMGA的合成路线示意图[37]

Fig. 3 Schematic illustration of the synthetic route for 3D MGA[37]

图4 3DGHPC的合成路线示意图[38]

Fig. 4 Schematic illustration of the synthetic route for 3D GHPC[38]

图5 GHMCS合成路线示意图[39]

Fig. 5 Schematic illustration of the synthetic route for GHMCS[39]

图6 STGS 合成路线示意图[40]

Fig. 6 Schematic representation of the procedure for preparing STGS samples[40]

图7 GS 合成路线示意图[41]

Fig. 7 Schematic representation of the procedure for preparing GS sample[41]

图8 KOH激发的石墨烯样品SEM照片[46]

Fig. 8 SEM images (a,b) of KOH-activated graphene sample[46]

图9 NaCl中AC和GAC电极CV曲线(扫描速度1 mV/s)[48]

Fig. 9 CV curves of AC and GAC electrodes in NaCl solutions at a scan rate of 1 mV/s[48]

图10 AC、MC和GE/MC电极的CDI曲线对比图[49]

Fig. 10 Comparison of CDI curves of the AC, MC and GE/MC electrodes[49]

图11 GR/CNT 合成示意图[53]

Fig. 11 Preparation process of GR/CNT composites[53]

图12 GR/CNT和GR电极充放电曲线[53]

Fig. 12 Charge/discharge cycling curves of the GR and GR/CNT electrodes[53]

图13 不同电极的CDI曲线对比图[61]

Fig. 13 Comparison of CDI curves of different electrodes[61]

图14 GA/TiO2合成路线示意图[66]

Fig. 14 Schematic illustration of the synthetic route for GA/TiO2[66]

图15 原位聚合法制备PANI 和石墨烯复合物[71]

Fig. 15 The in-situ polymerization of PANI in the presence of graphene sheets[71]

图16 G、PANI和G/PANI电极的CV曲线[71]

Fig. 16 CV curves of grapheme only, PANI only and G/ PANI[71]

图17 电极的脱吸附曲线[71]

Fig. 17 Regeneration of electrodes performance [71]

表1 不同石墨烯基电极材料的性能对比

Table 1 Comparison of the performance among different graphene-based electrode materials

Electrode materials	Specific surface area/(m²∙g^-1)	[Specific capacitance/ (F∙g^-1)]/[Scan rate/ (mV∙s^-1)]	Applied voltage/V	[Initial concentration/ (mg∙L^-1)]/[Initial conductivity/(μS∙cm^-1)]	Electrosorption capacity/(mg∙g^-1)	Ref.
GR	14.2	75.18/70.00	2.0	-/~50	1.85	[21]
GR	77.0	-	2.0	22.8/-	0.46	[17]
GR	222.1	-	2.0	-/~55	1.35	[26]
GR	-	-	2.0	-/86.9	0.88	[27]
GR	464.0	149.8/5.0	2.0	-/500	8.60	[19]
RGO-RF	406.4	135.7/10.0	2.0	-/~58	1.42	[35]
3DMGA	339.0	58.4/5.0	2.0	-/~105	5.39	[37]
3DGHPC	384.4	80.34/10.00	1.2	-/60	6.18	[38]
GHMCS	400.4	43.22/10.00	1.6	-/68.5	2.30	[39]
STGS	305.0	57/10	1.5	-/~106	4.95	[40]
GS	356.0	205.2/5.0	1.2	500/-	14.90	[41]
KOH-activated GR	3513.0	-	2.0	70/150	11.86	[46]
20%GR+AC	779.0	181/1	1.2	-/100	2.94	[48]
5%GR+MC	685.2	89.5/1.0	-	-/~90	0.73	[49]
GR+10%CNTs	479.5	68/10	2.0	-/57	1.41	[53]
10%GR+CNTs	438.6	311.1/10.0	1.6	-/100	0.88	[54]
GR+10%SWCNTs	391.0	213/10	2.0	780/1540	26.42	[55]
GR+15% SnO₂	-	323/5	1.4	-/~61	1.49	[60]
GR+MnO₂-NPs	-	180/10	1.2	-/~100	~3.50	[61]
GR+MnO₂-NRs	-	292/10	1.2	-/~100	5.01	[61]
GR+Ag	-	114.7/25.0	1.5	-/-	-	[64]
GR+Ag@C	-	107.6/25.0	1.5	-/-	-	[64]
GR+TiO₂	187.6	142.6/5.0	1.2	500/-	15.10	[66]
GR+20%TiO₂	-	443/10	0.8	~300/-	9.10	[67]
GR+4%PANI	394.0	-	1.2	500/-	-	[71]
GR+PCNF	474.0	151/-	1.2	100/-	7.80	[75]
10%GR+ACF	621.0	193/5	1.2	400/-	7.20	[76]

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