Graphene oxide membranes intercalated with strong polyelectrolytes toward high-output osmotic energy harvesting
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摘要: 二维纳米片有序组装形成的二维纳米通道薄膜由于其可控的通道高度和密集有序的孔道排列有望形成高性能盐差发电器件。然而，常规二维纳米通道薄膜受限于纳米片有限的极性基团密度，无法在通道内部有效富集反离子，导致其内部载流子浓度较低从而离子通量较差，严重限制了这类薄膜的盐差能输出功率密度。将氧化石墨烯(GO)纳米片与聚苯乙烯磺酸钠(PSS)充分混合，利用定向流场驱动两者自发有序堆叠构筑具有二维层状通道和高电荷密度的GO-PSS复合纳米通道薄膜。研究对比GO-PSS复合薄膜和常规GO薄膜的离子传输行为和盐差发电性能，考察离子强度、盐差度、PSS复合量、聚电解质类型等因素对薄膜离子传输行为和盐差发电性能的影响规律。研究表明，GO-PSS复合薄膜比常规GO薄膜具有更优异的离子选择性、离子通过量和盐差发电性能。在PSS含量为65wt%时，GO-PSS复合薄膜的输出功率密度高达11.27 W·m−2，远高于常规GO薄膜的3.37 W·m−2，说明复合强聚电解质是解决二维纳米通道薄膜功率密度低等问题的可行途径。Abstract: Two-dimensional nanochannel membranes offer great opportunities for developing efficient and robust devices for osmotic energy harvesting. However, low counterion concentration associated with the low charge density of nanosheets restricts their output performance. Herein, graphene oxide (GO) and poly(sodium 4-styrenesulfonate) (PSS) were assembled into composite nanochannel membranes featuring two-dimensional (2D) channels intercalated with abundant surface charges. The effect of ionic strength, salt concentration gradient, PSS content, and polyelectrolyte type on the transmembrane ionic transportation and osmotic energy harvesting of GO-PSS composite membranes was investigated. In contrast to pristine GO membranes, the incorporation of PSS simultaneously improves the ionic permeability and ion selectivity of GO-PSS composite membranes, thus leading to its higher output power density than that of pristine GO membranes. The GO-PSS composite membranes offer an output power density up to 11.27 W·m−2 by mixing seawater and river water, much higher than 3.37 W·m−2 of conventional GO membranes. This work highlights the significance of charge density and presents a general strategy for effectively improving ion transport through two-dimensional nanochannel membranes for high-output osmotic energy harvesting.
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Key words:
- graphene oxide /
- nanochannels /
- polyelectrolyte /
- charge density /
- osmotic energy /
- layered structure
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图 1 (a) 氧化石墨烯(GO)-聚苯乙烯磺酸钠(PSS)-55%薄膜的外观图像；(b) GO-PSS-55%薄膜的SEM断面图；(c) GO薄膜和GO-PSS复合薄膜的XRD图谱；(d) GO薄膜和GO-PSS复合薄膜的表面电位
Figure 1. (a) Photograph of graphene oxide (GO)- poly(sodium 4-styrenesulfonate) (PSS)-55% membrane; (b) SEM image of GO-PSS-55% membrane; (c) XRD patterns of pristine GO membrane and GO-PSS-55% membrane; (d) zeta potentials of GO-PSS composite membranes with different PSS contents
图 2 (a) GO薄膜和GO-PSS复合薄膜在浓度为1 mmol·L−1的KCl溶液中的电压扫描曲线；(b) GO薄膜和GO-PSS复合薄膜在不同KCl浓度中的跨膜电导
Figure 2. (a) Current−voltage curves of GO membrane and GO-PSS composite membranes recorded in 1 mmol·L−1 KCl solution; (b) ionic conductance of GO membrane and GO-PSS composite membranes as a function of KCl concentration
图 3 (a) GO 薄膜和 GO-PSS 复合薄膜在不同盐度差条件 下的开路电压；(b) GO 薄膜和 GO-PSS 复合薄膜在不同 盐度差条件下的离子选择性
Figure 3. (a) Open-circuit voltage and (b) ion selectivity of GO membrane and GO-PSS composite membranes under different concentration gradients
图 4 (a) GO薄膜和GO-PSS-65%薄膜在50倍盐度差条件下的I值和P值随着外加负载的变化；(b) GO薄膜和GO-PSS复合薄膜在50倍盐度差条件下的P值变化；(c) GO-PSS-65%薄膜在50倍盐度差条件下的持续功率输出情况
Figure 4. (a) Current density and power density of GO membrane and GO-PSS-65% membrane as a function of RL under a concentration gradient of 0.01/0.5 mol·L−1 NaCl; (b) power density of GO-PSS composite membranes with different PSS contents; (c) power output variation of GO-PSS-65% membrane over time at a 50-fold concentration gradient
图 5 (a) GO-PSS-55%、GO-PAA-55%和 GO-PVA-55%薄 膜在 50 倍盐度差条件下的 I 值随着外加负载的变化；(b) 三种薄膜在 50 倍盐度差条件下的 P 值随着外加负载的变 化；(c) GO-PSS-55%薄膜与已报道的二维纳米通道薄膜 之间的性能比较
Figure 5. (a) I values of GO-PSS-55%, GO-PAA-55%, and GO-PVA-55% membranes as a function of RL under a concentration gradient of 0.01/0.5 mol·L−1 NaCl; (b) P values of these three membranes calculated from the I values; (c) comparison of GO-PSS-55% with the state-of-art two-dimensional nanochannel membranes in terms of converting osmotic energy from a concentration gradient of 0.01/0.5 mol·L−1 NaCl
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