Minority Groups in Block Copolymer Self-assembled into High-density Ion Transport Channels

Wei Wen; Peng-xiang Liu; Yu-rong Guo; Min Zhao; Liang-zhi Li; Long-cheng Gao

doi:10.11777/j.issn1000-3304.2025.25175

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Minority Groups in Block Copolymer Self-assembled into High-density Ion Transport Channels

Research Article | 更新时间：2026-02-01

- Minority Groups in Block Copolymer Self-assembled into High-density Ion Transport Channels
- Acta Polymerica Sinica Vol. 57, Issue 2, Pages: 522-529(2026)
- 作者机构：
  
  1.成都飞机工业(集团)有限责任公司成都 610092
  2.北京航空航天大学化学学院北京 100191
- 作者简介：
  
  Long-cheng Gao, E-mail: lcgao@buaa.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25175
  CLC：
- CSTR：32057.14.GFZXB.2025.7478
- Received：26 July 2025，
  
  Accepted：26 September 2025，
  
  Published Online：18 December 2025，
  
  Published：20 February 2026
- 稿件说明：
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文蔚, 刘鹏祥, 郭玉蓉, 赵敏, 李良志, 高龙成. 嵌段共聚物自组装诱导微量离子基团构筑高密度通道阵列. 高分子学报, 2026, 57(2), 522-529.

Wen, W.; Liu, P. X.; Guo, Y. R.; Zhao, M.; Li, L. Z.; Gao, L. C. Minority groups in block copolymer self-assembled into high-density ion transport channels. Acta Polymerica Sinica (in Chinese), 2026, 57(2), 522-529.
文蔚, 刘鹏祥, 郭玉蓉, 赵敏, 李良志, 高龙成. 嵌段共聚物自组装诱导微量离子基团构筑高密度通道阵列. 高分子学报, 2026, 57(2), 522-529. DOI： 10.11777/j.issn1000-3304.2025.25175. CSTR： 32057.14.GFZXB.2025.7478.

Wen, W.; Liu, P. X.; Guo, Y. R.; Zhao, M.; Li, L. Z.; Gao, L. C. Minority groups in block copolymer self-assembled into high-density ion transport channels. Acta Polymerica Sinica (in Chinese), 2026, 57(2), 522-529. DOI： 10.11777/j.issn1000-3304.2025.25175. CSTR： 32057.14.GFZXB.2025.7478.

摘要

离子交换膜(IEMs)是多种电化学系统的核心部件. 离子选择性与离子通量是评价IEMs的2大关键性能指标，兼具高选择性与高通量的IEMs一直是科研界和工业界追求的目标. 在传统IEMs中，离子基团组装形成三维的离子通道网络，当离子基团含量较低时，难以形成连续通道，导致通量受限；而增加离子基团含量虽可提升通量，却会引发膜材料的过度溶胀，致使选择性衰减. 如何用微量离子基团构筑高密度离子传输通道存在很大困难. 针对这一难题，我们提出通过微量离子基团的诱导组装策略，构建高密度1D离子通道阵列膜. 利用4-氨基偶氮苯(Azo)与微量马来酸酐接枝的聚(苯乙烯-乙烯/丁烯-苯乙烯)嵌段共聚物(SEBS)反应，在接枝偶氮苯的同时，原位产生羧基. 尽管Azo接枝在乙烯/丁烯段，但与苯乙烯段的相容性更好. 因此，在SEBS自组装过程中，Azo具有向苯乙烯区域迁移的趋势，诱导了羧基在两相界面富集，形成了高密度的离子通道阵列. 这种“以少聚多”的构筑方法相异于传统材料的设计思路，实现了离子通量与选择性的协同优化，表现出优异的盐差能转换能力(9.35 W/m

，500倍浓度梯度)，为下一代高性能IEMs的开发提供了新思路.

Abstract

Ion exchange membranes (IEMs) are essential components in various electrochemical systems. Ion selectivity and ion flux are the two key parameters for evaluating IEM performance

and achieving both high selectivity and high flux has long been a major challenge in both academic and industrial communities. In conventional IEMs

ionic groups assemble into a three-dimensional ion transport network. However

at low ionic group content

the formation of continuous ion channels is limited

resulting in low ion flux. Increasing the ionic group content can enhance ion flux but often leads to excessive swelling

thereby compromising selectivity. Constructing high-density ion transport channels with a minimal number of ionic groups remains a significant difficulty. To address this issue

we proposed a strategy to fabricate high-density ion channels by using tiny amounts of ionic groups. 4-Aminoazobenzene (Azo) was grafted onto a styrene-ethylene/butylene-styrene (SEBS) block copolymer containing a small amount of maleic anhydride (MA). During the grafting reaction

carboxylic acid groups were introduced in situ. Although the Azo units are grafted onto the ethylene/butylene segment

their stronger compatibility with the polystyrene (PS) domains drives their migration toward the PS regions during self-assembly. This process induces the interfacial enrichment of carboxyl groups

resulting in the formation of a high-density ion channel array. This "less-to-more" design concept differs from conventional material strategies and enables a synergistic e

nhancement of both ion flux and selectivity. The resulting membrane exhibited excellent osmotic energy conversion performance

achieving a power density of 9.35 W/m

under a 500-fold salinity gradient

offering a novel pathway for the development of next-generation high-performance IEMs.

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references

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