质子传导膜内受限空间离子扩散过程

doi:10.3969/j.issn.0438-1157.2013.02.038

化工学报 ›› 2013, Vol. 64 ›› Issue (2): 689-695.DOI: 10.3969/j.issn.0438-1157.2013.02.038

质子传导膜内受限空间离子扩散过程

青格乐图, 宋士强, 范永生, 王保国

清华大学化学工程系,化学工程联合国家重点实验室,北京 100084

收稿日期:2012-07-31 修回日期:2012-09-03 出版日期:2013-02-05 发布日期:2013-02-05
通讯作者: 王保国
作者简介:青格乐图(1987—),男,硕士研究生。
基金资助:
化学工程联合国家重点实验室2011年自主课题立项支持;国家自然科学基金项目(21076112,21276134);国家重点基础研究发展计划项目(2010CB227202)。

Ion diffusion behaviors through porous proton conductive membrane

QING Geletu, SONG Shiqiang, FAN Yongsheng, WANG Baoguo

State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Received:2012-07-31 Revised:2012-09-03 Online:2013-02-05 Published:2013-02-05
Supported by:
supported by the Project of State Key Laboratory of Chemical Engineering in 2011, the National Natural Science Foundation of China(21076112, 21276134) and the National Basic Research Program of China(2010CB227202).

摘要/Abstract

摘要： 以具有纳米尺度孔径的聚偏氟乙烯(PVDF)质子传导膜为对象,研究电解质溶液中水合离子在受限空间内的传递行为,证明使用纳米尺度多孔膜代替离子交换膜用于液流电池过程的可行性。利用渗透实验分别研究浓度场、压力场,以及不同渗透压条件下膜中离子扩散和水迁移现象,分析传质行为与膜结构和组成之间的关系。结果表明离子在纳米尺度孔径的PVDF膜中的扩散过程与溶液中类似,表观离子扩散系数不受浓度差推动力的影响;离子交换膜中的表观离子扩散系数随浓度差推动力提高而增加。在渗透压作用下,自制PVDF纳米孔膜的水迁移速率低于Nafion 117膜,水迁移带来的负面影响更小;对于H⁺/VO²⁺的离子选择系数超过300,有效透过H⁺而阻止VO²⁺,适用于全钒液流电池过程。

关键词: 全钒液流电池, 质子传导, 离子扩散系数, 受限空间, 膜结构

Abstract: To prove the feasibility that nano-scale porous membrane can replace ion exchange membrane used for vanadium redox flow battery(VRB), mass transfer of hydrated-ion in electrolyte solution through a limited space formed by PVDF nano-porous proton conductive membranes was studied.On a self-designed ion diffusion cell, NaCl and water permeation processes were measured under given concentration and hydrodynamic gradient, as well as osmotic pressure.The results obtained can be applied to correlate mass transport behaviors with membrane morphology.The results show that the behavior of ion diffusion through nano-scale limited space is similar to that in a bulk electrolyte solution; apparent diffusion coefficients are independent of ion concentration.In contrast, apparent diffusion coefficients of ion permeation through ion exchange membrane obviously increase with concentration gradient.For a given osmotic pressure, PVDF nano-porous proton conductive membranes have smaller water permeation rate than that of Nafion 117, and negative influence is also much smaller.Self-made PVDF proton conductive membrane can effectively reject VO²⁺, providing selectivity over 300 for H⁺/VO²⁺ electrolyte at ambient temperature, which means that it is possible to replace ion exchange membrane in flow battery application.

Key words: all-vanadium redox flow battery, proton conduction, ion diffusion coefficient, limited space, membrane morphology

中图分类号:

TQ150.1

青格乐图, 宋士强, 范永生, 王保国. 质子传导膜内受限空间离子扩散过程[J]. 化工学报, 2013, 64(2): 689-695.

QING Geletu, SONG Shiqiang, FAN Yongsheng, WANG Baoguo. Ion diffusion behaviors through porous proton conductive membrane[J]. CIESC Journal, 2013, 64(2): 689-695.

参考文献 19

[1]	Skyllas-Kazacos M, Chakrabarti M H, Hajimolana S A, Mjalli F S, Saleem M.Progress in flow battery research and development[J].J.Electrochem.Soc., 2011, 158(8):R55-R79
[2]	Weber A Z, Mench M M, Meyers J P, Ross P N, Gostick J T, Liu Qinghua.Redox flow batteries:a review[J].J.Appl.Electrochem., 2011, 41:1137-1164
[3]	Yin Haitao(尹海涛).Study on all-vanadium redox flow battery for electricity energy storage.Beijing:Tsinghua University, 2006
[4]	Jia Zhijun, Wang Baoguo, Song Shiqiang, Chen Xiao.Effect of polyhydroxy-alcohol on the electrochemical behavior of the positive electrolyte for vanadium redox flow batteries[J].J.Electrochem.Soc., 2012, 159(6): A843-A847
[5]	Chen Jinqing(陈金庆), Wang Baoguo(王保国), Yang Jichu(杨基础).Adsorption equilibria of VO2+/H+ in cation exchange membrane[J].Journal of Tsinghua University:Natural Science(清华大学学报:自然科学版), 2009, 49(6):884-887
[6]	Wang Baoguo(王保国).Review of the development of proton exchange membranes in the renewable energy technology[J].Membrane Science and Technology(膜科学与技术), 2010, 30(1):1-8
[7]	Chen Jinqing, Wang Baoguo, Yang Jichu.Adsorption and diffusion of VO2+ and VO2+ across cation membrane for all-vanadium redox flow battery[J].Solvent Extr.Ion Exch., 2009, 27:312-327
[8]	Chen Jinqing(陈金庆), Zhu Shunquan(朱顺泉), Wang Baoguo(王保国), Yang Jichu(杨基础).Model of open-circuit voltage for all-vanadium redox flow battery[J].CIESC Journal(化工学报), 2009, 60(1):211-215
[9]	Mai Zhensheng, Zhang Huamin, Li Xianfeng, Xiao Shaohua, Zhang Hongzhang.Nafion/polyvinylidene fluoride blend membranes with improved ion selectivity for vanadium redox flow battery application[J].J.Power Sources, 2011, 196:5737-5741
[10]	Trogadas P, Pinot E, Fuller T F.Composite solvent-casted Nafion membranes for vanadium redox flow batteries[J].Electrochem.Solid State Lett., 2012, 15(1):A5-A8
[11]	Vijayakumar M, Schwenzer B, Kim S, Yang Zhenguo, Thevuthasan S, Liu Jun, Graff G L, Hu Jianzhi. Investigation of local environments in Nafion-SiO2 composite membranes used in vanadium redox flow batteries[J].Solid State Nucl.Magn.Reson., 2012, 42:71-80
[12]	Teng Xiangguo, Lei Jie, Gu Xuecai, Dai Jicui, Zhu Yongming, Li Faqiang.Nafion-sulfonated organosilica composite membrane for all vanadium redox flow battery[J].Ionics, 2012, 18:513-521
[13]	Teng Xiangguo(滕祥国), Zhao Yongtao(赵永涛), Xi Jingyu(席靖宇),Wu Zenghua(武增华), Qiu Xinping(邱新平), Chen Liquan(陈立泉).Nafion/organic silica hybrid membrane for vanadium redox flow battery[J].Acta Chimica Sinica(化学学报), 2009, 67(6):471-476
[14]	Liu Ping(刘平), Qing Geletu(青格乐图), Guo Weinan(郭伟男), Chen Xiao(陈晓), Chu Xiao(初晓), Wang Baoguo(王保国).Scale-up of a novel proton conductive membrane and characterization for VRB application[J].Membrane Science and Technology(膜科学与技术), 2012, 32(2):24-29
[15]	Wang Baoguo(王保国), Long Fei(龙飞), Fan Yongsheng(范永生), Liu Ping(刘平).A method for manufacture proton conductive membrane:CN 2009100770246.2011-05-11
[16]	Wang Baoguo, Qing Geletu, Guo Weinan.Formation of PVDF nanoporous membrane using hydrophobic/hydrophilic based-on phase separation//The 7th Conference of Asesanian Membrane Society(AMS7).Busan, Korea, 2012:S1-005
[17]	Wang Baoguo, Song Shiqiang, Qing Geletu, Chen Xiao, Guo Weinan, Fan Yongsheng.Development of VRB stack and proton conductive membrane for electricity energy storage application//Swanbarton Limited, The International Flow Battery Forum.Munich, Germany:Compass Graphic Design Ltd., 2012:84
[18]	Wang Yundong(王运东), Luo Guangsheng(骆广生), Liu Qian(刘谦).Principle of Transport Processes(传递过程原理)[M].Beijing:Tsinghua University Press, 2002:294
[19]	Schmidt-Rohr K, Chen Qiang.Parallel cylindrical water nanochannels in Nafion fuel-cell membranes[J].Nat. Mater., 2008, 7:75-83

质子传导膜内受限空间离子扩散过程

Ion diffusion behaviors through porous proton conductive membrane

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 19

相关文章 15

编辑推荐

Metrics

本文评价

[1]	胡超, 董玉明, 张伟, 张红玲, 周鹏, 徐红彬. 浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液[J]. 化工学报, 2023, 74(S1): 338-345.
[2]	杜若晗, 逄博, 王宁, 崔福军, 郭明钢, 贺高红, 吴雪梅. 连续共价有机框架筛分复合膜及全钒电池性能[J]. 化工学报, 2022, 73(9): 4163-4172.
[3]	解文潇, 贾胜坤, 张会书, 罗祎青, 袁希钢. 受限空间内浮升气泡与液体间传质行为实验研究[J]. 化工学报, 2022, 73(7): 2902-2911.
[4]	王世茂, 杜扬, 李国庆, 齐圣, 王波, 李阳超. 局部开口受限空间油气爆燃的超压瞬变与火焰行为[J]. 化工学报, 2017, 68(8): 3310-3318.
[5]	王世茂, 杜扬, 梁建军, 周艳杰, 李国庆, 齐圣. 破坏压力对含有弱顶面受限空间内油气爆燃超压荷载的影响[J]. 化工学报, 2017, 68(12): 4865-4873.
[6]	朱乐, 齐亮, 姚克俭, 谢晓峰. 磁电复合场下正极钒离子的跨膜传质[J]. 化工学报, 2016, 67(S1): 148-158.
[7]	吴松林, 杜扬, 张培理, 梁建军. 点火方式对受限空间油气爆燃规律的影响[J]. 化工学报, 2016, 67(4): 1626-1632.
[8]	吴洪, 杨昊, 赵宇宁, 李震, 姜忠义. 磷酸化二氧化硅填充磺化聚醚醚酮质子交换膜的制备及表征[J]. 化工学报, 2016, 67(1): 358-367.
[9]	张友, 王树博, 齐亮, 姚克俭. 协同场作用下钒离子在质子交换膜中的传质过程[J]. 化工学报, 2015, 66(S1): 81-88.
[10]	李晨飞, 王树博, 谢晓峰, 张建文. 全钒液流电池石墨毡电极的Ga₂O₃修饰[J]. CIESC Journal, 2015, 66(S1): 277-281.
[11]	李彦, 徐铜文. 全钒液流电池用离子交换膜的研究进展[J]. 化工学报, 2015, 66(9): 3296-3304.
[12]	李明华, 范永生, 王保国. 全钒液流电池充电/放电过程模型[J]. 化工学报, 2014, 65(1): 313-318.
[13]	青格乐图, 郭伟男, 范永生, 王保国. 全钒液流电池用质子传导膜研究进展[J]. 化工学报, 2013, 64(2): 427-435.
[14]	徐　波1，齐　亮1，姚克俭1，谢晓峰2. 全钒液流电池电解液分布的数值模拟[J]. 化工进展, 2013, 32(02): 313-319.
[15]	徐波, 齐亮, 姚克俭, 刘然, 杨春, 谢晓峰. 全钒液流电池VO²⁺离子跨膜渗透行为[J]. 化工学报, 2012, 63(S2): 126-131.