基于亲核取代反应制备双离子侧链阴离子交换膜（英文）
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摘要
作为碱性燃料电池的关键组分,阴离子交换膜决定了其能量转化效率,输出功率密度及长期稳定性.最近,带有双离子侧链的阴离子交换膜,因其良好的微相分离能力,表现出了优异的离子电导率.然而,昂贵且复杂的合成方法限制了其商业化应用.为了解决这一问题,本文开发了一种简单、温和的合成方法.首先通过亲核取代反应将叔胺前驱体引入到聚合物主链上,避免了常用的氯/溴甲基化反应.随后与溴己基-N,N,N-三甲基铵进行简单的门秀金反应,以高产率获得目标聚合物电解质.所得到的阴离子交换膜表现出高的离子电导率,良好的燃料电池性能以及有限的溶胀,表明所提出的策略在燃料电池中具有应用前景.
As a critical component of alkaline fuel cells,anion exchange membranes determine the energy efficiency,output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6-bromo-N,N,N-trimethylhexan-1-aminium bromide, the polymer electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.
As a critical component of alkaline fuel cells,anion exchange membranes determine the energy efficiency,output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6-bromo-N,N,N-trimethylhexan-1-aminium bromide, the polymer electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.
引文
1 Zhang H,Shen PK.Advances in the high performance polymer electrolyte membranes for fuel cells.Chem Soc Rev,2012,41:2382-2394
2 Ran J,Wu L,He Y,et al.Ion exchange membranes:New developments and applications.J Membrane Sci,2017,522:267-291
3 Zakil FA,Kamarudin SK,Basri S.Modified Nafion membranes for direct alcohol fuel cells:An overview.Renew Sustain Energy Rev,2016,65:841-852
4 Lu S,Pan J,Huang A,et al.Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts.Proc Natl Acad Sci USA,2008,105:20611-20614
5 Zakaria Z,Kamarudin SK,Timmiati SN.Membranes for direct ethanol fuel cells:An overview.Appl Energy,2016,163:334-342
6 Zhang H,Shen PK.Recent development of polymer electrolyte membranes for fuel cells.Chem Rev,2012,112:2780-2832
7 Chen N,Zhu H,Chu Y,et al.Cobaltocenium-containing polybenzimidazole polymers for alkaline anion exchange membrane applications.Polym Chem,2016,8:1381-1392
8 Ge X,He Y,Guiver MD,et al.Alkaline anion-exchange membranes containing mobile ion shuttles.Adv Mater,2016,28:3467-3472
9 Zhao Y,Yu H,Xie F,et al.High durability and hydroxide ion conducting pore-filled anion exchange membranes for alkaline fuel cell applications.J Power Sources,2014,269:1-6
10 Zhu L,Zimudzi TJ,Li N,et al.Crosslinking of comb-shaped polymer anion exchange membranes via thiol-ene click chemistry.Polym Chem,2016,7:2464-2475
11 Zhu L,Zimudzi TJ,Wang Y,et al.Mechanically robust anion exchange membranes via long hydrophilic cross-linkers.Macromolecules,2017,50:2329-2337
12 Li N,Guiver MD.Ion transport by nanochannels in ion-containing aromatic copolymers.Macromolecules,2014,47:2175-2198
13 Gao L,He G,Pan Y,et al.Poly(2,6-dimethyl-1,4-phenylene oxide)containing imidazolium-terminated long side chains as hydroxide exchange membranes with improved conductivity.J Membrane Sci,2016,518:159-167
14 Guo D,Lai AN,Lin CX,et al.Imidazolium-functionalized poly(arylene ether sulfone)anion-exchange membranes densely grafted with flexible side chains for fuel cells.ACS Appl Mater Interfaces,2016,8:25279-25288
15 Lin CX,Huang XL,Guo D,et al.Side-chain-type anion exchange membranes bearing pendant quaternary ammonium groups via flexible spacers for fuel cells.J Mater Chem A,2016,4:13938-13948
16 Yan X,Gao L,Zheng W,et al.Long-spacer-chain imidazolium functionalized poly(ether ether ketone)as hydroxide exchange membrane for fuel cell.Int J Hydrogen Energy,2016,41:14982-14990
17 Zhang M,Liu J,Wang Y,et al.Highly stable anion exchange membranes based on quaternized polypropylene.J Mater Chem A,2015,3:12284-12296
18 Zhang M,Shan C,Liu L,et al.Facilitating anion transport in polyolefin-based anion exchange membranes via bulky side chains.ACS Appl Mater Interfaces,1944,8:23321-23330
19 Zuo P,Su Y,Li W.Comb-like poly(ether-sulfone)membranes derived from planar 6,12-diaryl-5,11-dihydroindolo[3,2-b]carbazole monomer for alkaline fuel cells.Macromol Rapid Commun,2016,37:1748-1753
20 Zheng J,Zhang Q,Qian H,et al.Self-assembly prepared anion exchange membranes with high alkaline stability and organic solvent resistance.J Membrane Sci,2017,522:159-167
21 Yang Z,Zhou J,Wang S,et al.A strategy to construct alkali-stable anion exchange membranes bearing ammonium groups via flexible spacers.J Mater Chem A,2015,3:15015-15019
22 Dang HS,Weiber EA,Jannasch P.Poly(phenylene oxide)functionalized with quaternary ammonium groups via flexible alkyl spacers for high-performance anion exchange membranes.J Mater Chem A,2015,3:5280-5284
23 Takaba H,Hisabe T,Shimizu T,et al.Molecular modeling of OH-transport in poly(arylene ether sulfone ketone)s containing quaternized ammonio-substituted fluorenyl groups as anion exchange membranes.J Membrane Sci,2017,522:237-244
24 Chen Y,Lin Q,Zheng Y,et al.Densely quaternized anion exchange membranes synthesized from Ullmann coupling extension of ionic segments for vanadium redox flow batteries.Sci China Mater,2019,62:211-224
25 Hu Y,Wang B,Li X,et al.Densely quaternized poly(arylene ether)s with distinct phase separation for highly anion-conductive membranes.J Power Sources,2018,387:33-42
26 Weiber EA,Jannasch P.Ion distribution in quaternary-ammonium-functionalized aromatic polymers:effects on the ionic clustering and conductivity of anion-exchange membranes.ChemSusChem,2015,7:2621-2630
27 Zhang W,Qiu X,Ueda M,et al.Synthesis and properties of poly(phenylene-co-arylene ether ketone)s with five quaternary ammonium groups on a phenyl unit for anion-exchange membranes.Solid State Ion,2018,314:187-194
28 Han J,Zhu L,Pan J,et al.Elastic long-chain multication crosslinked anion exchange membranes.Macromolecules,2017,50:3323-3332
29 He Y,Zhang J,Liang X,et al.Achieving high anion conductivity by densely grafting of ionic strings.J Membrane Sci,2018,559:35-41
30 Wang J,Gu S,Xiong R,et al.Structure-property relationships in hydroxide-exchange membranes with cation strings and high ionexchange capacity.ChemSusChem,2015,8:4229-4234
31 He Y,Si J,Wu L,et al.Dual-cation comb-shaped anion exchange membranes:Structure,morphology and properties.J Membrane Sci,2016,515:189-195
32 He Y,Wu L,Pan J,et al.A mechanically robust anion exchange membrane with high hydroxide conductivity.J Membrane Sci,2016,504:47-54
33 He Y,Pan J,Wu L,et al.A novel methodology to synthesize highly conductive anion exchange membranes.Sci Rep,2015,5:13417
34 Shi Q,Chen P,Zhang X,et al.Synthesis and properties of poly(arylene ether sulfone)anion exchange membranes with pendant benzyl-quaternary ammonium groups.Polymer,2017,121:137-148
35 Dai J,He G,Ruan X,et al.Constructing a rigid crosslinked structure for enhanced conductivity of imidazolium functionalized polysulfone hydroxide exchange membrane.Int J Hydrogen Energy,2016,41:10923-10934
36 Puthiyapura VK,Mamlouk M,Pasupathi S,et al.Physical and electrochemical evaluation of ATO supported IrO2catalyst for proton exchange membrane water electrolyser.J Power Sources,2014,269:451-460
37 Hnát J,PlevováM,?itka J,et al.Anion-selective materials with1,4-diazabicyclo[2.2.2]octane functional groups for advanced alkaline water electrolysis.Electrochim Acta,2017,248:547-555
38 Largier TD,Cornelius CJ.Random quaternary ammonium DielsAlder poly(phenylene)copolymers for improved vanadium redox flow batteries.J Power Sources,2017,352:149-155
39 Yan J,Zhu L,Chaloux BL,et al.Anion exchange membranes by bromination of tetramethylbiphenol-based poly(sulfone)s.Polym Chem,2017,8:2442-2449
40 He Y,Pan J,Wu L,et al.Facile preparation of 1,8-diazabicyclo[5.4.0]undec-7-ene based High performance anion exchange membranes for diffusion dialysis applications.J Membrane Sci,2015,491:45-52
41 Zhu Y,He Y,Ge X,et al.A benzyltetramethylimidazolium-based membrane with exceptional alkaline stability in fuel cells:role of its structure in alkaline stability.J Mater Chem A,2018,6:527-534
42 Xu J,Lin Q,Yu Y,et al.Facile synthesis of fluorinated poly(arylene ether)s with pendant sulfonic acid groups for proton exchange membranes.Int J Hydrogen Energy,2017,42:27100-27110
43 Chen X,LüH,Lin Q,et al.Partially fluorinated poly(arylene ether)s bearing long alkyl sulfonate side chains for stable and highly conductive proton exchange membranes.J Membrane Sci,2018,549:12-22
44 Chen N,Long C,Li Y,et al.A hamburger-structure imidazoliummodified silica/polyphenyl ether composite membrane with enhancing comprehensive performance for anion exchange membrane applications.Electrochim Acta,2018,268:295-303
45 Chen N,Long C,Li Y,et al.High-performance layered double hydroxide/poly(2,6-dimethyl-1,4-phenylene oxide)membrane with porous sandwich structure for anion exchange membrane fuel cell applications.J Membrane Sci,2018,552:51-60
46 Zhao Y,Feng L,Gao J,et al.Study on tunable crosslinking anion exchange membranes fabrication and degradation mechanism.Int J Hydrogen Energy,2016,41:16264-16274
47 Varcoe JR,Atanassov P,Dekel DR,et al.Anion-exchange membranes in electrochemical energy systems.Energy Environ Sci,2014,7:3135-3191
48 Deavin OI,Murphy S,Ong AL,et al.Anion-exchange membranes for alkaline polymer electrolyte fuel cells:comparison of pendent benzyltrimethylammonium-and benzylmethylimidazolium-headgroups.Energy Environ Sci,2012,5:8584
49 Hao J,Jiang Y,Gao X,et al.Functionalization of polybenzimidazole-crosslinked poly(vinylbenzyl chloride)with two cyclic quaternary ammonium cations for anion exchange membranes.J Membrane Sci,2018,548:1-10
50 Sun P,Li Z,Wang S,et al.Performance enhancement of polybenzimidazole based high temperature proton exchange membranes with multifunctional crosslinker and highly sulfonated polyaniline.J Membrane Sci,2018,549:660-669
51 Pan J,Chen C,Li Y,et al.Constructing ionic highway in alkaline polymer electrolytes.Energy Environ Sci,2014,7:354-360
52 Li N,Yan T,Li Z,et al.Comb-shaped polymers to enhance hydroxide transport in anion exchange membranes.Energy Environ Sci,2012,5:7888
2 Ran J,Wu L,He Y,et al.Ion exchange membranes:New developments and applications.J Membrane Sci,2017,522:267-291
3 Zakil FA,Kamarudin SK,Basri S.Modified Nafion membranes for direct alcohol fuel cells:An overview.Renew Sustain Energy Rev,2016,65:841-852
4 Lu S,Pan J,Huang A,et al.Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts.Proc Natl Acad Sci USA,2008,105:20611-20614
5 Zakaria Z,Kamarudin SK,Timmiati SN.Membranes for direct ethanol fuel cells:An overview.Appl Energy,2016,163:334-342
6 Zhang H,Shen PK.Recent development of polymer electrolyte membranes for fuel cells.Chem Rev,2012,112:2780-2832
7 Chen N,Zhu H,Chu Y,et al.Cobaltocenium-containing polybenzimidazole polymers for alkaline anion exchange membrane applications.Polym Chem,2016,8:1381-1392
8 Ge X,He Y,Guiver MD,et al.Alkaline anion-exchange membranes containing mobile ion shuttles.Adv Mater,2016,28:3467-3472
9 Zhao Y,Yu H,Xie F,et al.High durability and hydroxide ion conducting pore-filled anion exchange membranes for alkaline fuel cell applications.J Power Sources,2014,269:1-6
10 Zhu L,Zimudzi TJ,Li N,et al.Crosslinking of comb-shaped polymer anion exchange membranes via thiol-ene click chemistry.Polym Chem,2016,7:2464-2475
11 Zhu L,Zimudzi TJ,Wang Y,et al.Mechanically robust anion exchange membranes via long hydrophilic cross-linkers.Macromolecules,2017,50:2329-2337
12 Li N,Guiver MD.Ion transport by nanochannels in ion-containing aromatic copolymers.Macromolecules,2014,47:2175-2198
13 Gao L,He G,Pan Y,et al.Poly(2,6-dimethyl-1,4-phenylene oxide)containing imidazolium-terminated long side chains as hydroxide exchange membranes with improved conductivity.J Membrane Sci,2016,518:159-167
14 Guo D,Lai AN,Lin CX,et al.Imidazolium-functionalized poly(arylene ether sulfone)anion-exchange membranes densely grafted with flexible side chains for fuel cells.ACS Appl Mater Interfaces,2016,8:25279-25288
15 Lin CX,Huang XL,Guo D,et al.Side-chain-type anion exchange membranes bearing pendant quaternary ammonium groups via flexible spacers for fuel cells.J Mater Chem A,2016,4:13938-13948
16 Yan X,Gao L,Zheng W,et al.Long-spacer-chain imidazolium functionalized poly(ether ether ketone)as hydroxide exchange membrane for fuel cell.Int J Hydrogen Energy,2016,41:14982-14990
17 Zhang M,Liu J,Wang Y,et al.Highly stable anion exchange membranes based on quaternized polypropylene.J Mater Chem A,2015,3:12284-12296
18 Zhang M,Shan C,Liu L,et al.Facilitating anion transport in polyolefin-based anion exchange membranes via bulky side chains.ACS Appl Mater Interfaces,1944,8:23321-23330
19 Zuo P,Su Y,Li W.Comb-like poly(ether-sulfone)membranes derived from planar 6,12-diaryl-5,11-dihydroindolo[3,2-b]carbazole monomer for alkaline fuel cells.Macromol Rapid Commun,2016,37:1748-1753
20 Zheng J,Zhang Q,Qian H,et al.Self-assembly prepared anion exchange membranes with high alkaline stability and organic solvent resistance.J Membrane Sci,2017,522:159-167
21 Yang Z,Zhou J,Wang S,et al.A strategy to construct alkali-stable anion exchange membranes bearing ammonium groups via flexible spacers.J Mater Chem A,2015,3:15015-15019
22 Dang HS,Weiber EA,Jannasch P.Poly(phenylene oxide)functionalized with quaternary ammonium groups via flexible alkyl spacers for high-performance anion exchange membranes.J Mater Chem A,2015,3:5280-5284
23 Takaba H,Hisabe T,Shimizu T,et al.Molecular modeling of OH-transport in poly(arylene ether sulfone ketone)s containing quaternized ammonio-substituted fluorenyl groups as anion exchange membranes.J Membrane Sci,2017,522:237-244
24 Chen Y,Lin Q,Zheng Y,et al.Densely quaternized anion exchange membranes synthesized from Ullmann coupling extension of ionic segments for vanadium redox flow batteries.Sci China Mater,2019,62:211-224
25 Hu Y,Wang B,Li X,et al.Densely quaternized poly(arylene ether)s with distinct phase separation for highly anion-conductive membranes.J Power Sources,2018,387:33-42
26 Weiber EA,Jannasch P.Ion distribution in quaternary-ammonium-functionalized aromatic polymers:effects on the ionic clustering and conductivity of anion-exchange membranes.ChemSusChem,2015,7:2621-2630
27 Zhang W,Qiu X,Ueda M,et al.Synthesis and properties of poly(phenylene-co-arylene ether ketone)s with five quaternary ammonium groups on a phenyl unit for anion-exchange membranes.Solid State Ion,2018,314:187-194
28 Han J,Zhu L,Pan J,et al.Elastic long-chain multication crosslinked anion exchange membranes.Macromolecules,2017,50:3323-3332
29 He Y,Zhang J,Liang X,et al.Achieving high anion conductivity by densely grafting of ionic strings.J Membrane Sci,2018,559:35-41
30 Wang J,Gu S,Xiong R,et al.Structure-property relationships in hydroxide-exchange membranes with cation strings and high ionexchange capacity.ChemSusChem,2015,8:4229-4234
31 He Y,Si J,Wu L,et al.Dual-cation comb-shaped anion exchange membranes:Structure,morphology and properties.J Membrane Sci,2016,515:189-195
32 He Y,Wu L,Pan J,et al.A mechanically robust anion exchange membrane with high hydroxide conductivity.J Membrane Sci,2016,504:47-54
33 He Y,Pan J,Wu L,et al.A novel methodology to synthesize highly conductive anion exchange membranes.Sci Rep,2015,5:13417
34 Shi Q,Chen P,Zhang X,et al.Synthesis and properties of poly(arylene ether sulfone)anion exchange membranes with pendant benzyl-quaternary ammonium groups.Polymer,2017,121:137-148
35 Dai J,He G,Ruan X,et al.Constructing a rigid crosslinked structure for enhanced conductivity of imidazolium functionalized polysulfone hydroxide exchange membrane.Int J Hydrogen Energy,2016,41:10923-10934
36 Puthiyapura VK,Mamlouk M,Pasupathi S,et al.Physical and electrochemical evaluation of ATO supported IrO2catalyst for proton exchange membrane water electrolyser.J Power Sources,2014,269:451-460
37 Hnát J,PlevováM,?itka J,et al.Anion-selective materials with1,4-diazabicyclo[2.2.2]octane functional groups for advanced alkaline water electrolysis.Electrochim Acta,2017,248:547-555
38 Largier TD,Cornelius CJ.Random quaternary ammonium DielsAlder poly(phenylene)copolymers for improved vanadium redox flow batteries.J Power Sources,2017,352:149-155
39 Yan J,Zhu L,Chaloux BL,et al.Anion exchange membranes by bromination of tetramethylbiphenol-based poly(sulfone)s.Polym Chem,2017,8:2442-2449
40 He Y,Pan J,Wu L,et al.Facile preparation of 1,8-diazabicyclo[5.4.0]undec-7-ene based High performance anion exchange membranes for diffusion dialysis applications.J Membrane Sci,2015,491:45-52
41 Zhu Y,He Y,Ge X,et al.A benzyltetramethylimidazolium-based membrane with exceptional alkaline stability in fuel cells:role of its structure in alkaline stability.J Mater Chem A,2018,6:527-534
42 Xu J,Lin Q,Yu Y,et al.Facile synthesis of fluorinated poly(arylene ether)s with pendant sulfonic acid groups for proton exchange membranes.Int J Hydrogen Energy,2017,42:27100-27110
43 Chen X,LüH,Lin Q,et al.Partially fluorinated poly(arylene ether)s bearing long alkyl sulfonate side chains for stable and highly conductive proton exchange membranes.J Membrane Sci,2018,549:12-22
44 Chen N,Long C,Li Y,et al.A hamburger-structure imidazoliummodified silica/polyphenyl ether composite membrane with enhancing comprehensive performance for anion exchange membrane applications.Electrochim Acta,2018,268:295-303
45 Chen N,Long C,Li Y,et al.High-performance layered double hydroxide/poly(2,6-dimethyl-1,4-phenylene oxide)membrane with porous sandwich structure for anion exchange membrane fuel cell applications.J Membrane Sci,2018,552:51-60
46 Zhao Y,Feng L,Gao J,et al.Study on tunable crosslinking anion exchange membranes fabrication and degradation mechanism.Int J Hydrogen Energy,2016,41:16264-16274
47 Varcoe JR,Atanassov P,Dekel DR,et al.Anion-exchange membranes in electrochemical energy systems.Energy Environ Sci,2014,7:3135-3191
48 Deavin OI,Murphy S,Ong AL,et al.Anion-exchange membranes for alkaline polymer electrolyte fuel cells:comparison of pendent benzyltrimethylammonium-and benzylmethylimidazolium-headgroups.Energy Environ Sci,2012,5:8584
49 Hao J,Jiang Y,Gao X,et al.Functionalization of polybenzimidazole-crosslinked poly(vinylbenzyl chloride)with two cyclic quaternary ammonium cations for anion exchange membranes.J Membrane Sci,2018,548:1-10
50 Sun P,Li Z,Wang S,et al.Performance enhancement of polybenzimidazole based high temperature proton exchange membranes with multifunctional crosslinker and highly sulfonated polyaniline.J Membrane Sci,2018,549:660-669
51 Pan J,Chen C,Li Y,et al.Constructing ionic highway in alkaline polymer electrolytes.Energy Environ Sci,2014,7:354-360
52 Li N,Yan T,Li Z,et al.Comb-shaped polymers to enhance hydroxide transport in anion exchange membranes.Energy Environ Sci,2012,5:7888