CN115304747B - 膦酸烷基链修饰的共轭微多孔聚合物、制备方法及其应用 - Google Patents
膦酸烷基链修饰的共轭微多孔聚合物、制备方法及其应用 Download PDFInfo
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- XJIJQOFZIULKCI-UHFFFAOYSA-N 1,3,5-tris(4-ethynylphenyl)benzene Chemical compound C1=CC(C#C)=CC=C1C1=CC(C=2C=CC(=CC=2)C#C)=CC(C=2C=CC(=CC=2)C#C)=C1 XJIJQOFZIULKCI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 18
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 11
- -1 phosphonic acid alkyl chain modified p-dibromobenzene Chemical class 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- VUERQRKTYBIULR-UHFFFAOYSA-N fosetyl Chemical compound CCOP(O)=O VUERQRKTYBIULR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
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- 238000002156 mixing Methods 0.000 claims description 3
- VTIJFLNLHCYVPF-UHFFFAOYSA-N C[SiH](C)C.Br Chemical compound C[SiH](C)C.Br VTIJFLNLHCYVPF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical class C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000005859 coupling reaction Methods 0.000 abstract description 3
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- 238000013329 compounding Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- VALXCIRMSIFPFN-UHFFFAOYSA-N 2,5-dibromobenzene-1,4-diol Chemical compound OC1=CC(Br)=C(O)C=C1Br VALXCIRMSIFPFN-UHFFFAOYSA-N 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
本发明公开了一种膦酸烷基链修饰的共轭微多孔聚合物、制备方法及其应用。所述的膦酸烷基链修饰的共轭微多孔聚合物由1,3,5‑三(4‑乙炔基苯基)苯和膦酸烷基链修饰的对二溴苯通过Sonogasira coupling反应制得。本发明的共轭微多孔聚合物具有良好的化学和热稳定性,将其与磷酸复合压片制成的质子交换膜材料在无水状态下显示出良好的质子传导性能,适用于燃料电池领域。
Description
技术领域
本发明属于共轭微多孔聚合物(CMPs)技术领域,涉及一种膦酸烷基链修饰的共轭微多孔聚合物、制备方法及其在质子传导中的应用。
背景技术
质子交换膜燃料电池(PEMFCs)因其卓越的能量密度和绿色认证,有望代替化石燃料。然而PEMFCs具有不稳定、效率低下和不经济的特点,限制了其进一步推广。质子交换膜作为燃料电池的重要组成部分,如何提高其性能成为了至关重要的问题。
质子传导在很大程度上依赖于水介质,这导致PEMFCs增加了额外的加湿系统,使电池系统更加复杂,增加了整体成本。而且质子电导率会随着内部水分子的丢失和氢键的破坏而显著下降,导致燃料电池的输出功率发生衰减。因此需要开发新型的无水质子导体。在多孔结构固体中嵌入非挥发性液体酸是制备无水质子导体的预期解决方案。
共轭微多孔聚合物(CMPs)是一类由有机结构单元通过共价键连接而成的有机多孔材料,具有孔隙率高、比表面积大、质量轻、结构可预先设计、稳定性高等特点,被认为是很有应用前景的质子导体。设计结构合理的CMPs材料,利用CMPs的多孔特点与非挥发性质子酸结合,可以得到良好的无水质子交换膜材料。但是,简单的将非挥发性液体酸如磷酸(H3PO4)物理掺杂到多孔材料中具有一些缺点,如磷酸易渗出以及质子传导率低等。文献1【ACS Appl.Mater.Interfaces 2021,13,15536-15541】报道了氟链修饰的CMP物理掺杂磷酸用于无水质子传导,其最高质子传导率只有4.39×10-3Scm-1。文献2【Nat Commun 11,1981(2020)】报道了COF中物理掺杂磷酸用于无水质子传导,虽然在理论最大量的磷酸掺杂以及160℃高温下,其最高质子传导率能达到1.91×10-1Scm-1,但是其循环性能只维持20h左右。因此,设计具有高质子传导率,并且具有高长程稳定性的无水质子交换膜材料仍然是一项挑战。
发明内容
本发明的目的之一在于提供一种膦酸烷基链修饰的共轭微多孔聚合物,所述的膦酸烷基链修饰的共轭微多孔聚合物由1,3,5-三(4-乙炔基苯基)苯(4,4”-diethynyl-5'-(4-ethynylphenyl)-1,1':3',1”-terphenyl)和膦酸烷基链修饰的对二溴苯(1,4-dibromobenzene)通过Sonogasira coupling反应制得,其结构式如下:
本发明所述的1,3,5-三(4-乙炔基苯基)苯的结构式如下:
本发明所述的膦酸烷基链修饰的对二溴苯的结构式如下:
本发明的目的之二在于提供上述膦酸烷基链修饰的共轭微多孔聚合物的制备方法,具体包括以下步骤:
步骤1,将膦酸烷基链修饰的对二溴苯对应的膦酸乙基酯和溴化三甲基硅烷(TMSBr)加入无水二氯甲烷中,在氩气环境下、于室温下搅拌反应10~14h,然后加入甲醇,继续在室温下搅拌反应10~14h,反应结束后混合物在减压下浓缩,并在60~80℃真空下干燥12小时以上,得到膦酸烷基链修饰的对二溴苯,所述的膦酸烷基链修饰的对二溴苯对应的膦酸乙基酯的结构式如下:
步骤2,将膦酸烷基链修饰的对二溴苯、1,3,5-三(4-乙炔基苯基)苯、碘化亚铜(CuI)和四三苯基膦钯(Pd(PPh3)4)加入到三乙胺和N,N-二甲基甲酰胺(NEt3/DMF)混合溶剂中,然后将混合物在氩气环境下、于80~90℃搅拌反应60小时以上,反应完成后,冷却至室温,粗品依次用二氯甲烷和丙酮洗涤,再在干燥的丙酮中浸泡,真空干燥,得到膦酸烷基链修饰的共轭微多孔聚合物(CMP-Cn-P)。
优选地,步骤1中,膦酸烷基链修饰的对二溴苯对应的膦酸乙基酯和溴化三甲基硅烷的摩尔比为1:10~1:12。
优选地,步骤2中,1,3,5-三(4-乙炔基苯基)苯、膦酸烷基链修饰的对二溴苯的摩尔比为1:1~1:1.5。
优选地,步骤2中,CuI的摩尔量为1,3,5-三(4-乙炔基苯基)苯的5%~10%,Pd(PPh3)4的摩尔量为1,3,5-三(4-乙炔基苯基)苯的5%~10%。
优选地,步骤2中,三乙胺和N,N-二甲基甲酰胺混合溶剂中,三乙胺和N,N-二甲基甲酰胺的体积比为1:1。
优选地,步骤2中,二氯甲烷的洗涤次数为3次以上,丙酮的洗涤次数为3次以上。
优选地,步骤2中,在丙酮中浸泡的时间为12小时以上。
优选地,步骤2中,真空干燥温度为60~80℃,干燥时间为12小时以上。
本发明的目的之三在于提供基于上述膦酸烷基链修饰的共轭微多孔聚合物的质子交换隔膜的制备方法,包括以下步骤:
按比例将膦酸烷基链修饰的共轭微多孔聚合物和磷酸混合,研磨至混合均匀,然后在80~90℃下真空干燥12小时以上,再在氩气保护气氛、100~120℃下加热5~6小时,冷却后压片制成质子交换隔膜(CMP-Cn-P-XH3PO4,X为磷酸占隔膜总质量的百分比)。
优选地,磷酸占质子交换隔膜总质量的45%~60%。
本发明的目的之四在于提供上述基于膦酸烷基链修饰的共轭微多孔聚合物的质子交换隔膜在燃料电池中的应用。
本发明所述的燃料电池为质子交换膜燃料电池(PEMFC)。
与现有技术相比,本发明具有以下优点:
本发明通过在共轭微多孔聚合物材料中修饰膦酸烷基链,并掺入非挥发性的磷酸,使其具有优异的无水质子传导性能。本发明的质子交换隔膜材料作为电解质,表现出较高的质子传导率,并且具有优异的长程稳定性。例如,CMP-C2-P-60%H3PO4在130℃时的质子传导率可达到2.15×10-2S cm-1,CMP-C2-P-45%H3PO4在130℃循环48h,质子传导率是最初的87.6%。
附图说明
图1为C2-P-Br、1,3,5-三(4-乙炔基苯基)苯、膦酸烷基链修饰的共轭微多孔聚合物CMP-C2-P的PXRD谱图;
图2为C2-P-Br、1,3,5-三(4-乙炔基苯基)苯、膦酸烷基链修饰的共轭微多孔聚合物CMP-C2-P的FT-IR谱图;
图3为CMP-C2-P(a)、CMP-C4-P(b)和CMP-C6-P(c)的SEM图;
图4为CMP-C2-P(a)、CMP-C4-P(b)和CMP-C6-P(c)的TEM图;
图5为CMP-C2-P、CMP-C4-P和CMP-C6-P的BET曲线图;
图6为CMP-C2-P粉末和45%磷酸(H3PO4)掺杂,压成片状组装成纽扣电池的能斯特图谱;
图7为CMP-Cn-P(n=2,4,6)粉末和45%磷酸(H3PO4)掺杂,压成片状组装成纽扣电池,得出的电导率与温度的关系图;
图8为CMP-C2-P粉末和45%磷酸(H3PO4)掺杂,压成片状组装成纽扣电池,测试其130℃下的质子传导长程稳定性图。
具体实施方式
下面结合实施例和附图对本发明作进一步详述。
下述实施例中,采用的三乙胺和N,N-二甲基甲酰胺(NEt3/DMF)混合溶剂中,三乙胺和N,N-二甲基甲酰胺的体积比为1:1。
下述实施例中采用的1,3,5-三(4-乙炔基苯基)苯由商业购买获得。膦酸烷基链修饰的对二溴苯参考文献【ACS Applied Materials&Interfaces,12(19),21254-21262;Journal of Medicinal Chemistry,65(5),4030-4057】制备,以C2-P-Br为例,具体合成路线如下:
(1)化合物1:将2,5-二溴氢醌(2.679g,10.00mmol)、1,2-二溴乙烷(2.59ml,30.00mmol)和碳酸钾(6.911g,50.00mmol)溶于无水丙酮(50.00ml)。所得溶液在氩气环境下于90℃回流过夜。所得的混合物在真空下浓缩,然后重新溶解在二氯甲烷中并用水清洗。用无水MgSO4干燥并在真空下除去二氯甲烷后,用硅胶柱色谱法(石油醚/二氯甲烷=2:1,v/v)提纯粗品,得到化合物1。
(2)化合物2:将化合物1(1.500g,3.11mmol)、亚磷酸三乙酯(4.27ml,24.90mml)加入50.00ml的圆底烧瓶中。所得溶液在145℃下回流24小时。将得到的混合物重新溶解在二氯甲烷中并用水清洗。用无水MgSO4干燥并在真空下除去二氯甲烷后,用硅胶柱色谱法(乙酸乙酯)提纯粗品,得到化合物2。
(3)化合物C2-P-Br:将化合物2(0.994g,1.67mmol)和溴化三甲基硅烷(2.64g,20.01mmol)加入无水二氯甲烷(25.00ml)中。所得溶液在氩气环境下于室温下搅拌12小时。将甲醇(50.00mL)加入到所得溶液中。该混合物在室温下搅拌12小时。所得混合物在减压下浓缩,并在80℃真空下干燥12小时,得到膦酸烷基链修饰的对二溴苯(C2-P-Br)。
实施例1
膦酸烷基链修饰的共轭微多孔聚合物(CMP-C2-P)由1,3,5-三(4-乙炔基苯基)苯和C2-P-Br通过Sonogasira coupling反应制得,其结构式如下:
具体步骤如下:
将膦酸烷基链修饰的对二溴苯C2-P-Br(0.241g,0.50mmol)、1,3,5-三(4-乙炔基苯基)苯(0.126g,0.33mmol)、CuI(0.007g,0.04mmol)和Pd(PPh3)4(0.022g,0.02mmol)置于体积比为1:1的NEt3/DMF混合溶剂中,混合物在氩气气氛下于80℃搅拌60小时。反应完成后,冷却至室温。粗品用二氯甲烷(3×10ml)和丙酮(3×10ml)洗涤,在干燥的丙酮中浸泡12小时,在80℃真空下干燥12小时,得到黄色粉末状的CMP-C2-P。
CMP-C2-P-45%H3PO4的制备方法,具体步骤如下:按磷酸占隔膜总质量的45%,分别称取20mgCMP-C2-P与16.36mg磷酸混合,在研钵中充分研磨至混合均匀,放入真空干燥箱中85℃下干燥12小时,再在氩气保护气氛、100℃下加热5h,冷却压片制成质子交换隔膜(CMP-C2-P-45%H3PO4),组装纽扣电池,测量其在30~130℃下的质子传导曲线。
实施例2
实施例2与实施例1基本相同,唯一不同的是单体膦酸烷基链修饰的对二溴苯为C4-P-Br,具体为:
将膦酸烷基链修饰的对二溴苯C4-P-Br(0.255g,0.50mmol)、1,3,5-三(4-乙炔基苯基)苯(0.126g,0.33mmol)、CuI(0.007g,0.04mmol)和Pd(PPh3)4(0.022g,0.02mmol)置于体积比为1:1的NEt3/DMF混合溶剂中,混合物在氩气气氛下于80℃搅拌60小时。反应完成后,冷却至室温。粗品用二氯甲烷(3×10ml)和丙酮(3×10ml)洗涤,在干燥的丙酮中浸泡12小时,在80℃真空下干燥12小时,得到黄色粉末状的CMP-C4-P。
实施例3
实施例3与实施例1基本相同,唯一不同的是膦酸烷基链修饰的对二溴苯为C6-P-Br,具体为:
将膦酸烷基链修饰的对二溴苯C6-P-Br(0.269g,0.50mmol)、1,3,5-三(4-乙炔基苯基)苯(0.126g,0.33mmol)、CuI(0.007g,0.04mmol)和Pd(PPh3)4(0.022g,0.02mmol)置于体积比为1:1的NEt3/DMF混合溶剂中,混合物在氩气气氛下于80℃搅拌60小时。反应完成后,冷却至室温。粗品用二氯甲烷(3×10ml)和丙酮(3×10ml)洗涤,在干燥的丙酮中浸泡12小时,在80℃真空下干燥12小时,得到黄色粉末状的CMP-C6-P。
图1为C2-P-Br、1,3,5-三(4-乙炔基苯基)苯、膦酸烷基链修饰的共轭微多孔聚合物CMP-C2-P的PXRD谱图,判断CMP-C2-P是CMP,而不是COF。
图2为C2-P-Br、1,3,5-三(4-乙炔基苯基)苯、膦酸烷基链修饰的共轭微多孔聚合物CMP-C2-P的FT-IR谱图。可以看出,CMP-C2-P在2168cm-1和919cm-1处的红外吸收峰可以证实C-C键的形成和膦酸烷基链的成功修饰。
图3为CMP-Cn-P(n=2,4,6)的SEM图,可以看到CMP-C2-P、CMP-C4-P、CMP-C6-P均为珊瑚状团块形貌。
图4为CMP-Cn-P(n=2,4,6)的TEM图,可以看到CMP-C2-P、CMP-C4-P、CMP-C6-P均为层状结构。
图5为CMP-Cn-P的BET曲线图。通过观察氮气吸附发现,氮气吸附的大小顺序为CMP-C2-P>CMP-C4-P>CMP-C6-P,比表面积分别为648,443,297m2g-1。
图6为CMP-C2-P粉末和45%磷酸(H3PO4)掺杂,压成片状组装成纽扣电池,测试其30~130℃下的质子传导性能。可以看到,随着温度的升高,质子传导率逐渐增大,在130℃时达到最大,为1.12×10-2S cm-1。
图7为CMP-Cn-P(n=2,4,6)粉末和45%磷酸(H3PO4)掺杂,压成片状组装成纽扣电池,测试其30~130℃下的离子传导性能,得出的电导率与温度的关系图。可以看到电导率与温度的关系符合Arrhenius公式,且相同温度下,质子传导率顺序为C2>C4>C6。在磷酸掺杂下的膦酸烷基链修饰的共轭微多孔聚合物具有较高的质子传导性能,作为燃料电池隔膜材料具有重大的应用前景。
图8为CMP-C2-P粉末和45%磷酸(H3PO4)掺杂,压成片状组装成纽扣电池,测试其130℃下的质子传导长程稳定性图。可以看到,CMP-C2-P-45%H3PO4长程稳定性较好,循环48h,质子传导率保留87.6%。
Claims (10)
1.膦酸烷基链修饰的共轭微多孔聚合物,其特征在于,结构式如下:
2.根据权利要求1所述的膦酸烷基链修饰的共轭微多孔聚合物的制备方法,其特征在于,具体包括以下步骤:
步骤1,将膦酸烷基链修饰的对二溴苯对应的膦酸乙基酯和溴化三甲基硅烷加入无水二氯甲烷中,在氩气环境下、于室温下搅拌反应10~14h,然后加入甲醇,继续在室温下搅拌反应10~14h,反应结束后混合物在减压下浓缩,并在60~80℃真空下干燥12小时以上,得到膦酸烷基链修饰的对二溴苯,所述的膦酸烷基链修饰的对二溴苯对应的膦酸乙基酯的结构式如下:
所述的膦酸烷基链修饰的对二溴苯的结构式如下:
步骤2,将膦酸烷基链修饰的对二溴苯、1,3,5-三(4-乙炔基苯基)苯、碘化亚铜和四三苯基膦钯加入到三乙胺和N,N-二甲基甲酰胺混合溶剂中,然后将混合物在氩气环境下、于80~90℃搅拌反应60小时以上,反应完成后,冷却至室温,粗品依次用二氯甲烷和丙酮洗涤,再在干燥的丙酮中浸泡,真空干燥,得到膦酸烷基链修饰的共轭微多孔聚合物,所述的1,3,5-三(4-乙炔基苯基)苯的结构式如下:
3.根据权利要求2所述的制备方法,其特征在于,步骤1中,膦酸烷基链修饰的对二溴苯对应的膦酸乙基酯和溴化三甲基硅烷的摩尔比为1:10~1:12;步骤2中,1,3,5-三(4-乙炔基苯基)苯、膦酸烷基链修饰的对二溴苯的摩尔比为1:1~1:1.5,CuI的摩尔量为1,3,5-三(4-乙炔基苯基)苯的5%~10%,Pd(PPh3)4的摩尔量为1,3,5-三(4-乙炔基苯基)苯的5%~10%。
4.根据权利要求2所述的制备方法,其特征在于,步骤2中,三乙胺和N,N-二甲基甲酰胺混合溶剂中,三乙胺和N,N-二甲基甲酰胺的体积比为1:1;二氯甲烷的洗涤次数为3次以上,丙酮的洗涤次数为3次以上。
5.根据权利要求2所述的制备方法,其特征在于,步骤2中,在丙酮中浸泡的时间为12小时以上;真空干燥温度为60~80℃,干燥时间为12小时以上。
6.基于膦酸烷基链修饰的共轭微多孔聚合物的质子交换隔膜的制备方法,其特征在于,包括以下步骤:
按比例将权利要求1所述的膦酸烷基链修饰的共轭微多孔聚合物和磷酸混合,研磨至混合均匀,然后在80~90℃下真空干燥12小时以上,再在氩气保护气氛、100~120℃下加热5~6小时,冷却后压片制成质子交换隔膜。
7.根据权利要求6所述的制备方法,其特征在于,磷酸占质子交换隔膜总质量的45%~60%。
8.根据权利要求6~7任一所述的制备方法制得的基于膦酸烷基链修饰的共轭微多孔聚合物的质子交换隔膜。
9.根据权利要求8所述的基于膦酸烷基链修饰的共轭微多孔聚合物的质子交换隔膜在燃料电池中的应用。
10.根据权利要求9所述的应用,其特征在于,所述的燃料电池为质子交换膜燃料电池。
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