CN111416140B - 2,4,6-三氧代-1,3,5-三嗪-三磷酸盐掺杂pbi质子交换膜的制备方法 - Google Patents
2,4,6-三氧代-1,3,5-三嗪-三磷酸盐掺杂pbi质子交换膜的制备方法 Download PDFInfo
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- CN111416140B CN111416140B CN202010028562.2A CN202010028562A CN111416140B CN 111416140 B CN111416140 B CN 111416140B CN 202010028562 A CN202010028562 A CN 202010028562A CN 111416140 B CN111416140 B CN 111416140B
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- triphosphate
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- 238000002360 preparation method Methods 0.000 title claims description 30
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- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 8
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- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 13
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- 239000000243 solution Substances 0.000 description 12
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 11
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
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- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 6
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- 239000010452 phosphate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 4
- CGGUNVYOABLSQD-UHFFFAOYSA-N pyrazine-2,6-dicarboxylic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=N1 CGGUNVYOABLSQD-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
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- 159000000000 sodium salts Chemical class 0.000 description 4
- -1 2,4, 6-trioxo-1, 3, 5-triazine-triphosphate compound Chemical class 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
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- 229920006393 polyether sulfone Polymers 0.000 description 3
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- GMIOYJQLNFNGPR-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C=N1 GMIOYJQLNFNGPR-UHFFFAOYSA-N 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 229950009390 symclosene Drugs 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 3
- ZUUNZDIGHGJBAR-UHFFFAOYSA-N 1h-imidazole-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CNC(C(O)=O)=N1 ZUUNZDIGHGJBAR-UHFFFAOYSA-N 0.000 description 2
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 description 2
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 150000008301 phosphite esters Chemical class 0.000 description 2
- HTPGOQRGCUSPGR-UHFFFAOYSA-N phosphoric acid silane Chemical compound [SiH4].OP(O)(O)=O HTPGOQRGCUSPGR-UHFFFAOYSA-N 0.000 description 2
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- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- 229940048102 triphosphoric acid Drugs 0.000 description 2
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Fuel Cell (AREA)
Abstract
本发明报道了一种不溶性的2,4,6‑三氧代‑1,3,5‑三嗪‑三磷酸盐(金属离子为:Zr4+、Ce4+,Fe3+、La3+或Y3+等)作为质子导体掺杂到聚苯并咪唑(PBI)(PBI可以选用带有吡啶基团的、吡嗪基团的、咪唑基团的等)中制备了高温低湿度下使用的质子交换膜的制备方法,其特征在于,首先通过三步反应制备不溶性的2,4,6‑三氧代‑1,3,5‑三嗪‑三磷酸盐,研究其工艺条件,得到产品的离子交换容量(IEC)及产率。用其作为质子导体掺杂到新型PBI中,通过交联制备复合膜,该复合膜为高温低湿度下的质子交换膜,用于高温氢空气燃料电池、直接甲醇燃料电池和甲醇重整的高温燃料电池。
Description
技术领域
本发明涉及一种高温低湿度燃料电池中质子交换膜的制备方法,可用于固体酸催化剂、催化膜分离反应装置,燃料电池质子交换膜、电解膜、渗透膜、传感器材料等领域。
背景技术
全球能源消费的升级及环境污染日益严重,使得人们对能源可持续性提出了更高的要求。因此质子交换膜燃料电池(PEMFC)的开发研究受到人们的关注。然而,PEMFC的广泛商业化受到电极材料和质子交换膜(PEM)本身的高成本的严重阻碍。PEMFC可根据其工作温度分为:高温PEMFC(>120℃),和低温PEMFC(<120℃)。虽然高温能改善低温下存在的低传导率和低反应率及燃料渗透等问题,然而,随着温度的升高电池内部的相对湿度要降低,以减小电池内部的压力,然而,通常使用的Nafion膜在高温、低湿度下电导率会迅速下降,因此,高温PEMFC亟待解决的问题是研制新型的高温、低湿度下使用的质子交换膜。
聚苯并咪唑类高温质子交换膜是开发较早,且最具潜力的一种。为了提高燃料电池的高温低湿度工作条件下的电化学性能,一般采用掺杂磷酸的方式来实现,其主要原因是PBI本身不导电,掺杂的磷酸在低湿度下可以导电。关于磷酸基质子导体的专利文件也有公开,例如专利文献CN 108376791A公开了一种含双质子导体的有机-无机复合质子交换膜及其制备方法,以八乙烯基笼型倍半硅氧烷和乙烯基膦酸二乙酯经加成反应得到磷酸硅烷,高温无湿条件下具有较高的质子电导率;Li等人直接采用磷酸浸泡聚苯并咪唑膜,在30%RH 180℃下,质子电导率达到了0.2S/cm(Li,X,et al.J.Power Sources(电源杂志),2018,393:99-107.)。直接磷酸或液相膦酸盐掺杂的复合质子交换膜的电导率与质子受体掺杂度有很大关联,为了获得高的质子电导率,需要通过提高浸渍磷酸浓度或大量的磷酸盐掺杂以提高掺杂度。但是,在中或高RH下工作时,存在膜中的质子导体容易流失,造成性能衰减的问题。目前,高磷酸基含量,我们曾报道了磺化苯膦酸盐掺杂的复合质子交换膜(李忠芳等,(ZL 200810160560.8;ZL 200810160561.2;ZL 201110025204.7)。2,4,6-三氧代-1,3,5-三嗪-三磷酸基化合物未见报道。
发明内容
针对现有技术的不足,本发明提供一种高磷酸含量的2,4,6-三氧代-1,3,5-三嗪-三磷酸基化合物用其与可溶性高价金属离子的盐反应,制备不溶性的磷酸盐作为有机-无机质子导体材料用于掺杂到聚苯并咪唑类碱性高分子材料中制备高温低湿度质子交换膜,以解决磷酸掺杂已流失等问题。
本发明的技术方案如下:
1.新型不溶性异氰尿酸基三元磷酸盐(MTPA)的制备及工艺优化
以三氯异氰脲酸(TCCA)为原料,经过亚磷酸乙酯中进行反应,制备得到异氰尿酸基三磷酸酯(TTP),在浓盐酸中水解得到异氰尿酸基三元磷酸(TPA),与可溶性的高价金属离子反应得到异氰尿酸基三元磷酸盐(MTPA):TCCA搅拌下在0.5~2h内分批慢慢加入亚磷酸酯中,升温至80~120℃反应6~12h,冷却后减压蒸去亚磷酸酯,得到异氰尿酸基三元磷酸酯;将TTP在浓盐酸中加热、搅拌、回流反应12~36h,在50℃~70℃下,减压蒸出HCl、醇和水,用水和有机溶剂萃取,将水相浓缩,真空干燥得异氰尿酸基三元磷酸(TPA);TPA与可溶性的高价金属离子反应得到不溶性的异氰尿酸基三元磷酸盐(MTPA)
反应步骤如下:
(1)磁力搅拌下,在三口圆底烧瓶中加入60mL亚磷酸三乙酯(TEP,0.34mol),在冰浴中冷却,1h内分批加入三氯异氰尿酸(TCCA),与TEP的投料摩尔比控制在1:(1.2~2),继续反应2h,得明黄色澄清溶液;将三口圆底烧瓶转移到加热装置内,保持磁力搅拌并回流,升温至90~120℃,保温12h后,自然冷却至室温,加入50mL石油醚(沸程30~60℃)萃取,取下清液在60~90℃烘干至质量恒定,得黄褐色粘稠溶液;
(2)将步骤(1)得到的黄褐色粘稠溶液与HCl溶液混合,磁力搅拌下,120~150℃下回流反应24h后,静置6h,加入30mL乙酸乙酯,得白色固体,乙酸乙酯洗涤3次,在100~120℃烘干,得到2,4,6-三氧代-1,3,5-三嗪-三磷酸;
(3)取7.3g 2,4,6-三氧代-1,3,5-三嗪-三磷酸粉末(0.02mol)置于烧杯中,加入20mL去离子水,搅拌至完全溶解,逐滴加入金属离子的盐酸水溶液,控制固态酸与金属离子的摩尔比为1:(1~4),沉淀抽滤、水洗3次至滤液pH为中性,120℃烘干至质量恒定,得金属离子掺杂质子导体M-TPA(M为金属离子);其反应方程式如下式所示:
2.耐高温高分子材料聚苯并咪唑(PBI)的制备
(1)含有吡啶基团的聚苯并咪唑(PPBI)的制备:用2,6-吡啶二甲酸与3,3’-二氨基联苯胺(DABz)反应制备,具体反应步骤为:在装有电动搅拌和氮气保护的三口烧瓶中加入多聚磷酸(PPA)(100g),氮气保护下160℃搅拌1h以除去多余的水分及空气。将DABz(4.00g,18.7mmol)以及2,6-吡啶二甲酸(3.12g,18.7mmol)混合均匀,慢慢加入到三口烧瓶中。控制氮气流速,防止DABz被氧化,同时将反应温度提升到200℃并继续保温、搅拌反应5~8h。随着反应时间的增加,聚合体系逐渐变得粘稠。待粘度合适时停止反应,反应混合液慢慢转移到大量去离子水中抽丝,洗净、烘干,粉碎,去离子水多次洗涤以除去多聚磷酸和未反应的反应物,即得到PPBI,用乌氏粘度计测定PPBI的分子量。其粘均分子量为4.5万到5万。
(2)其它带吡啶基团的PBI的制备方法:同(1)的方法,只是将2,6-吡啶二甲酸分别换成2,5-吡啶二甲酸或2,3-吡啶二甲酸即可,其它操作同(1),即可得到含有不同吡啶基团的PPBI,产品分别记为:2,5-PPBI或2,3-PPBI。
(3)其他PBI制备方法同合成实验中的(1)部分。只是将2,6-吡啶二羧酸改为其它二羧酸(如,间苯二甲酸、2,6-吡嗪二甲羧酸、2,3-吡嗪二甲酸、2,5-吡嗪二甲酸等),ABPBI的制备是用3,4-二氨基苯甲酸替代2,6-吡啶二甲酸与3,3’-二氨基联苯胺(DABz)两种原料,只用3,4-二氨基苯甲酸即可。
3.制膜工艺采用流延法;为了提升膜的机械性能、抗氧化性能,改善其干湿变形性采用了交联剂进行交联。交联剂选用多官能度的交联剂。
4.复合膜的高温低湿度质子交换膜的制备
(1)以2,4,6-三氧代-1,3,5-三嗪-三磷酸锆(ZrTPA)掺杂到聚苯并咪唑(PPBI)的复合质子交换膜的制备为例:以ZrTPA掺杂30%为例。取1.0g PPBI加入10mL N,N’-二甲基乙酰胺(DMAc)中,在80℃下磁力搅拌24h使其充分溶解,抽滤除去不溶物。在50℃下向滤液中加入交联剂0.05g 1,3,5-三(环氧乙烷-2-基甲基)-1,3,5-三嗪-2,4,6-三酮(异氰尿酸三缩水甘油酯,TGIC),继续搅拌2.5h使其充分溶解。再加入0.52g ZrTPA的钠盐,继续搅拌3h使其充分分散在铸膜液中。超声振荡1h以除去气泡,而后将其浇铸在玻璃板上,在60℃下流延12h,120℃下加热12h除去溶剂,而后在160℃下加热6h使PPBI和TGIC进行充分交联。将得到的膜在0.1mol L-1H2SO4水溶液中室温下浸泡24h,使掺杂到膜中的ZrTPA的钠盐充分酸化为ZrTPA,而后在去离子水中浸泡24h(每6h换水一次)以洗去膜中的硫酸,得到PPBI-TGIC(5%)/ZrTPA(30%)复合膜。
本发明的创新点:
(1)本发明所用的质子导体是不溶性的含有多磷酸基团、且空间分布均匀的2,4,6-三氧代-1,3,5-三嗪-三磷酸盐,其盐为聚合物,且分子中还有多个未反应的羟基,可用于质子导体,且不易流失。复合膜的电导率不会随着时间的延长而降低,复合膜的耐久性优良。
(2)该盐是有机-无机复合的质子导体材料,可以与高分子材料混合均匀,不分相。质子导体与碱性高分子材料PBI之间可以形成盐键或氢键,其复合膜内的氢键网络可以形成质子的传递通道,该质子通道起到在高温、低湿度下质子传导的作用。
(3)由于高温质子导体分子中各基团均具有很好的耐温性能,所以该复合膜可以在低湿度、250℃下使用,当然,在低温下也有很好的电导率,所以该复合膜适用的温度范围是-15℃到250℃,相对湿度范围0到50%。
(4)为了更好地提高复合膜的机械性能、抗氧化性能以及提升复合膜的干湿变形性,本发明采用多官能度的交联剂对PBI分子之间进行交联,以得到体型的高分子材料,从而提高膜的机械性能、抗氧化性能,改善其干湿变形性。由于采用多官能度的交联剂,所以交联剂的添加量可以比较小,且交联效果很好。
具体实施方式
下面结合实施例对本发明的方法作进一步说明,但不限于此。
[实施例1]:CeTPA质子导体的制备,步骤如下:
磁力搅拌下,在三口圆底烧瓶中加入60mL亚磷酸三乙酯(TEP,0.34mol),在冰浴中冷却,1h内分批加入三氯异氰尿酸(TCCA),TCCA与TEP的投料摩尔比为1:1.5,继续反应2h,得明黄色澄清溶液;将三口圆底烧瓶转移到加热装置内,保持磁力搅拌并回流,升温至100℃,保温12h后,自然冷却至室温,加入50mL石油醚(沸程30~60℃)萃取,取下清液在60℃烘干至质量恒定,得黄褐色粘稠溶液;将黄褐色粘稠溶液与100mL HCl溶液混合,磁力搅拌下,150℃下回流反应24h后,静置6h,加入30mL乙酸乙酯,得白色固体,乙酸乙酯洗涤3次,在120℃烘干,得到TPA粉末;取7.3g TPA粉末(0.02mol)置于烧杯中,加入20mL去离子水,搅拌至完全溶解,逐滴加入硝酸铈铵(Ce(NH4)2(NO3)6)的盐酸水溶液,控制固态酸与Ce的摩尔比为1:2,沉淀抽滤、水洗3次至滤液pH为中性,120℃烘干至质量恒定,得CeTPA-1:2质子导体,备用。
[实施例2]:其它配比的CeTPA的制备方法同实施例1,这是改变硝酸铈铵与TPA的摩尔配比即可。
其它金属的可溶性盐与TPA制备不溶性盐MTPA的方法同实施例1,只是将其它可溶性的盐替代硝酸铈铵即可。制备的MTPA中Mn+可以是Zr4+,Fe3+,La3+或Y3+等。不同金属离子及不同金属离子与TPA摩尔配比的盐的制备工艺及性能测试结果见表1所示。
[实施例3]:聚苯并咪唑类高分子材料的制备
(1)含有吡啶基团的聚苯并咪唑(PPBI)的制备:用2,6-吡啶二甲酸与3,3’-二氨基联苯胺(DABz)反应制备,具体反应步骤为:在装有电动搅拌和氮气保护的三口烧瓶中加入多聚磷酸(PPA)(100g),氮气保护下160℃搅拌1h以除去多余的水分及空气。将DABz(4.00g,18.7mmol)以及2,6-吡啶二甲酸(3.12g,18.7mmol)混合均匀,慢慢加入到三口烧瓶中。控制氮气流速,防止DABz被氧化,同时将反应温度提升到200℃并继续保温、搅拌反应5~8h。随着反应时间的增加,聚合体系逐渐变得粘稠。待粘度合适时停止反应,反应混合液慢慢转移到大量去离子水中抽丝,洗净、烘干,粉碎,去离子水多次洗涤以除去多聚磷酸和未反应的反应物,即得到PPBI,用乌氏粘度计测定PPBI的分子量。其粘均分子量为4.5万到5万。
(2)其它带吡啶基团的PBI的制备方法:同(1)的方法,只是将2,6-吡啶二甲酸分别换成2,5-吡啶二甲酸或2,3-吡啶二甲酸即可,其它操作同(1),即可得到含有不同吡啶基团的PPBI,产品分别记为:2,5-PPBI或2,3-PPBI。
(3)其他PBI制备方法同实施例6中的(1)部分。只是将2,6-吡啶二羧酸改为其他二羧酸(如,间苯二甲酸、2,6-吡嗪二甲羧酸、2,5-吡嗪二甲羧酸或2,3-吡嗪二甲羧酸,2,4-咪唑二甲酸等)
[实施例4]:以MTPA作为质子导体用于高温质子交换膜的制备
以30%ZrTPA掺杂到聚苯并咪唑(PPBI)的复合质子交换膜的制备为例。取1.0gPPBI加入10mL N,N’-二甲基乙酰胺(DMAc)中,在80℃下磁力搅拌24h使其充分溶解,抽滤除去不溶物。在50℃下向滤液中加入交联剂0.05g 1,3,5-三(环氧乙烷-2-基甲基)-1,3,5-三嗪-2,4,6-三酮(异氰尿酸三缩水甘油酯,TGIC),继续搅拌2.5h使其充分溶解。再加入0.45gZrTPA的钠盐,继续搅拌3h使其充分分散在铸膜液中。超声振荡1h以除去气泡,而后将其浇铸在玻璃板上,在60℃下流延12h,120℃下加热12h除去溶剂,而后在160℃下加热6h使PPBI和TGIC进行充分交联。将得到的膜在0.1mol L-1H2SO4水溶液中室温下浸泡24h,使掺杂到膜中的ZrTPA的钠盐充分酸化为ZrTPA,而后在去离子水中浸泡24h(每6h换水一次)以洗去膜中的硫酸,得到PPBI-TGIC(5%)/ZrTPA(30%)复合膜。
[实施例5]:其它ZrTPA掺杂量的PBI复合膜的制备方法同实施例4只是改变ZrTPA掺杂量即可。
[实施例6]:其它交联剂交联的复合膜的制备同实施例4,只是把交联剂TGIC改为其它交联剂如,高氯含量的氯甲基化聚醚砜、氯甲基化PBI或聚二氯磷腈等即可。
[实施例7]:其它MTPA盐掺杂的复合膜的制备同实施例4,只是将的用其它MTPA盐替代ZrTPA即可。不同类型的复合膜不同温度、不同相对湿度下的电导率测试结果如表2所示。
[实施例8]:电池膜电极制备及单电池性能测试
用传统的方法和工艺制备膜电极,只是用本发明的复合膜替代Nafion膜。制备的膜电极组装单电池,进行电池性能测试。按照单电池组装的方法,把制备的膜电极组装成单电池并且连接到燃料电池测试系统进行测试,阳极用相对湿度为50%的氢气为燃料,流速40mL/min,电池的工作温度150℃,阴极用氧气流速20mL/min,背压0.2MPa。电池性能测试前首先进行活化,再测试其性能。不同膜的MEA测试结果如表3所示。
[实施例9]:用其它复合膜制备的燃料电池膜电极及性能测试同实施例8,只是用其它复合膜替代PPBI-TGIC(5%)/ZrTPA(30%)复合膜即可。不同膜的MEA测试结果如表3所示。
表1 MTPA类质子导体的制备工艺条件及性能对比
注:IEC的单位为meq·g-1。
表2 MTPA掺杂到PBI制备的复合膜在不同性低湿度下的质子电导率(S/cm)
注:2,6-PzPBI:2,6-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,6-PyPBI:2,6-吡啶二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,5-PzPBI:2,5-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,3-PzPBI:2,3-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,5-PyPBI:2,5-吡啶二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,3-PyPBI:2,3-吡啶二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,4-MzPBI:2,4-咪唑二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
多官能度的交联剂缩写及中文全称:
TGIC:1,3,5-三(环氧乙烷-2-基甲基)-1,3,5-三嗪-2,4,6-三酮
TGDDM:N,N,N’,N’-四环氧丙基-4,4’-二氨基二苯甲烷
CMPSU:氯甲基化聚醚砜
CMPBI:氯甲基化聚苯并咪唑
PDCP:聚二氯磷腈
表3 MTPA掺杂到PBI制备的复合膜制备的膜电极的性能
注:2,6-PzPBI:2,6-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,6-PyPBI:2,6-吡啶二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,3-PzPBI:2,3-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
多官能度的交联剂缩写及中文全称:
TGIC:1,3,5-三(环氧乙烷-2-基甲基)-1,3,5-三嗪-2,4,6-三酮
TGDDM:N,N,N’,N’-四环氧丙基-4,4’-二氨基二苯甲烷
CMPSU:氯甲基化聚醚砜
PDCP:聚二氯磷腈。
Claims (4)
1.2,4,6-三氧代-1,3,5-三嗪-三磷酸盐掺杂PBI质子交换膜的制备方法,其特征在于:用耐高温的和不溶性2,4,6-三氧代-1,3,5-三嗪-三磷酸盐MTPA作为质子导体掺杂到聚苯并咪唑PBI通过交联制备高温和低湿度下使用的质子交换膜,其制备过程包括:
(1)以三氯异氰脲酸TCCA为原料,经过亚磷酸乙酯中进行反应,制备得到异氰尿酸基三磷酸酯TTP,在浓盐酸中水解得到异氰尿酸基三元磷酸TPA,与可溶性的高价金属离子反应得到2,4,6-三氧代-1,3,5-三嗪-三磷酸盐MTPA:TCCA原料搅拌下在0.5~2h内分批慢慢加入亚磷酸乙酯中,升温至80~120℃反应6~12h,冷却后减压蒸去亚磷酸乙酯,得到TTP;将TTP在浓盐酸中加热、搅拌、回流反应12~36h,在50℃~70℃下,减压蒸出HCl、醇和水,用水和有机溶剂萃取,将水相浓缩,真空干燥得TPA;TPA与可溶性的高价金属离子反应得到不溶性的2,4,6-三氧代-1,3,5-三嗪-三磷酸盐MTPA;
(2)聚苯并咪唑的制备是用3,3’-二氨基联苯胺DABz与含有碱性基团的芳香二酸为原料,在多聚磷酸PPA中,惰性气体保护下,200℃,反应3~8h,得到聚苯并咪唑,其粘均分子量为4.5~5万;
(3)采用流延成膜法制备复合膜,按照质子导体掺杂量20wt%~60wt%,用多官能度的交联剂进行交联制备复合膜;
制备的复合质子交换膜在-15℃~250℃,相对湿度0~50%下使用,其膜电极制备过程中也用相应的MTPA作为质子添加剂,用于高温氢-空气燃料电池、直接甲醇燃料电池或甲醇重整的燃料电池;燃料电池对氢气或氧气的纯度要求降低。
2.权利要求1所述的2,4,6-三氧代-1,3,5-三嗪-三磷酸盐掺杂PBI质子交换膜的制备方法,其特征在于:MTPA中的Mn+是Zr4+,Fe3+,La3+或Y3+中的一种或几种的混合物;MTPA是不溶性的盐,是有机-无机杂化材料,耐高温,其中,磷酸基团上未参与反应的羟基表现出酸性,用于不溶性的耐高温的质子导体。
3.权利要求1所述的2,4,6-三氧代-1,3,5-三嗪-三磷酸盐掺杂PBI质子交换膜的制备方法,其特征在于:所用的聚苯并咪唑高分子材料是含有吡嗪、吡啶或咪唑类碱性基团的聚苯并咪唑,这些PBI有更多的碱性基团,掺杂质子导体的量会增加,制备的复合膜的质子电导率会更高。
4.权利要求1所述的2,4,6-三氧代-1,3,5-三嗪-三磷酸盐掺杂PBI质子交换膜的制备方法,其特征在于:交联剂选用多官能度的交联剂,多官能度以在同等交联的情况下所用交联剂最少,对复合膜的电导率影响最小。
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