CN114751741A - 一种多孔导电陶瓷纤维膜及其制备方法 - Google Patents
一种多孔导电陶瓷纤维膜及其制备方法 Download PDFInfo
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- CN114751741A CN114751741A CN202210399081.1A CN202210399081A CN114751741A CN 114751741 A CN114751741 A CN 114751741A CN 202210399081 A CN202210399081 A CN 202210399081A CN 114751741 A CN114751741 A CN 114751741A
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- ceramic fiber
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- 239000012528 membrane Substances 0.000 title claims abstract description 135
- 239000000919 ceramic Substances 0.000 title claims abstract description 130
- 239000000835 fiber Substances 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 51
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 dicyanofuranyl phthalic anhydride phenylboronic acid Chemical compound 0.000 claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- JNVLJWBOAWSXKO-UHFFFAOYSA-K trichloronickel Chemical compound Cl[Ni](Cl)Cl JNVLJWBOAWSXKO-UHFFFAOYSA-K 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000011282 treatment Methods 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 94
- 238000003756 stirring Methods 0.000 claims description 91
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 54
- 229910052786 argon Inorganic materials 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 28
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000008064 anhydrides Chemical class 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- KCSYJHQYWTYFCM-UHFFFAOYSA-N furan-2,5-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)O1 KCSYJHQYWTYFCM-UHFFFAOYSA-N 0.000 claims description 14
- SJJFAKPPWNLWOX-UHFFFAOYSA-N furan-3,4-dicarbonitrile Chemical compound N#CC1=COC=C1C#N SJJFAKPPWNLWOX-UHFFFAOYSA-N 0.000 claims description 14
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000001307 helium Substances 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- KIPMDPDAFINLIV-UHFFFAOYSA-N 2-nitroethanol Chemical compound OCC[N+]([O-])=O KIPMDPDAFINLIV-UHFFFAOYSA-N 0.000 claims description 7
- BFZHKYHKEHKTDP-UHFFFAOYSA-N 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-benzofuran-1,3-dione Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C(=O)OC2=O)C2=C1 BFZHKYHKEHKTDP-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 7
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000990 Ni alloy Inorganic materials 0.000 abstract description 7
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000002070 nanowire Substances 0.000 abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005219 brazing Methods 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 abstract description 5
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 abstract description 4
- BHVDDZIVQHJKFL-UHFFFAOYSA-N [B+]=O.[O-2].[O-2].[Ti+4] Chemical compound [B+]=O.[O-2].[O-2].[Ti+4] BHVDDZIVQHJKFL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- OZVCIJIOEZNZFL-UHFFFAOYSA-H dialuminum;phthalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C1=CC=CC=C1C([O-])=O.[O-]C(=O)C1=CC=CC=C1C([O-])=O.[O-]C(=O)C1=CC=CC=C1C([O-])=O OZVCIJIOEZNZFL-UHFFFAOYSA-H 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- NTZDHEDPRZGUHW-UHFFFAOYSA-N furan-2,3-dicarbonitrile Chemical compound N#CC=1C=COC=1C#N NTZDHEDPRZGUHW-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- HAIMOVORXAUUQK-UHFFFAOYSA-J zirconium(iv) hydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[Zr+4] HAIMOVORXAUUQK-UHFFFAOYSA-J 0.000 description 1
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- C04B2235/6567—Treatment time
Abstract
本发明公开了一种多孔导电陶瓷纤维膜及其制备方法,涉及陶瓷纤维膜技术领域。本发明在制备多孔导电陶瓷纤维膜时,先利用盐酸处理氢氧化锆,制备得到含有氧氯化锆的功能化氢氧化锆;再将钛酸四氨基乙醇酯和二氰基呋喃基二甲酸酐基苯硼酸包裹功能化氢氧化锆微粒,形成以功能化氢氧化锆微粒为支撑体的二氧化钛‑氧化硼复合溶胶和噁唑啉,制备得到陶瓷纤维膜浆料;再利用三氯化镍对陶瓷纤维膜浆料电处理耦合烧结,硼化锆、硼化钛、碳纳米线和钎料钛镍合金,制备得到多孔导电陶瓷纤维膜;本发明制备得到的多孔导电陶瓷纤维膜具有良好的抗氧化性、耐高温性、导电性和弯曲强度。
Description
技术领域
本发明涉及陶瓷纤维膜领域,具体为一种多孔导电陶瓷纤维膜及其制备方法。
背景技术
在过去的两个世纪,膜技术已经被广泛应用于液体和气体的分离、膜反应器、热交换等各个领域。其中,膜分离技术是一种新型的、髙效的分离技术,因具有节约能源和环境友好的特征而成为21世纪分离技术研究的热点,已经成为从根本上解决全球能源、环境、健康等重大问题的关键技术之一。
在各类膜材料中,聚合物膜由于其制备工艺简单、比表面积大和分离效果好而被广泛应用。但同时聚合物膜由于其较差的化学稳定性、容易被破坏等特征极大地限制了它的应用。与聚合物膜相比,多孔陶瓷纤维膜因具有化学稳定性好、环境友好、易于再生、生物稳定性好、结构可调等诸多优点,而成为膜科学领域的热点之一,并被广泛应用于能源工业、化学工程、生物工程、食品工业、医药行业、环境工程等领域。很多导电性好的多孔陶瓷纤维膜常常被运用在电池领域,但是长时间在1600℃左右的环境下操作,多孔陶瓷纤维膜的弯曲强度等各项性能迅速降低,大大地缩减了多孔陶瓷纤维膜的使用寿命,增加了多孔陶瓷纤维膜的使用成本。因此,如何制备出导电性和耐高温性良好的多孔陶瓷纤维膜成为当前技术领域的一大难题。
本发明发现了这一现象,并通过制备多孔导电陶瓷纤维膜来解决这一难题。
发明内容
本发明的目的在于提供一种多孔导电陶瓷纤维膜及其制备方法,以解决现有技术中存在的问题。
为了解决上述技术问题,本发明提供如下技术方案:
一种多孔导电陶瓷纤维膜的制备方法,所述多孔导电陶瓷纤维膜是利用三氯化镍对陶瓷纤维膜浆料电处理耦合烧结制备得到;所述陶瓷纤维膜浆料是将钛酸四氨基乙醇酯和二氰基呋喃基二甲酸酐基苯硼酸包裹功能化氢氧化锆微粒制备得到;所述功能化氢氧化锆微粒是利用盐酸处理氢氧化锆微粒制备得到。
进一步的,所述多孔导电陶瓷纤维膜的制备方法如下:在17~19℃、48~50%湿度和氩气保护条件下,将陶瓷纤维膜浆料放入浆料罐中,以9~11mL/min将内絮凝剂去离子水和陶瓷纤维膜浆料分别从内管径为1.5~1.7mm、外管径为2.5~2.7mm的纺丝头中挤出,于陶瓷纤维膜浆料质量10~13倍的去离子水中浸泡23~25h,以3~5℃/min升温至150~250℃,以3~5ml/min通入陶瓷纤维膜浆料0.3~0.5倍的三氯化镍,保温22~26h,自然冷却至室温捞出,在0.04~0.06MPa和氩气保护条件下,放入300~500℃的管式炉中,保温70~90min,随后以9~11℃/min升温至650~750℃,保温1~3h,制备得到陶瓷纤维膜坯料;在2.6~3.0V和900~1100℃下,将陶瓷纤维膜坯料放入电解池中电解7~9h后捞出,以9~11℃/min升温至1700~1800℃,保温3~5h,自然冷却至室温,制备得到多孔导电陶瓷纤维膜。
进一步的,所述电解池的负极为陶瓷纤维膜坯料、正极为石墨、电解液为熔融的氯化钙。
进一步的,所述陶瓷纤维膜浆料的制备方法如下:在24~26℃下,将二氰基呋喃基二甲酸酐基苯硼酸和去离子水按质量比1:2~1:4混合,以300~500r/min搅拌20~40min,制备得到二氰基呋喃基二甲酸酐基苯硼酸溶液;在24~26℃下,将功能化氢氧化锆微粒、二氰基呋喃基二甲酸酐基苯硼酸和钛酸四氨基乙醇酯按质量比1:1:1.2~1:3:1.4混合,以600~800r/min搅拌1~3h,随后以30~40滴/min滴加功能化氢氧化锆微粒质量1~3倍的二氰基呋喃基二甲酸酐基苯硼酸溶液,以600~800r/min搅拌20~40min,随后在氦气保护条件下,以3~5℃升温至100~120℃,继续搅拌3~5h,静置47~49h,制备得到陶瓷纤维膜浆料。
进一步的,所述功能化氢氧化锆微粒的制备方法如下:在24~26℃和氩气保护条件下,将氢氧化锆微粒和质量分数为30~50%的盐酸溶液按质量比1:0.3~1:0.5混合,以600~800r/min搅拌30~50min,放入40~60℃烘箱烘1~3h,制备得到功能化氢氧化锆微粒。
进一步的,所述氢氧化锆微粒的粒径为20~30μm。
进一步的,所述二氰基呋喃基二甲酸酐基苯硼酸的制备方法如下:在24~26℃和氩气保护条件下,将2,5-二氰基呋喃和溴按质量比1:1.2~1:1.4混合,以600~800r/min搅拌1~3h,随后加入2,5-二氰基呋喃质量1~3倍的邻苯二甲酸酐-4-硼酸频哪醇酯混合,以300~500r/min搅拌20~40min,随后以3~5℃/min升温至70~90℃,以30~40滴/min滴加3,4-二氰基呋喃质量0.01~0.02倍的三氯化硼,以600~800r/min搅拌1~3h,过滤,随后以3~5℃/min降温至24~26℃,加入3,4-二氰基呋喃质量0.006~0.008倍的高碘酸钠,继续搅拌1~3h,制备得到二氰基呋喃基二甲酸酐基苯硼酸。
进一步的,所述钛酸四氨基乙醇酯的制备方法如下:在60~80℃和氩气保护条件下,将钛酸四硝基乙醇酯和钯碳按质量比1:0.005~1:0.007混合,以600~800r/min搅拌20~40min,以3~5m3/min通入氢气,继续搅拌1~3h,制备得到钛酸四氨基乙醇酯。
进一步的,所述钛酸四硝基乙醇酯的制备方法如下:将四乙基溴化铵溶液放入阳极为钛、阴极为石墨的电解池中,在电流密度为200~400A*m-2、1~2V电位、60~80℃以及氩气保护条件下,电处理50~70min,制备得到钛酸四硝基乙醇酯。
进一步的,所述四乙基溴化铵溶液的制备方法如下:在24~26℃和氩气保护条件下,将2-硝基乙醇和四乙基溴化铵按质量比1:0.01~1:0.012混合,以300~500r/min搅拌20~40min,制备得到四乙基溴化铵溶液。
与现有技术相比,本发明所达到的有益效果是:
本发明在制备多孔导电陶瓷纤维膜时,先将钛酸四氨基乙醇酯和二氰基呋喃基二甲酸酐基苯硼酸包裹功能化氢氧化锆微粒,制备得到陶瓷纤维膜浆料;再利用三氯化镍对陶瓷纤维膜浆料电处理耦合烧结,制备得到多孔导电陶瓷纤维膜;其中,功能化氢氧化锆是利用盐酸处理氢氧化锆制备得到的。
首先,在二氰基呋喃基二甲酸酐基苯硼酸的硼酸作用下,钛酸四氨基乙醇酯水解脱去乙醇胺后反应交联,形成以功能化氢氧化锆微粒为支撑体的二氧化钛-氧化硼复合溶胶层,增强了陶瓷纤维膜浆料的抗氧化性能;在功能化氢氧化锆微粒中的氧氯化锆的催化作用下,部分乙醇胺和二氰基呋喃基二甲酸酐基苯硼酸中的氰基反应交联形成噁唑啉,后续烧结时噁唑啉作为碳源,与二氧化钛-氧化硼复合气凝胶中部分二氧化钛、氧化硼以及功能化氢氧化锆微粒烧结得到的氧化锆反应,形成硼化锆、硼化钛和一氧化碳,增强了多孔导电陶瓷纤维膜的耐高温性能,同时,一氧化碳逸出在陶瓷纤维膜中形成大量空隙,降低了陶瓷纤维膜的机械性能。
其次,在三氯化镍的催化作用下,部分乙醇胺的氨基和二氰基呋喃基二甲酸酐基苯硼酸中的二甲酸酐反应,形成聚酰亚胺,烧结后聚酰亚胺在陶瓷纤维膜内部原位形成碳纳米线,和硼化钛形成导电通路,增强了多孔导电陶瓷纤维膜的导电性;噁唑啉快速捕捉镍离子,烧结后形成氧化镍和碳层,氧化镍和部分二氧化钛还原、熔合形成钛镍合金,熔融状态下的钛镍合金在毛细作用下嵌入到陶瓷纤维膜空隙中,将硼化钛和硼化锆稳固地钎焊连接在一起,增强了多孔导电陶瓷纤维膜的弯曲强度。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
为了更清楚的说明本发明提供的方法通过以下实施例进行详细说明,在将以下实施例中制备得到的多孔导电陶瓷纤维膜的各指标测试方法如下:
抗氧化性:取相同面积的实施例和对比例制备得到的多孔导电陶瓷纤维膜按照JC/T2530标准测定单位面积的质量变化来测定抗氧化性。
耐高温性:取相同长度和宽度的实施例和对比例制备得到的多孔导电陶瓷纤维膜按照GB/T14390标准测定高温条件下的弯曲强度来测定耐高温性。
导电性:取相同质量的实施例和对比例制备得到的多孔导电陶瓷纤维膜ASTMC773测试电导率。
弯曲强度:取相同长度和宽度的实施例和对比例制备得到的多孔导电陶瓷纤维膜按照ASTMC1161标准测定弯曲强度。
实施例1
一种多孔导电陶瓷纤维膜的制备方法,所述多孔导电陶瓷纤维膜的制备方法,包括以下制备步骤:
(1)在24℃和氩气保护条件下,将2-硝基乙醇和四乙基溴化铵按质量比1:0.01混合,以300r/min搅拌20min,制备得到四乙基溴化铵溶液;将四乙基溴化铵溶液放入阳极为钛、阴极为石墨的电解池中,在电流密度为200A*m-2、1V电位、60℃以及氩气保护条件下,电处理50min,制备得到钛酸四硝基乙醇酯;在60℃和氩气保护条件下,将钛酸四硝基乙醇酯和钯碳按质量比1:0.005混合,以600r/min搅拌20min,以3m3/min通入氢气,继续搅拌1h,制备得到钛酸四氨基乙醇酯;在24℃和氩气保护条件下,将2,5-二氰基呋喃和溴按质量比1:1.2混合,以600r/min搅拌1h,随后加入2,5-二氰基呋喃质量1倍的邻苯二甲酸酐-4-硼酸频哪醇酯混合,以300r/min搅拌20min,随后以3℃/min升温至70℃,以30滴/min滴加3,4-二氰基呋喃质量0.01倍的三氯化硼,以600r/min搅拌1h,过滤,随后以3℃/min降温至24℃,加入3,4-二氰基呋喃质量0.006倍的高碘酸钠,继续搅拌1h,制备得到二氰基呋喃基二甲酸酐基苯硼酸;在24℃和氩气保护条件下,将粒径为20μm氢氧化锆微粒和质量分数为30%的盐酸溶液按质量比1:0.3混合,以600r/min搅拌30min,放入40℃烘箱烘1h,制备得到功能化氢氧化锆微粒;在24℃下,将二氰基呋喃基二甲酸酐基苯硼酸和去离子水按质量比1:2混合,以300r/min搅拌20min,制备得到二氰基呋喃基二甲酸酐基苯硼酸溶液;在24℃下,将功能化氢氧化锆微粒、二氰基呋喃基二甲酸酐基苯硼酸和钛酸四氨基乙醇酯按质量比1:1:1.2混合,以600r/min搅拌1h,随后以30滴/min滴加功能化氢氧化锆微粒质量1倍的二氰基呋喃基二甲酸酐基苯硼酸溶液,以600r/min搅拌20min,随后在氦气保护条件下,以3℃升温至100℃,继续搅拌3h,静置47h,制备得到陶瓷纤维膜浆料;
(2)在17℃、48%湿度和氩气保护条件下,将陶瓷纤维膜浆料放入浆料罐中,以9mL/min将内絮凝剂去离子水和陶瓷纤维膜浆料分别从内管径为1.5mm、外管径为2.5mm的纺丝头中挤出,于陶瓷纤维膜浆料质量10倍的去离子水中浸泡23h,以3℃/min升温至150℃,以3ml/min通入陶瓷纤维膜浆料0.3倍的三氯化镍,保温22h,自然冷却至室温捞出,在0.04MPa和氩气保护条件下,放入300℃的管式炉中,保温70min,随后以9℃/min升温至650℃,保温1h,制备得到陶瓷纤维膜坯料;以陶瓷纤维膜坯料作为负极、石墨为正极放入氯化钙熔融体系中,在2.6V和900℃下电解7h后捞出,以9℃/min升温至1700℃,保温3h,自然冷却至室温,制备得到多孔导电陶瓷纤维膜。
实施例2
一种多孔导电陶瓷纤维膜的制备方法,所述多孔导电陶瓷纤维膜的制备方法,包括以下制备步骤:
(1)在25℃和氩气保护条件下,将2-硝基乙醇和四乙基溴化铵按质量比1:0.011混合,以400r/min搅拌30min,制备得到四乙基溴化铵溶液;将四乙基溴化铵溶液放入阳极为钛、阴极为石墨的电解池中,在电流密度为300A*m-2、1.5V电位、70℃以及氩气保护条件下,电处理60min,制备得到钛酸四硝基乙醇酯;在70℃和氩气保护条件下,将钛酸四硝基乙醇酯和钯碳按质量比1:0.006混合,以700r/min搅拌30min,以4m3/min通入氢气,继续搅拌2h,制备得到钛酸四氨基乙醇酯;在25℃和氩气保护条件下,将2,5-二氰基呋喃和溴按质量比1:1.3混合,以700r/min搅拌2h,随后加入2,5-二氰基呋喃质量2倍的邻苯二甲酸酐-4-硼酸频哪醇酯混合,以400r/min搅拌30min,随后以4℃/min升温至80℃,以35滴/min滴加3,4-二氰基呋喃质量0.015倍的三氯化硼,以700r/min搅拌2h,过滤,随后以4℃/min降温至25℃,加入3,4-二氰基呋喃质量0.007倍的高碘酸钠,继续搅拌2h,制备得到二氰基呋喃基二甲酸酐基苯硼酸;在25℃和氩气保护条件下,将粒径为25μm氢氧化锆微粒和质量分数为40%的盐酸溶液按质量比1:0.4混合,以700r/min搅拌40min,放入50℃烘箱烘2h,制备得到功能化氢氧化锆微粒;在25℃下,将二氰基呋喃基二甲酸酐基苯硼酸和去离子水按质量比1:3混合,以400r/min搅拌30min,制备得到二氰基呋喃基二甲酸酐基苯硼酸溶液;在25℃下,将功能化氢氧化锆微粒、二氰基呋喃基二甲酸酐基苯硼酸和钛酸四氨基乙醇酯按质量比1:2:1.3混合,以700r/min搅拌2h,随后以35滴/min滴加功能化氢氧化锆微粒质量2倍的二氰基呋喃基二甲酸酐基苯硼酸溶液,以700r/min搅拌30min,随后在氦气保护条件下,以4℃升温至110℃,继续搅拌4h,静置48h,制备得到陶瓷纤维膜浆料;
(2)在18℃、49%湿度和氩气保护条件下,将陶瓷纤维膜浆料放入浆料罐中,以10mL/min将内絮凝剂去离子水和陶瓷纤维膜浆料分别从内管径为1.6mm、外管径为2.6mm的纺丝头中挤出,于陶瓷纤维膜浆料质量12倍的去离子水中浸泡24h,以4℃/min升温至200℃,以4ml/min通入陶瓷纤维膜浆料0.4倍的三氯化镍,保温24h,自然冷却至室温捞出,在0.05MPa和氩气保护条件下,放入400℃的管式炉中,保温80min,随后以10℃/min升温至700℃,保温2h,制备得到陶瓷纤维膜坯料;以陶瓷纤维膜坯料作为负极、石墨为正极放入氯化钙熔融体系中,在2.8V和1000℃下电解8h后捞出,以10℃/min升温至1750℃,保温4h,自然冷却至室温,制备得到多孔导电陶瓷纤维膜。
实施例3
一种多孔导电陶瓷纤维膜的制备方法,所述多孔导电陶瓷纤维膜的制备方法,包括以下制备步骤:
(1)在26℃和氩气保护条件下,将2-硝基乙醇和四乙基溴化铵按质量比1:0.012混合,以500r/min搅拌40min,制备得到四乙基溴化铵溶液;将四乙基溴化铵溶液放入阳极为钛、阴极为石墨的电解池中,在电流密度为400A*m-2、2V电位、80℃以及氩气保护条件下,电处理70min,制备得到钛酸四硝基乙醇酯;在80℃和氩气保护条件下,将钛酸四硝基乙醇酯和钯碳按质量比1:0.007混合,以800r/min搅拌40min,以5m3/min通入氢气,继续搅拌3h,制备得到钛酸四氨基乙醇酯;在26℃和氩气保护条件下,将2,5-二氰基呋喃和溴按质量比1:1.4混合,以800r/min搅拌3h,随后加入2,5-二氰基呋喃质量3倍的邻苯二甲酸酐-4-硼酸频哪醇酯混合,以500r/min搅拌40min,随后以5℃/min升温至90℃,以40滴/min滴加3,4-二氰基呋喃质量0.02倍的三氯化硼,以800r/min搅拌3h,过滤,随后以5℃/min降温至26℃,加入3,4-二氰基呋喃质量0.008倍的高碘酸钠,继续搅拌3h,制备得到二氰基呋喃基二甲酸酐基苯硼酸;在26℃和氩气保护条件下,将粒径为30μm氢氧化锆微粒和质量分数为50%的盐酸溶液按质量比1:0.5混合,以800r/min搅拌50min,放入60℃烘箱烘3h,制备得到功能化氢氧化锆微粒;在26℃下,将二氰基呋喃基二甲酸酐基苯硼酸和去离子水按质量比1:4混合,以500r/min搅拌40min,制备得到二氰基呋喃基二甲酸酐基苯硼酸溶液;在26℃下,将功能化氢氧化锆微粒、二氰基呋喃基二甲酸酐基苯硼酸和钛酸四氨基乙醇酯按质量比1:3:1.4混合,以800r/min搅拌3h,随后以40滴/min滴加功能化氢氧化锆微粒质量3倍的二氰基呋喃基二甲酸酐基苯硼酸溶液,以800r/min搅拌40min,随后在氦气保护条件下,以5℃升温至120℃,继续搅拌5h,静置49h,制备得到陶瓷纤维膜浆料;
(2)在19℃、50%湿度和氩气保护条件下,将陶瓷纤维膜浆料放入浆料罐中,以11mL/min将内絮凝剂去离子水和陶瓷纤维膜浆料分别从内管径为1.7mm、外管径为2.7mm的纺丝头中挤出,于陶瓷纤维膜浆料质量13倍的去离子水中浸泡25h,以5℃/min升温至250℃,以5ml/min通入陶瓷纤维膜浆料0.5倍的三氯化镍,保温26h,自然冷却至室温捞出,在0.06MPa和氩气保护条件下,放入500℃的管式炉中,保温90min,随后以11℃/min升温至750℃,保温3h,制备得到陶瓷纤维膜坯料;以陶瓷纤维膜坯料作为负极、石墨为正极放入氯化钙熔融体系中,在3.0V和1100℃下电解9h后捞出,以11℃/min升温至1800℃,保温5h,自然冷却至室温,制备得到多孔导电陶瓷纤维膜。
对比例1
对比例1与实施例2的区别仅在于步骤(1)的不同,将步骤(1)修改为:在25℃和氩气保护条件下,将2-硝基乙醇和四乙基溴化铵按质量比1:0.011混合,以400r/min搅拌30min,制备得到四乙基溴化铵溶液;将四乙基溴化铵溶液放入阳极为钛、阴极为石墨的电解池中,在电流密度为300A*m-2、1.5V电位、70℃以及氩气保护条件下,电处理60min,制备得到钛酸四硝基乙醇酯;在70℃和氩气保护条件下,将钛酸四硝基乙醇酯和钯碳按质量比1:0.006混合,以700r/min搅拌30min,以4m3/min通入氢气,继续搅拌2h,制备得到钛酸四氨基乙醇酯;在25℃和氩气保护条件下,将2,5-二氰基呋喃和溴按质量比1:1.3混合,以700r/min搅拌2h,随后加入2,5-二氰基呋喃质量2倍的邻苯二甲酸酐-4-硼酸频哪醇酯混合,以400r/min搅拌30min,随后以4℃/min升温至80℃,以35滴/min滴加3,4-二氰基呋喃质量0.015倍的三氯化硼,以700r/min搅拌2h,过滤,随后以4℃/min降温至25℃,加入3,4-二氰基呋喃质量0.007倍的高碘酸钠,继续搅拌2h,制备得到二氰基呋喃基二甲酸酐基苯硼酸;在25℃下,将二氰基呋喃基二甲酸酐基苯硼酸和去离子水按质量比1:3混合,以400r/min搅拌30min,制备得到二氰基呋喃基二甲酸酐基苯硼酸溶液;在25℃下,将粒径为25μm氢氧化锆微粒、二氰基呋喃基二甲酸酐基苯硼酸和钛酸四氨基乙醇酯按质量比1:2:1.3混合,以700r/min搅拌2h,随后以35滴/min滴加氢氧化锆微粒质量2倍的二氰基呋喃基二甲酸酐基苯硼酸溶液,以700r/min搅拌30min,随后在氦气保护条件下,以4℃升温至110℃,继续搅拌4h,静置48h,制备得到陶瓷纤维膜浆料。其余制备步骤同实施例2。
对比例2
对比例2与实施例2的区别仅在于步骤(1)的不同,将步骤(1)修改为:在25℃和氩气保护条件下,将2,5-二氰基呋喃和溴按质量比1:1.3混合,以700r/min搅拌2h,随后加入2,5-二氰基呋喃质量2倍的邻苯二甲酸酐-4-硼酸频哪醇酯混合,以400r/min搅拌30min,随后以4℃/min升温至80℃,以35滴/min滴加3,4-二氰基呋喃质量0.015倍的三氯化硼,以700r/min搅拌2h,过滤,随后以4℃/min降温至25℃,加入3,4-二氰基呋喃质量0.007倍的高碘酸钠,继续搅拌2h,制备得到二氰基呋喃基二甲酸酐基苯硼酸;在25℃和氩气保护条件下,将粒径为25μm氢氧化锆微粒和质量分数为40%的盐酸溶液按质量比1:0.4混合,以700r/min搅拌40min,放入50℃烘箱烘2h,制备得到功能化氢氧化锆微粒;在25℃下,将二氰基呋喃基二甲酸酐基苯硼酸和去离子水按质量比1:3混合,以400r/min搅拌30min,制备得到二氰基呋喃基二甲酸酐基苯硼酸溶液;在25℃下,将功能化氢氧化锆微粒、二氰基呋喃基二甲酸酐基苯硼酸按质量比1:2混合,以700r/min搅拌2h,随后以35滴/min滴加功能化氢氧化锆微粒质量2倍的二氰基呋喃基二甲酸酐基苯硼酸溶液,以700r/min搅拌30min,随后在氦气保护条件下,以4℃升温至110℃,继续搅拌4h,静置48h,制备得到陶瓷纤维膜浆料。其余制备步骤同实施例2。
对比例3
对比例3与实施例2的区别仅在于步骤(1)的不同,将步骤(1)修改为:在25℃和氩气保护条件下,将2-硝基乙醇和四乙基溴化铵按质量比1:0.011混合,以400r/min搅拌30min,制备得到四乙基溴化铵溶液;将四乙基溴化铵溶液放入阳极为钛、阴极为石墨的电解池中,在电流密度为300A*m-2、1.5V电位、70℃以及氩气保护条件下,电处理60min,制备得到钛酸四硝基乙醇酯;在70℃和氩气保护条件下,将钛酸四硝基乙醇酯和钯碳按质量比1:0.006混合,以700r/min搅拌30min,以4m3/min通入氢气,继续搅拌2h,制备得到钛酸四氨基乙醇酯;在25℃和氩气保护条件下,将粒径为25μm氢氧化锆微粒和质量分数为40%的盐酸溶液按质量比1:0.4混合,以700r/min搅拌40min,放入50℃烘箱烘2h,制备得到功能化氢氧化锆微粒;在25℃下,将二氰基呋喃基二甲酸酐基苯硼酸和去离子水按质量比1:3混合,以400r/min搅拌30min,制备得到二氰基呋喃基二甲酸酐基苯硼酸溶液;在25℃下,将功能化氢氧化锆微粒、乙醇和钛酸四氨基乙醇酯按质量比1:2:1.3混合,以700r/min搅拌2h,随后以35滴/min滴加功能化氢氧化锆微粒质量2倍的质量分数为50%的乙醇水溶液,以700r/min搅拌30min,随后在氦气保护条件下,以4℃升温至110℃,继续搅拌4h,静置48h,制备得到陶瓷纤维膜浆料。其余制备步骤同实施例2。
对比例4
对比例4与实施例2的区别仅在于步骤(2)的不同,将步骤(2)修改为:在18℃、49%湿度和氩气保护条件下,将陶瓷纤维膜浆料放入浆料罐中,以10mL/min将内絮凝剂去离子水和陶瓷纤维膜浆料分别从内管径为1.6mm、外管径为2.6mm的纺丝头中挤出,于陶瓷纤维膜浆料质量12倍的去离子水中浸泡24h,以4℃/min升温至200℃,保温24h,捞出自然冷却至室温,在0.05MPa和氩气保护条件下,放入400℃的管式炉中,保温80min,随后以10℃/min升温至700℃,保温2h,继续升温至1750℃,保温4h,自然冷却至室温,制备得到多孔导电陶瓷纤维膜。其余制备步骤同实施例2。
效果例
下表1给出了采用本发明实施例1至3与对比例1至4制备得到的多孔导电陶瓷纤维膜的抗氧化性、耐高温性、导电性和韧性的分析结果。
表1
从表1中可发现实施例1、2、3制备得到的多孔导电陶瓷纤维膜具有良好的抗氧化性、耐高温性、导电性和弯曲强度;从实施例1、2、3和对比例1的实验数据比较可发现,使用功能化氢氧化锆制备陶瓷纤维膜浆料,形成噁唑啉,利用三氯化镍对陶瓷纤维膜浆料电处理耦合烧结,形成硼化钛、硼化锆和钎料钛镍合金,制备得到的多孔导电陶瓷纤维膜的耐高温性和弯曲强度较强;从实施例1、2、3和对比例2的实验数据可发现,使用钛酸四氨基乙醇酯制备陶瓷纤维膜浆料,形成噁唑啉、二氧化钛,后续利用邻苯二甲酸铝对陶瓷纤维膜浆料进行烧结,形成硼化钛、碳纳米线和钎料钛镍合金,制备得到的多孔导电陶瓷纤维膜的抗氧化性、耐高温性、导电性和弯曲强度较强;从实施例1、2、3和对比例3的实验数据可发现,使用二氰基呋喃基二甲酸酐基苯硼酸制备陶瓷纤维膜浆料,形成噁唑啉,后续利用邻苯二甲酸铝对陶瓷纤维膜浆料进行烧结,形成硼化钛、硼化锆、碳纳米线和钎料钛镍合金,制备得到的多孔导电陶瓷纤维膜的耐高温性、导电性和弯曲强度较强;从实施例1、2、3和对比例4的实验数据可发现,利用三氯化镍对陶瓷纤维膜浆料电处理耦合烧结制备多孔导电陶瓷纤维膜,形成碳纳米线和钎料钛镍合金,制备得到的多孔导电陶瓷纤维膜的导电性和弯曲强度较强。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何标记视为限制所涉及的权利要求。
Claims (10)
1.一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述多孔导电陶瓷纤维膜是利用三氯化镍对陶瓷纤维膜浆料电处理耦合烧结制备得到;所述陶瓷纤维膜浆料是将钛酸四氨基乙醇酯和二氰基呋喃基二甲酸酐基苯硼酸包裹功能化氢氧化锆微粒制备得到;所述功能化氢氧化锆微粒是利用盐酸处理氢氧化锆微粒制备得到。
2.根据权利要求1所述的一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述多孔导电陶瓷纤维膜的制备方法如下:在17~19℃、48~50%湿度和氩气保护条件下,将陶瓷纤维膜浆料放入浆料罐中,以9~11mL/min将内絮凝剂去离子水和陶瓷纤维膜浆料分别从内管径为1.5~1.7mm、外管径为2.5~2.7mm的纺丝头中挤出,于陶瓷纤维膜浆料质量10~13倍的去离子水中浸泡23~25h,以3~5℃/min升温至150~250℃,以3~5ml/min通入陶瓷纤维膜浆料0.3~0.5倍的三氯化镍,保温22~26h,自然冷却至室温,在0.04~0.06MPa和氩气保护条件下,放入300~500℃的管式炉中,保温70~90min,随后以9~11℃/min升温至650~750℃,保温1~3h,制备得到陶瓷纤维膜坯料;在2.6~3.0V和900~1100℃下,将陶瓷纤维膜坯料放入电解池中电解7~9h后捞出,以9~11℃/min升温至1700~1800℃,保温3~5h,自然冷却至室温,制备得到多孔导电陶瓷纤维膜。
3.根据权利要求2所述的一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述电解池的负极为陶瓷纤维膜坯料、正极为石墨、电解液为熔融的氯化钙。
4.根据权利要求2所述的一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述陶瓷纤维膜浆料的制备方法如下:在24~26℃下,将二氰基呋喃基二甲酸酐基苯硼酸和去离子水按质量比1:2~1:4混合,以300~500r/min搅拌20~40min,制备得到二氰基呋喃基二甲酸酐基苯硼酸溶液;在24~26℃下,将功能化氢氧化锆微粒、二氰基呋喃基二甲酸酐基苯硼酸和钛酸四氨基乙醇酯按质量比1:1:1.2~1:3:1.4混合,以600~800r/min搅拌1~3h,随后以30~40滴/min滴加功能化氢氧化锆微粒质量1~3倍的二氰基呋喃基二甲酸酐基苯硼酸溶液,以600~800r/min搅拌20~40min,随后在氦气保护条件下,以3~5℃升温至100~120℃,继续搅拌3~5h,静置47~49h,制备得到陶瓷纤维膜浆料。
5.根据权利要求4所述的一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述功能化氢氧化锆微粒的制备方法如下:在24~26℃和氩气保护条件下,将氢氧化锆微粒和质量分数为30~50%的盐酸溶液按质量比1:0.3~1:0.5混合,以600~800r/min搅拌30~50min,放入40~60℃烘箱烘1~3h,制备得到功能化氢氧化锆微粒。
6.根据权利要求5所述一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述氢氧化锆微粒的粒径为20~30μm。
7.根据权利要求4所述的一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述二氰基呋喃基二甲酸酐基苯硼酸的制备方法如下:在24~26℃和氩气保护条件下,将2,5-二氰基呋喃和溴按质量比1:1.2~1:1.4混合,以600~800r/min搅拌1~3h,随后加入2,5-二氰基呋喃质量1~3倍的邻苯二甲酸酐-4-硼酸频哪醇酯混合,以300~500r/min搅拌20~40min,随后以3~5℃/min升温至70~90℃,以30~40滴/min滴加3,4-二氰基呋喃质量0.01~0.02倍的三氯化硼,以600~800r/min搅拌1~3h,过滤,随后以3~5℃/min降温至24~26℃,加入3,4-二氰基呋喃质量0.006~0.008倍的高碘酸钠,继续搅拌1~3h,制备得到二氰基呋喃基二甲酸酐基苯硼酸。
8.根据权利要求4所述的一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述钛酸四氨基乙醇酯的制备方法如下:在60~80℃和氩气保护条件下,将钛酸四硝基乙醇酯和钯碳按质量比1:0.005~1:0.007混合,以600~800r/min搅拌20~40min,以3~5m3/min通入氢气,继续搅拌1~3h,制备得到钛酸四氨基乙醇酯。
9.根据权利要求8所述的一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述钛酸四硝基乙醇酯的制备方法如下:将四乙基溴化铵溶液放入阳极为钛、阴极为石墨的电解池中,在电流密度为200~400A*m-2、1~2V电位、60~80℃以及氩气保护条件下,电处理50~70min,制备得到钛酸四硝基乙醇酯。
10.根据权利要求9所述的一种多孔导电陶瓷纤维膜的制备方法,其特征在于,所述四乙基溴化铵溶液的制备方法如下:在24~26℃和氩气保护条件下,将2-硝基乙醇和四乙基溴化铵按质量比1:0.01~1:0.012混合,以300~500r/min搅拌20~40min,制备得到四乙基溴化铵溶液。
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