CN1668680A - 包含1,1－二氟乙烯的多孔高分子膜 - Google Patents
包含1,1－二氟乙烯的多孔高分子膜 Download PDFInfo
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- CN1668680A CN1668680A CNA038170825A CN03817082A CN1668680A CN 1668680 A CN1668680 A CN 1668680A CN A038170825 A CNA038170825 A CN A038170825A CN 03817082 A CN03817082 A CN 03817082A CN 1668680 A CN1668680 A CN 1668680A
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- solvent
- film
- solution
- polymkeric substance
- vinylidene fluoride
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000012528 membrane Substances 0.000 title abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 238000007614 solvation Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000011877 solvent mixture Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 26
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 8
- 238000007766 curtain coating Methods 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 4
- 125000003368 amide group Chemical group 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 38
- 238000005266 casting Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 238000003756 stirring Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 9
- 229920006373 Solef Polymers 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- JNUZADQZHYFJGW-JOCHJYFZSA-N (2R)-N-[3-[5-fluoro-2-(2-fluoro-3-methylsulfonylanilino)pyrimidin-4-yl]-1H-indol-7-yl]-3-methoxy-2-(4-methylpiperazin-1-yl)propanamide Chemical compound FC=1C(=NC(=NC=1)NC1=C(C(=CC=C1)S(=O)(=O)C)F)C1=CNC2=C(C=CC=C12)NC([C@@H](COC)N1CCN(CC1)C)=O JNUZADQZHYFJGW-JOCHJYFZSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000009685 knife-over-roll coating Methods 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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Abstract
一种制备多孔聚合物结构的方法，该方法包括：制备在溶剂/非溶剂混合物中的含有聚合物的溶液，该聚合物含有1，1－二氟乙烯；将该溶液保持在高温下直到该聚合物完全溶剂化；流延该溶液形成薄层；和干燥该薄层形成膜。在制备溶液时，在加入溶剂之前，将聚合物分散在非溶剂中，以防止形成微粒凝胶。在高温下进行长时间的溶剂化提供了稳定的溶液，并能够形成具有可控孔隙率的膜。
Description
本发明涉及多孔高分子膜。本发明特别涉及制备多孔高分子膜的方法，并涉及这种膜在锂电池或燃料电池中的用途。
用锂金属阳极和可以嵌入或插入锂离子的材料的阴极制备电池已问世多年。这种电池可以利用锂盐在有机液体如碳酸异丙烯酯中的溶液作为电解质，和如滤纸或聚丙烯等作为隔离物。最近还公开了固态离子导电聚合物作为电解质的用途。对于二次或可充电锂电池，由于枝晶生长引起的问题使得使用锂金属阳极不能令人满意。现在通过使用在非常低的电压下能够可逆嵌入锂离子的材料如石墨，得到所谓的“锂离子”、“摇椅”或“摇摆”的可充电锂电池可以消除这个问题。这些锂电池以下述原理工作：它们不合锂金属，而是含有锂离子，锂离子在循环的充电和放电期间在两种嵌入材料之间来回摇摆。
Gozdz等人(US 5,296,318)公开了一种聚合物电解质，它包括75-92％1，1-二氟乙烯和8-25％六氟丙烯的共聚物，掺混了锂盐和相容性溶剂如碳酸亚乙酯/碳酸异丙烯酯混合物，并由在低沸点溶剂如四氢呋喃中的溶液进行流延。GB 2 309 701 B(AEA Technology)描述了如何通过将适当的单不饱和基团接枝到聚合物链上来提高聚合电解质组合物的粘结性，在这种情况下聚合物链可以是均聚物PVdF，或基本由1，1-二氟乙烯组成的共聚物或三聚物。也可以通过首先制备聚合物材料的多孔薄膜，然后将该薄膜浸没在锂盐在有机溶剂中的溶液中以使电解质溶液与聚合物薄膜结合来制备固体聚合物电解质，如EP 0730 316 A(Elf Atochem)所述。但是，使用已知的方法制备多孔膜难以获得尺寸基本均匀的微孔，并难以控制所得薄膜的孔隙率。
燃料电池使用多孔膜隔离阳极和阴极。该膜典型地为多层组合并且可包括例如一层多孔膜和一层或多层扩散层。需要改进的膜来改善气体向燃料电池板的均匀扩散。
本发明提供一种制备多孔聚合物膜的方法，该方法包括：
a)通过在将溶剂加入之前将聚合物分散在非溶剂中制备在溶剂/非溶剂混合物中的含有聚合物的溶液，该聚合物含有1，1-二氟乙烯；
b)将该溶液保持在高温下直到该聚合物完全溶剂化；
c)流延该溶液形成薄层；和
d)干燥该薄层形成膜。
该聚合物典型地主要包括1，1-二氟乙烯。因此该聚合物可以是均聚物，如聚二氟乙烯(PVdF)，或1，1-二氟乙烯与例如六氟丙烯的共聚物，或三聚物。典型的优选级聚合物为PVdF均聚物Solvay Solef 1015或6020、共聚物Solvay Solef 20615或20815或Atochem 2801和包括1，1-二氟乙烯、六氟丙烯和三氟氯乙烯的三聚物，如WO 02/11230所述。
该聚合物也可以是这样一种聚合物，其中聚合物链主要由1，1-二氟乙烯组成，在该链上接枝单不饱和羧酸、磺酸或膦酸、酯或酰胺。待接枝到聚合物链上的单体应该在碳链R-上只具有一个双键和一个或多个羧基基团-COOH、磺酸基团-SO2OH、膦酸基团-PO(OH)2、酯基团-COOR’或酰胺基团-CONH2。一般碳链R-上具有少于5个碳原子的较小单体是优选的。例如丙烯酸；巴豆酸、乙烯基乙酸、甲基丙烯酸(丁烯酸的异构体)；戊烯酸的异构体，如烯丙基乙酸等。也可以使用相应的酰胺(和取代的酰胺)。在酯中，基团R’可以是甲基、乙基或丁基；例如可以使用诸如丙烯酸甲酯或丙烯酸丁酯等酯。用于接枝的一些优选单体为丙烯酸或二甲基丙烯酰胺，但能引入最终基团的其它单体也是适用的。
接枝可通过辐射方法实现。例如可使聚合物链基材与接枝单体材料一起经历连续或间歇辐照；或者更优选在基材与单体材料接触之前对其进行预辐照。辐射可以是电子束、γ-射线或X-射线辐射。辐射显然是通过产生自由基来激活基材(聚合物链)。接枝度由几个因素决定，最重要的是：聚合物基材被辐照预激活的程度、被激活聚合物与接枝单体材料的接触时间长度、单体穿透聚合物的程度、及聚合物与单体接触时的温度。所得材料中接枝度理想地占最终重量的2-20％，更优选占3-12％，例如5％或10％。
其它组分也可存在于溶液中，例如粘度改性剂，如羧甲基纤维素，和表面张力改性剂，如草酸或马来酸。
聚合物与非溶剂混合形成浆料，然后加入溶剂形成均匀溶液。典型地，形成聚合物和非溶剂的浆料并加热到约60℃，优选在非金属容器(例如玻璃的或塑料的，例如聚丙烯的)中搅拌下进行，然后快速加入溶剂(例如约1升/5秒)。
如果先将聚合物与溶剂混合，然后再向溶液中加入非溶剂，则产生微粒凝胶，于是溶液不稳定并且不能得到可再生的膜。
非溶剂是一种当单独使用时不溶解聚合物的液体。非溶剂不应该只能溶解在溶剂中，还应该以基本所有的比例与溶剂混溶。典型地，非溶剂的沸点高于溶剂，优选高20℃，更优选高40℃或更高。非溶剂的实例包括含有6-20个碳原子的醇，例如辛醇、癸醇和十二烷醇及其混合物，优选癸醇、十二烷醇及其混合物。特别优选的非溶剂为50∶50的十二烷醇和癸醇的混合物或单独的十二烷醇。
溶剂是一种可以溶解或溶胀聚合物的溶剂。溶剂可以选自例如酮、醚、N，N-二甲基甲酰胺(DMF)、N，N-二甲基乙酰胺(DMA)、N，N-二乙基乙酰胺、N-甲基-2-吡咯烷酮(NMP)、六甲基磷酰胺、四甲基脲和二甲亚砜(DMSO)或其混合物。DMF和NMP是优选的溶剂。更优选NMP作为溶剂。
溶液中非溶剂与溶剂的比例可以变化。典型地，非溶剂在溶剂/非溶剂混合物中的比例为2-30wt％，优选5-15wt％，更优选7-10wt％。
聚合物在溶液中的量一般为3-30wt％，优选5-20wt％，更优选8-15wt％。
聚合物的溶剂化在高温进行。高温指室温(定为20℃)以上的温度。所选温度对所用聚合物和溶剂/非溶剂的组合以及进行溶剂化所用的时间是特定的。典型的高温至少为40℃，更典型至少为50℃，例如55℃。如果溶剂化进行得时间较长，则可以采用较低的温度。
典型的溶剂化进行几天。溶剂化过程继续直到聚合物完全被溶剂化。溶剂化所需的精确时间依溶剂/非溶剂混合物、所用聚合物和温度的选择而变化。典型的溶剂化进行4-14天，优选5-10天，且最优选5-7天。例如，PVdF(Solvay Solef 6020/1001)在N-甲基-2-吡咯烷酮及癸醇和十二烷醇的50∶50混合物中完全溶剂化典型地要5-14天，根据溶液中非溶剂与溶剂的比例一般要10天。在溶剂化过程中凝胶形成很慢，可以忽略。在不形成微粒凝胶的情况下也能进行溶剂化。
一旦聚合物完全溶剂化，溶液在室温下几周内都是稳定的。因此，溶液的粘度不随时间而变，溶液的颜色保持恒定，并且没有溶剂或非溶剂从溶液中分离出来。另外溶液流延形成具有一致性能的可再生膜。因此，不必立即将溶液流延成薄膜。
溶液一般流延在非多孔基材如铝箔或聚酯薄膜上。铝箔一般厚约20μm，而聚酯薄膜一般厚约100μm。如果阳极或阴极由不具有太多孔的材料制成，则溶液也可流延到阳极或阴极上。
当流延溶液时，溶液一般以厚度小于0.5mm，优选小于0.3mm的薄层流延在基材上。
一般在干燥机中经过至少两个连续的干燥区才能形成薄膜；薄膜不与任何液体接触。优选干燥机具有3或4个干燥区，最优选4个干燥区。每一个区保持不同的温度并且沿着薄膜移动的方向各区的温度依次升高。当使用连续辊衬刮刀辊涂法在移动网上制备膜时，干燥区中的典型温度值如下：
第一区 50-120℃
第二区 80-150℃
典型的温度配对可以是例如第一区65℃和第二区100℃，或第一区95℃和第二区120℃。如果干燥机具有3或4个干燥区，则各区之间的温度变化可以更缓和。例如，在干燥机具有4个干燥区时，可依次设定各区的温度为65℃、75℃、95℃和110℃。
移动网的速率一般为0.2-5.0m/min。网的移动速率依干燥区的长度和干燥区的数量而变化。干燥机具有的干燥区越多，网可以移动得越快而不会对膜性能产生不利影响。
在气体存在下干燥溶液形成膜。在一个实施方案中，该气体为干燥气体，例如干燥空气。例如，可以使用露点低于-20℃，例如-35℃至-37℃的空气。但是，该气体不必是无水的。该气体也可以是潮湿的空气，例如在相对湿度34％且16℃的环境条件下所提供的空气。但是如果空气湿度变化，膜的渗透性也将发生变化。
可以通过改变非溶剂与溶剂的比例、聚合物与溶剂/非溶剂的比例、第一和第二干燥区的温度及移动网的速率来控制所得多孔聚合物膜的孔隙率。
所制备膜的孔隙率可以在Gurley机上测量。给出的是使用该机器测定的不同薄膜的相对孔隙率。该机器测定100cm3空气在小的标准压力差(1.215kPa)下通过1平方英寸(6.45cm2)膜所用的时间(秒)。得到被称作Gurley数或Gurley值的读数。这也可以表示为以Gurley秒为单位。市售薄膜的Gurley数(Gurley秒)为400-600。Gurley数＜60的薄膜在用于电池时倾向于短路。但是，它们适用于燃料电池。Gurley数为50-200，更优选60-100的薄膜是本发明情况中优选的。随着Gurley数增加，膜的孔隙率下降，表明更难使空气通过膜。这可能是由于根据孔的分布膜具有较小的孔或较少较大孔所致。
根据本发明可制备薄至5μm的薄膜。因此，薄膜的厚度至少为5μm，优选10-30μm，更优选15-25μm，最优选17-22μm。
本发明的一个优点在于，可以制备具有足以用于电池的强度的薄膜。该薄膜也不会遭受短路。
在第二方面，本发明提供一种包含聚合物的膜，该聚合物包含厚度为5-30μm且Gurley数为5-300(Gurley秒)的1，1-二氟乙烯。该膜的Gurley数为50-200，更优选60-100，最优选70-90。这种膜迄今为止尚不存在。
本发明还提供本发明的膜或根据本发明制备的膜作为电池中隔离物的用途。该膜适用于不同类型的电池，例如镍镉、镍金属氢化物、锂离子和锂聚合物电池。可控的孔隙率和膜厚度以及这些膜的高强度使它们在这类应用中特别有利。
本发明还提供本发明的膜或根据本发明制备的膜在燃料电池中的用途。本发明还提供包括本发明膜的层压制件以及该层压制件在燃料电池中的用途。
现在通过实施例更详细地描述本发明。
实施例
在这些实施例中所描述的膜的Gurley数是在由GurleyInstruments of 514 Fulton Street，Troy，New York，USA制造的4340型Automatic Densometer上获得的。
实施例1
将100g特性粘度为0.210l/g(DMF，25℃)的PVdF(Solef 6020)分散在70g辛醇中。搅拌浆料并加入900g DMF。将该混合物在55℃搅拌1天并在55℃再保持6天直到达到完全溶剂化。
使用辊衬刮刀辊涂系统将溶液流延在以0.5m/min移动的聚酯网上。刮刀间隙设置为0.32mm，并且干燥区温度设置为第1区65℃、第2区100℃。得到厚度为17μm且空气渗透率为32 Gurley秒的成品微孔薄膜。
升高第1区的干燥温度至80℃、第2区的温度至105℃，得到厚度为17μm且空气渗透率为85 Gurley秒的薄膜。
再升高第1区的干燥温度至95℃、第2区的温度至110℃，得到厚度为17μm且空气渗透率为93 Gurley秒的薄膜。
实施例2
将100g特性粘度为0.210l/g(DMF，25℃)的PVdF(Solef 6020)分散在80g癸醇中。搅拌浆料并加入900g NMP。如实施例1所述搅拌并加热该混合物直到达到完全溶剂化。
使用辊衬刮刀辊涂系统将溶液流延在以0.5m/min移动的聚酯网上。刮刀间隙设置为0.32mm。干燥区温度和薄膜性能列于下表1中。
表1
| 实施例2.1 | 实施例2.2 | |
| 第1干燥区温度(℃) | 95 | 110 |
| 第2干燥区温度(℃) | 110 | 130 |
| 薄膜厚度(μm) | 14 | 16 |
| 空气渗透率(Gurley秒) | 12 | 40 |
实施例3
将100 g特性粘度为0.210l/g(DMF，25℃)的PVdF(Solef6020)分散在70g癸醇和十二烷醇的1∶1混合物(重量)中。搅拌浆料并加入900gNMP。将该混合物在55℃搅拌1天，并在55℃再保持10天直到达到完全溶剂化。
使用辊衬刮刀辊涂系统将溶液流延在以0.5m/min移动的聚酯网上。刮刀间隙设置为0.32mm。干燥区温度和薄膜性能列于下表2中。
表2
| 实施例3.1 | 实施例3.2 | |
| 第1干燥区温度(℃) | 75 | 110 |
| 第2干燥区温度(℃) | 110 | 130 |
| 薄膜厚度(μm) | 13 | 18 |
| 空气渗透率(Gurley秒) | 70 | 180 |
实施例4
将100g特性粘度为0.210l/g(DMF，25℃)的PVdF(Solef6020)分散在100g癸醇和十二烷醇的1∶1混合物(重量)中。搅拌浆料并加入900gNMP。如实施例3所述搅拌并加热该混合物直到达到完全溶剂化。
使用辊衬刮刀辊涂系统将溶液流延在以0.5m/min移动的聚酯网上。刮刀间隙设置为0.32mm。干燥区温度和薄膜性能列于下表3中。
表3
| 实施例4.1 | 实施例4.2 | |
| 第1干燥区温度(℃) | 75 | 110 |
| 第2干燥区温度(℃) | 110 | 130 |
| 薄膜厚度(μm) | 22 | 24 |
| 空气渗透率(Gurley秒) | 9 | 55 |
从以上实施例可见，如果干燥器设置在较高温度，并且非溶剂的比例较低，则孔隙率变小(即Gurley数增加)。如果非溶剂与溶剂间的沸点之差大于25℃，则薄膜的品质显著提高。
实施例5
将100g特性粘度为0.210l/g(DMF，25℃)的PVdF(Solef 6020)分散在100g十二烷醇中。搅拌浆料并加入900g NMP。如实施例1所述搅拌并加热该混合物直到达到完全溶剂化。
使用辊衬刮刀辊涂系统将溶液流延在以0.5m/min移动的聚酯网上。刮刀间隙设置为0.30mm。干燥区温度和薄膜性能列于下表4中。
表4
| 实施例5 | |
| 第1干燥区温度(℃) | 75 |
| 第2干燥区温度(℃) | 110 |
| 薄膜厚度(μm) | 24 |
| 空气渗透率(Gurley秒) | 76 |
实施例6
将100g特性粘度为0.210l/g(DMF，25℃)的PVdF(Solef 6020)分散在80g十二烷醇中。搅拌浆料并加入900g NMP。如实施例1所述搅拌并加热该混合物直到达到完全溶剂化。
使用辊衬刮刀辊涂系统将溶液流延在以0.5m/min移动的聚酯网上。刮刀间隙设置为0.32mm。干燥区温度和薄膜性能列于下表5中。
表5
| 实施例6 | |
| 第1干燥区温度(℃) | 85 |
| 第2干燥区温度(℃) | 110 |
| 薄膜厚度(μm) | 22 |
| 空气渗透率(Gurley秒) | 146 |
实施例7
将100g特性粘度为0.210l/g(DMF，25℃)的PVdF(Solef 6020)分散在60g十二烷醇中。搅拌浆料并加入900g NMP。如实施例1所述搅拌并加热该混合物直到达到完全溶剂化。
使用辊衬刮刀辊涂系统将溶液流延在以0.5m/min移动的聚酯网上。刮刀间隙设置为0.30mm。干燥区温度和薄膜性能列于下表6中。
表6
| 实施例7 | |
| 第1干燥区温度(℃) | 85 |
| 第2干燥区温度(℃) | 110 |
| 薄膜厚度(μm) | 19 |
| 空气渗透率(Gurley秒) | 88 |
Claims (11)
1.一种制备多孔聚合物膜的方法，该方法包括：
a)通过在加入溶剂之前将聚合物分散在非溶剂中制备在溶剂/非溶剂混合物中的含有聚合物的溶液，该聚合物含有1，1-二氟乙烯；
b)将该溶液保持在高温下直到该聚合物完全溶剂化；
c)流延该溶液形成薄层；和
d)干燥该薄层形成膜。
2.根据权利要求1的方法，其中所述溶液包含聚二氟乙烯(PVdF)。
3.根据权利要求1或2的方法，其中所述溶剂为N，N-二甲基甲酰胺(DMF)、N，N-二甲基乙酰胺(DMA)或N-甲基-2-吡咯烷酮(NMP)。
4.根据上述任意一项权利要求的方法，其中所述非溶剂为辛醇、癸醇、十二烷醇或其混合物。
5.根据上述任意一项权利要求的方法，其中所述溶液进行溶剂化最高达14天。
6.根据上述任意一项权利要求的方法，其中将单不饱和羧酸、磺酸或膦酸、酯或酰胺基团接枝到1，1-二氟乙烯上。
7.由根据上述任意一项权利要求的方法制备的膜。
8.包括根据权利要求1-6任意一项的方法制备的膜的层压制件。
9.根据权利要求1-5任意一项的方法制备的膜或根据权利要求7-9任意一项的膜在电池中的用途。
10.根据权利要求1-6任意一项的方法制备的膜在燃料电池中的用途。
11.根据权利要求8的层压制件在燃料电池中的用途。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0216834.2A GB0216834D0 (en) | 2002-07-19 | 2002-07-19 | Porous polymeric membrane |
| GB0216834.2 | 2002-07-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1668680A true CN1668680A (zh) | 2005-09-14 |
Family
ID=9940795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA038170825A Pending CN1668680A (zh) | 2002-07-19 | 2003-06-23 | 包含1,1－二氟乙烯的多孔高分子膜 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US7166644B2 (zh) |
| EP (1) | EP1523515B1 (zh) |
| JP (1) | JP4264415B2 (zh) |
| KR (1) | KR100982905B1 (zh) |
| CN (1) | CN1668680A (zh) |
| AU (1) | AU2003250374A1 (zh) |
| GB (1) | GB0216834D0 (zh) |
| TW (1) | TWI312787B (zh) |
| WO (1) | WO2004009684A1 (zh) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2005254448A1 (en) * | 2004-01-20 | 2005-12-29 | Kirby W. Beard | Highly microporous polymers and methods for producing and using the same |
| WO2007140252A1 (en) * | 2006-05-25 | 2007-12-06 | Drexel University | Filled nanoporous polymer membrane composites for protective clothing and methods for making them |
| FR2921518B1 (fr) * | 2007-09-26 | 2009-12-11 | Commissariat Energie Atomique | Procede d'elaboration de membranes conductrices de protons de pile a combustible par radiogreffage |
| EP2106801A1 (en) | 2008-04-04 | 2009-10-07 | Giuliani International Limited | IL-25 for use in the treatment of inflammatory diseases |
| EP2130547A1 (en) | 2008-06-06 | 2009-12-09 | Giuliani International Limited | IL-25 for use in the treatment of inflammatory diseases |
| KR102255814B1 (ko) * | 2016-11-29 | 2021-05-24 | 닛토덴코 가부시키가이샤 | 층을 전사하기 위한 전사 시트 및 전극 촉매층이 부착된 시트 |
| FR3089226B1 (fr) * | 2018-11-30 | 2021-08-06 | Arkema France | Procédé de préparation de films de polymère fluoré poreux |
| JP7240608B2 (ja) * | 2019-08-29 | 2023-03-16 | トヨタ自動車株式会社 | 非水溶性高分子の多孔質体の製造方法 |
| JP7281086B2 (ja) * | 2019-10-09 | 2023-05-25 | トヨタ自動車株式会社 | 多孔質体の製造方法 |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3620895A (en) * | 1969-01-03 | 1971-11-16 | Polaroid Corp | Corrugated micropermeable membrane |
| CA1068458A (en) * | 1975-07-17 | 1979-12-25 | Hiroshi Mano | Process for producing porous materials |
| US4267364A (en) * | 1977-04-20 | 1981-05-12 | E. I. Dupont De Nemours And Company | Fluorinated ion exchange polymer containing carboxylic groups, process for making same, and film and membrane thereof |
| US4384047A (en) * | 1980-03-28 | 1983-05-17 | Pennwalt Corporation | Porous vinylidene fluoride polymer membrane and process for its preparation |
| US4399025A (en) * | 1980-10-28 | 1983-08-16 | Delta Central Refining, Inc. | Solvent extraction process for rerefining used lubricating oil |
| US4433082A (en) * | 1981-05-01 | 1984-02-21 | E. I. Du Pont De Nemours And Company | Process for making liquid composition of perfluorinated ion exchange polymer, and product thereof |
| JPS6211521A (ja) | 1985-07-09 | 1987-01-20 | Fuji Photo Film Co Ltd | カ−トリツジ型ミクロフイルタ−の製造方法 |
| FR2614214B1 (fr) * | 1987-04-23 | 1993-02-12 | Commissariat Energie Atomique | Membrane semi-permeable organominerale et son procede de fabrication. |
| EP0335805A3 (en) * | 1988-04-01 | 1990-04-25 | Terumo Kabushiki Kaisha | Method of manufacturing porous membrane and porous membrane manufactured by the same method |
| US5158721A (en) * | 1989-11-30 | 1992-10-27 | Millipore Corporation | Porous membrane formed from interpenetrating polymer network having hydrophilic surface |
| US6013688A (en) * | 1992-05-06 | 2000-01-11 | Corning Costar Corporation | PVDF microporous membrane and method |
| US5384047A (en) | 1993-01-22 | 1995-01-24 | Refractron Technologies Corporation | Filter dryer body |
| US5296318A (en) * | 1993-03-05 | 1994-03-22 | Bell Communications Research, Inc. | Rechargeable lithium intercalation battery with hybrid polymeric electrolyte |
| TW342537B (en) | 1995-03-03 | 1998-10-11 | Atochem North America Elf | Polymeric electrode, electrolyte, article of manufacture and composition |
| DE69700138T2 (de) * | 1996-01-31 | 1999-09-02 | Aea Technology Plc | Polyvinylidenfluorid als polymerer Festelektrolyt für Lithium-Ionen-Batterien |
| GB2309701B (en) * | 1996-01-31 | 1999-06-16 | Aea Technology Plc | Organic electrolyte composition |
| GB9708365D0 (en) * | 1997-04-25 | 1997-06-18 | Johnson Matthey Plc | Proton conducting membranes |
| US6248469B1 (en) * | 1997-08-29 | 2001-06-19 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
| EP1265950B1 (en) * | 1999-12-23 | 2005-07-27 | AEA Technology Battery Systems Limited | Microporous membrane |
| GB0014464D0 (en) * | 2000-06-15 | 2000-08-09 | Aea Technology Plc | A cell incorporating a porous membrane |
| GB0018635D0 (en) * | 2000-07-31 | 2000-09-13 | Aea Technology Plc | Polymer electrolyte |
| GB0024347D0 (en) * | 2000-10-05 | 2000-11-22 | Aea Technology Plc | Electrolyte for a secondary cell |
-
2002
- 2002-07-19 GB GBGB0216834.2A patent/GB0216834D0/en not_active Ceased
-
2003
- 2003-06-23 KR KR1020057000969A patent/KR100982905B1/ko active IP Right Grant
- 2003-06-23 AU AU2003250374A patent/AU2003250374A1/en not_active Abandoned
- 2003-06-23 CN CNA038170825A patent/CN1668680A/zh active Pending
- 2003-06-23 JP JP2004522283A patent/JP4264415B2/ja not_active Expired - Lifetime
- 2003-06-23 WO PCT/GB2003/002682 patent/WO2004009684A1/en active Application Filing
- 2003-06-23 US US10/520,943 patent/US7166644B2/en not_active Expired - Lifetime
- 2003-06-23 EP EP03765144.5A patent/EP1523515B1/en not_active Expired - Lifetime
- 2003-06-30 TW TW092117807A patent/TWI312787B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW200404823A (en) | 2004-04-01 |
| GB0216834D0 (en) | 2002-08-28 |
| WO2004009684A1 (en) | 2004-01-29 |
| JP4264415B2 (ja) | 2009-05-20 |
| EP1523515A1 (en) | 2005-04-20 |
| US7166644B2 (en) | 2007-01-23 |
| TWI312787B (en) | 2009-08-01 |
| AU2003250374A1 (en) | 2004-02-09 |
| KR20050021518A (ko) | 2005-03-07 |
| US20060148911A1 (en) | 2006-07-06 |
| JP2005533884A (ja) | 2005-11-10 |
| KR100982905B1 (ko) | 2010-09-20 |
| EP1523515B1 (en) | 2019-09-04 |
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