CN1297457A - 离聚物和离子导电组合物 - Google Patents
离聚物和离子导电组合物 Download PDFInfo
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- CN1297457A CN1297457A CN99805082A CN99805082A CN1297457A CN 1297457 A CN1297457 A CN 1297457A CN 99805082 A CN99805082 A CN 99805082A CN 99805082 A CN99805082 A CN 99805082A CN 1297457 A CN1297457 A CN 1297457A
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- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- GSJFXBNYJCXDGI-UHFFFAOYSA-N methyl 2-hydroxyacetate Chemical class COC(=O)CO GSJFXBNYJCXDGI-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
公开的是含有带氟烷基磺酸盐侧基的官能化聚烯烃的离聚物,以及通过添加溶剂由此离聚物形成的离子导电组合物。
Description
发明领域
本发明涉及含有带氟化烷基磺酸盐侧基的官能化聚烯烃的离聚物和通过在其中加入溶剂而形成的离子导电组合物。本发明的离子导电组合物可用在电池、燃料电池、电解电池、离子交换膜、传感器、电化学电容器和改性电极中。
本发明的技术背景
由含有离子侧基的有机聚合物形成离子导电膜和凝胶,在本领域中是早就为人所熟知的。这样的聚合物称为离聚物。在广泛传播的商业应用中,特别广为人知的离聚物膜是E.I.Du Pont公司的Nafion_膜。如专利US-3,282,875所公开,Nafion_是由四氟乙烯(TFE)和全氟(3,6-二氧杂-4-甲基-7-辛烯磺酰氟)共聚而得到的。如专利US-4,358,545所公开,TFE和全氟(3-氧杂-4-戊烯-磺酰氟)的共聚物也是已知的。如在专利US-3,282,875中所公开的,如此形成的共聚物通过水解,通常通过暴露在适当的碱的水溶液中,而转化为离聚物的形式。在本领域中众所周知,锂、钠和钾都适于作为上述离聚物的阳离子。
在上述聚合物中,氟原子提供了许多好处。在靠近侧链中磺酰基的碳原子上的氟基团提供了电负性,使阳离子足够活泼,因此提供了高的离子导电率。用氢取代这些氟原子会导致离子迁移率明显降低,因此也就损失了导电率。
其它的氟原子则为聚合物提供与含氟聚合物相关的化学稳定性和热稳定性。在如众所周知的“氯碱”工艺的一些应用中,这已被证实是有相当价值的。然而,在不太需要较高化学稳定性和热稳定性的场合,高氟代的聚合物也有缺点。氟代的单体比其烯烃对应物要昂贵得多,需要高的加工温度,而且经常需要昂贵的耐腐蚀加工设备。再有,难以形成氟聚合物的溶液和分散液。此外,难以与氟聚合物形成强的粘合键。比如,在用于电化学电池的材料中,具有较好的加工性能是要以牺牲一些化学和热稳定性为代价的。因此就有动机开发一种离聚物,该离聚物具有非氟的聚合物骨架,且带有高度活泼的阳离子。
许多出版物公开过这类聚醚,即或者在聚醚中具有相邻的离子片段,或者它与离子盐相结合。电导率为等于或小于10-5S/cm。Le Nest等人在《聚合物通讯》(Polymer Communication)28,303(1987)中公开过一种由磷酸盐或硫代磷酸盐物质相连的被水解为相关的锂离聚物的聚醚二醇低聚物。在与碳酸丙烯酯一起使用时,可以得到1x10-4~10x10-4S/cm的电导率。相关技术的综述可以在Fauteux等人的《电化学》(Electrocjimica)Acta 40,2185(1995)中找到。
Benrabah等人在《电化学》(Electrocjimica)Acta 40,2259(1995)中公开了用氧四氟磺酸锂和衍生物交联的聚醚。不加入对质子有惰性的溶剂。由于添加了锂盐,电导率达到小于10-4S/cm。
Armand等人在美国专利5,627,292中公开了由乙烯基氟代乙氧基磺酰氟或具有氟代乙氧基磺酰氟基团的环醚与聚环氧乙烷、丙烯腈、吡啶和其它单体形成的共聚物。形成了磺酸锂离聚物。不加入对质子有惰性的溶剂,电导率小于10-4S/cm。
Narang等人在美国专利5,633,098中公开了具有官能化聚烯烃骨架和含有四氟乙氧基磺酸锂侧基的丙烯酸酯共聚物。含有磺酸根的共聚单体的摩尔含量是50~100%。该组合物被公开含有聚合物和由碳酸丙烯酯、碳酸乙烯酯和二甲氧基乙烷组成的混合溶剂。此组合物的离子电导率为10-4~10-3S/cm。
Brookhart等人在WO 9623010A2中公开了由乙烯和1,1,2,2-四氟-2-[(1,1,2,2,3,3,4,4-八氟-9-癸烯基)氧]乙烷磺酰氟通过使用二亚胺-过渡金属配合物的催化反应形成的共聚物。这样形成的聚合物含有聚乙烯骨架和烷基支链,其中聚乙烯骨架具有随机分布的1,1,2,2-四氟-2-[(1,1,2,2,3,3,4,4-八氟(最大多数是)辛基)氧]乙烷磺酰氟的侧基。
发明概述
本发明提供一种含有骨架和侧基的离聚物,该骨架基本上由亚甲基单元组成,而侧基包括如下通式的离子基团:
-Rn-Rf-CF2CF2-SO2-X-(SO2Rf)a-M+
这里,M+是一价金属阳离子;Rf基团是独立地选自线性或支化的全氟亚烷基基团、含O或Cl的全氟亚烷基基团和全氟芳基基团;R是烃基,而n=0或1;a=0~2;X=0、N或C;所述的离子基团进一步限制在当X=0时,a=0,X=N时,a=1,X=C时,a=2。
本发明还提供一种离子导电组合物,它包括了上述的离聚物,并在其中浸透的液体。
本发明还公开了一种制造离聚物的方法,该方法包括将包括骨架和侧基的聚烯烃与碱金属的碱溶液接触,该骨架基本由亚甲基和次甲基单元组成,而侧基包括如下通式的离子基团:
XSO2-CF2CF2-Rf-Rn-这里X是F或Cl,Rf是线性或支化的全氟亚烷基、含O或Cl的全氟亚烷基或全氟芳基,R是烃基,其中n=0或1。
进一步公开的是制造导电组合物的方法,该方法包括将上述离聚物与液体接触。
在本文中还包括的是一种电极,它包括至少一种电极活性材料、与其混合的在本文中公开的离聚物和浸透它们的液体。
进一步公开的是电化学电池,它包括正电极、负电极,位于正电极和负电极之间的隔离件,以及将此电池与外界负载或电源相连的装置,其中在隔离件、阳极和阴极中至少一件含有上述的离聚物。
详细说明
在本发明的聚烯烃离聚物的一个优选实施方案中,骨架基本由烯烃基团组成,其1~20mol%具有如下通式的侧基
M+ -SO3-CF2CF2-O-[(CFR1CF2)x-Oy]n-(CH2)z- (Ⅰ)这里,M+是碱金属阳离子,R1是全氟烷基或氟,x=0、1、2或3,y=0或1,n=0、1、2或3,而z是2~6的整数。最优选M+是锂离子,R1是氟,x=1,y=0,n=1或2,z=4。
构成本发明聚烯烃离聚物骨架的烯烃基团基本是未被取代的,只是在本发明优选实施方案中骨架烯烃基团中有1~20mol%具有如通式(Ⅰ)的侧基。在一个最优选的实施方案中,骨架烯烃基团的2~10mol%带有如通式(Ⅰ)的侧基。
正如在本领域中已知的,聚烯烃的支化度和支化类型取决于在聚合时使用的单体和实施聚合的方法。通过各种催化方法聚合的乙烯具有短的支链,其支链数为每1000个亚甲基中有<1个到大约150个,这取决于使用的催化剂和反应条件。如此形成的短支链大多数是甲基或乙基。
当聚合用的烯烃单体高于乙烯时,支化数目明显增加,因为这时在每个单体单元中都有至少一个固有的侧链。
在实践中发现,支链对本发明导电组合物的离子电导率有明显的影响。为了得到最高的电导率,当从本文叙述的催化路线合成的聚合物生成本发明的离聚物时,优选每1000个亚甲基有5~90个甲基支链的支链数。当用下面叙述的接枝聚合物路线制备离聚物时,尚可得到更大的支化度。
本发明的优选离聚物习惯上按照本领域中已知的方法生成,即将非离子的磺酰卤化物母体与碱金属氢氧化物的溶液接触,从而使聚合物水解为碱金属盐。在实施本发明时发现,通过先将非离子母体用碱金属氢氧化物处理,然后用酸的水溶液进行离子交换,最容易生成本发明酸式离聚物。用本领域中已知的离子交换方法可以将其它的一价金属如铜或银交换为碱金属离子。
实施本发明的优选母体聚合物,可以通过一种或几种烯烃单体(优选是乙烯)和优选如下式的取代烯烃共聚单体进行共聚来制备。
FSO2-CF2CF2-O-[(CFR1CF2)x-Oy]n-(CH2)z-CH=CH2这里,R1是全氟烷基或氟,x=0、1、2或3,y=0或1,n=0、1、2或3,z是2~6的整数。更优选R1是氟,x=1,y=0,n=1或2,而z=4。在本领域中这样的共聚是众所周知的,用已知催化的方法如Brookhart等人在WO9623010A2中叙述的方法以及如下所显示的方法很容易获得该共聚单体。
如Brookhart公开和如下文所举例的二亚胺-过渡金属配合物是本发明方法制备优选的非离子母体聚合物的优选催化剂。在如此形成的聚合物中,骨架基本由烯烃基团组成,其中的1~20%(mol),优选2~10%(mol)含有侧基1,1,2,2-四氟-2-[(1,1,2,2,3,3,4,4-八氟(大多数是)辛基)氧]乙烷磺酰氟,该聚合物每1000个亚甲基支链数少于150个,优选5~90个烷基支链,最经常是甲基和乙基。催化剂的结构对支链的数目有决定性的影响。其它的适合于实施本发明的催化剂包括茂金属催化剂和齐格拉-纳塔催化剂。最优选的催化剂是在下面表2中结构B和D与PMAO一起混合使用的镍二亚胺催化剂。这类催化剂使良好的共聚单体配合速度、在优选范围的支链含量和高的聚合物产率达到所预期的结合。
在使用优选的二亚胺镍催化剂的情况下,在实施本发明时发现,使用较松散的催化剂会导致较高的聚合物支化度。松散的催化剂越少,与含磺酰基的取代烯烃共聚单体相关的配合越高。
本发明的优选共聚单体在茂金属催化的共聚中得到的支化度(参见例如Yang等人的J.Am.Chem.Soc.116,pp10015ff,1994)一般较低,伴随着电导率也较低。然而,使用第三共聚单体,优选链中含有三个或更多碳原子的烯烃,与茂金属或齐格拉-纳塔催化剂混合就能够增大所得到的聚合物的支化度,同时该聚合物也就有较高的离子电导率。
为了形成本发明的离聚物,其它手段也是适当的。这包括将通式如下的基团接枝到基本未被取代的聚烯烃上、优选是聚乙烯,形成本发明的离聚物。
FSO2-CF2CF2-O-[(CFR1CF2)x-Oy]n-(CH2)z-这里,R1是全氟烷基或氟,x=0、1、2或3,y=0或1,n=0、1、2或3,z是2~6的整数。优选R1是氟,x=1,y=0,n=1,而z=2。在本领域中,许多在聚烯烃上接枝的方法是已知的。发现的一个适当的方法在下面举例说明。
在另一个实施方案中,按照Desmarteau在《氟化学杂志》(J.Fluotine Chem.)52,pp.7ff,1991中叙述的方法,将骨架基本由聚烯烃基团组成,并含有1~20mol%通式如下的侧基聚合物与R’f-SO2-N(Na)SiMe3反应
XSO2-CF2CF2-Rf-Rn-其中X是F或Cl,Rf是线性或支化的全氟亚烷基、含O或Cl的全氟亚烷基或全氟芳基,而R是烃基,其中n=0或1。得到的聚合物具有基本未被取代的烯烃基团骨架,其中含有1~20mol%具有如下式的侧基。可以用本领域中已知的简单阳离子交换母体用比如锂离子取代钠离子其中Rf和R’f是线性或支化的全氟亚烷基、含O或Cl的全氟亚烷基或全氟芳基,但无须都相同,R是烃基,其中n=0或1。
在另一个实施方案中,将骨架基本由烯烃基团组成,其中含1~20mol%通式如下的侧基聚合物与用Seppelt在《无机化学》(Inorg.Chem.)27,pp.2135ff,1998中的方法制备的(R’f-SO2)2-C(MgBr)2反应,在THF溶液中混合并在室温下搅拌过夜,然后除去溶剂并用盐酸水溶液处理几小时。然后过滤溶液,用水洗涤,再用碱金属的碱溶液处理。
XSO2-CF2CF2-Rf-Rn-其中X是F或Cl,Rf是线性或支化的全氟亚烷基、含O或Cl的全氟亚烷基或全氟芳基,而R是烃基,其中n=0或1。
所得到的聚合物具有基本未被取代的烯烃基团骨架,其中含1~20mol%通式如下式的侧基。其中M+是碱金属,Rf和R’f是线性或支化的全氟亚烷基、含O或Cl的全氟亚烷基或全氟芳基,但无须都相同,R是烃基,其中n=0或1。
在实施本发明时发现,共聚单体共聚程度对本发明导电组合物的电导率有深奥地呈非线性影响关系。对于共聚单体浓度低于大约2%(mol)时,电导率为0~大约10-5S/cm,几乎不受支化度或使用液体的影响。具有导电率为10-5S/cm或更小的导电组合物来说,其用途是比较有限的。
在加入大约2~3mol%的共聚单体时,离子电导率就明显地增大,对支化和用来形成导电组合物的液体的选择表现出很强的依存性。在大约加入3~10mol%的范围内共聚单体的,达到10-5~10-2S/cm的电导率,而观察到对共聚单体的浓度有适中的依存性。当共聚单体的浓度为10mol%时,比大约6~7%(mol)的浓度只获得不大的额外收效。本发明人相信,此“减弱回馈”效应的一个原因是,为了在聚合物中能够引入更高浓度共聚单体而所需要的催化剂,所产生的聚合物支化较少,使得两个效应有点自我抵消。不过,在本发明的导电组合物中,当使用碳酸丙烯酯作为液体,而且聚合物中共聚单体的浓度小于10mol%时,观察到比10-5S/cm大得多的电导率,这和本领域所公开的完全不同。
在本发明的一个优选实施方案中,在离聚物中离子官能团的含量优选为1~10mol%,最优选为3~7mol%。
虽然对由本发明的离聚物制备的制品的形状和尺寸没有限制,薄膜和膜片都是特别有用的。本发明的离聚物并不是全热塑性的,不能象衍生它们的非离子母体那么容易加工。比如,发现通过本领域中广为人知而且将要在下面叙述的方法制备该母体聚合物的膜片是很方便的。特别方便的是用螺杆挤出机和平模来挤出薄膜。另外,可以熔融压制薄膜。此外可以通过在基底上浇注和凝固,从母体聚合物的溶液或分散液浇注出薄膜。没有哪个特定的方法比其它方法更为优选,特定的方法将按照特定实践者的需要来选择。
本发明的离聚物在干燥时,显示出的室温离子电导率大约是10-7~10-6S/cm。然而,在实施本发明时发现,当本发明的离聚物浸透液体时,许多液体会成数量级地增加电导率。因而发现,为了实现本发明最有用的实施方案,在本发明的离聚物中浸透液体形成的导电组合物是所希望的。
将根据用途来决定所用的液体。一般说来,在实施本发明时发现,含液体离聚物的电导率随着吸收的重量%增加、液体介电常数增加、液体的路易斯碱性增加而增加,同时发现电导率随着使用液体粘度增加和分子尺寸的增加而降低。因此在给定的膜片中,强碱性、低粘度、小分子尺寸但低介电常数的溶剂比大分子尺寸、高粘度、低碱性而很高介电常数的溶剂能提供更好的电导率。当然,也会有其它的考虑。比如,不希望离聚物在此液体中有太大的溶解度;或者,在所预期的应用中,液体可以是电化学不稳定的。
一个特别优选的实施方案包括与质子惰性溶剂一起使用的锂离聚物、该溶剂优选是在锂电池中使用的有机碳酸酯类。
优选的本发明电极包括一种或几种呈颗粒状活性电极材料的混合物、本发明的离聚物、至少一种电子导电添加剂和至少一种碳酸酯。有用的活性阴极材料实施例包括但不限于碳(石墨、焦碳、新生碳、多并苯等)和添加锂的碳、金属锂氮化物如Li2.6Co0.4N、氧化锡、碱性玻璃、金属锂和锂合金,如锂与铝、锡、镁、硅、锰、铁和锌的合金。使用碳的添加锂阴极是优选的。可以使用的阳极活性材料包括,但不限于此过渡金属氧化物和硫化物、含锂的过渡金属氧化物和硫化物以及有机硫化物。这样的例子是氧化钴、氧化锰、氧化钼、氧化钒、硫化钛、硫化钼和硫化铌、含锂的氧化物,如尖晶石锂锰氧化物Li1+xMn2-xO4、掺铬的尖晶石锂锰氧化物LixCryMnzO4、LiCoO2、LiNiO2、LiNixCo1-rO2,这里x是0<x<1,优选的范围是0.5<x<0.95、LiCoVO4和它们的混合物。优选LiNixCo1-xO4。特别优选的电子导电添加剂是碳黑,优选MMM.S.A.碳公司,布鲁塞尔,比利时出品的Super P碳黑,浓度是在1~10%的范围。优选在最终电极中锂离聚物的体积百分数为4~40%。
习惯上可以通过将所有聚合物组分溶解于普通溶剂以及和碳黑颗粒及电极活性颗粒一起混合来制备本发明的电极。对于阳极,优选的电极活性材料是LiNixCo1-xO2,其中0<x<1,而对于阴极,优选的电极活性材料是石墨化的新生碳(mesocarbon)微珠。比如优选的本发明锂电池电极可以通过将本发明的离聚物溶解于丙酮和二甲基甲酰胺的混合物,然后加入电极活性材料的颗粒和碳黑,再在基底上沉积一层薄膜并干燥来制造。由此得到的优选电极将包括电极活性材料、导电碳黑和本发明的离聚物,在此离聚物与电极活性材料的重量比优选为0.05~0.8,而碳黑与电极活性材料的重量比优选为0.01~0.2。离聚物与电极活性材料的重量比最优选范围为0.1~0.25,而碳黑与电极活性材料的重量比最优选为0.02~0.1。然后可以用本领域中已知的技术将溶液浇注到适当的载体如玻璃板或集电器金属箔上成为电极,并形成薄膜。如在下面将要叙述的,用层压成型的方法,可以将如此制造的电极随后被加入到多层电化学电池结构中。
可以希望在本发明的分离器组合物中加入诸如为了改善各组分粘结或提供由其制造的制品结构完整性等目的所常采用的助剂。一种特别优选的添加材料是SiO2,如在上面所叙述,可以简单地加入并将其颗粒分散到形成分离器的相同溶液中。优选平均颗粒度小于1.0μm的二氧化硅颗粒,在混合物中二氧化硅的含量不多于总重量的50%。
在另一个方法中,可以先将电极活性材料和任选的碳黑和其它助剂的分散液浇注在一个表面上,然后将本发明的离聚物加入到有机碳酸酯溶液中。
在下面的特定实施方案中进一步说明本发明。
实施例
下面将叙述的母体非离子聚合物Ⅰ~ⅪⅤ是通过乙烯和如下式的共聚单体共聚而得到的
FSO2-CF2CF2-O-(CF2)n(CH2)4CH=CH2这里,n=2或4。使用的溶剂是甲苯,只是在合成聚合物Ⅺ时使用的是二氯甲烷。
参见表1,在置于氮气吹扫的干燥箱中的Sehlenk烧瓶中将所指定量的指定催化剂、共聚单体和溶剂混合来合成聚合物Ⅰ~Ⅹ和聚合物ⅪⅤ。在表2中提供了指定的催化剂结构。然后将混合物从干燥箱中取出,放在1atm的乙烯氛围中。用乙烯吹扫此混合物15min,同时浸入冰水浴中冷却。然后加入2.2mL的7.1%聚甲基铝氧烷(PMAO)甲苯(对于聚合物Ⅶ和ⅪⅤ是4.4mL)溶液中来引发反应,将混合物在指定的时间内搅拌。在指定时间终了时,在反应混合物中缓慢加入5mL甲醇,然后将混合物倾倒在150mL甲醇中,再加入1.5mL浓盐酸水溶液。得到的混合物搅拌大约30min。过滤得到的白色固体聚合物,每次用20mL的甲醇洗涤,共洗涤6次,并在真空中干燥。
在Schlenk烧瓶中将指定量的指定催化剂、共聚单体和二氯甲烷溶剂混合来合成聚合物Ⅺ。将混合物放在室温和1atm乙烯氛围中来引发反应。不加入PMAO,在搅拌下反应进行4,260min;得到的聚合物是油状液体。过滤反应物。在搅拌下向滤液中加入350mL甲醇。分离油性沉淀并再次溶解于100mL二氯甲烷中,然后加入305mL甲醇。分离出浅黄色油状产物并在真空中干燥。如此制得的材料具有-66℃的玻璃化温度,没有熔点。
在置于干燥箱中的Schlenk烧瓶中混合指定量的指定催化剂、共聚单体和溶剂来制备聚合物Ⅻ和ⅩⅢ。将混合物放在1atm的乙烯氛围中并用乙烯吹扫15min。加入10mL的7.1%PMAO甲苯溶液来引发反应,在指定温度下持续搅拌到指定时间。在反应混合物中缓慢加入350mL甲醇,然后加入5mL浓盐酸。过滤白色固体聚合物,用甲醇洗涤并在真空下干燥。
用聚乙烯标准通过凝胶渗透色谱测定分子量。用Du Pont 912型差热扫描热量计,从冷却到-100℃,然后以10℃/min的速度加热到150℃来测定熔点。在下面叙述的实施例中,按照罗马数字Ⅰ~ⅩⅦ来标识聚合物。在表1中,用相当于在表2中所列催化剂的字母标识来标识使用的催化剂。用质子和13C核磁共振测定聚合物中共聚单体的%含量。
表1:聚合物Ⅰ~ⅪⅤ的合成
聚合物 | 反应条件 | 产物 | ||||
催化剂 | 共聚单体 | |||||
种类 数量(mmol) | n= 数量 溶剂量 反应温度 反应时间(ml) (℃) (min) | 每1000个CH2的Me数 | 共聚单体(%mol) | Mw/Mn×10-3 | 熔点(℃) | |
Ⅰ | A 0.017 | 2 10ml 30 0 28 | 52 | 1.6 | 289/117 | 106 |
Ⅱ | B 0.017 | 2 10ml 30 0 18 | 49 | 4.4 | 186/72 | 94 |
Ⅲ | C 0.017 | 2 10ml 30 0 30 | 5 | 3.4 | 122/42 | 125 |
Ⅳ | D 0.017 | 2 10ml 30 0 30 | 11 | 3.7 | 251/49 | 124 |
Ⅴ | E 0.017 | 2 10ml 30 0 30 | 6 | 6.9 | 67/25 | 126 |
Ⅵ | F 0.0141 | 2 10ml 30 0 30 | 4 | 5.3 | 26/9 | 126 |
Ⅶ | D 0.034 | 2 10ml 70 0 30 | 20 | 2.6 | 173/35.9 | 118 |
Ⅷ | D 0.017 | 2 20ml 20 0 105 | 8 | 10.8 | 246/44 | 127 |
Ⅸ | B 0.017 | 4 9.8g 30 0 30 | 77 | 3.9 | 330/141 | 102 |
Ⅹ | B 0.017 | 4 3.26g 35 0 35 | 98 | 3.5 | 156/90 | 94 |
Ⅺ | G 0.1 | 2 10.13g 50 23 4260 | 105 | 3.4 | 203/124 | 无 |
Ⅻ | H 0.0077 | 2 5g 35 23 30 | 3 | 5.7 | 31.6/11.2 | 113 |
ⅩⅢ | H 0.0077 | 2 5g 35 0 30 | 2 | 3.4 | 117/52 | 102 |
ⅩⅣ | B 0.035 | 4 19.6g 60 0 28 | 81 | 4.6 | 162/67 | 101 |
G Pd(CH2)3C(O)OCH3({2,6-[CH(CH3)2]2C6H3}2DAB(CH3)2)SbF6
H 二氯rac-亚乙基二(茚基)合锆(Ⅳ)
在下面叙述的母体非离子聚合物ⅩⅤ和ⅩⅥ是通过如下式的共聚单体和丙烯共聚而得到的
FSO2-CF2CF2-O-(CF2)2(CH2)4-CH=CH2
使用的溶剂是甲苯。
将放在干燥箱里的Schlenk烧瓶中的2.3mg(0.0055mmol)催化剂二氯rac-亚-乙基二(茚基)合锆(Ⅳ)、2.72g(7.11mmol)的FSO2-CF2CF2-O-(CF2)2(CH2)4-CH=CH2和25mL甲苯混合来合成聚合物ⅩⅤ。将其在水冰浴中放置在3psig的丙烯氛围中,并用丙烯吹扫10min。在混合物中加入PMAO(7.2mL的7.1wt%甲苯溶液)。在0℃下的3psig的丙烯氛围中搅拌1hr以后,向反应混合物中缓慢加入甲醇(150mL),再加入5mL浓盐酸。过滤白色的固体聚合物,用甲醇洗涤并在真空下干燥。得到1.35g共聚物。基于13C核磁共振标定聚合物是全同立构的。1H核磁共振(TCE-d2)指征出加入了2.9mol%共聚单体进入该共聚物中。差热扫描热量计测定的共聚物熔点是133℃。凝胶渗透色谱(TCB,135℃,聚乙烯标准):Mw=23,200;Mn=11,000;Mw/Mn=2.1。
将放在干燥箱里的Schlenk烧瓶中的2.3mg(0.0055mmol)催化剂二氯rac-亚乙基二(茚基)合锆(Ⅳ)、5.5g(0.0144mol)的FSO2-CF2CF2-O-(CF2)2(CH2)4-CH=CH2和25mL甲苯混合来合成聚合物ⅩⅥ。将其在水冰浴中放置在3psig的丙烯氛围中,并用丙烯吹扫10min。在混合物中加入PMAO(4.0mL的12.9wt%甲苯溶液)。在0℃下的3psig的丙烯氛围中搅拌2hr以后,向反应混合物中缓慢加入甲醇(5mL)。然后将混合物倾倒在150mL甲醇中,再加入5mL浓盐酸。在室温下搅拌20min以后,过滤白色的固体聚合物,用甲醇洗涤并在真空下干燥。得到4.6g共聚物。基于13C核磁共振测定表明聚合物是全同立构的。1H核磁共振(TCE-d2)指出加入了3.8mol%的共聚单体共聚到该共聚物中。差热扫描热量计测定的共聚物熔点是124℃。凝胶渗透色谱(TCB,135℃,聚乙烯标准):Mw=39,200;Mn=20,900;Mw/Mn=1.9。
通过在高密度聚乙烯上接枝CH2=CH(CF2)O(CF2)2SO2F得到在下面叙述的母体非离子聚合物ⅩⅦ。
通过在氮气下,将125℃的13.03g高密度聚乙烯(Aldrich,Mw=125,000)溶解在100mL间二氯化苯中,形成的溶液与10.15gCH2=CH(CF2)O(CF2)2SO2F混合,然后缓慢加入过氧化叔丁基(1.23g过氧化叔丁基在20mL间二氯化苯中)的二氯化苯溶液中。在7hr内完成添加。然后将此溶液搅拌过夜。将溶液倒入500mL甲醇中,在实验室掺混机中掺混,然后是过滤,进行甲醇溶解、掺混和过滤的步骤总共重复4次。然后用甲醇洗涤固体聚合物3次并在真空中干燥。得到21.3g白色聚合物。基于1H核磁共振测定表明,共聚单体加入的摩尔百分数为5.4%,基于核磁共振测定表明支化度为7个甲基/1000个CH2。凝胶渗透色谱(TCB,135℃,聚乙烯标准):Mw=65,700;Mn=4,820;P/D=15.3。基于差热扫描热量计的共聚物熔点为118℃。
本发明中由本发明的聚合物制造的薄膜标识为F1~F16、F19、F21~F23。
发现聚合物Ⅵ特别脆而难以进一步加工,这可能是因为分子量低,不能加工成独立式的薄膜。在室温下聚合物Ⅺ是油状的,不能加工成独立式的薄膜。
在上面标识为聚合物Ⅰ~Ⅴ和聚合物Ⅶ~Ⅹ,以及Ⅻ~ⅩⅦ的所有除聚合物Ⅵ之外其它聚合物都可制成薄膜。将大约0.25~5.0g的干聚合物放在从Du Pont公司,Wilmington,DE购得的两片Kapton_聚酰亚胺薄膜之间,并插入装有Omron电子公司(Schaumburg,IL)的E5CS温度控制器的型号为P218C(Pasadena液压工业公司,Industry市,CA)的液压机的两块平板之间,就得到尺寸为3.75cmx3.75cm~7.5emx7.5cm的在表3中标为“MP”的熔融模压薄膜。预热聚合物2min,然后压制2min,然后再在压力下冷却。得到薄膜的厚度大约在63~127μm之间。在表3中提供了使用的特定温度和压力。
将0.25~5.0g聚合物溶解于指定的溶剂,加热溶剂直至聚合物溶解,然后浇注到有2.5cmx2.5cm凹槽的玻璃浇注皿上,得到在表3中标为“soln”的溶液浇注薄膜。在室温下蒸发溶剂剩下厚度大约为25~127μm的聚合物薄膜。
表3-制造聚合物薄膜
聚合物 | 薄膜试样# | 成膜条件 |
Ⅹ | F1F2 | MP100°MP100° |
Ⅸ | F3F4 | MP103℃/625psi/2minMP103℃/625psi/2min |
Ⅷ | F5 | SOLN二氯化苯 |
Ⅲ | F6F7 | SOLN氯苯SOLN氯苯 |
Ⅰ | F8 | MP |
Ⅳ | F9 | MP |
Ⅱ | F10F11 | MP240℃/2500lbs/in2MP240℃/2500lbs/in2 |
Ⅴ | F12 | MP240℃/2500lbs/in2 |
Ⅶ | F13F14 | MP240℃/2500lbs/in2MP240℃/2500lbs/in2 |
Ⅻ | F15 | MP140℃/2500psi |
ⅩⅢ | F16 | MP140℃/2500lbs/in2/2min |
ⅩⅣ | F19 | MP |
ⅩⅤ | F21 | MP |
ⅩⅥ | F22 | MP160℃/2500psi/2min |
ⅩⅦ | F23 | MP250℃/3000psi/2min |
实施例1~22
在表3中叙述的每个薄膜试样F1~F16、F19、F21~F23再加上两份油状聚合物Ⅺ,用水和甲醇比例为1∶1的LiOH饱和溶液处理使聚合物Ⅺ进行水解,然后在室温下用1∶1甲醇水溶液漂洗,然后再在新鲜的1∶1水甲醇混合物中加热。然后将试样干燥,除非另有规定,干燥在大约220乇的压力下,在VWR科学公司,West Chester,PA购买的型号1430真空烘箱中进行。表4提供了薄膜浸润在LiOH溶液中的时间和温度、室温漂洗的时间、温热漂洗的温度和时间,以及水解膜干燥的温度和时间。
表4.聚合物的水解/锂化
锂离聚物试样 | 薄膜试样号 | 聚合物# | 用LiOH处理 | 漂洗处理 | 干燥(℃/天) | |
室温(1hr) | 加热 | |||||
S1 | F1 | Ⅹ | 50℃下4hr,室温12hr | 无 | 60℃下6hr | 50/10 |
S2 | F2 | Ⅹ | 50℃下6hr | 12 | 50℃下4hr | 50/5 |
S3 | F3 | Ⅸ | 60℃下6hr | 12(只用水) | 60℃下6hr | 50/3 |
S4 | F4 | Ⅸ | 65℃下6hr | 12 | 65℃下4hr | 50/5 |
S5 | F5 | Ⅷ | 60℃下6hr | 48 | 60℃下4hr | 50/8 |
S6 | F6 | Ⅲ | 65℃下6hr | 48 | 60℃下4hr | 50/7 |
S7 | F7 | Ⅲ | 60℃下2hr | 48 | 60℃下4hr | 50/7 |
S8 | F8 | Ⅰ | 45℃下8hr,室温12hr | 24 | 45℃下4hr | 室温/6 |
S9 | F9 | Ⅳ | 65℃下6hr | 12 | 65℃下4hr | 室温/3,50/3 |
S10 | F10 | Ⅱ | 60℃下6hr | 12 | 60℃下4hr | 50/8 |
S11 | F11 | Ⅱ | 60℃下6hr | 48 | 60℃下4hr | 55/10 |
S12 | F12 | Ⅴ | 60℃下6hr | 12 | 60℃下2hr,水中60℃下2hr | 室温/650/5 |
S13 | F13 | Ⅶ | 70℃下6hr | 12 | 60℃下4hr | 50/12 |
S14 | F14 | Ⅶ | 70℃下6hr | 72 | 70℃下4hr | 55/10 |
S15 | F15 | Ⅻ | 65℃下6hr | 12 | 65℃下4hr | 50/8 |
S16 | F16 | ⅩⅢ | 65℃下6hr | 12 | 65℃下4hr | 50/6 |
S17 | F17 | Ⅺ | 80℃下6hr,室温12hr80℃下2hr | * | 无 | |
S18 | F18 | Ⅺ | 80℃下6.5hr,室温12hr80℃下4.5hr | ** | 70/2 |
表4(续)
锂离聚物试样 | 薄膜试样号 | 聚合物# | 用LiOH处理 | 漂洗处理 | 干燥(℃/天) | |
S19 | F19 | ⅩⅣ | 70℃下6hr | 48 | 70℃下4hr | 55/12 |
S21 | F21 | ⅩⅤ | 70℃下6hr,室温12hr | 无 | 70℃下4hr | 55/11 |
S22 | F22 | ⅩⅥ | 80℃下6hr | 12 | 80℃下4hr | 65/12 |
S23 | F23 | ⅩⅦ | 2.0gLiOH在2/15/100的水/DMSO/甲醇60℃下/8hr,然后室温14hr | 50/1 | ||
*在具有MWCO=3500的渗析管中对水渗析7天 | ||||||
*在具有MWCO=3500的渗析管中对水渗析12天 |
实施例23
将4.43g聚合物ⅪⅤ试样进行水解,其中该试样是以由实施例ⅪⅤ中所述呈刚聚合好的聚合物碎屑状存在,先将其浸入到过量的已预热到70℃的LiOH的水/甲醇饱和溶液中2hr,其中该饱和溶液中水/甲醇为1∶1,然后加热到75℃再保持2hr,然后冷却到室温并保持12hr,再次加热到75℃并保持4hr。然后在室温下将得到的水解聚合物用1∶1的水/甲醇混合物漂洗12hr,再在80℃下用新鲜的1∶1水/甲醇混合物漂洗4hr,再在室温下以1∶1水/甲醇混合物漂洗12hr。
然后将水解的聚合物溶解于四氢呋喃中,并经浇注在玻璃板上,蒸发四氢呋喃及将膜从板上揭下而浇注成薄膜。在下面将如此得到的水解薄膜标识为试样S20。
实施例24
将0.2817g如上面所述制备的含锂聚合物试样S19放入10mL四氢呋喃中,缓慢地温热直至溶解。加入0.056gCabot Cab-o-sil_TS530并搅拌直至分散开。将此分散液浇注到直径50mm的Teflon_PFA圆Petri氏培养皿上,让溶剂蒸发形成水解薄膜,在下面标识为试样S24。
实施例25~181
将实施例1~24、S1~S24的干燥水解膜转移到一个密封同时仍然温热的容器中,并转送到具有干燥氮气正压力的手套箱中,其中从密封容器中取出膜片让其达到室温。然后仍然在手套箱内将膜片切成尺寸无1.0cmx1.5cm的几段。然后一般将刚刚制备好的试样在真空下在100℃加热24~48hr。
然后在室温下将冷却的1.0cmx1.5cm的膜片试样浸入装有过量的一种或几种液体的密封玻璃瓶中24hr。使用的液体都是商品,刚买来就使用。在浸渍以后,从液体浴中取出膜片试样,用纸巾擦干除去过量的液体并进行测试。
使用Y.Sone等人在《电化学学会志》(J.Electrochem.Soc.)143,1254(1996)中题为《用四电极交流阻抗法测量的Nafion_117的质子电导率》的文章中叙述的所谓四点探针技术测量离子电导率。所叙述的方法用于电解质水溶液膜。此方法被改进,为的是在这里得到非水溶剂报告的测量结果,改进之处是将所述的设备放在用干燥氮气吹扫的密封手套箱内,为的是尽可能少曝露在水分中。在已经公布的方法中,此方法还可以通过用点探针代替平行线形探针通过整个测试试样的宽度来实现改进。
将1.0cmx1.5cm的试样擦干,在电导池中固定。在10Hz~100,000Hz的范围内测定电池的阻抗,在较高频率范围(一般为500~5000Hz)的0相角值规定为试样体积电阻,单位是Ω。然后用电池常数和被液体浸润薄膜的厚度,将原电阻值转化为单位是S/cm的电导率。
使用下面的缩写词:
DEC 碳酸二乙酯
DEE 二乙氧基乙烷
DMC 碳酸二甲酯
DME 1,2-二甲氧基乙烷
DMF N,N-二甲基甲酰胺
DMSO 二甲基亚砜
EC 碳酸亚乙酯(1,3-二氧戊环-2-酮)
GBL γ-丁内酯
MA 醋酸甲酯
MeOH 甲醇
MG 甘醇酸甲酯
NMF N-甲基甲酰胺
NMP N-甲基吡咯烷酮
PC 碳酸亚丙酯
PEG 聚乙二醇
THF 四氢呋喃
实施例25~138
在如此进行的电导率测试中,其中本发明的水解膜,即S1~S24与指定的液体结合,形成本发明的导电组合物,如同已经叙述过的,发现在表5中显示的组合物具有大于10-5S/cm的室温离子电导率。
表5
实施例25~138:通过混合液体和薄膜形成的离子导电组合物,
它们具有大于10-5S/cm的电导率水解的薄膜试样 浸透的液体
S2 PC/DME;EC/DME
S4 PC/DME;EC/DM E;PC;DMSO;DMF
S9 PC;PC/DMC;PC/DME;EC/PC;EC/DMC;EC/DME
S10 PC;EC/DME;DMSO;DMC;THF;PC/DME;PC/DMSO;
PC/DMC
S11 PC/DEC;EC/DMC;EC/PC;NMF;DME;PC;DME;EC/PC/DMC
S12 PC;DME;GBL;DEE;PC/DME;GBL/DMSO;PC/DEE
S13 PC;EC/DME;DMSO;DMF;GBL;PC/DMSO;PC/GBL
S14 PC/DEC;EC/DMC;EC/PC;NMF;DME;PC;DME;EC/PC/DMC
*S15 PC;DME;GBL;DMF;DMSO;EC/DME;PC/EC;PC/DME;
PC/GBL;PC/DMF;PC/DMSO;EC/PC/DME
S16 PC;DME;DMSO;DMF;DEC;GBL;NMP;MG;PC/DME;
PEG/DME;PC/DMSO;PC/DMF;PC/GBL;THF/GBL;NMP/DMF;
MA/GBL;MG/DMSO;EC/DMC;EC/DME
S19 DMSO;DMF;GBL
S20 PC;EC/DMC;EC/PC/DMC
S21 DMSO;DMF;GBL
S22 DME;EC/DMC;DMSO;GBL;DMF
S23 PC;DMSO;PC/DME
S24 EC/DMC;GBL;DMSO;EC/PC/DMC;EC/DMC/GBL;
EC/DMC/DMSO
观察到,在上述的各实施例中使用的试样S15,在浸渍到在表5所列的许多溶剂中时,仍在特别高的程度上保留其物理完整性。
实施例139-140
按照上述的方法将各种水解的薄膜试样S2、S4、S5、S6和S7浸入到PC中,只是浸渍时间是2hr或54hr不同,如表6所指出。
表6
在室温下在PC中水解薄膜的离子电导率
6hr | 54hr | |
S2 | 3.91x10-5 | 9.80x10-5 |
S5 | 2.06x10-4 | 1.89x10-4 |
S5 | 糊状物 | ~3.4x10-4 |
S6 | 2.34x10-4 | 2.82x10-4 |
S7 | 1.61x10-4 | 2.2x10-4 |
S4 | 2.12x10-4 | 2.86x10-4 |
实施例141~150
将聚合物Ⅺ水解形成的油状聚合物与表7中所列的溶剂混合,在指定温度下形成凝胶。用Orien浸入式电导率探头进行电导率测。结果列在表7中。
表7
聚合物Ⅺ凝胶溶液的离子电导率
混合溶剂 | 浓度(M) | 温度(℃) | 离子电导率(S/cm) |
PC | 0.00375 | 55 | 2.42x10-5 |
PC/DME | 0.00375 | 55 | 6.12x10-5 |
PC/DME | 0.0375 | 55 | 2.93x10-4 |
PC/DME/DMF | 0.00341 | 55 | 3.60x10-5 |
PC/DME/DMF | 0.01875 | 55 | 2.37x10-4 |
DMF | 0.025 | 29 | 4.48x10-4 |
DMF | 0.025 | 35 | 4.60x10-4 |
DMF | 0.025 | 40 | 4.90x10-4 |
DMF | 0.025 | 55 | 5.70x10-4 |
DMF | 0.025 | 75 | 6.40x10-4 |
实施例150~173
对于呈如上所述制备的含锂形式且呈酸性的表8所列水解薄膜试样,评估其在水性介质中的电导率。通过将膜片浸入到过量的1.0M硝酸中(试剂级,EM科学公司,Gibbstown,NJ)1hr,然后在80℃下用去离子水漂洗1hr,再在去离子水中冷却的方法,从锂式膜片制备酸式膜片。
然后将薄膜浸入到去离子水中并加热到80℃恒温2hr,再在室温下冷却来处理此薄膜。用如上所述同样程序测量电导率,只是所有测量都在手套箱以外进行。
表8
在室温下与液体去离子水平衡的呈Li+和H+形式的
乙烯和氟磺酸盐共聚物的离子电导率
离子电导率(S/cm) | ||
试样 | H+形式 | Li+形式 |
S8 | <3.0×10-7 | 0.000435 |
S9 | 0.0336 | 0.00531 |
S2 | 0.00064 | 7.06×10-5 |
S4 | 0.0401 | 0.00746 |
S13 | 0.0227 | 0.00490 |
S10 | 0.0560 | 0.0112 |
S15 | 0.0361 | 0.01002 |
S16 | 0.01455 | 0.00164 |
S11 | 0.0420 | 0.00859 |
S14 | 0.0348 | 0.00651 |
S24 | 0.0297 | 0.00757 |
S23 | 0.0648 | 0.0116 |
实施例174
按照Desmarteau在《氟化学杂志》(J.Fluorine Chem.)52,pp7ff(1991)中报道的方法(此文献在此引作参考),将如在上面公开所合成的聚合物Ⅸ与CF3CF2SO2NNaSi(CH3)3反应。在室温下将如此合成的聚合物用过量的30%的硫酸处理6hr,形成质子形式(H+)的聚合物。然后在室温下,在大量过量的0.1M的LiOH水/甲醇溶液中很容易地对如此形成的质子形式聚合物进行离子交换5hr,其中水/甲醇为50/50。得到的聚合物是含有基本上未被取代的骨架和3.9mol%侧基的聚合物,侧基的通式是:
Li酰亚胺离聚物可通过核磁共振和元素分析进行确认。
实施例175
按照Seppelt在《无机化学》(Inorg.Chem.)27,pp.2135ff(1988)中公开的方法,从CH2(SO2CF2CF3)2和CH3MgBr合成(CF3CF2SO2)2C(BrMg)2。在如上所公开方法合成的聚合物Ⅸ在THF的溶液中,在0℃和搅拌下加入(CF3CF’2SO2)2C(BrMg)2。在添加完毕以后,反应混合物在室温下搅拌过夜。然后用泵抽出THF,加入3M的盐酸,将溶液搅拌几小时并过滤。用水洗涤固体除去无机盐,然后在室温下用0.1M的LiCl水/甲醇的溶液处理过夜,其中水/甲醇为50/50。得到RfSO2C(Li)(SO2CF3)2。
得到的离聚物是具有基本上未被取代的骨架和3.9mol%侧基聚合物,侧基的通式是:
Li甲基化合物离聚物可通过核磁共振和元素分析进行确认。
实施例176
将干燥的0.5g实施例23的水解聚合物试样放在装有12g四氢呋喃的密封烧瓶中,在400rpm和65℃下搅拌4hr。加入烘制过的二氧化硅(0.125g的TS530,Cabot公司,Boston,MA),继续搅拌几分钟使二氧化硅分散。通过玻璃棉垫过滤悬浮液,以除去任何凝胶的颗粒,用切口高度为0.050″的医用刮板将滤液浇到购自Du Pont的Mylar_聚酯薄膜上。在环境温度下让THF蒸发,得到厚度32~40μm的薄膜。在下面叙述的电池结构中,如此得到的薄膜用作隔离薄膜。
制造在下面叙述的电池中使用的正电极时应用实施例23中水解聚合物的第二种试样:将0.2g干燥的离聚物放在装有7g四氢呋喃的密封烧瓶中,在400rpm和70℃的温度下搅拌2hr。加入碳黑(0.05g,SP黑,MMM S.A.碳公司,布鲁塞尔,比利时)和石墨(0.75g中间相碳(mesophase carbon)微珠MCMB 25-28,大阪气体,日本),再搅拌混合物15min。将浆液倒在购自Du Pont的硅烷化Mylar_上,在环境温度下让THF蒸发。
从石墨薄膜上冲下一块直径12mm的圆形正电极,在100℃的真空下干燥,得到质量11.6mg(8.7mg石墨)和厚度160μm的一块石墨薄膜。从上面的隔离膜上冲下一块隔离件(质量11.5mg,厚43μm,直径19mm的圆片)。将其浸入过量的无水EC/DMC中10min,吸收液体21.8mg。将其与锂箔负电极组装成型号2325的纽扣电池。将此电池以0.5mA的恒定电流放电至0.01V的电压,至此点上直至电流跌至0.05mA前,电压一直保持恒定。第一次放电容量为2.42mAh,相应的是每克石墨正电极材料放电容量为280mAh。电池以0.5mA速率充电至1.2V,然后电压恒定在1.2V,直到充电电流降至0.05mA以下为止。充电容量为1.97mAh,这表明在第一次放电/充电循环中电化学效率是81%。以和上面相类似的方式将此电池反复放电和充电,第14次放电容量为1.85mAh。
Claims (28)
1.一种含有骨架和侧基的离聚物,骨架基本上由亚甲基和次甲基结构单元组成,而侧基包括如下通式的离子根:
-Rn-Rf-CF2CF2-SO2-X-(SO2Rf)a -M+
这里,M+是一价金属阳离子;Rf基团是独立地选自线性或支化的全氟亚烷基基团、含O或Cl的全氟亚烷基基团和全氟芳基基团;R是烃基,而n=0或1;a=0~2;X=0、N或C;所述的离子根进一步限制在当X=0时,a=0;X=N时,a=1;X=C时,a=2。
2.权利要求1的离聚物,其中a=0;x=0;Rf由如下通式表示
-O-[(CFRf’CF2)x-Oy]m-这里Rf’是全氟烷基或氟,x=0、1、2或3,y=0或1,而m=0、1、2或3;Rn用下式表示
-(CH2)z-这里z是2~6的整数。
3.如权利要求2的离聚物,其中M+是碱金属阳离子,Rf’是氟,x=1或2,y=0,m=1或2,z=4,而R是乙基、丙基或丁基。
4.权利要求3的离聚物,其中M+是锂阳离子。
5.权利要求1的离聚物,其中所述离子基团的含量是1~20mol%。
6.如权利要求1的离聚物,其中所述离子基团的含量是2~10mol%。
7.权利要求1的离聚物,其中在骨架中每1000个亚甲基基团上的短支链不超过150个。
8.权利要求1的离聚物,其中在骨架中每1000个亚甲基基团上的短支链为5~90个。
9.呈薄膜或片状形式的权利要求1的离聚物。
10.权利要求1的离聚物,还包括与之混合的无机颗粒。
11.权利要求10的离聚物,其中的无机颗粒是平均颗粒尺寸小于1.0μm的二氧化硅颗粒,在混合物中此二氧化硅的含量不超过总重量的50%。
12.含有权利要求1中的离聚物和在其中浸有液体的离子导电组合物。
13.权利要求12的离子导电组合物,其中的液体是水或甲醇。
14.权利要求12的离子导电组合物,其中的液体是质子惰性的。
15.权利要求14的离子导电组合物,其中的液体选自有机碳酸酯及其混合物。
16.权利要求13的离子导电组合物,其中的液体是碳酸亚乙酯和至少一种选自碳酸二甲酯、碳酸甲乙酯和碳酸二乙酯的液体的混合物。
17.权利要求12的离子导电组合物,其中的M+是锂阳离子,R=(CH2)4,Rf(CF2)x,X=0,a=0,所述离子基团的含量是2~10mol%,另外,它在骨架中的每1000个亚甲基结构单元还含有不超过150个短支链,而且液体选自有机碳酸酯及其混合物。
18.呈选自薄膜、片状和凝胶状形式的权利要求12的离子导电组合物。
19.呈选自薄膜、片状和凝胶状形式的权利要求17的离子导电组合物。
20.权利要求18的离子导电组合物,它还含有一种微孔电绝缘聚合物薄膜或片,在它们的微孔中浸有凝胶。
21.权利要求19的离子导电组合物,它还含有一种微孔电绝缘聚合物薄膜或片,在它们的微孔中浸有凝胶。
22.一种制备离聚物的方法,该方法包括将包括骨架和侧基的聚烯烃与碱金属的碱溶液接触,该骨架基本由亚甲基和次甲基结构单元组成,而侧基包括如下式的离子根:
XSO2-CF2CF2-Rf-Rn-这里X是F或Cl,Rf是线性或支化的全氟亚烷基、含O或Cl的全氟亚烷基或全氟芳基,R是烃基,其中n=0或1。
23.制备导电组合物的方法,该方法包括将权利要求1的离聚物与液体混合。
24.包括至少一种电极活性材料、与之混合的权利要求1的离聚物和浸透其中的液体的电极。
25.权利要求24的电极,其中的M+是锂阳离子,Rn=(CH2)4,Rf(CF2)x,X=0,a=0,所述离子基团的含量是2~10mol%,它在骨架中的每1000个亚甲基结构单元中还含有不超过150个短支链,而且液体选自有机碳酸酯及其混合物。
26.权利要求25的电极,它还含有碳黑。
27.权利要求26的电极,其中离聚物与电极活性材料的重量比为0.05~0.8,而碳黑与电极活性材料的重量比为0.01~0.2。
28.包括正电极、负电极、在正电极和负电极之间的隔离件和将该电池与外部负载或电源相连的装置的电化学电池,其中隔离件、正电极和负电极当中至少一件包括了权利要求1中的离聚物。
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JPS5785826A (en) * | 1980-11-17 | 1982-05-28 | Japan Atom Energy Res Inst | Cation exchange membrane |
JPS57131376A (en) * | 1981-02-06 | 1982-08-14 | Japan Atom Energy Res Inst | Electrolyzing method for water |
US5627292A (en) * | 1992-02-21 | 1997-05-06 | Centre National De La Recherche Scientifique | Monomers derived from perhalogenated sultones and polymers obtained from these monomers |
US5548055A (en) * | 1995-01-13 | 1996-08-20 | Sri International | Single-ion conducting solid polymer electrolytes |
CZ235197A3 (en) * | 1995-01-24 | 1997-12-17 | Du Pont | Alpha olefins, olefin polymers and process for preparing thereof |
US5798417A (en) * | 1996-10-15 | 1998-08-25 | E. I. Du Pont De Nemours And Company | (Fluorovinyl ether)-grafted high-surface-area polyolefins and preparation thereof |
US6100324A (en) * | 1998-04-16 | 2000-08-08 | E. I. Du Pont De Nemours And Company | Ionomers and ionically conductive compositions |
-
1998
- 1998-04-16 US US09/061,132 patent/US6100324A/en not_active Expired - Lifetime
-
1999
- 1999-04-15 CA CA002326845A patent/CA2326845A1/en not_active Abandoned
- 1999-04-15 EP EP99918576A patent/EP1082358B1/en not_active Expired - Lifetime
- 1999-04-15 AU AU36455/99A patent/AU3645599A/en not_active Abandoned
- 1999-04-15 DE DE69918107T patent/DE69918107T2/de not_active Expired - Fee Related
- 1999-04-15 CN CN99805082A patent/CN1297457A/zh active Pending
- 1999-04-15 WO PCT/US1999/008255 patent/WO1999052954A1/en active IP Right Grant
- 1999-04-15 JP JP2000543510A patent/JP2002511502A/ja not_active Withdrawn
- 1999-04-15 KR KR1020007011363A patent/KR100541312B1/ko not_active IP Right Cessation
-
2000
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100449829C (zh) * | 2004-06-30 | 2009-01-07 | Tdk株式会社 | 直接醇型燃料电池及其制造方法 |
US8652704B2 (en) | 2004-06-30 | 2014-02-18 | Tdk Corporation | Direct alcohol fuel cell with cathode catalyst layer containing silver and method for producing the same |
CN102459361A (zh) * | 2009-06-12 | 2012-05-16 | 索尔维索莱克西斯公司 | 具有低表面张力、低液体粘度以及高固体含量的氟代离聚物分散体 |
CN102459361B (zh) * | 2009-06-12 | 2019-07-05 | 索尔维索莱克西斯公司 | 具有低表面张力、低液体粘度以及高固体含量的氟代离聚物分散体 |
Also Published As
Publication number | Publication date |
---|---|
JP2002511502A (ja) | 2002-04-16 |
DE69918107T2 (de) | 2005-01-27 |
KR20010042662A (ko) | 2001-05-25 |
EP1082358A1 (en) | 2001-03-14 |
EP1082358B1 (en) | 2004-06-16 |
KR100541312B1 (ko) | 2006-01-16 |
WO1999052954A1 (en) | 1999-10-21 |
CA2326845A1 (en) | 1999-10-21 |
US6100324A (en) | 2000-08-08 |
US6268430B1 (en) | 2001-07-31 |
DE69918107D1 (de) | 2004-07-22 |
AU3645599A (en) | 1999-11-01 |
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