CN104582820B - 具有高分子化合物作为氧化还原对的氧化还原液流电池和用于存储电能的半透膜 - Google Patents
具有高分子化合物作为氧化还原对的氧化还原液流电池和用于存储电能的半透膜 Download PDFInfo
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Abstract
本发明的任务是,通过使用新材料和膜以尽可能低耗费地制造成本有利和耐用的氧化还原液流电池,即使在可能的电池损坏情况下其氧化还原活性化合物也极少造成环境负担。根据本发明,使用例如氧化还原活性的聚合物或寡聚物的高分子化合物作为所述氧化还原活性组分,使用用于分离高分子氧化还原活性组分的尺寸排阻膜(3)作为所述膜。
Description
本发明涉及氧化还原液流电池,一般的说法也称作氧化还原液流电池或氧化还原流电池,用于存储电能。该氧化还原液流电池包含两个极性专用室,在两个室中分别存在溶解形式的氧化还原活性的化学化合物和/或氧化还原活性的化合物,分别与液体存储器连接。通过这种方式,例如溶于水中或溶于有机溶剂中的氧化还原活性化合物构成了两个独立的循环,它们通过所述极性专用室之间的膜来分离。经由这种膜来实现两个室之间的离子交换。
所述电池尤其适用于静态存储应用,例如作为风力发电装置的缓冲电池,或者作为电网中负载平衡的功率储备和调节储备,但也可作为移动的能量存储器,例如用于电动汽车和电子设备的运转。
现有的氧化还原液流电池(RFB)是电化学能量存储器。在电极上进行电势调节所需的化合物是溶解的氧化还原活性物质,它在充电或放电过程中在电化学反应器中各自转换成其他的氧化还原阶段。为此,将电解质溶液(阴极电解液、阳极电解液)从容器中取出并主动泵送至电极。反应器中的阴极室和阳极室通过离子选择性的膜来分离,所述膜主要显示出对质子的高选择性。一旦电解质溶液被泵送,就可以获得电流。充电过程只是将所述过程进行简单的反转。因此,可存储在RFB中的能量的量与贮存容器的大小直接成正比。与此相反,可获得的功率是电化学反应器的大小的函数。
RFB具有复杂的系统工程(BoP-工厂电力平衡),大约对应于燃料电池。单个反应器的常见构造尺寸在约2kW至50kW的范围内变动。所述反应器可以非常简单地模块式组合,也可以适合几乎任意的容器大小。
特别有意义的RFB是在两侧利用钒作为氧化还原对来工作的氧化还原液流电池(VRFB)。在1986年首次描述了这样的体系(AU 575247 B)并代表了目前的技术标准。对其他无机低分子量的氧化还原对也进行了研究,其中包括基于铈(B.Fang,S.Iwasa,Y.Wei,T.Arai,M.Kumagai:"A study of the Ce(III)/Ce(IV)redox couple for redox flowbattery application",Electrochimica Acta 47,2002,3971-3976)、钌(M.H.Chakrabarti,E.Pelham,L.Roberts,C.Bae,M.Saleem:"Ruthenium based redoxflow bat tery for solar energy storage",Energy Conv.Manag.52,2011,2501-2508]、铬(C-H.Bae,E.P.L.Roberts,R.A.W.Dryfe:"Chromium redox couples for applicationto redox flow batteries",Electrochimica Acta 48,2002,279-87)、铀(T.Yamamura,Y.Shiokawa,H.Yamana,H.Moriyama:"Electrochemical investigation of uraniumβ-diketonates for all-uranium redox flow battery",Electrochimica Acta 48,2002,43-50)、锰(F.Xue,Y.Wang,W.Hong Wang,X.Wang:"Investigation on the electrodeprocess of the Mn(II)/Mn(III)couple in redox flow battery",ElectrochimicaActa 53,2008,6636-6642)和铁(Y.Xu,Y.Wen,J.Cheng,G.Cao,Y.Yang:"A study of ironin aqueous Solutions for redox flow battery application",Electrochimica Acta55,2010,715-720)。但是,这些体系基于有毒或对环境有害的含金属的电解质。
目前可以得到的VRFB-反应器是1kW至20kW的区块通过模块式地互相连通可以实现更高的功率。每个单个区块包含多个平面电池,将这些电池串联以得到更高的电压。这种所谓的两极结构方式很大程度上对应了PEM燃料电池的结构方式。作为膜使用具有磺酸基团的全氟化聚合物,大多是DuPont 117。也描述了其他聚合物,例如基于SPEEK(Q.Luo,H.Zhang,J.Chen,D.You,C.Sun,Y.Zhang:"Nafion/SPEEK composite:Preparation and characterization of Nafion/SPEEK layered composite membraneand its application in vanadium redox flow battery",J.Memb.Sci.325,2008,553-558)、PVDF(J.Qiu,J.Zhang,J.Chen,J.Peng,L.Xu,M.Zhai,J.Li,G.Wei:"Amphoteric ionexchange membrane synthesized by radiation-induced graft copolymerization ofstyrene and dimethylaminoethyl methacrylate into PVDF film for vanadium redoxflow battery applications",J.Memb.Sci.334,2009,9-15)、QPPEK(S.Zhang,C.Yin,D.Xing,D.Yang,X.Jian:"Preparation of chloromethylated/quaternized poly(phthalazinone ether ketone)anion exchange membrane materials for vanadiumredox flow battery applications",J.Memb.Sci.363,2010,243-249)、无氟的磺化聚亚芳基(D.Chen,S.Wang,M.Xiao,Y.Meng:"Synthesis and properties of novelsulfonated poly(arylene ether sulfone)ionomers for vanadium redox flowbattery",Energy Conv.Manag.51,2010,2816-2824)或者具有SiO2的无机-有机复合材料(J.Xi,Z.Wu,X.Qiu,L.Chen:"Nafion/SiO2hybrid membrane for vanadium redox flowbattery",J.Pow.Sour.166,2007,531-536),但是与Nafion膜不同的是它们的还不实用和不能商业提供。这也同样适用于纳滤膜,它可以使酸性电解质中的质子通过而截留钒盐(Hongzhang Zhang,Huamin Zhang,Xianfeng Li,Zhensheng Mai,Jianlu Zhang:Nanofiltration(NF)membranes:the next generation Separators for all vanadiumredox flow batteries(VRBs)",Energy&Environmental Science,2011,4,1676-1679)。在此同样的缺点是,如高昂的费用和损坏情况下的环境负担以及电池的低使用寿命。
对于目前的现有技术来说,离子传导膜的使用限制了进一步的商业化,因为标准的膜价格贵、含氟、机械不稳定;另外,所述膜膨胀非常严重,并且由于钒离子的扩散而容易造成电化学短路。
至今为止在RFB中极少使用纯有机的氧化还原化合物(Redoxverbindung)。因此,在具有离子传导膜的RFB中使用低分子量的2,2,6,6-四甲基哌啶基氧(TEMPO)和N-甲基邻苯二甲酰亚胺(Z.Li,S.Li,S.Q.Liu,K.L.Huang,D.Fang,F.C.Wang,S.Peng:"Electrochemical properties of an all-organic redox flow battery using 2,2,6,6-tetramethyl-1-piperidinyloxy and N-methylphthalimide",Electrochem.SolidState Lett.14,2011,A171-A173)。另外,尽管红荧烯良好的电化学特性,由于高成本和非常低的溶解性而将其排除(参见H.Charkrabarthi,R.A.W.Dryfe,E.P.L.Roberts,Jour.Chem.Soc.Pak.2007,29,294-300"Organic Electrolytes for Redox FlowHatteries")。
基于2,3,6-三甲基喹喔啉的电池也使用昂贵的离子选择性膜(F.R.Brushett,J.T.Vaughey,A.N.Jansen:An All-Organic Non-aqueous Lithium-IonRedox Flow Battery",Adv.Energy Mater.2012,2,1390-1396)。
基于吡嗪的氰基氮杂碳(Cyanoazacarbone)(US 8,080,327 B1)既可以用作阴极电解液也可以用作阳极电解液,其中使用分离电极室间的、基于阳离子交换和阴离子交换的离子传导性膜。所述膜价格昂贵,且分别只能通过特定级别的离子。这尤其是在不利的体系构造上显示出来,在阴极电解液循环和阳极电解液循环之间还必须使用电解质贮存器。这对保证阴离子和阳离子的负载平衡/混合是必要的,其中阴离子经由阳离子交换膜扩散至贮存器,阳离子经由阴离子交换膜扩散至贮存器。
除了有机氧化还原化合物之外,还描述了对低分子量金属有机化合物(M.H.Chakrabartia,R.A.W.Dryfe,E.P.L.Roberts:Evaluation of electrolytes forredox flow battery applications“,Electrochimica Acta,52,2007,2189-2195)。在此,使用络合无机金属盐的有机配体。这种配体例如是联吡啶、三联吡啶、菲咯啉或咪唑(US2012/0171541 A1)。这种体系也必须使用价格昂贵的离子传导膜,如或胺官能化的聚苯乙烯衍生物。这也同样适用于例如使用阴离子交换膜的,基于低分子量的钌-联吡啶络合物的氧化还原液流电池。其他的膜相反地对所述络合物是可以透过的,并且在此过程中导致电池极低的效率(Y.Matsuda,K.Tanaka,M.Okada,Y.Takasu,M.Morita,T.Matsumura-Inoue:A rechargeable redox battery utilizing rutheniumcomplexes with non-aqueous organic electrolyte",J.Applied Electrochem.18,1988,909-914)。
因此,本发明的目的在于,通过使用新型材料和膜以尽可能低耗费地制造成本有利和耐用的的氧化还原液流电池,即使在可能的电池损坏情况下其氧化还原活性化合物也极少造成环境负担。
所述目的通过用于存储能量的氧化还原液流电池根据本发明来实现,所述氧化还原液流电池包含反应池,该反应池具有两个用于阳极电解液和阴极电解液的极性专用室(1,2),所述室(1,2)分别与液体存储器连接并通过用于离子交换的膜来分隔,其中所述室(1,2)分别填充了氧化还原活性组分,所述氧化还原活性组分以本体形式、溶解或分散在电解质溶剂中的形式存在,并且其中溶解了导电盐和可能的其他添加剂,使用高分子化合物作为所述氧化还原活性组分,和使用尺寸排阻膜(3)作为所述膜,所述尺寸排阻膜(3)用于分离以本体形式、溶解或分散形式存在的高分子氧化还原活性组分。
氧化还原液流电池中优选室(1,2)分别填充了氧化还原活性组分,所述氧化还原活性组分以本体形式、或者溶解在水中或有机溶剂中的形式存在。
术语“尺寸排阻膜”在本说明书的范围内应理解为,具有至少下列特征的膜:
о分离阴极室和阳极室
о截留高分子氧化还原活性组分
о可以透过起到电荷平衡作用的电解质的导电盐,也就是可以透过导电盐的阴离子和阳离子。
根据本发明所用的膜的截留原理是基于尺寸排阻原则,即,所述膜根据尺寸在氧化还原活性成分和导电盐的离子之间进行区分,所述尺寸可以例如通过摩尔质量(数均)、重复单元的数目、离子半径和/或惯量半径来描述。
“选择性”在本说明书范围内应理解为分离极限,在此极限下分子不再能有效地通过膜。这意味着,在分子的预先给定分子量下,至少90%的分子被所述膜截留。
所提出的尺寸排阻膜如半透膜或透析膜,将高分子氧化还原活性组分分隔在两个室内,优选选择性至少为500g/mol,更优选至少为550g/mol,其中作为高分子组分使用氧化还原活性的、对应的摩尔质量大于尺寸排阻膜的选择性的、有机材料或金属有机材料、聚合物或寡聚物。
根据本发明使用的尺寸排阻膜根据物理(机械)膜分离方法进行分离。尺寸排阻膜在此应用的原理是,在用于阳极电解液和阴极电解液的极性专用室中,尺寸大于膜的孔径的所有粒子都被膜截留下来。
根据本发明使用的尺寸排阻膜可以由各种不同材料构成,前提是保证前面列出的功能性。根据不同的应用情况,所述尺寸排阻膜的材料可以选自塑料、陶瓷、玻璃、金属或纺织面料。所述材料的实例是有机聚合物,如纤维素或改性的纤维素,例如纤维素醚或纤维素酯、聚醚砜、聚砜、聚偏二氟乙烯、聚酯、聚氨酯、聚酰胺、聚丙烯、聚氯乙烯、聚丙烯腈、聚苯乙烯、聚乙烯醇、聚环氧丙烷、聚酰亚胺、聚四氟乙烯和它们的衍生物,或者另外的陶瓷、玻璃或毡。由多种材料构成的尺寸排阻膜(复合材料)也是可行的。
所述尺寸排阻膜可以过滤器元件的各种表现形式来应用。这种膜的实例是平面膜、袋式过滤器和中空纤维模块。这些实施形式对本领域技术人员是公知的。
优选使用平面膜。
根据本发明使用的尺寸排阻膜可以用于获得更好的稳定性。
根据本发明使用的尺寸排阻膜的厚度在宽的范围内波动。典型的厚度在1μm和5mm之间的范围内,特别优选在10μm和200μm之间的范围内。
根据本发明使用的高分子氧化还原活性组分可以是任意化合物,只要可以至少两种不同的稳定的氧化级存在,并且其分子量使其不能通过根据本发明使用的尺寸排阻膜。
高分子的氧化还原活性组分可以是聚合物或寡聚物,其中寡聚物应理解为摩尔质量为500至5000g/mol(数均)的化合物,聚合物应理解为摩尔质量大于5000g/mol(数均)的化合物。
典型的根据本发明使用的氧化还原活性组分是寡聚物或聚合物,它们具有包含一个或更多个活性单元的聚合物主链。所述活性单元可以各种方式连接在聚合物主链上。可以存在活性单元在聚合物主链上的共价连接,即所述活性单元作为侧链共价结合在聚合物主链上,例如经由C-C键或者经由桥基团,如-O-、-S-、-NH-、CO-、-CONH-或-COO-。但是,所述活性单元还可以构成聚合物主链(Polymerrückgrad)的组成部分,并共价构建在聚合物主链中,例如经由C-C键或者经由桥基团,如-O-、-S-、-NH-、CO-、-CONH-或-COO-。最后,所述活性单元还可以配位或者经由超分子相互作用结合在聚合物主链上,例如经由氢桥键、离子相互作用、π-π相互作用,或者作为路易斯酸结合到具有路易斯碱特性的在主链上连接的基团上,或作为路易斯碱结合到具有路易斯酸特性的结合在主链上连接的基团上。
可以构成聚合物主链的化合物的实例是,由烯属不饱和羧酸或它们的酯或酰胺衍生的聚合物,如聚甲基丙烯酸酯、聚丙烯酸酯或聚丙烯酰胺;由烯属不饱和芳基化合物衍生的聚合物,如聚苯乙烯;由乙烯基酯饱和羧酸衍生的聚合物或它们的衍生物,如聚乙酸乙烯酯或聚乙烯醇;由烯烃和双环烯烃或多环烯烃衍生的聚合物,如聚乙烯、聚丙烯或聚降冰片烯;由构成酰亚胺的四羧酸和二胺衍生的聚酰亚胺;由天然存在的聚合物和它们的化学改性衍生物衍生的聚合物,如纤维素或纤维素醚,以及聚氨酯、聚乙烯醚、聚噻吩、聚乙炔、聚亚烷基二醇、聚-7-氧杂降冰片烯、聚硅氧烷、聚亚烷基二醇及其衍生物,如它们的醚,优选聚乙二醇和它们的衍生物。特别优选使用的构成聚合物主链的物质类是,聚甲基丙烯酸酯、聚丙烯酸酯、聚苯乙烯、聚亚烷基二醇和聚乙烯基醚。
可以构成活性单元的化合物的实例是,可以形成氮氧自由基或2,2-二苯基-1-苦基肼基自由基的化合物,沃斯特(Wurster)盐、醌;可以形成加尔万氧基(Galvinoxyl)自由基、苯氧基自由基、三芳基甲基自由基、聚氯三苯基甲基自由基、非那烯基(Phenalenyl)自由基、环戊二烯基自由基、氧化亚胺自由基、四联氮基(verdazyl)自由基、氮碳氮氧(nitronylnitroxide)自由基或噻唑基自由基;靛蓝、二硫化物、硫富瓦烯(thiafulvalene)、硫醚,硫杂环戊烷基(thiolane)、噻吩、紫罗碱、四酮哌嗪、喹喔啉、三芳基胺、冠4烯、蒽醌硫醚(Anthrachinonylsulfid)、酞嗪、噌啉、二茂铁、咔唑、聚吲哚、聚吡咯、聚苯胺、聚噻吩、聚N,N'-二烯丙基-2,3,5,6-四酮哌嗪、2,5-二叔丁基-4-甲氧基-苯氧基-丙基酯、聚-2-苯基-1,3-二硫杂环戊烷、聚[甲烷特屈儿四硫代-亚甲基]、聚-2,4-二硫代-戊烯(pentanylen)、聚乙烯-1,1,2,2-四硫醇、聚-3,4-乙烯二氧噻吩、5,5-双甲基硫代-2,2-联噻吩、聚-1,2,4,5-四丙基(tetrakispropyl)硫代苯、聚-5-氨基-1,4-二氢苯并[d]-1',2'-二硫杂二烯(dithiadien)-共-苯胺、聚-5,8-二氢-1H,4H-2,3,6,7-四硫杂-蒽、聚蒽[1',9',8'-b,c,d,e][4',10',5'-b',c',d',e']双-[1,6,6a6a-SIV-三硫]-并环戊二烯(pentalen)、多烯寡聚硫化物(Polyenoligosulfid)、聚-1,2-联噻吩-3-基甲基二硫烷、聚-3-噻吩基甲基二硫醚-共-苄基二硫醚、聚四硫代萘、聚萘并[1,8-cd][1,2]二硫醇、聚-2,5-二巯基-1,3,4-噻二唑、多硫化物、聚硫氰、聚薁、聚芴、聚萘、聚蒽、聚呋喃、四硫富瓦烯或聚氧吩嗪,和它们的异构体和衍生物。
所述活性单元优选与聚合物主链共价结合。此外还可以使用聚合物加成物。
特别优选使用包含形成氮氧自由基、四联氮基(Verdazyl)自由基或氮碳氮氧(Nitronylnitroxid)自由基的基团、紫罗碱或醌作为氧化还原活性组分的聚合物。
形成氮氧自由基的基团的实例是哌啶,特别是2,2,6,6-四烷基取代的衍生物,特别优选2,2,6,6-四烷基-4-氨基取代的衍生物,或2,2,6,6-四烷基-4-羟基取代的衍生物。
紫罗碱的实例是联吡啶基衍生物,尤其是特别在4,4'位置烷基取代的4,4'-联吡啶基衍生物。优选还可以使用“延长的”紫罗碱;在此是由亚芳基单元、亚烷基单元、亚烷基醚单元或噻吩单元构建的、位于吡啶单元之间并与其共价结合的寡聚物。
醌的实例是酚的氧化产物,如对苯二酚、蒽醌或1,4-二羟基萘的氧化产物。除了1,4-苯醌之外还优选1,4-萘醌。
尤其特别优选使用具有选自聚甲基丙烯酸酯、聚丙烯酸酯、聚苯乙烯、聚亚烷基二醇或聚乙烯基醚的聚合物主链的聚合物,且共价结合在其上的氧化还原活性组分选自形成氮氧自由基、四联氮基(Verdazyl)自由基或氮碳氮氧(Nitronylnitroxid)自由基的基团、紫罗碱或醌。
具有聚甲基丙烯酸酯主链或聚丙烯酸酯主链,所述主链具有共价结合在其上的形成氮氧自由基的基团的聚合物的实例是,具有2,2,6,6-四烷基取代的哌啶的聚甲基丙烯酸酯或聚丙烯酸酯,所述2,2,6,6-四烷基取代的哌啶经由4-氧原子结合在聚甲基丙烯酸酯或聚丙烯酸酯的羧基基团上。这种聚合物的特别优选的实例是聚(2,2,6,6-四甲基哌啶基氧-甲基丙烯酸酯-共-聚(乙二醇)-甲基醚-甲基丙烯酸酯)。
包含具有共聚的紫罗碱残基的聚亚烷基二醇主链的聚合物的实例是,具有经由吡啶-氮原子结合在乙二醇的C原子上的、共聚的4,4'-联吡啶基残基的聚乙二醇。这种聚合物的特别优选的实例是聚(4,4'-联吡啶-共-聚(乙二醇))。
高分子氧化还原活性组分的平均摩尔质量(数均)典型地是至少500g/mol,优选至少550g/mol,特别优选至少1000g/mol,且特别优选为1000至500000g/mol,和尤其是1000至50000g/mol。
包含氧化还原活性组分的聚合物可以作为线型聚合物或作为分支聚合物存在,例如作为梳形聚合物或星形聚合物、树形聚合物、梯形聚合物、环形聚合物、聚索烃或聚轮烃存在。
优选使用分支的聚合物,特别是梳形聚合物或星形聚合物、树形聚合物、梯形聚合物、环形聚合物、聚索烃或聚轮烃存在。这些类型的特征在于增加的溶解性,并且所得到的溶液的粘度通常低于相应的线型聚合物的粘度。
根据本发明所用的电解质的粘度通常在1mPas至106mPas的范围内,特别优选102mPas至104mPas(在25℃下利用旋转粘度计、板/板测定)。
另外,根据本发明所用的、包含氧化还原活性组分的聚合物的溶解性可以通过共聚或官能化得到改善,例如用聚乙二醇、聚甲基丙烯酸、聚丙烯酸、聚-2-甲基噁唑啉或聚苯乙烯磺酸酯的共聚或官能化。
根据本发明所用的、包含氧化还原活性组分的聚合物的制备可以通过常用的聚合方法来实现。
上述方法的实例是本体聚合、在溶液中的聚合、沉淀聚合、或者乳液或悬浮液聚合、以及类似聚合的官能化。这些方式对本领域技术人员来说是公知的。
氧化还原活性组分可以这样使用,原样,也就是没有溶剂的情况下使用,只要在使用温度下它是液态的。但是,该氧化还原组分优选与溶剂一起使用。
根据本发明的氧化还原液流电池除了包含上述组分之外,还可以包含其他这种电池常用的元素或组分。这些组分中的一些是强制性地,其他组分可以根据具体情况来使用。
强制存在的组分的实例是:
电极,例如由石墨、石墨纤维网、石墨纸、碳纳米管毯(Carbon-Nano-Tube-Teppichen)或石墨烯构成的电极
电流导体,例如由石墨或金属构成的电流导体
包含溶解于其中的导电盐的电解质;在此可以是液态氧化还原活性的聚合物,或者是由氧化还原活性的聚合物和电解质溶剂构成的溶液、乳液或悬浮液
电解质-溶剂的实例是:水或有机溶剂,例如乙腈、有机碳酸酯、醇、二甲基甲酰胺、二甲基亚砜、二甲基乙酰胺、二氯甲烷、硝基甲烷、四氢呋喃,优选水、乙腈和有机碳酸酯
电解质导电盐的实例是:包含阴离子以及阳离子的盐,所述阴离子选自PF6、BF4、SbF6、AsF6、ClO4、CF3SO3、SO2C2F5、C4F9SO3、(CF3SO3)N2、OH、SO4、F、Cl、Br或I;所述阳离子选自H、碱金属阳离子或碱土金属阳离子,以及取代或未取代的铵阳离子
输送手段,例如泵,以及用于运输和储存氧化还原活性组分的容器和管道
可任选存在的组分的实例是:
电解质包含的除了其中溶解的导电盐之外的电解质添加剂
电解质添加剂的实例是表面活性剂、粘度调节剂、杀虫剂、缓冲剂、稳定剂、催化剂、导电添加剂(Leitadditive)、防冻剂、温度稳定剂
通过两个室内所述以本体形式、溶解或分散形式存在的高分子氧化还原活性组分,和利用所述选择性来分离其流动循环,从而构造氧化还原液流电池,它不包含成本密集和有毒或有害的、在损坏情况下可能流出和对环境造成负担的电解质。
两个单独的流动循环的分隔膜也可以以相对低耗费地制造和使用。该膜优选由有机材料构成并根据目的构造成聚合物膜。
至今为止,对根据本发明的氧化还原液流电池的研究,特别是多次重复充电/放电试验,表明在其应用中与开篇描述的体系相比具有明显延长的使用寿命和极低的生产成本。
根据本发明的氧化还原液流电池可以用于各种领域。最宽泛意义上可以是用于移动和静态应用的电能存储器。本发明还涉及所述氧化还原液流电池用于此目的的用途。
应用实例是用在电动汽车领域,如作为陆地运输工具、空中运输工具和水路运输工具的存储器;用作静态存储器,用于紧急备用动力供给、峰值负载平衡;以及用于中间存储来自可再生能源的电能,特别是在光伏和风力发电行业。
根据本发明的氧化还原液流电池优选用作电能的静态存储器。
根据本发明的氧化还原液流电池可以以公知方式串联或并联地互相接通。
以下借助附图以图示的氧化还原液流电池作为实施例进一步详细说明本发明。
所述氧化还原液流电池由两个结构相同和制成特氟龙空心体的半电池(1)和(2)构成,其中半电池(1)起到阴极电解液-室的作用,半电池(2)起到阳极电解液-室的作用。
两个半电池(1,2)(为了清楚起见放大显示)经由排除极限为1000g/mol的尺寸排阻膜(3)连接。
每个半电池(1,2)都具有流入套管(4)和流出套管(5),半电池(1,2)经由所述套管借助软管分别与贮存容器(液体存储器)连接,贮存容器包含用于对应半电池(1)或(2)的阴极电解液或阳极电解液(为了清除起见没有在图中示出)。
在充电/放电过程中,阴极电解液或阳极电解液(分别作为单独的液体循环通过氧化还原液流电池的半电池(1)或(2))通过泵(同样为了清楚起见没有示出)从相应存储容器泵出通过对应的半电池(1)或(2)(箭头表示流入套管和流出套管(4,5))。
每个半电池(1,2)分别具有由石墨/石墨纤维网构成的内电极,在其上分别在半电池(1,2)中发生本身已知的电极反应。所述内电极分别被引出作为极性依赖型电流导体(6),用于半电池(1,2)的电连接。
作为阳极电解液使用聚(2,2,6,6-四甲基哌啶基氧-甲基丙烯酸酯-共-聚(乙二醇)甲基醚-甲基丙烯酸酯)在碳酸丙烯酯中的溶液(10mg/mL)。作为阴极电解液使用聚(4,4'-联吡啶-共-聚(乙二醇))在碳酸丙烯酯中的溶液(10mg/mL)。两种溶液中均掺入四丁基六氟磷酸铵(0.1mol/L)作为导电盐。这样得到的电池可以在500μΑ的恒定电流下充电和放电,其中放电电压为约1.1V。
附图标记:
1,2-半电池
3-尺寸排阻膜
4-流入套管
5-流出套管
6-电流导体
Claims (21)
1.用于存储电能的氧化还原液流电池,它包含反应池,该反应池具有两个用于阳极电解液和阴极电解液的极性专用室(1,2),所述室(1,2)分别与液体存储器连接并通过用于离子交换的膜来分隔,其中所述室(1,2)分别填充了氧化还原活性组分,所述氧化还原活性组分以溶解在电解质溶剂中的形式存在,并且其中溶解了导电盐和可能的其他添加剂,其特征在于,使用数均分子量500g/mol至500000g/mol的高分子化合物作为所述氧化还原活性组分,和使用尺寸排阻膜(3)作为所述膜,所述尺寸排阻膜(3)用于分离以溶解形式存在的高分子量氧化还原活性组分,其中用作氧化还原活性组分的所述高分子量化合物为聚合物,所述聚合物包含形成氮氧自由基、四联氮基(Verdazyl)自由基或氮碳氮氧(Nitronylnitroxid)自由基的基团、紫罗碱或醌,所述尺寸排阻膜的选择性是至少500g/mol,且具有至少下列特征:分离阴极室和阳极室,截留高分子量氧化还原活性组分,可以透过起到电荷平衡作用的电解质的导电盐,并且其中“选择性”表示分离极限,在此极限下分子不再能有效地通过膜,这意味着,在分子的预先给定分子量下,至少90%的分子被所述膜截留。
2.根据权利要求1的氧化还原液流电池,其特征在于,所述室(1,2)分别填充了氧化还原活性组分,该组分以溶解在水中或溶解在有机溶剂中的形式存在。
3.根据权利要求1的氧化还原液流电池,其特征在于,使用半透膜作为尺寸排阻膜。
4.根据权利要求1的氧化还原液流电池,其特征在于,使用透析膜作为尺寸排阻膜。
5.根据权利要求1的氧化还原液流电池,其特征在于,高分子量氧化还原活性组分的对应摩尔质量大于等于550g/mol。
6.根据权利要求1的氧化还原液流电池,其特征在于,所述尺寸排阻膜由塑料、陶瓷、玻璃、金属、复合材料或纺织面料或它们的组合构成。
7.根据权利要求1的氧化还原液流电池,其特征在于,所述尺寸排阻膜由有机聚合物构成。
8.根据权利要求1的氧化还原液流电池,其特征在于,所述尺寸排阻膜由纤维素或改性的纤维素构成,由聚醚砜、聚砜、聚偏二氟乙烯、聚酯、聚氨酯、聚酰胺、聚丙烯、聚氯乙烯、聚丙烯腈、葡聚糖、木质素、聚环氧丙烷、聚乙烯亚胺、聚丙烯酸、聚苯乙烯、聚乙烯醇、聚苯醚、聚酰亚胺、聚四氟乙烯或它们的衍生物构成。
9.根据权利要求1的氧化还原液流电池,其特征在于,所述尺寸排阻膜由有机材料构成。
10.根据权利要求9的氧化还原液流电池,其特征在于,所述尺寸排阻膜构造成聚合物膜。
11.根据权利要求1的氧化还原液流电池,其特征在于,所述尺寸排阻膜的厚度在1μm和5mm之间的范围内。
12.根据权利要求11的氧化还原液流电池,其特征在于,所述尺寸排阻膜的厚度在10μm和200μm之间的范围内。
13.根据权利要求1的氧化还原液流电池,其特征在于,使用聚合物作为氧化还原活性组分,所述聚合物具有选自聚甲基丙烯酸酯、聚丙烯酸酯、聚苯乙烯、聚亚烷基二醇或聚乙烯基醚的聚合物主链,且共价结合在其上的氧化还原活性组分选自形成氮氧自由基、四联氮基自由基或氮碳氮氧自由基的基团、紫罗碱或醌。
14.根据权利要求1的氧化还原液流电池,其特征在于,使用聚合物作为氧化还原活性组分,所述聚合物作为线型聚合物或作为分支聚合物存在。
15.根据权利要求1的氧化还原液流电池,其特征在于,所述聚合物作为梳形聚合物或星形聚合物、树形聚合物、梯形聚合物、环形聚合物、聚索烃或聚轮烃存在。
16.根据权利要求1的氧化还原液流电池,其特征在于,所使用的电解质的粘度在1mPas至106mPas的范围内,在25℃下利用旋转粘度计,板/板测定。
17.根据权利要求16的氧化还原液流电池,其特征在于,所使用的电解质的粘度在102mPas至104mPas的范围内。
18.根据权利要求1的氧化还原液流电池用于存储移动和静态应用的电能的用途。
19.根据权利要求18的用途,其特征在于,所述氧化还原液流电池用在电动汽车领域,或者所述氧化还原液流电池用作静态存储器,用于紧急备用动力供给、峰值负载平衡,以及用于中间存储来自可再生能源的电能。
20.根据权利要求19的用途,其特征在于,所述氧化还原液流电池作为陆地运输工具、空中运输工具和水路运输工具的存储器。
21.根据权利要求19的用途,其特征在于,所述氧化还原液流电池在光伏和风力发电行业用作静态存储器。
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