CN1290213C - 电化学电池的中孔网状电极 - Google Patents
电化学电池的中孔网状电极 Download PDFInfo
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- CN1290213C CN1290213C CNB028102622A CN02810262A CN1290213C CN 1290213 C CN1290213 C CN 1290213C CN B028102622 A CNB028102622 A CN B028102622A CN 02810262 A CN02810262 A CN 02810262A CN 1290213 C CN1290213 C CN 1290213C
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Abstract
一种高动力比率的电化学电池,其中至少有一个电极是由包含纳米粒子的微型结构的电活性材料构成,这些纳米粒子形成一个中孔组织的三维框架结构,它具有大的比表面积的双连连接,内含有电解质。一种制备电极的低温方法,它采用了快速贴附薄膜形式的电活性材料。公开了所述电极在高功率锂离子插入式电池组,光生伏打电池,超电容器,和快速电化学器件中的应用。
Description
发明领域
本发明涉及电极和含有上述电极的电化学电池。尤其是,它涉及应用以下材料的电化学电池,这类材料例如非水有机电解质,固态高分子电解质等等,更具体而言,它涉及其多孔电极材料,亦即以离散为其特色的阳极和阴极电极材料,优选掺杂的或非掺杂氧化物,氢氧化物或硫属元素化物的纳米粒子,任选地加上微粒子,这些粒子处于直接的电气和机械接触状态下,从而形成中孔网状涂层。
当使电解质处于与这中孔型三维框架结构相接触状态时,它便与电活性固体形成一个具有非常大的表面积的双连结合,从而能提供极高的快速充放电,高容量,高循环能力特性和高的使用可靠性。
本发明还涉及利用选定的电活性材料制备上述类型的柔性电极的方法,尤其是采用将处于5℃-60℃下呈分散状态的粒子涂料与可固化的有机粘结剂相混合,随后采用例如在优选的70℃-240℃的某一温度下加热的方法滚压和固化这多孔涂层。
这些新型多孔电极的应用包括电化学器件,例如高功率电池组,光生伏打电池,超电容器以及快速电化色器件。
现有技术描述
电化学电池已采用将微米级粒子在高温下烧结或粘结的方法使其键合,在超电容器,光电化学和电化变色的应用中用作电极活性材料,以及用于离子插入式电池组。
欧洲专利申请EP0709906A1公开了一种由平均粒径为33μm的电活性粉末的氧化锂钴烧结物质组成的正电极。将这些粒子用施加高压的方法压制成厚1.5mm的片剂,并同时在350℃-700℃下进行烘焙处理。据报道,在升高的温度下干燥后改善了电阻率,这大概与该活性物质内部发生的一定程度的烧结有关,因而使这活性材料中的连接性多少有点改善。
USPP5604057公开了一种阴极,它包含非晶形的超微米级微孔的可插入锂的氧化锰,它具有的内表面积大于约100m2/g。电极的制备采用了使该氧化物与粘结剂,包括可任选的一种导电聚合物相混合,然后使该复合材料在高达400℃的某一温度下加热的方法。将温度限制于此值是为了防止氧化锰结晶。建议采用高表面积和非晶形性质的活性材料,似乎增加了所制备的电极的初始容量,但连接性受阻。这些粒子的内连接性差,所以在制作电极的混合物中要求有粘结剂和/或导电粘结剂。采用非晶形材料电极结构的别的缺点就是置于温度中会由于结晶而改变其结构,从而限制了所报道的因其非晶形结构而带来的好处。
USPP5211933和USPP5674644公开了一种尖晶石LiMn2O4和层状LiCoO2相的低温制备方法,,而尖晶石LiMn2O4和层状LiCoO2是使用了醋酸盐前体在温度低于400℃下制备的。制得的LiMn2O4粉末包含有粒度为0.3μm-1μm的晶粒或晶体。将其压制成片剂,该片剂含有上述粉末和约10%的炭黑,并用作锂离子式电池组的正电极。申请专利的粒子粒径有些大,以便期望能适合作快速放电电极,但利用专用粘结剂并不能确保活性材料粒子内部的连接性,而采用将碳粉末混合到活性粉末中的方法提高了连接性。
USP5700442公开了几种插入化合物,它们是基于可用作锂电池组中的正电极活性材料氧化锰的,其制备方法是使β-MnO2粉末与锂化合物在150℃-500℃下发生反应,经足够的时间,使这些固体前体转变成尖晶石型。所制得的粉末的比表面积低于7m2/g。根据此文中申请专利的低比表面积可推论出大粒径不适于作快速放电电极。
欧洲专利申请EP0814524A1公开了一种尖晶石型锂锰络合氧化物,它用作锂离子式二次电池组的阴极活性材料。这平均的粒子直径为15μm,和比表面积为2-10m2/g。此文中申请专利的这样低的比表面积,使得这大粒径对于快速放电电极来说并不是最佳的。
USP5569561公开了一种方法,在该方法中,将纳米粒子与碳粉末和高分子粘结材料一起压制成片剂形状,然后在160℃下干燥12小时;这方法生产出图2所列举的电极,这电极呈脆性,非柔性薄膜形,这种薄膜不适宜用来制造常规卷筒型电池组。参阅图2,根据以前技术生产的电化学发生器器件21的电极/电介质交界面23/29限于低表面积的电极,其中电极的大部分可透入的孔隙被压缩粘结剂所阻塞。此外,活性物质/电子导体交界面23/25部分地被绝缘粘结剂粒子24所遮断。
WO-A-991/59218描述了一种方法,该方法涉及溶胶凝胶沉淀和随后对该电活性固体材料进行烘焙处理。它公开了制造具有最佳性能的电化学发生器所要求的特殊的中孔形态的电极的方法。它还公开了利用表面活化剂组件作模板,以便在电活性固体形成过程中导出所需的电极结构。
一种将刚性半导体薄膜直接烧结在导电电极上的类似方法,已用于所有早先公开的染料太阳能电池,可参阅例如欧洲专利EP333641,列举在图1上。虽然在这些较早公开的资料中已认识到了使用中孔电极形态的锂插入式电池组性能的优点,但是能够在充电过程中保持电子电荷迁移的电活性薄膜的制备和限定只能应用于刚性载体的纳米粒子之间的刚性烧结互连所牵涉及到的高温烧结步骤已限制了它们的应用领域。
本发明的一个目的是要提供一种具有由呈弥散状态的离散纳米粒子形成的中孔框架结构的电极,能以低的成本,且无需使用复杂的反应设备制备。
本发明的再一个目的是要提供一种生产电化学器件的简单而又方便的方法,这种电化学器件具有基于中孔框架结构的奇特的复合电极结构,而这复合电极结构则是由固化有机粘结剂的互连网构成的一个稳定的双连续渗透网络。
本发明的还有一个目的是要提供一种可使用具有高表面积的纳米粒子来形成中孔结构的电化学发生器,但可无需在纳米粒子之间使用刚性互连或高温烧结步骤来制备它。
发明概述
已意外地发现,离散固体接触状纳米粒子涂层能形成中孔框架结构,这些纳米粒子没有采用在升高的温度下熔化或局部熔化的方法使其烧结在一起,而这中孔框架结构显示出的电活性,离子插入和动力特性与根据以前技术得知的热烧结层的相类似。还已发现,这样的中孔框架结构可利用呈弥散状态的离散固体纳米粒子制得,将这些纳米粒子在环境温度下,但不要求立即加热或冷却,聚集在一起形成一个稳定层。
根据本发明提供的一种电极,它包含:
(a)一种电极活性材料,采用氮的解吸等温线孔隙率测定法测出其显示出中孔孔隙率,其中电极活性材料包括含有纳米粒子和任选的微粒子的离散固体接触状颗粒;
(b)可固化的有机粘结剂;和
(c)一种与电极活性材料的操作有关的导电装置。
本发明还提供一种包含本发明的电极的电化学电池,以及所述电池在例如光生伏打电池,电致变色装置或能够双相地传输电流的离子插入式电池组中的应用。
本发明还提供一种制备本发明的电极的方法,该方法包含提供一种置于合适液体中的电极活性材料的胶态分散体,将这分散体与可固化的有机粘结剂相混合,然后将所得混合物在5℃-60℃的某一温度下置于载体上,以生成电极活性层,随后将上述活性层置于比用来制备分散体的液体的沸腾温度低的温度下进行干燥。
简而言之,本发明提供了一篇新颖和实用的生产电化学器件的物件。这电化学器件包括至少一层由固体离散粒子制成的多孔电极层,优选这些粒子中至少10%是纳米级的(亦即粒径低于50nm的),它具有一种新颖的电活性材料结构,该结构则是基于彼此直接电接触的纳米粒子构成一个电子传导双连渗透网络,并借助于互连粘结网络使其固定在一起。
定义
文中所采用的术语“中孔”的定义是一种主流孔径在2nm-50nm范围内的多孔材料,与国际理论与应用化学协会(IUPAC)的定义相应;孔径超过50nm的材料被称为“大孔”。
术语“胶态晶体”系指由在没有添加剂的情况下,通过自组合形成的周期排列的六角或立方阵列的纳米粒子所组成的粒子实体。天然胶态晶体的一个实例是蛋白石。
术语“离散”系指有着独立个性的不同的单体,但并不阻碍这些单体的相互接触。文中所用术语“微粒子”系指形成尺度为0.05-约30微米的单个实体之晶粒或粒状材料,它可以是复合物,但这术语不适用于由能再分开的许多实体组成的粒子聚集体,术语“聚集体”适用于上述实体,而本文中对于小于50毫微米的单个实体使用的术语是“纳米粒子”。
术语“中孔范围的”系指“纳米粒子”的特征尺寸。
术语“活性” 系指一种材料,在电化学或光电化学转换过程中涉及的这材料是可逆的,它或者作为离子插入,或者作为被染料敏化的半导体,或者与氧化还原生色团连接触。
文中术语“交界面”应理解为意指下列材料之间的交界区域(1)电极的活性材料和(2)处于接触状态中的迁移材料,用来迁移离子,空穴和电子。术语“电子学的”意指涉及电子或空穴,但不涉及离子。术语“电解质”意指一种呈原子,分子,或离子的固体或液体形态的传输工具。
文中所用术语“烧结”通常系指离散粒子局地被熔化粘结并形成不再能识别离散粒子的单个实体。
附图简述
参阅附图,在作为非限制实例给出的以下实例中进一步陈述了本发明的特点和优点,其中:
图1表示按照现有技术用烧结纳米粒子制成的粗制薄膜型染料敏化光电化学器件的示意剖面图;
图2描绘现有技术的复合型纳米粒子电池组的示意剖面图;
图3A描绘本发明的纳米结构型电极涂层的示意剖面图,图中包括蒸发式金属集电极;和
图3B是本发明的电极涂层的示意剖面图,图中包括粒径呈双峰分布的纳米粒子和多孔微粒子,它们被涂覆在柔性金属集电极箔上;
图4表示本发明的一种电化学发生器的剖面图,图中包括(1,2)为活性材料中孔电极涂层,(3)为多孔或中孔隔离层,(4,5)为集电极;
图5表示沉积在带有氧化铝中孔覆盖层的铜箔上的中孔TiO2涂层的循环伏安图。电解质:EC∶DMC 1∶1,1M Li-酰亚胺,电极:带有氧化铝隔离层的TiO2,厚度4.5微米;总的厚度:9-10微米。
————扫描速度20mv/秒, ----扫描速度10——mv/秒。
图6表明上述电池中所采用的电解质和它们的化学特性的实例。
图7表明在组合式二次电池组中,由处于恒等电势-扫描状况下的电极和普通电解质组成的电池,其充电/放电循环情况,以便证明所述中孔多层系统TiO2/Al2O3/LiCoO2改善了充电/放电时的动力学特性,所述中孔多层系统含有作为阳极的TiO2/Al2O3,与层状隔离层连同LiCoO2一起作为活性材料用作负电极。
图8表明处在本发明的薄层中孔电池组电池的稳态电流下的电解质的功用,正如由模拟模型所提供的,作为电极活性涂层厚度的函数,借助在多层设计内部的Li+离子和各种耦合阴离子的浓度分布图,陈述了完全中孔电池的电解质迁移工况。
参看图1,光电化学电池11包含有玻璃盖板13,其上贴附着一层透明导电薄膜14,任选地涂以铂催化剂,以及氧化还原电解质15,例如碘-碘化物电荷载流子,光线12可穿透以上各层。
利用粗糙的半导体薄膜17以及附着在该薄膜表面上,并与电解质15连接的光敏染料16,使光能转变成电子。这半导体薄膜采用烧结在刚性导体18上的方法使其与导体产生电子学上的接触。
参看图2,电化学发生器20,它包含纳米粒子状电极22,离子导电电解质27,上述电极22由埋置在碳粒子24和粘结剂25中的电化学活性材料纳米粒子23构成的压缩烧结物制成,粘结在刚性金属导电电极26上,部分的上述电解质27是在储存器28或多孔分隔器内。上述纳米粒子状电极面对着一个标准对电极21。
参看图3A,电化学电池的电极40的一种实施方案,该方案包含离散状电活性纳米粒子41,粘结剂粒子42和集电极43,纳米粒子41与更多的纳米粒子相接触形成渗滤簇,粘结剂粒子42弥散在纳米粒子簇周围形成网络,上述集电极43则包含有一层导电薄膜。
参看图3B,电化学电池的电极50的另一种实施方案,该方案包含离散状电活性纳米粒子41,微粒子53,块状集电极54,粘结剂粒子42和导电粒子55,纳米粒子41与更多的纳米粒子和微粒子53相接触形成渗滤簇,这些渗滤簇完全与块状集电极54相接触,粘结剂粒子42稀疏地弥散于整个渗滤簇中。在这些粒子之间形成的孔隙内则充满电解质56。
发明内容
本发明的电极用电极活性材料优选自非过渡或过渡金属的氧化物,硫属元素化物,氢氧化物,羟基氧化物,含氧酸,氧基氢化物或硫氰酸,或选自周期元素表的族IB,IIA,IIB,IIIA,IVA,IVB,VA,VB,VIB,VIIB和VIII元素的锂化或局部锂化形式,和它们的混合物。
优选的电极活性材料包含双峰粒径分布的粒子,优选包含至少10重量%的平均粒径小于50nm的纳米粒子和粒径大于50nm的微粒子,它们的比表面积为0.1m2/g-500m2/g。
电极活性材料优选基本上不含微粒子,而含有纳米粒子,这些纳米粒子显示出电化学活度和呈现由基本上为同一尺寸的粒子构成的六角或立方阵列的形式。
在本发明电极内的可固化有机粘结剂粒子优选的使用量为0.5重量%-10重量%,更优选1重量%-5重量%,这种粘结剂优选包含具有玻璃化转变温度至少为50℃的高分子材料,这种材料优先选自聚偏氟乙烯,聚四氟乙烯,氟橡胶,(它是四氟乙烯,偏二氟乙烯和六氟丙烯的三元共聚物),例如聚乙烯吡咯烷酮,聚酰胺,聚氨酯之类的聚乙烯聚合物;乙烯丙烯酸(EAA)共聚物,乙烯甲基丙烯酸(EMAA)共聚物,聚乙烯(PE),聚丙烯(PP),乙烯丙烯二烯三元共聚物(EPDM),聚亚烷基氧化物,聚丁烯,离子化交联乙烯甲基丙烯酸共聚物,乙烯正丙烯酸丁酯(EnBA)聚合物,乙烯醋酸乙烯酯(EVA)聚合物,乙烯丙烯酸乙酯(EEA)共聚物,乙烯丙烯酸甲酯(EMA)共聚物,双烯丙基靛酚二酰亚胺(bisallylnadiimide)或烯丙基靛酚二酰亚胺(allylnadiimide),聚砜类,聚醚砜类,聚酰亚胺类,聚酰胺-酰亚胺类,环氧树脂类,例如氯甲酯化聚亚芳基醚酮,丙烯酰化聚亚芳基醚酮之类的聚亚芳基醚酮类,聚丙烯腈,丁腈橡胶,二元乙丙橡胶,丁苯橡胶,聚醚二酰亚胺,聚苯乙烯,氯甲化聚醚砜类,丙烯酰化聚醚砜类,聚甲基丙烯酸甲酯,聚硫橡胶,氰乙基纤维素,甲基纤维素,和其低聚物和混合物;或其前体,选自噻吩,亚苯基,吡咯,乙炔,异硫茚(isothionaphtene),苯胺,亚乙基二羟基噻吩,亚苯基亚乙烯基和丙烯腈,和它们的非掺杂的、掺杂的和取代的衍生物和它们的共聚物。
可固化的有机粘结剂可以进一步与电子导电材料相混合或用其取代,上述电子导电材料取自非掺杂或掺杂本征导电聚合物,聚噻吩,聚亚苯基,聚吡咯,聚乙炔,异硫还烷,聚苯胺,聚乙烯二羟基噻吩(PEDOT),聚亚苯基亚乙烯基,由丙烯腈等,其取代衍生物和其共聚物形成的导电梯形聚合物,导电粒子,炭黑,碳和石墨化碳及石墨的细颗粒,乙炔黑,碳晶须,碳素纳米微管,富勒烯,高导电胶态金属和掺杂金属氧化物,上述金属的合金,金属纳米纤维;和其混合物。
将导电装置方便地置于由塑性材料制成的载体上。
电极活性材料可采用固熔体取代方法进行掺杂,其中0.2%-49%的非过渡金属或过渡金属的原子选自元素周期中族IB,IIB,IIIA,IVA,IVB,VA,VB,VIB,VIIB和VIII元素之别的过渡金属或非过渡金属及其混合物所取代。掺杂电极用活性材料的电极电势相对于原始电极活性材料的电极电势移位了0.05V以上,掺杂电极活性材料的熔点相对于原始电极活性材料的熔点移位了10℃以上。
电极活性材料可以通过在其上吸附增感染料,氧化还原发色团,或电荷转移敏化剂的方法加以改进。
在本发明的电化学电池中,这一或每个电极的电极活性材料优选包含纳米粒子,这些纳米粒子组合成离散接触状粒子,以便形成含有用作电化学媒介的电互连固态相材料和用于电子迁移的中孔网状三维双连结构,而该结构则与粒间互连空间相接触,粒间互连空间用以包含离子迁移用电解质。
在优选实施方案中,电化学电池包含一个正电极和一个负电极,其中正电极和/或负电极的电极活性层还包含一层惰性层,用作多孔隔离层以防止正负电极直接接触和短路。所述隔离层优先选自绝缘陶瓷材料,更优选Al2O3,SiO2,硅烷化二氧化硅,ZrO2,Ta2O5或LiLa0.35Ti0.55O3。
多孔隔离层另外还可包含可固化的有机粘结剂,优选在上文中所定义的这类有机粘结剂。
本发明的电化学电池可以呈高功率离子插入式电池组形式、高功率超电容器形式或混合式电池形式,这混合式电池含有超电容器式电极和离子插入式电池组型电极。
在制备本发明的电极所用方法的一种实施方案中,优选将惰性绝缘隔离层材料置于电极活性层上,隔离层材料任选包含可固化的有机粘结剂。在电极活性层中和在隔离层材料中如果有粘结剂,则本发明的方法包含固化该粘结剂的附加步骤。这固化可以采用任何合适的方式实施,例如,作为例子,可采用电磁辐射和/或UV(紫外线)辐射和臭氧和/或加热方法,加热温度优选70℃-240℃,更优选90℃-170℃。
固化电极活性材料和隔离层材料,可以通过对构成所述材料的粒子进行光激发而加速,所述光激发导致电子跃迁,从而在粒子内生成电子和空穴偶电荷载流子,随后这电荷载流子与粘结剂或别的添加剂发生反应,由此增强了粒子网络的交联。
在浇注电极活性材料和任选的隔离层材料之后,优选采用施压的方法。
另外还可以采用某种涂覆方法为中孔电极涂以导电金属或金属氧化层,作为实例例如可采用蒸发法,溅镀法,金属粉末喷吵法或金属粉末印刷法。
以下各节依次描述了具有创新意义的中孔涂层的特征和特性,使用新型中孔涂层的新式电化学器件,电极形成的方法,和使用本发明的电极的器件的形成。后面这些是创新电极结构的实施方案实例,所制得的产品和方法。
1.中孔三维网络电极结构和连接
与现有技术得知的特性相比,本发明提供了一种新型的电化学电池结构,其中使用的电极中至少一个电极具有由离散纳米粒子和任选的微粒子制成的中孔框架结构,此外,这种电极可以采用不需要加热烧结电活性粒子的方法来制备。
本发明涉及一种高功率密度的电化学电池,更准确而言,涉及一种电池,其中至少一个电极其特征在于中孔三维框架结构。这电极由处于直接的电和机械接触状态的固体粒子状物质组成,形成一层中孔网络层,从而保证电流的流动遍及和穿越涂层。这电极与起集电极作用的导电装置有关。电解质存在于所述电极的中孔网络中,与电活性固体形成具有极大表面积的双连连接。电解质保证离子在电化学电池的负电极和正电极之间迁移。
中孔电极的形态设计成能克服常规大表面积电极所遇到的阻碍离子在电解质中扩散的问题。新颖形态赋予三维结构具有电连接性,机械稳定性和使得电解质能进入到全部孔隙中。本发明提供一种具有大的离子插入容量和高的电功率密度的电极,这使得其特别适于用作主要或二次电化学发生器中以碱或碱土插入金属离子为主的阴极或阳极,例如锂离子电池组。
电极中至少有一个电极是由中型,双连续结构构成,它由互连固体材料和带中孔的互连网络组成。这种电活性固体可以或者是借助插入方法用来容纳离子的基体或者用作电活性染料涂层的大表面基质。同时,它的固有导电性在该器件的电活性运作过程中起维持电流流动的作用。所述电活性固体与充满电解质的互连孔隙相接触,后者起离子迁移作用。所述电极其特征在于在固体和电解质之间存在着极大的交界面,所含电极材料在10和3000m2/g之间,使得有可能在固体和液相之间快速交换离子。这固相的网状结构设计成能克服常规大表面积电极所遇到的阻碍离子在电解质中扩散的问题。本发明公开的特殊的三维结构电极具有固相的互连性和机械稳定性,从而为电解质轻易进入到全部孔隙创造了条件。此外,它使电流在固体内部的传导甚至在没有导电添加剂的情况下也变成可能,而在常规器件中使导电添加剂与电活性材料相混合,以提高电极的电子导电性。
2.电极和电化学器件的形成
这种中孔形态形式的电活性材料可以用下述方法制得,作为实例,可采用将固体粒子的胶态分散体浇注在用作集电极的导电薄膜上。
本发明的一项特殊性能是,所采用的电极可在环境温度条件下,采用以下方法制得,即这方法涉及使电活性材料从分散状态浇注成薄膜状态。这薄膜含有活性电极材料和高分子粘结剂,作为实例,这活性电极材料是金属氧化物,例如呈中型尺度的粒子形式的TiO2。
这粘结剂是稳定薄膜所必需的。加入粘结剂的比例是不会使粒子彼此隔离或堵塞孔隙,但其量要足以生产出能扩展到整个涂层的渗透性互连网络。高分子量聚合物被发现特别适用于这样一类网络。粒子之间的电接触是电化学器件充电和放电过程中电子在电极内流动和流出电极所必需的。隔离粒子将会导致电荷透过电极活化涂层中断,破坏了电子循环过程。本发明的一项重要发现就是电子穿流能有效通过由中型氧化物粒子形成的网络而不会烧结粒子。不管粒子组合所采用的条件是否是适度的和是否存在有保证涂层具有机械稳定性的高分子粘结材料,大电流能流过涂层,从而使它们在电化学器件中起电极一样的作用成为可能。这一发现使本领域内的某些技术人员感到十分意外,人们原以为粒子必需通过加热使它们熔合在一起才能形成可使电荷轻易通过的网络。
可以做到快速地将薄膜浇注到载体或集电极上,从而能在短时间内形成大面积的活性电极。本公开内容的这个特性特别重要,因为本发明的目的就是要提供一种由中孔材料构成的电池组,而这种材料能在环境温度下高产地制备,随后在比较适度的加热条件下固化这粘结聚合物。
在浇注混合物的制备步骤中,将纳米粒子与不会溶解连接聚合物或染料的挥发性载体相混合。这种载体例如水,邻苯二甲酸二丁酯,邻苯二甲酸二辛酯,和醋酸盐,乙烯碳酸盐,辛烯碳酸盐,磷酸三丁酯,萘烷酮,甘醇二甲醚和低分子量聚合物,这样的混合是求得具有理想流变性质的组合物所必需的,最后,冷却或加热这组合物,以便形成可涂覆的材料。本领域的那些技术人员将能理解采取的以下措施,即为了适应采用的特定技术,可能必需对溶液的粘性和流变特性做某些调整,而通过改变载体的分子量和/或浓度可以实现这样的调整。
在浇注步骤中,可以采用任何能呈分散状态的贴附方法将离散粒子浇注在适合的基质上(例如金属或透明导电氧化物电极),这种方法包括:预定量涂敷法,例如盖板模涂敷,槽或挤压涂敷,滑式或阶梯式涂敷,和帘式涂敷;滚动涂敷,例如刮板式涂敷,正反向滚涂;照相式涂敷;浸涂;喷涂;半月板涂;旋涂;刷涂;气压式刮涂;丝网印刷法;静电印刷法;热印刷法,油墨喷射法;和其它类似的技术。尤其优选高生产效率的预定量涂敷方法。
粘结剂优选有弹性而非脆性的,化学惰性的,耐热的高分子材料,它有着低热膨胀系数,是热塑性塑料或可以被聚合的或可用其它方法固化的。适合的粘结材料可选自热塑性的,可用化学方法固化的或可辐射固化的聚合物。
此外,导电聚合物固有地能和先前所述非导电粘结剂相粘结或取代。它们选自聚苯胺,聚噻吩,聚亚苯基,聚吡咯,聚乙炔,聚异硫茚,聚苯硫醚,聚对亚苯,聚乙烯-双氧基噻吩(PEDOT),聚苯乙烯撑,聚杂环乙烯撑,导电聚丙烯腈,其取代衍生物,其共聚物和其混合物。
最后所得的柔性聚合物电极涂层,可以或者直接将其浇注在最终的集电极上呈双连续模式,从而把每个电极隔离,或者连续地浇注在一临时载体上,然后切割并与呈网格形式的集电极接触,或直接将其喷射或蒸敷在电极活性材料上。
本发明的方法的重要优点是容许将各种材料用作集电极载体,包括镀金属塑料或金属箔层压塑料,它们均是热敏感的和不能忍受高温烧结步骤。在常规离子插入式电池组中,在固体粒子置于集电极上之后,为了保证这些固体粒子之间的电连接,对电化学活性基体材料加热是必需的。
本发明提供的电化学电池可以在比较低的温度下制备,由此开创出新的所述电化学电池的实施方案,例如在常规塑料基质上呈柔性状态。因为不需要采用高温烧结步骤,来生产用离散粒子尤其是纳米粒子制作的性能良好的电极,这些粒子能置于塑性材料上,从而开创了一个新的应用领域。
3.电化学发生器实施方案
在电化学电池中起阳极作用的二氧化钛(TiO2)中孔电极,是按照本发明采用浇注了TiO2粒子胶态分散体的薄膜制得。所使用的TiO2粉末是从德国Degussa公司购买的P-25,它是一种含有大约30%金红石和70%锐钛矿的混合物。其平均粒径为25nm,用BET(表面积测定法)测得的比表面积为45m2/g。制得的含水分散体含有20重量%的TiO2,通过添加聚还氧乙烷(弗卢卡分子量为1 000 000)使其稳定。分散体的聚合物重量含量小于TiO2约20倍。利用刮片技术将分散体散布在起集电极作用的铜箔上,以形成4-20微米厚的薄膜。采用60-90℃的干燥空气气流吹除水分。将呈浓缩状的分散体施加在基质上。其稠度由混合物中的水的比例和浇注涂层的环境干燥的效率控制。
在其组合物中含有呈中孔形态形式的电活性材料这种类型的电极,它具有高的储能容量和高功率密度并可应用于主要的和二次电化学发生器。在这一类发生器中使用的电解质优选含有质子或锂离子的那一种。其他的碱金属或碱土金属也可使用。按照一种优选的实施方案,这电解质含有能促使其变成以下一种盐形态的锂离子,这类盐例如四氟硼酸盐,六氟磷酸盐,六氟锑酸盐,六氟砷酸盐,三氟甲基磺酸盐,双三氟磺酰基二酰亚胺,三(三氟磺酰基)甲基化物,三氟甲磺酸盐,三氟醋酸盐,叔氯铝酸盐或全氟丁基磺酸盐。根据优选的实施方案,电解质溶剂是一种非质子或是一种液态盐,例如碳酸亚乙酯,碳酸异丙烯酯,碳酸二甲酯,碳酸二乙酯,二氧戊环,丁内酯,甲氧丙腈,甲氧乙氧丙腈,甲氧二乙氧基丙腈,甲氧乙腈,四氟丙醇或这些溶剂的混合物。本发明的其它优选实施方案采用熔盐作为含盐的锂离子的溶剂,例如甲基乙基咪唑盐,三氟甲磺酸盐或甲基乙基咪唑盐,双三氟磺酰基二酰亚胺,和上述负离子的对应的二甲基乙基咪唑盐。至少一个呈中孔涂层形式的电极所用材料可以是电活性材料,但按照本优选的实施方案,选定这种材料为的是形成含有碱或碱土金属的插入化合物,借此制成二次电化学发生器。这类电活性材料将选自例如过渡金属的氧化物或硫属元素化物或其锂化型或部分锂化型,例如TiO2,Nb2O5,WO3,MoO3,MnO2,LiyMn2O4,HfO2,TiS2,WS2,TiSe2,LiyNiO2,LiyCoO2,Liy(NiCo)O2或SnyO2。按照本发明的优选实施方案,可能是阴极或阳极的某个电极,取决于用作对电极的该电极的电活度,它是由呈锐钛矿或金红石形式的,或由呈这二种多晶型体混合物形式的中孔二氧化钛构成。在有锂离子存在的情况下,呈中孔形式的二氧化钛有形成层间化合物LiyTiO2的倾向,其中插入系数为0.6-0.8之间的某一高值。对于其中y=0.8和由锂金属制成对电极的电池,假如电池电压的平均值是1.5v,在理论上其能量密度是400wh/kg。这样大的容量与高值的比功率高值有关,后者达到的值为2.3kw/kg。用现有生产技术不可能取得这样的结果,例如,W,J,莫克林等人所述的(固态离子型表面活性剂53-56(1992年)P694-700),其中常规TiO2电极的比功率和容量二者都显著地低。
当将还能容许插入锂离子的电活性化合物用作其它电极时,本发明的电化学发生器是“摇椅”型二次(可再充电的)发生器,M,阿芒特首次对其原理作了陈述(先进电池组用的材料,D,W,莫夫等人编辑,Plenum出版社出版,纽约,1980年,P.145)。按照本发明的优选实施方案,摇椅构型使用呈锐钛矿结构形式的TiO2作为阳极材料,而呈非晶形或结晶形的LiyMn2O4用作阴极。由本发明公开的LiyMn2O4(y≤2)材料也是以中孔形态的形式出现,用以生产大容量的阴极,亦即接近于理论上的最大值280Ahkg-1。这样的TiO2/LiyMn2O4摇椅型电池组的总容量高达140Ahkg-1,平均电池电压为2伏,和基于这种材料密度的功率密度为2000-3000w/kg。对于这样的TiO2/LiyMn2O4摇椅型薄层电池构型测得的功率密度为0.5-1.5mw cm-2μm-1。
总的来说,所述电池构型和电池组器件的中孔电极结构还能保证在快速放电过程中改善固体的局部热扩散或热交换,因而能本征地保护电池组的敏感(活性)材料免于性能下降,这是因为使其暴露在极限温度下的情况降至了最低程度。
电极的机械强度由于存在有高分子粘结剂而得以提高,从而产生了中孔网络的结构刚性和坚固性,因此能承受住表面张力,亦即当孔中充满电解质时,在高的局部压力作用下不会破损,最重要的是,能够承受住在摇椅式电池组运行过程中,由于Li+的插入/提取造成的容积膨胀/收缩所引起的应变和机械应力,这点对阴极尤为重要。后者的作用导致改善了结构完整性,从而在电池周期工作中产生增强循环的效能,虽然由于活性材料的衰变和不均匀性(电连接性和导电性降低)使容量衰减至最小程度。因此,由于上述较小尺度的“粒子”或“晶粒”或所述的包含中孔电极的基本结构件的存在,确保了有较好的固相连接性。
粘结剂材料的明智选择,使得可在比较低的重量百分比下,达到所希望的对薄膜的稳定作用变成可能。本文所使用的糊剂配方由超过90重量%的活性材料组成,聚合物的含量少于10重量%。事实是,用含量如此低的聚合物制备的薄膜是稳定的并显示出极好的活度,因为锂离子插入式电极是特别地不平常的。用常规插入方法制得的中孔电极除了要求碳氟聚合物材料外还要大量的碳。这碳能降低薄膜的电阻而这聚合物则起增塑剂作用。这些材料将其重量加到了电池组中,使得电池组的电能密度和功率降低了。本发明能提供保证在没有碳和增塑剂添加物的情况仍能很好地起作用的电极。
本发明的再一个优点就是制造如图4所示的电化学电池的二个电极所用的多孔无机薄膜,能够使其和电化学涂层附着在一起,从而简化了电池的生产
按照本发明的优选实施方案的制备结果形成颗粒状网络,这种网络由于形成了足够的渗透路径而提高了Li+的插入动力。这金属氧化物涂层的密度(和孔隙或未来的无水电解质质量对氧化物质量之比)可以由氧化物分散体的溶剂(例如水)稀释度和所加入的前体溶液的聚集状态(氧化物质量对水之比)来控制。中孔空隙的充分连接性与低的弯曲度相结合,使较低的孔隙度(较高的活性质量对空隙(供电解质之用)之比)仍能对电解质功能亦即Li+扩散性起着很有效的作用。
在电池组器件中,建议采用二个无机电极而不是碳或锂金属的电极使其具有了安全性,因为在前一种情况中实质上消除了爆炸危险。根据上述本发明的优选实施方案,在电池组的设计原理中包含有对安全性的考虑,即只采用对水不敏感的和低毒性的材料制作电极以及电解质。常规的碳电极表面极易起反应,在大电流强度下尤其如此,故要求采取超载保护措施。许多叠层式电化学电池,例如图4所描述的,是用包含有陶瓷纳米材料的组合物制备,并对其电学的和物理的使用适应性进行了试验。以下实例是说明这种制备和应用的。
实例1 含水二氧化钛分散体的制备
从德国FranKfurt am Main;Degussa-Huls AG;购买的24.5g的纳米结晶体TiO2(P-25,主要是锐钛矿),在40℃下将其分散在170g的去离子水中,然后置这混合物于超声波下长达数分钟。接着,通过添加1重量%KOH的水溶液的等分试样,将分散体的pH调整到4.5。重复超声波处理,并添加更多的水以便达到最终重量200g。于是,制得的分散体包含12.5重量%的TiO2。
实例2 用作涂料溶液的糊剂的制备
将按照实例1所述制备的65.04g分散体,在温度40℃下与7.2g的去离子水混合。接着加入7.5重量%的聚乙二醇水溶液(平均分子量为100,000,从瑞士Bachs的弗兰克化学工业公司购得),然后再通过添加水使溶液的总重上升至80g。最后通过超声波处理使溶液均质。
实例3 单层涂层的涂覆
将涂料溶液浇注在薄的铜箔上,而该铜箔则是层压在透明的薄型聚乙烯对苯二酸酯载体上的,浇注在每平方米载体表面上的糊剂填充量为100g。接着,在30℃下使涂敷层干燥60分钟。载体的最终的填充量为10gTiO2/m2和0.4g聚乙二醇/m2。
实例4 重叠涂层的涂覆
将从德国Frankfurt am Main,Degussa-Huls AG处购得的14.5g的AluC(含有96.6重量%的Al2O3)在25℃下弥散于62.9g的去离子水和0.2g的含水乳酸(90重量%)中,在搅拌60分钟后,加入15.4g的聚乙烯醇水溶液(7.5重量%,水解度98-99%,分子量85000-146000,从Aldrich化学制品公司购得)。添加去离子水,以达到最终重量为100g。并利用超声波使溶液均质。
将这涂料溶液在40℃下浇注到按实例3所述方法制备的涂层上,从而产生40g/m2的填充量,然后在30℃干燥这二层重叠涂层达60分钟。不计涂料添加剂,一平方米的涂覆重叠涂层承载4.5gTiO2,0.18g聚乙二醇(PEG),6.04g Al2O3和0.76g聚乙烯醇(PVA)。
实例5
“摇椅”型二次电化学发生器实施方案已由在图4所述的电池构型中分别为TiO2/LiCoO2的正电极和负电极构成。使这中孔涂层置于起集电极作用的导体上。这样一种器件显示出在短路情况下有20C(或C/0.05)的放电率。
根据优选的实施方案,由10微米的每层为上述活性材料的中孔涂层构成的30cm2的电池组电池,它包含30-40微米的纯纤维素纸的隔离层并采用包含甲氧丙腈和双(三氟磺酰)二酰亚氨基锂的电解质,这样的电池组电池被发现能保持10C(或C/0.1)的放电率和维持1.8-1.5V的电池电压,从而导致功率密度在1500W/kg以上和能量密度在210wh/kg以上。
实例6
由纳米级氧化物形成的厚度4μm-20μm的典型电极涂层的孔隙率估计为30%-70%,利用质量对表面面积测量法测定。图5表明包含4.5微米TiO2的多层构型阳极的充电/放电特性,在该阳极上覆盖着按照实例4所述方法制备的中孔氧化铝Al2O3涂层。这样一种电极的总的厚度是9-10μm。
这阳极活性层和隔离层的组合物,即Al2O3/TiO2多层电极是由4.5μm厚的电荷渗透多孔涂层TiO2(p-25)和5μm厚的隔离层(电绝缘但能传导离子)构成,其中TiO2涂层包含4%PEG100K作为粘结剂,而隔离层则含有12.6%PVA作为粘结剂。利用活性涂层的电流聚集器是由层压在PET柔性基质上的铜质薄膜制成。电解质组合物是含有1M双(三氟磺酰)二酰亚氨基锂的碳酸亚乙酯和碳酸异丙烯酯的1∶1重量比的混合物。在图5上描述了电压扫描速率10和20mv/s。
与阳极活性材料相同但没有氧化铝的中孔覆盖层相比,氧化铝涂层的存在增加了Li+插入/提取的充电和放电电流。在任一个或二个电极活性涂层上加上中孔覆盖层,它在阳极和阴极之间起着惰性和电绝缘隔离层作用,在此得到了证实。对于我们非常特殊的系统来说,似乎可以采用使粒径减小到纳米范围并同时保证具有有效的粒子连接性的方法,便可达到比早先材料具有证实了的更高的插入动力的可逆性。在充电和放电过程中,电解质的运作和Li+的迁移得到了增强,从而导致在电解质中有较低的电阻损失和较高的充电率性能。活性材料可视作低电阻同时由于有效的互连性和孔隙结构的形成使其具有增加了电化学可逆性和更大的容量。
实例7
优先动力学也由LiCoO2电极阴极活性涂层(在20μm厚的Al箔集电极上二面有60μm的涂层)和上述按照实例6中的优选实施方案制得的阳极组成的成套电极的组合件得到例证。所述组合件是通过在阴极每一侧各匹配一个阳极来实现的。二个阳极部件存在着电连接,从而形成上述二次电池组的一个电极。充电和放电状况由图7上曲线表明,该图表示整套电池的循环工作特性。在电极表面积为4.5-5cm2的情况下,充电/放电电流是1mA,容量估计为0.6mAh,此时对应的充电和放电率为1.5-2C。电解质组合物是EC∶DMC=1∶1其中包括1M双(三氟磺酰)二酰亚氨基锂。
实例8
利用中孔电极插入式电池能模拟稳态状态下的薄层电池离子迁移状况。这电池构型由二个1mm厚的锂插入中孔基体组成,中间被20um厚的惰性和绝缘的中孔隔板所隔开,其中活性材料涂层之一起插入电极作用,而另一个起反插入(锂提取)电极作用。在一羟基锂盐中的初始电解质的浓度是1M,在与碳酸异丙烯酯情况(3*10-6cm2/s)相对应的电解质中Li+的自由流扩散系数近似为3cP。
在所述模拟结果中,Li+的浓度分布曲线(还有重叠曲线是负离子的浓度分布曲线)表示在图8a上,而当大约6mA/cm2电流流过电池时的电池两端的电压降表示在图8b上,最小电流限制了向插入电极一侧供应Li+的数量。此外没有考虑基体固体的导电性。电极孔隙率是50%,而对于隔离层而言是90%。
厚度大于1000μm(1mm)的任何涂层会增加极限电流。应注意,在这事例中支持电解质的缺乏帮助了锂离子的扩散或迁移,但以电池两端的呈I*R压降形式的电势为代价(如图8b所示,此处正好不足0.2V)。这计算显示,对于上述构型中的厚10μm的电极来说,就电解质的性能而论,电流高达500mA/cm2是可能的。
此外,TiO2/纤维素纸/LiyMn2O4电池,它具有厚度约为10μm的活性中孔涂层,在有熔盐的情况下,在短路时它能输出大于5mA/cm2的电流,这熔盐含有1-2M的双(三氟磺酰)二酰亚氨基锂,它具有比碳酸异丙烯酯时要高得多的粘度(>40CP),因而具有较低的Li+扩散系数。
实例9
根据对电解质的调研和特征观点,通常寻求的特性是低粘度,低挥发性,锂盐电解质的可溶性,和电化学稳定性/与电极材料的化学相容性。用合成法合成离子液体,这离子液体在室温下有着在上述方面的非常引人注意的特性。从表明在图6a上的实例可见,它们的电化学稳定性范围满足4V阴极材料的要求。电势采用其与碘化物/三碘化物的关系表示,即+0.15V对AgCl。二甲基乙基咪唑二酰亚胺提供了最佳阴极稳定性的优点。
可以达到使双(三氟磺酰)二酰亚氨基锂在甲氧基二乙氧基丙腈和在甲氧丙腈中的溶解度大于2M。图6b提供了被电化学窗所证明的这最新合成有机溶剂的电化学稳定性。甲氧丙腈对应的稳定性范围,用粗线表示在这图上,而锂基体TiO2和锰酸锂的使用范围则对照这标尺(二茂铁电势是+0.4v对AgCl)确定在图6c上。
这些分子结构设计成能利用醚类对Li+的强溶剂化特性,并与这些化合物的低粘度和比较高的沸点结合起来,低的粘度有利于Li+的扩散,而较高的沸点能降低挥发度。粘度为2.7cP的甲氧乙氧丙腈也已合成,而甲氧丙腈显示粘度为1.1cP和甲氧乙氧丙腈为5cP。它们的沸点在10mm Hg时分别为240℃,165℃和152℃。
实例10
用TiO2/LiyMn2O4分别作负电极和正电极的“摇椅”型二次电化学发生器按图5所述制得,只是隔离层(图5中序号3)是由8微米厚的和孔隙率为60%的中孔二氧化锆涂层制成。这二氧化锆涂层是根据P.伯霍特等人在物理化学杂志(B)(1998)102,P1498-1507上所述制备,显示的性能特征与实例5中所公开的氧化铝的那些特征相一致。
但是,对于注入了电解质的组合式电池,这中孔隔离层对于电解质的渗透和在中孔内的留置是有利的。所以,总的说来,在充电/放电运作过程中,电解质在电池的有效留置采用了和通过电解质的注入将气体从上述电池的空隙中排出一样的作用原理。此外,为了有效的适应充电/放电循环过程中容积的变化,中孔电极隔离层计及了电解质的移动,但是,迫使气体从电池涂层(图5上序号1,2,3)排出是利用了液体电解质注入中孔产生的毛细管作用。
实例11 柔性电化色显示器
由互连半导体TiO2纳米晶体(平均粒径15nm)网络组成的透明中孔电极,被置于按照实例3所述方法制得的透明导电聚合物(聚酯,其上覆盖有氧化铟锡)上。TiO2薄膜厚4微米。因为这氧化物晶体的小尺度是处于纳米量极,所以这薄膜具有非常大的内表面积。4微米厚的涂层的粗糙因数接近约500。由纳米晶状Al2O3粒子(粒径约为20nm)组成的厚5-10微米的第二多孔绝缘薄膜被置于按照实例4所述制备的第一涂层的上层。将这薄膜浸入溶解于乙醇中的N-甲基,N′-羟基丙基紫罗碱的2*10-4M溶液中达2小时,以便使紫罗碱衍生物的分子层吸附在TiO2纳米晶体的表面上。紫罗碱起电子中继作用。它在氧化状态下呈无色而在还原状态下它转变成兰色。类似地,将由互连导电SnO2纳米晶体(平均粒径10nm)网络组成的中孔电极置于按照实例3所述方法制得的透明导电聚合物(聚酯,其上覆盖有氧化铟锡)上。SnO2涂层厚5微米。因为这氧化物晶体的小尺寸处于纳米量极。所以这薄膜具有非常大的内表面积。5微米厚的涂层的粗糙因数接近约750。将这薄膜磷酸化吩噻嗪中2小时,其结构在下面给出。在这些条件下,吩噻嗪在SnO2纳米晶体表面上自组合成分子涂层。吩噻嗪也起电子中继作用。它在还原状态下呈无色,而在氧化状态下它转变成兰色。
无色 红色
在把室温下的熔盐电解质N-甲基,N-乙基-咪唑bistrif1ylimide注入二薄膜的孔隙容积内之后,用层叠方式将它们层压成电化学电池并加以密封。采用1.2V的电位差加到二电极上的方法使这器件在小于1秒钟的时间内,从无色转换成深色状态(光学吸光度处在接近1的可见范围内),从而导致在阴极上紫罗碱发生还原作用而在阳极上吩噻嗪发生氧化作用。使电势反转便能使薄膜的颜色脱色。这循环可重复数千次而性能不会有显著降低。此外在显色之后,在开路状态下,存储效应寿命可达500s以上。
引用的参考资料
1.P.巴伯克思,J.M.特瑞思肯和F.K.席库海,固态化学杂志94[1]P185-196(1991)
2.C.巴律盖,A.卡勒罗,J.摩洛勒斯和J.L.特雷多,活性固体,7,P263-271(1989)
Claims (31)
1.一种电极,它包括:
(a)一种电极活性材料,采用氮的解吸等温线孔隙率法测出其显示出中孔孔隙率,其中所述电极活性材料包括含有电极活性材料的纳米粒子或者含有电极活性材料的纳米粒子和微粒子的离散固体接触状颗粒,所述电极活性材料选自非过渡金属或过渡金属的氧化物,硫属元素化物,氢氧化物,羟基氧化物,含氧酸,氧基氢化物或硫氰酸,或选自周期元素表的族IB,IIA,IIB,IIIA,IVA,IVB,VA,VB,VIB,VIIB和VIII元素的锂化或局部锂化形式,和它们的混合物;
(b)可固化的有机粘结剂;和
(c)一种与电极活性材料的操作有关的导电装置。
2.权利要求1的电极,其中所述电极活性材料包含双峰粒径分布的粒子,包含至少10重量%的平均粒径小于50nm的纳米粒子和粒径大于50nm的微粒子,它们的比表面积为0.1m2/g-500m2/g。
3.权利要求1或2的电极,其中所述电极活性材料不含微粒子,而含有纳米粒子,这些纳米粒子显示出电化学活度和呈现由基本上为均匀尺寸的粒子形式的六角或立方阵列。
4.权利要求1或2的电极,其中所述可固化有机粘结剂粒子使用量为所述电极活性材料的粒子的0.5重量%-10重量%,这种粘结剂包含具有玻璃化转变温度至少为50℃的高分子材料。
5.权利要求4的电极,其中所述可固化有机粘结剂粒子使用量为所述电极活性材料的粒子的1重量%-5重量%。
6.权利要求4的电极,其中可固化有机粘结剂的高分子材料选自聚偏氟乙烯,聚四氟乙烯,氟橡胶,聚乙烯聚合物,聚酰胺,聚氨酯类;乙烯丙烯酸(EAA)共聚物,乙烯甲基丙烯酸(EMAA)共聚物,聚乙烯(PE),聚丙烯(PP),乙烯丙烯二烯三元共聚物(EPDM),聚环氧烷,聚丁烯,离子化交联乙烯甲基丙烯酸共聚物,乙烯正丙烯酸丁酯(EnBA)聚合物,乙烯醋酸乙烯酯(EVA)聚合物,乙烯丙烯酸乙酯(EEA)共聚物,乙烯丙烯酸甲酯(EMA)共聚物,双烯丙基靛酚二酰亚胺或烯丙基靛酚二酰亚胺,聚砜类,聚醚砜类,聚酰亚胺类,聚酰胺-酰亚胺类,环氧树脂类,聚亚芳基醚酮类,聚丙烯腈,丁腈橡胶,二元乙丙橡胶,丁苯橡胶,聚醚二酰亚胺,聚苯乙烯,氯甲基化聚醚砜类,丙烯酰化聚醚砜类,聚甲基丙烯酸甲酯,聚硫橡胶,氰乙基纤维素,甲基纤维素,及其低聚物和混合物;或其前体,选自噻吩,亚苯基,吡咯,乙炔,异硫茚,苯胺,亚乙基二羟基噻吩,亚苯基亚乙烯基和丙烯腈,和它们的非掺杂的、掺杂的、和取代的衍生物和它们的共聚物。
7.权利要求1或2的电极,其中所述可固化的有机粘结剂可以进一步与电子导电材料相混合或用电子导电材料取代,上述电子导电材料取自非掺杂的、或掺杂的本征导电聚合物,聚噻吩,聚亚苯基,聚吡咯,聚乙炔,聚异硫茚,聚苯胺,聚乙烯二羟基噻吩(PEDOT),聚亚苯基亚乙烯基,由丙烯腈、形成的导电梯形聚合物,所述导电梯形聚合物的取代衍生物和所述导电梯形聚合物的共聚物,导电粒子,炭黑,碳和石墨化碳及石墨的细颗粒,乙炔黑,碳晶须,碳素纳米微管,富勒烯,高导电胶态金属和掺杂金属氧化物,上述金属的合金,金属纳米纤维;和其混合物。
8.权利要求1或2的电极,其中导电装置置于由塑性材料制成的载体上。
9.权利要求1或2的电极,其中所述电极活性材料可采用固熔体取代方法进行掺杂,其中0.2%~49%的非过渡金属或过渡金属的原子被选自元素周期中族IB,IIB,IIIA,IVA,IVB,VA,VB,VIB,VIIB和VIII元素之其它过渡金属或非过渡金属及其混合物所取代。
10.权利要求1或2的电极,其中电极活性材料可以通过在其上吸附增感染料,氧化还原发色团,或电荷转移敏化剂的方法加以改性。
11.一种电化学电池,它包含权利要求1定义的一个或多个电极。
12.权利要求11的电化学电池,其中这一个或每个电极的电极活性材料包含纳米粒子,这些纳米粒子组合成离散接触状粒子,以便形成含有电互连固态相材料的中孔网状三维双连结构,而该结构则与用以包含电解质的粒间互连空间相接触。
13.权利要求11的电化学电池,它包含一个正电极和一个负电极,其中正电极和/或负电极的电极活性层还包含一层惰性层,用作多孔隔离层以防止正负电极直接接触和短路。
14.权利要求13的电化学电池,其中所述隔离层由绝缘陶瓷材料形成。
15.权利要求13的电化学电池,其中所述隔离层由Al2O3,SiO2,硅烷化二氧化硅,ZrO2,Ta2O5或LiLa0.35Ti0.55O3形成。
16.权利要求13的的电化学电池,其中多孔隔离层另外还包含可固化的有机粘结剂。
17.权利要求16的电化学电池,其中所述可固化有机粘结剂包含具有玻璃化转变温度至少为50℃的高分子材料。
18.权利要求17的电化学电池,其中可固化有机粘结剂的高分子材料选自聚偏氟乙烯,聚四氟乙烯,氟橡胶,聚乙烯聚合物,聚酰胺,聚氨酯类;乙烯丙烯酸(EAA)共聚物,乙烯甲基丙烯酸(EMAA)共聚物,聚乙烯(PE),聚丙烯(PP),乙烯丙烯二烯三元共聚物(EPDM),聚环氧烷,聚丁烯,离子化交联乙烯甲基丙烯酸共聚物,乙烯正丙烯酸丁酯(EnBA)聚合物,乙烯醋酸乙烯酯(EVA)聚合物,乙烯丙烯酸乙酯(EEA)共聚物,乙烯丙烯酸甲酯(EMA)共聚物,双烯丙基靛酚二酰亚胺或烯丙基靛酚二酰亚胺,聚砜类,聚醚砜类,聚酰亚胺类,聚酰胺-酰亚胺类,环氧树脂类,聚亚芳基醚酮类,聚丙烯腈,丁腈橡胶,二元乙丙橡胶,丁苯橡胶,聚醚二酰亚胺,聚苯乙烯,氯甲基化聚醚砜类,丙烯酰化聚醚砜类,聚甲基丙烯酸甲酯,聚硫橡胶,氰乙基纤维素,甲基纤维素,及其低聚物和混合物;或其前体,选自噻吩,亚苯基,吡咯,乙炔,异硫茚,苯胺,亚乙基二羟基噻吩,亚苯基亚乙烯基和丙烯腈,和它们的非掺杂的、掺杂的、和取代的衍生物和它们的共聚物。
19.权利要求16或17的电化学电池,其中所述可固化的有机粘结剂可以进一步与电子导电材料相混合或用其取代,上述电子导电材料取自非掺杂的、或掺杂的本征导电聚合物,聚噻吩,聚亚苯基,聚吡咯,聚乙炔,聚异硫茚,聚苯胺,聚乙烯二羟基噻吩(PEDOT),聚亚苯基亚乙烯基,由丙烯腈、形成的导电梯形聚合物,所述导电梯形聚合物的取代衍生物和所述导电梯形聚合物的共聚物,导电粒子,炭黑,碳和石墨化碳及石墨的细颗粒,乙炔黑,碳晶须,碳素纳米微管,富勒烯,高导电胶态金属和掺杂金属氧化物,上述金属的合金,金属纳米纤维;和其混合物。
20.权利要求11或12的电化学电池,其呈高功率离子插入式电池组形式;或高功率超电容器形式;或混合式电池形式,所述混合式电池含有超电容器式电极和离子插入式电池组型电极。
21.权利要求11或12的电化学电池在光生伏打电池中、或在电致变色装置中、或在能够双相地传输电流的离子插入式电池组中的应用。
22.权利要求1的电极的制备方法,该方法包括提供一种电极活性材料的胶态分散体,将所述分散体与可固化的有机粘结剂相混合,然后在5℃-60℃的温度下,将所得混合物沉积在载体上,以生成电极活性层,随后将上述活性层在比制备分散体的液体的沸腾温度低的温度下进行干燥。
23.权利要求22的方法,还包含将惰性绝缘隔离层材料置于所述电极活性层上,所述隔离层材料包含或者不包含可固化的有机粘结剂。
24.权利要求22的方法,还包含固化存在于电极活性层中的粘结剂的步骤。
25.权利要求23的方法,还包含固化存在于隔离层材料中的粘结剂的步骤。
26.权利要求24或25的方法,其中所述粘结剂是采用电磁辐射和/或紫外线辐射和臭氧和/或加热方法来固化的。
27.权利要求24或25的方法,其中所述粘结剂是在70℃-240℃的温度下加热来固化的。
28.权利要求24或25的方法,其中所述粘结剂是在90℃-170℃的温度下加热来固化的。
29.权利要求22或23的方法,其中在浇注电极活性材料之后或者在浇注电极活性材料和隔离层材料之后,采用施压的方法。
30.权利要求22或23的方法,另外还包含采用涂覆方法为中孔电极涂以导电金属或金属氧化层。
31.权利要求30的方法,其中所述涂覆方法选自蒸发法,溅镀法,金属粉末喷吵法和金属粉末印刷法。
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KR20030093252A (ko) | 2003-12-06 |
EP1374325A2 (en) | 2004-01-02 |
EP1244168A1 (en) | 2002-09-25 |
CN1520620A (zh) | 2004-08-11 |
US20040131934A1 (en) | 2004-07-08 |
AU2002242732B2 (en) | 2007-07-19 |
WO2002075826A3 (en) | 2002-12-19 |
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