CN102881461A - 包含由胶状分散体形成的涂层的固体电解电容器 - Google Patents
包含由胶状分散体形成的涂层的固体电解电容器 Download PDFInfo
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- CN102881461A CN102881461A CN2012100604619A CN201210060461A CN102881461A CN 102881461 A CN102881461 A CN 102881461A CN 2012100604619 A CN2012100604619 A CN 2012100604619A CN 201210060461 A CN201210060461 A CN 201210060461A CN 102881461 A CN102881461 A CN 102881461A
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- electrolytic capacitor
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
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Abstract
本发明涉及一种固体电解电容器,包括一阳极体、一层覆盖在阳极体上的介质层、一种覆盖在介质层上的固体电解质和一种覆盖在固体电解质上的胶粒涂层。所述涂层是由一种胶粒分散体形成的。分散体胶粒包括至少两种不同的聚合物成分–即导电聚合物和胶乳聚合物。这种涂料的一个优点是由于胶乳聚合物具有相对较软的性质,有助于在封装期间机械稳定电容器。这有助于限制固体电解质的剥离及电容器形成期间否则可能发生的任何其它损害。此外,胶乳聚合物还可以增强胶粒在有些应用中需要的水介质中的分散能力。
Description
技术领域
本发明涉及一种固体电解电容器,特别涉及一种包含由胶状分散体形成的涂层的固体电解电容器。
背景技术
固体电解电容器(如钽电容器)对电子电路的微型化做出了重要贡献,并且使这种电路可以在极端环境中使用。传统固体电解电容器通常通过在金属引线周围压制金属粉末(如钽)、烧结压制部件、对烧结阳极进行阳极氧化,然后涂上一层固体电解质而形成。固体电解质层可由导电聚合物(如聚3,4-乙烯基二氧噻吩)形成,例如,Sakata等人的专利号为5,457,862、Sakata等人的专利号为5,473,503、Sakata等人的专利号为5,729,428的美国专利和Kudoh等人的专利号为5,812,367的美国专利中有所描述。这些电容器的导电聚合物电解质常规通过将其顺序浸渍到包含聚合物层各组分的单独溶液中而形成。例如,用于形成导电聚合物的单体通常在一种溶液中涂覆,而催化剂和掺杂剂在另一种单独的溶液或几种溶液中涂覆。然而,这种技术的一个问题是通常很难获得相对较厚的固体电解质而且成本很高,固体电解质厚度大有助于实现良好的机械强度和电气性能。此外,这些聚合物还会在电容器封装期间与部件剥离,对电气性能造成不良影响。为了解决这个问题,人们进行了种种尝试。例如,Merker等人的美国专利US 6,987,663描述了使用一种覆盖固体电解质表面的聚合物外层。遗憾的是,这种技术仍然存在问题,聚合物外层与固体电解电容器通常采用的端接固体电解电容器的石墨/银层之间很难实现良好的粘附。此外,这种聚合层很难在水介质中分散,而在某些应用中需要使用水介质。
因此,需要提供一种具有良好的机械强度和电气性能的固体电解电容器。
发明内容
本发明的一个实施例公开了一种固体电解电容器,其包括一阳极体、一层覆盖在阳极体上的介质层、一层覆盖在介质层上的固体电解质和一层覆盖在固体电解质上的胶粒涂层(colloidal particle coating)。所述涂层是由包含至少一种导电聚合物和至少一种胶乳聚合物的胶粒分散体形成。
在本发明的另一个实施例中,其公开了一种形成固体电解电容器的方法。所述方法包括对阳极体进行阳极氧化;在所述阳极氧化的阳极体上涂覆一层固体电解质;然后,在所述固体电解质上涂覆一层胶粒涂层。所述胶粒涂层是由包含至少一种导电聚合物和至少一种胶乳聚合物的胶粒分散体形成。
本发明的其它特点和方面将在下文进行更详细的说明。
附图说明
本发明的完整和具体说明,包括对于本领域技术人员而言的最佳实施方式,将结合附图和附图标记在具体实施方式中作进一步描述,在附图中,同一附图标记表示相同或者相似部件。其中:
图1是本发明固体电解电容器的一个实施例的剖视图;
图2是本发明可以使用的“核-壳”颗粒形态的一个实施例的分解示意图;及
图3是本发明可以使用的微凝胶粒子形态的一个实施例的示意图。
具体实施方式
对于本领域技术人员来说,下面的内容仅作为本发明的具体实施方式,并不是对本发明保护范围的限制。
总的来说,本发明涉及一种固体电解电容器,所述固体电解电容器包括一阳极体、一层覆盖在所述阳极体上的介质层、一层覆盖在所述介质层上的固体电解质和一层覆盖在所述固体电解质上的胶粒涂层。所述涂层是由一种胶粒分散体形成的。所述胶粒分散体包括至少两种不同的聚合物成分-即导电聚合物和胶乳聚合物。这种涂层的一个优点是由于胶乳聚合物具有相对较软的性质,有助于在封装期间机械稳定电容器。这有助于限制固体电解质的剥离及电容器形成期间可能发生的任何其它损害。此外,胶乳聚合物还可以增强胶粒在有些应用中需要使用的水介质中的分散能力。
下面将更为详细地说明本发明的各种实施例。
I.阳极体
阳极体可采用荷质比较高的阀金属组合物形成,如大约40,000μF*V/g或更高,在一些实施例中,大约50,000μF*V/g或更高,在一些实施例中,大约60,000μF*V/g或更高,在一些实施例中,大约70,000-700,000μF*V/g。阀金属组合物包含一种阀金属(即能够氧化的金属)或阀金属基的化合物,如钽、铌、铝、铪、钛及它们的合金、它们的氧化物、它们的氮化物等。例如,阀金属组合物可以包含一种铌的导电氧化物,如铌氧原子比为1∶1.0±1.0的铌的氧化物,在一些实施例中,铌氧原子比为1∶1.0±0.3,在一些实施例中,铌氧原子比为1∶1.0±0.1,在一些实施例中,铌氧原子比为1∶1.0±0.05。例如,铌的氧化物可以是NbO0.7、NbO1.0、NbO1.1和NbO2。在优选的实施例中,组合物包含NbO1.0,这是一种导电的氧化铌,即使在高温烧结后仍能保持化学稳定。这种阀金属氧化物的实例在Fife的专利号为6,322,912的美国专利中、Fife等人的专利号为6,391,275的美国专利中、Fife等人的专利号为6,416,730的美国专利中、Fife的专利号为6,527,937的美国专利中、Kimmel等人的专利号为6,576,099的美国专利中、Fife等人的专利号为6,592,740、Kimmel等人的专利号为6,639,787、Kimmel等人的专利号为7,220,397的美国专利中,及Schnitter的申请公开号为2005/0019581的美国专利申请中、Schnitter等人的申请公开号为2005/0103638的美国专利申请中及Thomas等人的申请公开号为2005/0013765的美国专利申请中均有所描述,对于所有目的以上专利均以全文的形式引入到本专利中作为参考。
通常可以采用常规的制造程序来形成阳极体。在一个实施例中,首先选择具有某种粒径的氧化钽或氧化铌粉末。例如,颗粒可以是片状、角状、节状及上述混合体或者变体。颗粒的筛分粒度分布至少为大约60目,在一些实施例中为大约60目到大约325目,一些实施例中为大约100目到大约200目。另外,比表面积大约是0.1-10.0m2/g,在一些实施例中,是大约0.5-5.0m2/g,在一些实施例中,大约是1.0-2.0m2/g。术语“比表面积”是指按照《美国化学会志》1938年第60卷309页上记载的Bruanauer、Emmet和Teller发表的物理气体吸附法(B.E.T.)测定的表面积,吸附气体为氮气。同样,体积(或者斯科特)密度一般大约为0.1-5.0g/em3,在一些实施例中大约为0.2-4.0g/cm3,一些实施例中大约为0.5-3.0g/em3。
为了便于制造阳极体,在导电颗粒中还可以加入其它组分。例如,导电颗粒可选择性的与粘结剂(binder)和/或润滑剂混合,以保证在压制成阳极体时各颗粒彼此适当地粘结在一起。合适的粘结剂包括樟脑、硬脂酸和其它皂质脂肪酸、聚乙二醇(Carbowax)(联合碳化物公司)、甘酞树脂(Glyptal)(美国通用电气公司)、萘、植物蜡以及微晶蜡(精制石蜡)、聚合物粘结剂(例如聚乙烯醇、聚(乙基-2-噁唑啉)等)。粘结剂可在溶剂中溶解和分散。溶剂实例包括水、醇等。使用粘结剂和/或润滑剂时,其百分含量大约为总重量的0.1%-8%。然而,应该理解的是,本发明并不要求使用粘结剂和润滑剂。
得到的粉末可以采用任一种常规的粉末压模压紧。例如,压模可为采用单模具和一个或多个模冲的单站压模。或者,还可采用仅使用单模具和单个下模冲的砧型压模。单站压模有几种基本类型,例如,具有不同生产能力的凸轮压力机、肘杆式压力机/肘板压力机和偏心压力机/曲柄压力机,例如可以是单动、双动、浮动模压力机、可移动平板压力机、对置柱塞压力机、螺旋压力机、冲击式压力机、热压压力机、压印压力机或精整压力机。如果需要的话,在压制后,可在某一温度(例如,大约150℃-大约500℃)、真空条件下对颗粒加热几分钟,脱除任何粘结剂/润滑剂。或者,也可将颗粒与水溶液接触而脱除粘结剂/润滑剂,如Bishop等人的专利号为6,197,252的美国专利所述,对于所有目的该专利以全文的形式引入本专利中作为参考。
压制阳极体的厚度相对较薄,例如大约等于或小于4毫米,在一些实施例中,大约为0.05-2毫米,在一些实施例中,大约为0.1-1毫米。也可以选择阳极体的形状,以改善电容器的电气性能。例如,阳极体可以是弧形、正弦曲线形状、矩形、U-形、V-形等。所述阳极体还可以为“槽”形,槽内包括一个或多个沟槽、凹槽、低洼或者凹陷,以增加表面积-体积比,最大程度地降低ESR并延长电容的频率响应。此类“槽”形阳极,例如,在Webber等人的专利号为6,191,936的美国专利中、在Maeda等人的专利号为5,949,639的美国专利中;和Bourgault等人的专利号为3,345,545的美国专利中,以及在Hahn等人的公开号为2005/0270725的美国专利申请中进行了描述,对于所有目的以上全部专利均以全文的形式引入本专利中作为参考。
如果需要的话,还可将一阳极引线与阳极体连接。阳极引线可以是线状、片状等,可以采用阀金属化合物,如钽、铌、铌的氧化物等形成。所述引线的连接可采用任何已知的技术完成,例如将引线焊接到阳极体上或在阳极体形成期间将引线嵌入阳极体内。
II.介质层
阳极体可以进行阳极氧化,以在阳极上面和/或内部形成一层介质层。阳极氧化是一种电化学过程,通过阳极氧化,阳极被氧化而形成一种介电常数相对较高的材料。例如,钽阳极可经阳极氧化变为五氧化二钽(Ta2O5)。一般来说,阳极氧化首先是在阳极上涂覆一种电解质,例如将阳极浸到电解质中。电解质通常为液体,如溶液(如水溶液或非水溶液)、分散体、熔体等。电解质中通常使用溶剂,比如水(如去离子水);醚(如二乙醚和四氢呋喃);醇(如甲醇、乙醇、正丙醇、异丙醇和丁醇);甘油三酯;酮(例如,丙酮、甲基乙基酮和甲基异丁基酮);酯(例如,乙酸乙酯、乙酸丁酯、二乙二醇乙醚乙酸酯、丙二醇甲醚乙酸酯);酰胺(例如,二甲基甲酰胺、二甲基乙酰胺、二甲基辛/癸脂肪酸酰胺和N-烷基吡咯烷酮);腈(如乙腈、丙腈、丁腈和苄腈);亚砜或砜(例如,二甲亚砜(DMSO)和环丁砜);等等。溶剂大约占电解质的50wt%-99.9wt%,在一些实施例中大约占75wt%-99wt%,在一些实施例中大约占80wt%-95wt%。虽然并不要求,但是,为了获得所需的氧化物,通常使用水溶剂(如水)。实际上,水大约占电解质中所用溶剂的50wt%或更多,在一些实施例中,大约占70wt%或更多,在一些实施例中大约占90wt%-100wt%。
电解质是离子导电的,其在温度25℃测定的离子电导率大约是1毫西/厘米(“mS/cm”)或更高,在一些实施例中,大约是30mS/cm或更高,在一些实施例中,大约是40mS/cm-100mS/cm。为了增强电解质的离子电导率,可以采用在溶剂中能够离解而形成离子的化合物。适用于此目的的合适的离子化合物包括,例如,酸,如盐酸、硝酸、硫酸、磷酸、多磷酸、硼酸(boric acid)、有机硼酸(boronic acid)等;有机酸,包括羧酸,如丙烯酸、甲基丙烯酸、丙二酸、琥珀酸、水杨酸、磺基水杨酸、己二酸、马来酸、苹果酸、油酸、五倍子酸、酒石酸、柠檬酸、甲酸、乙酸、乙醇酸、草酸、丙酸、邻苯二甲酸、间苯二甲酸、戊二酸、葡糖酸、乳酸、天冬氨酸、谷氨酸、衣康酸、三氟乙酸、巴比妥酸、肉桂酸、苯甲酸、4-羟基苯甲酸、氨基苯甲酸等;磺酸,例如甲磺酸、苯磺酸、甲苯磺酸、三氟甲磺酸、苯乙烯磺酸、萘二磺酸、羟基苯磺酸、十二烷基磺酸、十二烷基苯磺酸等;聚合物酸,例如,聚(丙烯酸)或聚(甲基丙烯酸)及它们的共聚物(例如,马来酸-丙烯酸共聚物、磺酸-丙烯酸共聚物、苯乙烯-丙烯酸共聚物)、角叉菜酸、羧甲基纤维素、藻酸等。选择离子化合物的浓度,以获得需要的离子电导率。例如,酸(如磷酸)可以占电解质的大约0.01wt%-5wt%,在一些实施例中占大约0.05wt%-0.8wt%,在一些实施例中占大约0.1wt%-0.5wt%。如果需要,电解质中还可以使用离子化合物的混合物。
电流通过电解质,形成介质层。电压值控制介质层的厚度。例如,一开始以恒电流模式建立电源供应,直到达到需要的电压。然后,可将电源供应切换到恒电位模式,以确保在阳极表面形成需要厚度的介质层。当然,也可以采用人们熟悉的其它方法,如脉冲或阶跃恒电位法。电压通常大约是4V-200V,在一些实施例中,大约是9V-100V。在阳极氧化期间,电解质可保持在较高温度,如大约30℃或更高,在一些实施例中,大约40℃-200℃,在一些实施例中,大约50℃-100℃。阳极氧化还可在室温或更低温度下进行。所得到的介质层可在阳极表面形成或在阳极孔内形成。
III.固体电解质
如上所述,固体电解质覆盖在介质层上,通常作为电容器的阴极。固体电解质可以采用本领域熟知的各种材料制造,如无机材料(如二氧化锰)或有机材料(如导电聚合物、7,7′,8,8′-四氰基对二次甲基苯醌(7,7′,8,8′-tetracyanoquinodimethane)(“TCNQ”)络合物等)。在一个具体实施例中,采用一种导电聚合物作为固体电解质。一般来说,此类导电聚合物是π-共轭的,并在氧化或还原后具有本征导电性,例如,氧化后电导率至少大约为1μS·cm-1。此类π-共轭的导电聚合物的实例包括,例如,聚杂环类(例如聚吡咯、聚噻吩、聚苯胺等)、聚乙炔、聚-对苯撑、聚苯酚盐等。
尤其适合的导电聚合物是取代聚噻吩,下文将更详细地对其进行说明。此类取代聚噻吩可在氧化催化剂存在下由噻吩单体化学聚合而形成。氧化催化剂可以采用过渡金属盐,如包含铵、钠、金、铁(III)、铜(II)、铬(VI)、铈(IV)、锰(IV)、锰(VII)或钌(III)阳离子的无机或有机酸盐。尤其适合的过渡金属盐包括卤化物(如FeCl3或HAuCl4);其它无机酸盐(如Fe(C1O4)3、Fe2(SO4)3、(NH4)2S2O8或Na3Mo12PO40);有机酸盐和包含有机基的无机酸盐。带有机基团的无机酸盐实例包括,例如,C1-C20烷醇的硫酸单酯铁(III)盐(如月桂基硫酸铁(III)盐)。同样,有机酸盐实例包括,例如,C1-C20烷基磺酸(例如,甲烷磺酸、乙烷磺酸、丙烷磺酸、丁烷磺酸或十二烷基磺酸)铁(III)盐;脂肪族全氟磺酸(如三氟甲烷磺酸、全氟丁烷磺酸或全氟辛烷磺酸)铁(III)盐;脂肪族C1-C20羧酸(如2-乙基己基羧酸)铁(III)盐;脂肪族全氟羧酸(如三氟乙酸或全氟辛酸)铁(III)盐;选择性地被C1-C20烷基取代的芳香族磺酸(如苯磺酸、邻-甲苯磺酸、对-甲苯磺酸或十二烷基苯磺酸)铁(III)盐;环烷烃磺酸(如樟脑磺酸)铁(III)盐等。也可以使用上文提到的这些盐的混合物。
如果需要的话,单体可在前体溶液中进行聚合。溶液中可以使用溶剂(如极性质子溶剂或非极性溶剂),例如,水、二醇(如乙二醇、丙二醇、丁二醇、三甘醇、己二醇、聚乙二醇、乙氧基二甘醇、二丙二醇等);乙二醇醚(如甲基乙二醇醚、乙基乙二醇醚、异丙基乙二醇醚等);醇(例如,甲醇、乙醇、正丙醇、异丙醇和丁醇);酮(例如,丙酮、甲基乙基酮和甲基异丁基酮);酯(例如,乙酸乙酯、醋酸丁酯、二乙二醇乙醚乙酸酯、丙二醇甲醚乙酸酯、碳酸乙二酯、碳酸丙二酯等);酰胺(例如,二甲基甲酰胺、二甲基乙酰胺、二甲基辛/癸脂肪酸酰胺和N-烷基吡咯烷酮);亚砜或砜(例如,二甲亚砜(DMSO)和环丁砜);酚类化合物(如甲苯、二甲苯等)等。水是尤其适合用于反应的溶剂。采用溶剂时,前体溶液中溶剂总含量占大约40wt%-90wt%,在一些实施例中占大约50wt%-85wt%,在一些实施例中占大约60wt%-80wt%。
噻吩单体的聚合通常在温度大约10℃-100℃的条件下进行,在一些实施例中,在大约15℃-75℃的条件下进行。反应结束后,可采用已知的过滤技术脱除任何盐类杂质。为了提纯分散体,还可以采用一个或多个清洗步骤。
可以采用各种方法将固体电解质涂覆在阳极部件上面。在一个实施例中,氧化剂和单体前体或者顺序涂覆或者一起涂覆,使聚合反应在部件上原位进行。用于形成一层导电聚合物涂层的合适的涂覆技术包括丝网印刷、浸渍、电泳涂装和喷涂等。举例来说,单体前体(如3,4-乙烯基二氧噻吩)可以首先与氧化剂混合形成溶液。一种合适的氧化剂是甲苯磺酸铁(III)CLEVIOSTM C。CLEVIOSTM C是CLEVIOSTM M的商业催化剂,其中CLEVIOSTM M是PEDT单体3,4-乙烯基二氧噻吩。一旦形成混合物,则可将阳极部件浸入到溶液中,这样,在阳极部件表面形成聚合物。或者,氧化剂和前体也可以分别涂覆到阳极部件上。在一个实施例中,例如,氧化剂可以溶解在有机溶剂(例如,丁醇)中,然后,以浸渍溶液的形式涂覆到阳极部件上。然后,干燥阳极部件,脱除其上面的溶剂。然后,将阳极部件浸到包含合适单体的溶液中。
除原位涂覆外,固体电解质还可以预聚合的固体导电聚合物颗粒分散体的形式涂覆到部件上。虽然其粒径可以不同,但是,一般要求粒径较小,以增加粘附到阳极部件上的表面积。例如,颗粒平均粒径大约为1-200纳米,在一些实施例中大约为2-100纳米,在一些实施例中大约为4-50纳米。颗粒的直径可采用人们已知的方法测定,如超速离心法、激光衍射法等。颗粒的形状同样可以有所不同。例如,在一个具体的实施例中,颗粒为球形。然而,应该理解的是,本发明也预计到有其它形状,如板状、棒状、盘状、柱状、管状、不规则形状等。分散体中颗粒的浓度可以根据要求的分散体粘度和分散体涂覆到电容器上的具体方式而不同。然而,一般来说,颗粒占分散体的大约0.1wt%-10wt%,在一些实施例中占大约0.4wt%-5wt%,一些实施例中占大约0.5wt%-4wt%。
如果需要的话,可形成一层或多层固体电解质。不管所采用的层数多少,固体电解质可选择性地在涂覆到阳极部件上后进行愈合。愈合可以在固体电解质层每次涂覆之后进行或在所有涂层涂覆完成之后进行。在一些实施例中,例如,固体电解质可通过将颗粒浸入到电解质溶液,例如,酸溶液中,然后,对溶液施加恒定的电压,直到电流降低到预定的水平进行愈合。必要时,这种愈合可在多个步骤中完成。在涂布上述一些层或所有层后,必要时,可清洗颗粒,除去各种副产品、多余氧化剂等。此外,在某些情况下,在上述某些或全部浸渍操作后可进行干燥。例如,在涂覆氧化剂和/或清洗颗粒后,可能需要干燥,以打开颗粒的孔,使它在后面的浸渍步骤中能够接收液体。
IV.胶粒涂层
如上所述,电容器还包含一种导电的胶粒涂层。胶粒涂层包括至少两种不同的聚合物成分-即导电聚合物和胶乳聚合物。适合在胶粒分散体中使用的胶乳聚合物通常是在引发剂、表面活性剂等的存在下在分散介质(如水)中由一种或多种单体通过乳液聚合制备而成。乳液聚合通常为一步工艺或多步工艺。用于形成胶乳聚合物的单体可以是乙烯属不饱和单体。单乙烯属不饱和单体(monoethylenicallyunsaturated monomer)尤其适合用于本发明。
在一个具体实施例中,胶乳聚合物是由两种或多种非离子单乙烯属不饱和单体形成的共聚物。合适的此类单体类型是不包含活性官能团的离子单体,如苯乙烯、α-甲基苯乙烯、对-甲基苯乙烯、叔丁基苯乙烯等。当然,本发明也可以采用包含至少一种官能团(如羟基、羧基、酰胺基、胺基等)的非离子单体。这种官能单体的一个优点是它们能够在乳液聚合期间进一步反应。示例非离子型官能单体可以包括(甲基)丙烯酸酯,如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸二烯丙酯、(甲基)丙烯酸异丙烯酯等;羟基(甲基)丙烯酸酯,如(甲基)丙烯酸羟基丁烯酯等;烷氧基(甲基)丙烯酸酯,如乙酰乙酸基(甲基)丙烯酸乙酯、甲氧基丁烯基(甲基)丙烯酸酯等;甲基丙烯酰胺,如乙基(甲基)丙烯酰胺、(甲基)丙烯酰胺、N-正-辛基丙烯酰胺、N-叔-丁基丙烯酰胺、N-(3-二甲基氨丙基)(甲基)丙烯酰胺、N-(3-二甲基氨基-2,2-二甲基丙基)(甲基)丙烯酰胺、N-二甲基氨甲基(甲基)丙烯酰胺、N-二甲基氨乙基(甲基)丙烯酰胺、N-(4-吗啉甲基)(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N,N-二乙基(甲基)丙烯酰胺、N-乙烯基己内酰胺等;氨基烷基(甲基)丙烯酸酯,如二甲基氨乙基(甲基)丙烯酸酯、二乙基氨乙基(甲基)丙烯酸酯、二甲基氨丙基(甲基)丙烯酸酯、3-二甲基氨基-2,2-二甲基丙基-1(甲基)丙烯酸酯、2-N-吗啉乙基(甲基)丙烯酸酯、2-N-哌啶乙基(甲基)丙烯酸酯等;吡咯烷酮,如N-乙烯基吡咯烷酮、N-丙烯酰氧基乙基吡咯烷酮等;等等,以及上述任何单体的混合物。本文所用术语“(甲基)丙烯酸酯”既包括丙烯酸酯也包括甲基丙烯酸酯,术语“(甲基)丙烯酰胺”既包括丙烯酰胺,也包括甲基丙烯酰胺。尤其适合用于本发明的共聚物包括聚(苯乙烯-共-乙酰乙酸基甲基丙烯酸乙酯)和聚[(苯乙烯-共-乙二醇)甲基丙烯酸酯]。
当然,胶乳聚合物还可以包含其它单体成分,如聚乙烯属不饱和单体。合适的聚乙烯属不饱和单体包括含有至少两个可以加成聚合的亚乙烯基基团的共聚用单体(comonomer),并且是含2-6个酯基的多元醇的乙烯属不饱和单羧酸酯。此类共单体包括亚烷基二醇二丙烯酸酯和二甲基丙烯酸酯,例如,乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、丙二醇二丙烯酸酯和三乙二醇二甲基丙烯酸酯、1,3-二甲基丙烯酸甘油酯、1,1,1-三羟甲基丙烷二甲基丙烯酸酯、1,1,1-三羟甲基乙烷二丙烯酸酯、季戊四醇三甲基丙烯酸酯、1,2,6-己烷三丙烯酸酯、山梨醇五甲基丙烯酸酯、亚甲基双丙烯酰胺、亚甲基双甲基丙烯酰胺、二乙烯基苯、甲基丙烯酸乙烯酯、巴豆酸乙烯酯、丙烯酸乙烯酯、乙烯基乙炔、三乙烯基苯、氰脲酸三烯丙酯、二乙烯基乙炔、二乙烯基乙烷、二乙烯基硫、二乙烯醚、二乙烯砜、二烯丙基氨腈、乙二醇二乙烯醚、邻苯二甲酸二丙烯酯、二乙烯基二甲基硅烷、甘油三乙烯醚(glycerol trivinyl ether)、己二酸二乙烯酯;二环戊烯(甲基)丙烯酸酯;二环戊烯氧基(甲基)丙烯酸酯、二醇单二环戊烯醚(glycol monodicyclopentenyl ethers)的不饱和酯;具有不饱和乙烯属端基的α,β-不饱和一元羧酸和二元羧酸的烯丙酯,包括甲基丙烯酸烯丙酯、丙烯酸烯丙酯、马来酸二烯丙酯、富马酸二烯丙酯、衣康酸二烯丙酯,等等。
胶乳聚合物还可以使用不同的添加剂通过乳液聚合形成。例如,可以采用引发剂,如过硫酸盐、可溶于水或二醇的有机过氧化物和偶氮类引发剂。更具体地说,合适的引发剂可以包括过氧化氢、过二硫酸钾或过二硫酸铵、过氧化二苯甲酰、月桂基过氧化物、二叔丁基过氧化物、2,2′-偶氮二异丁腈、过氧化氢叔丁酯、过氧化苯甲酰及它们的混合物。氧化还原反应引发体系,如铁催化的过氧化氢叔丁酯与异抗坏血酸的反应也是有用的。乳液聚合中还可以使用还原剂。合适的还原剂是那些可以提高聚合速率的物质,包括,例如,亚硫酸氢钠、连二亚硫酸纳、甲醛次硫酸氢钠、磷钼酸钠、抗坏血酸、异抗坏血酸等。为了控制反应的pH值,乳液聚合中还可以使用缓冲剂。合适的缓冲剂包括但不限于铵和钠的碳酸盐和碳酸氢盐。乳液聚合中还可以使用提高聚合速率的聚合催化剂,催化剂与上述还原剂一起,可以在反应条件下促进聚合引发剂的分解。合适的催化剂包括但不限于过渡金属化合物,例如,如七水硫酸亚铁、氯化亚铁、硫酸铜、氯化铜、醋酸钴、硫酸钴及它们的混合物。
本发明的胶乳聚合物可以是未交联的或是交联的。当交联时,所得颗粒有时候被称为“微凝胶粒子”,即分子内交联的大分子。为此,可能要使用交联剂,如多官能团不饱和化合物,包括但不限于,二乙烯基苯、甲基丙烯酸烯丙酯、丙烯酸烯丙酯、多官能团丙烯酸酯及它们的混合物。合适的多官能团丙烯酸酯包括但不限于,乙二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇四丙烯酸酯及它们的混合物。可以控制乳液聚合中交联单体的用量,将胶乳的凝胶分率(gel fraction)控制在20%-100%。凝胶分率是不溶于溶剂的物质的含量。
如上所述,胶粒涂层还包括一种导电聚合物。虽然导电聚合物的实际含量取决于所采用的材料及颗粒的形态,但是,导电聚合物的含量通常占分散体的大约0.5-30wt%,在一些实施例中,占大约1-25wt%,在一些实施例中,占大约2-15wt%。在上述浓度时,导电聚合物可以赋予分散体所需的电导率大小。上述导电聚合物通常是π-共轭的,并在氧化或还原后具有导电性,例如,氧化后电导率至少约为1μS·cm-1。此类π-共轭的导电聚合物的实例包括,例如,聚杂环类(例如聚吡咯、聚噻吩、聚苯胺等)、聚乙炔、聚-对苯撑、聚苯酚盐等。尤其适合的导电聚合物是具有下述通式结构的取代聚噻吩:
其中,
T是O或S;
D是任选C1-C5烯烃取代基(例如,亚甲基、乙烯基、正丙烯基、正丁烯基、正戊烯基等);
R7是线性或支链的任选C1-C18烷基取代基(例如,甲基、乙基、正丙基或异丙基、正丁基、异丁基、仲丁基或叔丁基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1-乙基丙基、1,1-二甲基丙基、1,2-二甲基丙基、2,2-二甲基丙基、正己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十六烷基、正十八烷基等);任选C5-C12环烷基取代基(如环戊基、环己基、环庚基、环辛基、环壬基、环癸基等);任选C6-C14芳基取代基(如苯基、萘基等);任选C7-C18芳烷基取代基(如苄基,邻、间、对-甲苯基、2,3-、2,4-、2,5-、2,6、3,4-、3,5-二甲苯基、三甲苯基等);任选C1-C4羟烷基取代基或羟基取代基;及
q是0-8的整数,在一些实施例中,是0-2的整数,在一些实施例中,是0;及
n是2-5,000,在一些实施例中,n是4-2,000,在一些实施例中,n是5-1,000;“D”或“R7”的取代基实例包括,例如,烷基、环烷基、芳基、芳烷基、烷氧基、卤素、醚、硫醚、二硫化物、亚砜、砜、磺酸酯、氨基、醛、酮、羧酸酯、羧酸、碳酸酯、羧酸酯、氰基、烷基硅烷和烷氧基硅烷基、羧酰胺基等。
尤其适合的噻吩聚合物是“D”为任选取代C2-C3烯烃取代基的噻吩聚合物。例如,聚合物可为具有下述通式结构的选择性取代的聚(3,4-乙烯基二氧噻吩):
形成例如上文所述导电聚合物的方法是本领域熟悉的。例如,Merker等人的专利号为6,987,663的美国专利描述了由单体前体形成取代聚噻吩的各种不同方法,对于所有目的该专利以全文的形式引入本专利中作为参考。例如,单体前体具有以下结构:
其中,
T、D、R7和q定义如上文所述。尤其适合的噻吩单体是其中“D”为任选取代的C2-C3烯基的噻吩单体。例如,可以使用具有下述通式结构式的任选取代3,4-烯烃基二氧噻吩:
式中R7和q定义如上文所述。在一个具体的实施例中,“q”是0。一种商业可得的合适的3,4-烯烃基二氧噻吩实例是H.C.Starck GmbH以CleviosTM M名称销售的产品。其它合适的单体在Blohm等人的美国专利号为5,111,327专利中和Groenendaal等人的美国专利号为6,635,729的专利中进行了说明,对于所有目的以上专利以全文的形式引入本专利中作为参考。也可以采用这些单体的衍生物,例如上述单体的二聚体或三聚体。分子量更高的衍生物,如单体前体的四聚体、五聚体等适合用于本发明。衍生物可以由相同的或不同的单体单元构成,可以以纯态形式使用及以与另一种衍生物和/或单体的混合物的形式使用。还可以使用这些单体前体的氧化形式或还原形式。
为了制备胶粒涂层,如上文所述的导电聚合物的单体前体通常需要在如上文所述氧化剂存在的条件下发生氧化聚合。氧化聚合通常在胶乳聚合物存在的条件下进行。在这种氧化聚合的过程中,胶乳聚合物一开始可以分散在液体介质(通常包括水)中。为了增加导电聚合物在分散介质中的溶解度,还可以使用第二溶剂来形成溶剂混合物。合适的第二溶剂可以包括,例如,二醇(如乙二醇、丙二醇、丁二醇、三甘醇、己二醇、聚乙二醇、乙氧基二甘醇、二丙二醇等);乙二醇醚(如甲基乙二醇醚、乙基乙二醇醚、异丙基乙二醇醚等);醇(例如,甲醇、乙醇、正丙醇、异丙醇和丁醇);酮(例如,丙酮、甲基乙基酮和甲基异丁基酮);酯(例如,乙酸乙酯、醋酸丁酯、二乙二醇乙醚乙酸酯、丙二醇甲醚乙酸酯、碳酸乙二酯、碳酸丙二酯等);酰胺(例如,二甲基甲酰胺、二甲基乙酰胺、二甲基辛/癸脂肪酸酰胺和N-烷基吡咯烷酮);亚砜或砜(例如,二甲亚砜(DMSO)和环丁砜)等。此类溶剂混合物通常含大约20wt%-80wt%的水,在一些实施例中,大约含30wt%-70wt%的水,在一些实施例中含大约40wt%-60wt%的水;第二溶剂的含量大约为20wt%-80wt%,在一些实例中大约为30wt%-70wt%,在一些实施例中,大约为40wt%-60wt%。
氧化剂和单体前体可以顺序或一起施加到分散介质中。举例而言,单体前体(如3,4-乙烯基二氧噻吩)可以首先与分散介质(如水/醇)混合,然后施加胶乳粒子。然后,所得混合物用氧化剂涂覆。根据使用的氧化剂和要求的反应时间,聚合在温度大约-10℃-250℃的条件下进行,在一些实施例中在大约0℃-150℃的条件下进行。
导电聚合物形成后,通常位于粒子表面上或表面附近,从而增强了分散体的总电导率。此外,通常不带电荷的胶乳聚合物基本包含在粒子内部结构中,因而并不会大幅抑制导电性。尽管如上文所述,但是还可以使用不同的粒子形态以获得所需的分散体特性。例如,在一个实施例中,形成核-壳型粒子,其中胶乳聚合物(“核”)外面被导电聚合物(“壳”)覆盖。例如,参考图2,图中显示了这种形态的一个实施例。更具体地说,图中显示的粒子100包括由噻吩聚合物(如聚(3,4-二氧噻吩))形成的外壳102及由胶乳聚合物(如聚[(苯乙烯-共-乙二醇)甲基丙烯酸酯])形成的内核104。然而,在其它实施例中,粒子可以具有一种复合形态,其中胶乳聚合物交联而形成微凝胶。在这种实施例中,导电聚合物可以是包含在凝胶结构内的棒状、带状等形式。例如,参考图3,图中显示了这种形态的一个实施例。更具体地说,图中显示的复合粒子200包括由噻吩聚合物(如聚(3,4-二氧噻吩))形成的棒202,所述棒202包含在胶乳聚合物(如聚[(苯乙烯-共-乙二醇)甲基丙烯酸酯])的交联网络或“微凝胶”204中。
胶状分散体粒子通常较小,例如,平均粒径为大约1-700纳米,在一些实施例中,为大约10-600纳米,在一些实施例中,为大约50-500纳米。颗粒的直径可采用人们熟知的方法测定,如超速离心法、激光衍射法等。颗粒的形状同样可以有所不同。例如,在一个具体的实施例中,颗粒为球形。然而,应该理解的是,本发明也预计到有其它形状,如板状、棒状、盘状、柱状、管状、不规则形状等。
胶状分散体一旦形成,即可采用各种已知的方法涂覆到阳极体上,如旋涂、浸渍、倾倒、滴加、注射、喷涂、刮片、刷涂或印刷(如喷墨打印法、丝网印刷法或移印法)。虽然,根据采用的涂布技术,分散体的粘度可以有所变化,但是,其粘度一般为大约0.1mPa·s-100,000(在剪切速率100s-1时测定),在一些实施例中为大约1mPa·s-10,000mPa·s,在一些实施例中为10-1,500mPa·s,在一些实施例中为大约100mPa·s-1000mPa·s。一旦涂覆完成,即可对该层进行干燥和清洗。
V.其它层
除上文提到的各层外,本发明的电容器还可选择性地包含其它层。例如,可在胶粒涂层外覆盖一种外部涂层。例如,外部涂层可包含至少一种炭质层和至少一种覆盖在炭质层上的金属层。金属层可作为电容器的可焊接导体、接触层和/或电荷收集器。金属层可由导电金属形成,如铜、镍、银、锌、锡、钯、铅、铝、钼、钛、铁、锆、镁及它们的合金。银是尤其适合在这里使用的金属层的导电金属。炭质层可限制金属层和固体电解质之间的接触,否则,这种接触会增加电容器的电阻。碳质层可采用各种已知碳质材料形成,如石墨、活性碳、碳黑等。碳质层的厚度一般大约为1μm-50μm,在一些实施例中是大约2μm-30μm,在一些实施例中是大约5μm-10μm。同样,金属层的厚度一般大约为1μm-100μm,在一些实施例中大约为5μm-50μm,在一些实施例中大约为10μm-25μm。
参考图1,图中显示了固体电解电容器10的一个具体实施例,包括覆盖在阳极体上12上的介质层14,阳极体内嵌入一根引线15。虽然没有具体示出,但是,介质层14通常覆盖在阳极体12的外表面上并且也位于其内部孔结构内。还形成一层覆盖在介质层14上的固体电解质20。此外,前述胶状分散体涂覆到电容器上,形成覆盖在固体电解质20上的胶粒涂层22。还示出了一种包含炭质层和银层(未单独示出)的外部涂层24。应该理解的是,此处使用词语“覆盖”指的是在前一层完成后涂覆特殊的涂料或层。然而,涂料或层的某些部分,与前一层混合或流过前一层,因此,涂料或层并非严格地全部遮盖前一涂料或层。例如,胶粒涂料层的某些部分可能进入阳极没有固体电解质存在的某些孔中。但是,涂层仍然被称为覆盖固体电解质。
本发明的电解电容器还包含一个阳极端子和一个阴极端子,电容器元件的阳极引线与阳极端子电连接,电容器元件的阴极与阴极端子电连接。可以采用任何导电材料来形成这些端子,如导电金属(如铜、镍、银、锌、锡、钯、铅、铝、钼、钛、铁、锆、镁及它们的合金)。尤其适合的导电金属包括,例如铜、铜合金(例如铜-锆、铜-镁、铜-锌或铜-铁)、镍及镍合金(如镍-铁)。通常选择端子的厚度,以最小化电容器的厚度。例如,端子的厚度大约为0.05-1毫米,在一些实施例中大约为0.05-0.5毫米,大约为0.07-0.2毫米。端子可采用本领域公知的任何技术连接,如焊接、粘接等。例如,在一个实施例中,先将导电粘合剂(adhesive)涂在阳极端子和/或阴极端子表面。导电粘合剂包括,例如,树脂组合物中包含的导电金属颗粒。金属颗粒可以是银、铜、金、铂、镍、锌、铋等。树脂组合物包括热固性树脂(如环氧树脂)、固化剂(如酸酐)和偶联剂(如硅烷偶联剂)。合适的导电粘合剂在Osako等人的公开号为2006/0038304的美国专利申请中进行了描述,对于所有目的该专利以全文的形式引入本专利中作为参考。
一旦电容器元件连接好,引线框架可封装在一个外壳内,然后,采用二氧化硅或任何其它已知的封装材料填充外壳。树脂外壳的宽度和长度随目标应用而变化。例如,合适的外壳包括,“A”、“B”、“F”、“G”、“H”、“J”、“K”、“L”、“M”、“N”、“P”、“R”、“S”、“T”、“W”、“Y”或“X”外壳(AVX公司)。不管所用外壳规格如何,电容器元件封装时,至少一部分阳极端子和阴极端子暴露在外。在某些情况下,阳极端子和阴极端子的暴露部分以“面朝下”的结构位于电容器下表面,用于安装到电路板上。这可以提高电容器的体积效率,也可以减少其在电路板上所占的空间。在封装后,阳极端子和阴极端子的暴露部分可以进行老化、筛选和修整到要求的尺寸。
通过下述实施例可以更好地理解本发明。
测试程序
等效串联电阻(ESR)
等效串联电阻可以采用带Kelvin引线的Keithley 3330精密LCZ测试仪,在直流偏压2.2伏特、峰-峰正弦信号0.5伏特时进行测定。工作频率采用100kHz,温度采用23℃+2℃。
电容(CAP)
电容可以采用带Kelvin引线的Keithley 3330精密LCZ测试仪,在直流偏压2.2伏特、峰-峰正弦信号0.5伏特时进行测定。工作频率采用120Hz,温度采用23℃+2℃。
漏电流(DCL)
漏电流采用泄漏试验仪在温度25℃和达到额定电压条件至少30秒后测定。
温度/压力测试
在温度和压力测试之后,测定某些电气性能。更具体地说,将100个样品放进加有水的压力锅中,在125℃保持100小时。然后,采用上文所述方式测定样品。
实例1
粒子一开始由聚[(苯乙烯-共-乙二醇)甲基丙烯酸酯](“PS-PEGMA”)形成。在聚[(乙二醇)甲基丙烯酸酯]存在条件下,粒子由苯乙烯通过无表面活性剂乳液聚合形成。粒子由紧密的疏水性富-聚苯乙烯的核和亲水性的富-PEGMA的溶胀壳组成。PS-PEGMA的粒径由重量比(fleet ratio)(Wp/Wm)控制,其中Wp是PEGMA的宏观重量,Wm是PS的重量。更具体地说,Wu等(Macromolecules 27.1994;298)对颗粒大小和无表面活性剂的大分子单体/单体乳液之间的重量比(fleetratio)的定量关系进行了说明,如下所述:
其中Rh是粒子的流体动力学半径,NA是阿伏加德罗(Avogadro)常数,ρ是微球体的平均密度,Mp是稳定剂的摩尔质量,b是稳定剂壳层的厚度。采用吴氏模型,得出实例1的粒子的流体动力学半径(Rh)是162纳米。
实例2
将40g实例1的PS-PEGMA分散体用160g去离子水稀释,并放进搅拌的反应器中。然后,采用注射器加入0.2g 3,4-乙烯基二氧噻吩单体(CLEVIOSTM M),在室温搅拌所得混合物15分钟。逐滴加入氧化剂/掺杂剂-甲苯磺酸铁(III)(CLEVIOSTM C)的丁醇溶液以开始聚合。几分钟后,分散体出现颜色,表明聚合已经开始。6小时后,形成复合粒子,将其从反应容器中移出。采用超滤法洗涤复合粒子,脱除未反应的单体和所有副产物。在预先形成的聚合物核存在的条件下,聚(3,4-乙烯基二氧噻吩)(“PEDT”)通过氧化聚合而直接沉积在PS-PEGMA粒子表面。采用元素分析法测定PEDT的沉积量,得出其占PS-PEGMA粒子重量的4.3%(理论计算值是5.0%;反应产率是86%)。
实例3
将规格为1.70mm×1.05mm×2.4mm的钽阳极在液体电解质(正磷酸的水溶液)在13.5V条件下阳极氧化至100μF。然后,将阳极浸到甲苯磺酸铁(III)(CleviosTM C)的丁醇溶液中5分钟,之后浸到3,4-乙烯基二氧噻吩(CleviosTMM)中1分钟,形成固体电解质。聚合45分钟后,在介质表面形成一层聚(3,4-乙烯基二氧噻吩)层。在甲醇中清洗部件,清除反应副产物,在液体电解质(4-甲苯磺酸水溶液)中重新进行阳极氧化,并重新在甲醇中清洗。重复聚合周期4次。然后,将部件浸到固含量为1%的实例2的PS-PEGMA/PEDT粒子分散体中。然后,将部件在125℃干燥20分钟。再次重复此过程2次。然后,在部件上涂上石墨和银,并通过将阳极粘到引线框架袋(pocket)上进行组装,切割阳极线,并将其激光焊接到引线框架立柱(upstand)上,并模制成电容器。采用这种方式制造多个部件(500个样品)用于测试。
实例4
除采用CleviosTM K(固含量1%)用于形成导电聚合物涂层而不是实例3中采用的PS-PEGMA/PEDT粒子之外,按照实例3所述方法制备500个电容器。然后,对实例3和4制备的电容器进行电气性能测试。平均结果见表1。
表1初始电气性能
DCL[μA] | ESR[mΩ] | CAP[μF] | |
实例3 | 8.3 | 78 | 92.4 |
实例4 | 48.5 | 75 | 91.3 |
在上文所述“温度/压力试验”后,对实例3和实例4制备的各100个电容器样品进行测试。结果见表2。
表2:温度/压力试验后的电气性能
DCL[μA] | ESR[mΩ] | Cap[μF] | |
实例3 | 3.2 | 80 | 98.3 |
实例4 | 12.9 | 79 | 98.0 |
如以上结果所示,在温度/压力试验前后,实例3的漏电流都远低于实例4。
本领域技术人员在不违背本发明精神和范围的情况下可做作出种种的改进和变形。另外,应理解的是,各个实施例可以整体或部分互换。此外,本领域技术人员将意识到,前面的描述仅用作举例,并不意图限制在这类所附的权利要求中进一步描述的发明。
本发明涉及一种固体电解电容器,包括一阳极体、一层覆盖在阳极体上的介质层、一种覆盖在介质层上的固体电解质和一种覆盖在固体电解质上的胶粒涂层。所述涂层是由一种胶粒分散体形成的。分散体胶粒包括至少两种不同的聚合物成分-即导电聚合物和胶乳聚合物。这种涂料的一个优点是由于胶乳聚合物具有相对较软的性质,有助于在封装期间机械稳定电容器。这有助于限制固体电解质的剥离及电容器形成期间否则可能发生的任何其它损害。此外,胶乳聚合物还可以增强胶粒在有些应用中需要的水介质中的分散能力。
Claims (25)
1.一种固体电解电容器,包括:
一阳极体;
一层覆盖在阳极体上的介质层;
一种覆盖在介质层上的固体电解质;及
一种覆盖在固体电解质上的胶粒涂层,其中所述胶粒涂层是由胶粒分散体形成,其中所述胶粒包含至少一种导电聚合物和至少一种胶乳聚合物。
2.根据权利要求1所述的固体电解电容器,其中所述胶乳聚合物是由至少一种单乙烯属不饱和单体形成。
3.根据权利要求2所述的固体电解电容器,其中所述单体包括苯乙烯、α-甲基苯乙烯、对-甲基苯乙烯、叔丁基苯乙烯或它们的组合。
4.根据权利要求2所述的固体电解电容器,其中所述单体包括一种官能单体,所述官能单体选自由(甲基)丙烯酸酯、羟基(甲基)丙烯酸酯、烷氧基(甲基)丙烯酸酯、(甲基)丙烯酰胺、氨烷基(甲基)丙烯酸酯、吡咯烷酮及它们的组合所组成的族。
5.根据权利要求1所述的固体电解电容器,其中所述胶乳聚合物是聚[(苯乙烯-共-乙二醇)甲基丙烯酸酯]。
6.根据权利要求1所述的固体电解电容器,其中所述导电聚合物包括聚吡咯、聚噻吩、聚苯胺、聚乙炔、聚-对-苯撑、聚酚盐或它们的组合。
7.根据权利要求6所述的固体电解电容器,其中所述导电聚合物是取代聚噻吩。
8.根据权利要求7所述的固体电解电容器,其中所述取代聚噻吩是聚(3,4-乙烯基二氧噻吩)。
9.根据权利要求1所述的固体电解电容器,其中所述导电聚合物占胶粒涂层的大约0.5 wt% 至大约 30 wt%。
10.根据权利要求1所述的固体电解电容器,其中至少部分胶粒具有核-壳结构,其中所述核包括胶乳聚合物,所述壳包括导电聚合物。
11.根据权利要求1所述的固体电解电容器,其中至少部分胶粒包括位于胶乳聚合物交联网络内的导电聚合物。
12.根据权利要求1所述的固体电解电容器,其中所述胶粒为球形。
13.根据权利要求1所述的固体电解电容器,其中所述固体电解质包含一种导电聚合物。
14.根据权利要求1所述的固体电解电容器,进一步包括一种覆盖在胶粒涂层上的外部涂层,所述外部涂层包含炭质层和覆盖在炭质层上的金属层。
15.根据权利要求1所述的固体电解电容器,其中所述阳极体包括钽、铌或它们的导电氧化物。
16.一种形成固体电解电容器的方法,包括:
对阳极体进行阳极氧化;
在阳极氧化的阳极体上涂覆一种固体电解质;及
在固体电解质上涂覆一种胶粒涂层,其中所述胶粒涂层由胶粒分散体形成,其中所述胶粒包含至少一种导电聚合物和至少一种胶乳聚合物。
17.根据权利要求16的方法,其中所述涂层通过施加导电聚合物的单体前体和胶乳聚合物到液体介质中,然后在氧化剂存在下氧化聚合单体前体而形成。
18.根据权利要求17所述的方法,其中所述液体介质包括水。
19.根据权利要求18所述的方法,其中所述液体介质进一步包括一第二溶剂,所述第二溶剂的含量占液体介质的大约20 wt% 至大约80 wt%。
20..根据权利要求16所述的方法,其中所述胶乳聚合物是由至少一种单乙烯属不饱和单体形成。
21.根据权利要求20所述的方法,其中所述胶乳聚合物是聚[(苯乙烯-共-乙二醇)甲基丙烯酸酯]。
22.根据权利要求16所述的方法,其中所述导电聚合物是聚(3,4-乙烯基二氧噻吩)。
23.根据权利要求16所述的方法,其中所述导电聚合物占胶粒涂层的大约0.5 wt% 至大约 30 wt%。
24.根据权利要求16所述的方法,其中至少部分胶粒具有核-壳结构,其中所述核包括胶乳聚合物,所述壳包括导电聚合物。
25.根据权利要求16所述的方法,其中所述固体电解质包括一种导电聚合物。
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CN106057470B (zh) * | 2015-04-02 | 2019-03-15 | 株式会社东金 | 固体电解电容器 |
CN110730995A (zh) * | 2017-07-03 | 2020-01-24 | 阿维科斯公司 | 包含纳米涂层的固体电解质电容器 |
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US8451588B2 (en) | 2013-05-28 |
GB2488867A (en) | 2012-09-12 |
US20120229955A1 (en) | 2012-09-13 |
JP5894460B2 (ja) | 2016-03-30 |
GB201202471D0 (en) | 2012-03-28 |
KR20120104121A (ko) | 2012-09-20 |
JP2012191197A (ja) | 2012-10-04 |
DE102012203422A1 (de) | 2012-09-13 |
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