CN102643518B - 电解质材料调配物、由其形成的电解质材料聚合物及其用途 - Google Patents
电解质材料调配物、由其形成的电解质材料聚合物及其用途 Download PDFInfo
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- CN102643518B CN102643518B CN201210151759.0A CN201210151759A CN102643518B CN 102643518 B CN102643518 B CN 102643518B CN 201210151759 A CN201210151759 A CN 201210151759A CN 102643518 B CN102643518 B CN 102643518B
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Abstract
本发明提供一种电解质材料调配物,其包含:(a)具有式(I)结构的单体及(b)具有式(II)结构的单体,式中的A、X、B1、B2、R1至R3、q及w如说明书中所定义,且以100重量份的(a)单体计,(b)单体的含量为约1重量份至约800重量份。本发明还提供一种由该电解质材料调配物经聚合反应形成的电解质材料聚合物;以及包含该电解质材料聚合物的固态电容。
Description
技术领域
本发明涉及电解质材料调配物;本发明还涉及由该电解质材料调配物所形成的电解质材料聚合物;本发明还涉及利用该电解质材料聚合物的固态电容。
背景技术
电容器为一种广泛使用于各类电子产品中的电子组件,而随着电子产品趋向小型化、轻量化的发展,电容器也存在小型化、大电容量及可在高电压下使用等需求。
一般而言,电容器可依电解质型态分为液态电容及固态电容。液态电容如铝质液态电容,其是采用液态电解质作为电荷传导的物质,液态电解质一般包含高沸点醇类、离子液体、硼酸、磷酸、有机羧酸、铵盐、高极性有机溶剂、以及少量水等成分。上述成分除作为电荷传导的物质外,也有修补电容器阳极表面的介电层破损的功能。以分别使用铝及氧化铝作为阳极及阳极表面的介电层的铝质液态电容为例,若介电层存在缺陷,则会使得铝层裸露(此将导致泄漏电流),此时液态电解质可于电容器充放电的过程中,与裸露的铝金属反应产生氧化铝,达到修补介电层的功能。然而,液态电容普遍存在导电率较低及不耐高温等缺点,且在修补介电层的过程中会产生氢气,易导致电容爆裂,损坏电子产品。
固态电容器是采用固态电解质作为电荷传导的物质,固态电解质的实例例如有机半导体络合物盐类(如四氰基对苯醌二甲烷(tetracyanoquinodimethane,TCNQ)、无机半导体(如MnO2)或导电聚合物,其中又以具备高耐热性及高导电性能的导电聚合物为佳。固态电容具有使用寿命长、稳定性高、等效串联电阻(equivalent series resistance,ESR)低、容变率低、耐高温且耐高电流等优点,且相较于液态电容,不会有电解质泄漏或电容器爆裂的问题。因此,业界目前 均致力于固态电容的研发。
US 4609971揭露一种采用导电性高分子的固态电容,其是将电容器的阳极铝箔含浸于由导电高分子聚苯胺(polyaniline)粉末及掺杂剂LiClO4所组成的混合溶液,随后将铝箔上的溶剂驱除,以制得含导电高分子聚苯胺的固态电容。然而,聚苯胺分子体积太大,不易渗入阳极铝箔的微孔中,故所制得的电容器的浸渍效果差且阻抗高。为了使高分子更易渗入阳极铝箔的微孔中,US 4803596揭露一种以化学氧化聚合法制备采用导电性高分子作为电解质的固态电容的方法,其是将阳极铝箔分别浸渍含导电性高分子单体的溶液及含氧化剂的溶液后,于适当条件下使导电性高分子单体聚合,并重复多次浸渍及聚合步骤,以形成足量的导电性高分子电解质。US 4910645则揭露以聚3,4-亚乙基二氧噻吩(poly-3,4-ethylenedioxythiophene,PEDOT)为电解质的铝固态电容,其是使用单体3,4-亚乙基二氧噻吩(3,4-ethylenedioxythiophene,EDOT)搭配氧化剂对甲苯磺酸铁(iron(III)p-toluenesulphonate)而制得。由于PEDOT具有耐热性佳、导电度高、电荷传导速度快、无毒、寿命长等优点,故被普遍使用于固态电容以作为电解质。然而,由此所形成的导电性高分子颗粒大小不一且粒径分布大(即跨度值(span值)大),且先形成的导电高分子之间会进一步形成凝集现象,此将造成未反应的单体分子及氧化剂分子的移动性变差,导致聚合反应无法完全,从而不易于电极(如铝箔)表面及孔隙上形成完整且聚合度高的高分子结构,而多以不易黏着于电极表面或表面孔隙而易于脱落的粉状结构存在,故由PEDOT所制得的固态电容于应用在高电压(如16V以上)情况下的稳定性差,可耐受的工作电压有限。因此,如何开发能耐电压更高且具有较佳稳定性的固态电容,实为业界所殷切企盼者。
发明内容
本发明的一个目的在于提供一种电解质材料调配物,包含:
(a)具有式(I)结构的单体;以及
(b)具有式(II)结构的单体,
其中,
A为经(RX)p取代的C1至C4亚烷基;
X为O或S;
B1为O、S或N;
B2为N或C;
R1、R2、R3及RX为各自独立为H、或经取代或未经取代的C1至C20烷基或烷氧基、或经取代或未经取代的C6至C20芳基;
p为0至2的整数;以及
q及w各自独立为0或1的整数;
其中,以100重量份的(a)单体计,(b)单体的含量为1重量份至800重量份。
本发明的另一个目的在于提供一种作为电解质材料的聚合物,其是由上述电解质材料调配物聚合而得。
本发明的再一个目的在于提供一种固态电容,包含一阳极、一形成于该阳极上的介电层、一阴极、以及一位于该介电层与该阴极间的固态电解质,其中,该固态电解质是前述的聚合物。
为让本发明的上述目的、技术特征及优点更明显易懂,下面以具体实施例详细说明。
发明效果:
本发明的有益效果在于通过添加具有式(II)结构的单体和具有式(I)结构的单体形成高聚合度且粒径均匀的导电高分子。当此导电高分子充当固态电解质,应用于固态电容时,可有效提升固态电容耐电压值及提高电容量。
附图说明
图1为一供形成本发明的固态电容的电容组件的一种实施例的概略图。
其中,1为电容组件、131为阳极箔、133为阳极导线、151为阴极箔、153为阴极导线、171为隔离纸。
具体实施方式
以下将具体地描述根据本发明的部分具体实施方式;但是,在不背离本发明的精神下,本发明尚可以多种不同形式的实施方式来实践,不应将本发明保护范围解释为限于说明书所陈述,且为明确起见,图式中可能标示各组件及区域的尺寸,而未按照实际比例绘示。此外,为便于理解本文所陈述的内容,在下文中定义若干术语。
首先,除非文中有另外说明,在本说明书中(尤其是在后述专利申请范围中),所使用的“一”、“该”及类似用语应理解为包含单数及复数形式,且所使用的“经取代”一词是以取代基取代氢,该取代基可为除氢以外的任何基团或原子。且用语“约”意指由一般熟习此项技术者所测定的特定值的可接受误差,该可接受误差视量测方式而定。
在本说明书中,“烃基”是包含直链或支链的碳链基团,在部分实施例中,烷基为具有1至20个碳原子(C1至C20)、1至15个碳原子(C1至C15)、1至10个碳原子(C1至C10)或1至6个碳原子(C1至C6)的碳链基团。烷基的实施例包括,但不限于,甲基、乙基、丙基(含所有异构形式)、丁基(包含所有异构形式)、戊基(包含所有异构形式)及己基(包含所有异构形式)。
“亚烷基”是指直链或支链的二价碳链基团,其中该亚烷基可视情况经取代基取代。在部分实施方式中,亚烷基为具有1至4个碳原子(C1至C4)的二价碳链基团。亚烷基的实施例包括,但不限于,亚甲基、亚乙基、亚丙基(包含所有异构形式)、亚丁基(包含所有异构形式)。
“烷氧基”表示经由氧原子连接至分子其余部分(如上述烷基)的基团。 烷氧基的实施例包括,但不限于,甲氧基、乙氧基、正丙氧基、2-丙氧基、正丁氧基、异丁氧基、第三丁氧基、环己氧基、苯氧基、苄氧基及2-萘氧基。
“芳基”是指单环或多环(如双环或三环)的芳香基团,其中这些环中的至少一者为芳香环。在部分实施例中,芳基为具有6至20个碳原子(C6至C20)、6至15个碳原子(C6至C15)或6至10个碳原子(C6至C10)的单价芳香基团。芳基的实施例包括,但不限于,苯基、萘基、芴基、薁基、蒽基、菲基、芘基、联苯基、联三苯基。芳基也指双环或三环状碳环,其中这些环中之一为芳族环且其余可为饱和、部分不饱和或芳族环,例如,二氢萘基、茚基、二氢茚基或四氢萘基(萘满基)。
本发明的电解质材料调配物可透过聚合反应形成可作为固态电容的电解质材料的聚合物,该聚合物本身的耐电压(withstand voltage,或称“火花电压”)性质优异,可提高固态电容可耐受的工作电压,使得固态电容即使在高电压(如16V以上)下也具有优异稳定性。此外,由于所提供的聚合物具有优异耐电压性质,当本发明电解质材料调配物使用于固态电容以提供电解质材料时,可搭配以耐电压性质较低的铝箔作为电极。于前述搭配使用中,因铝箔的孔隙较大,相对的表面积也较大,故能提高电容的电容量;再者,于电容制造过程中,大孔隙的铝箔亦有利于调配物所含的单体的渗透,从而得以在铝箔表面及该表面的孔隙形成完整(聚合程度高)的高分子结构,故所提供的聚合物电解质材料可充分黏着于电极表面及表面的孔隙,不易脱落。
特定言之,本发明涉及一种电解质材料调配物,其包含:
(a)具有式(I)结构的单体;以及
(b)具有式(II)结构的单体,
在(a)单体中,A为经(RX)p取代的C1至C4亚烷基;X为O或S;RX为H、经取代或未经取代的C1至C20烷基或烷氧基、或经取代或未经取代的C6至C20芳基;及p为0至2的整数。特定言之,(a)单体可例如选自以下群组,但不以此为限:
其中R4及R5各自独立为H、或经取代或未经取代的C1至C15烷基或烷氧基、或经取代或未经取代的C6至C15芳基,较佳地,R4及R5为可相同或不相同且各自独立为H、C1至C3烷基或烷氧基。
在本发明的部分实施方式中,(a)单体是(3,4-亚乙基二氧噻吩(3,4-ethylenedioxythiophene,EDOT))、(噻吩并[3,4-d][1,3]间二氧杂环戊烯(thieno[3,4-d][1,3]dioxole))或(3-甲基-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧七环(3-methyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine))。
本发明调配物所使用的(b)单体能和(a)单体形成高聚合度且粒径分布均匀的导电高分子结构。在(b)单体中,B1为O、S或N;B2为N或C;q及w各自独立为0或1的整数;R1、R2及R3各自独立为H、或经取代或未经取代的C1至C20烷基或烷氧基、或经取代或未经取代的C6至C20芳基(B1为O或S时,q为0;B2为N时,w为0)。特定言之,(b)单体可例如选自以下群组,但不以此为限:
及前述的组合,且R1、R2及R3各自独立为H、C1至C3烷基或烷氧基。在本发明的部分实施方式中,(b)单体是
本发明电解质材料调配物中,(a)单体与(b)单体的比例并无特殊限制,可视使用者需要调配,然而,若(b)单体的含量过低,恐不利于所应用的固态电容的耐电压性质,反之,若(b)单体的含量过高,则恐不利于所应用的固态电容的电容量。因此,一般而言,以100重量份的(a)单体计,(b)单体的含量为约1重量份至约800重量份,优选为,(b)单体的含量为约5重量份至约400重量份。在本发明的部分实施方式中,以100重量份的(a)单体计,(b)单体的含量为约5重量份至约400重量份。
本发明的电解质材料调配物可透过氧化聚合反应促使(a)单体及(b)单体形成导电高分子,透过氧化聚合反应所得的导电高分子,具有耐高电压特性,特别适合作为固态电容的电解质材料。所述氧化聚合反应是在氧化剂存在下进行的聚合反应,其中,依所使用的氧化剂种类及完成反应所需时间长短的考量,氧化聚合反应一般是在约25℃至约260℃、优选为约85℃至约160℃的温度条件下进行。当应用于固态电容时,可透过如下“一液法”或“两液法”两种方式,在电容组件中氧化聚合(a)单体及(b)单体以形成所述聚合物。
所谓“一液法”,是指将(a)单体、(b)单体及选用的氧化剂溶于溶剂中,形成反应溶液,随后将电容组件含浸于该反应溶液中预定时间,加热该经含浸的电容组件,使得电容组件中的(a)单体及(b)单体氧化聚合成聚合物。至于“两液法”,则是将(a)单体及(b)单体溶于溶剂中,形成第一反应溶液,以及将选用的氧化剂溶于第二溶剂中,形成第二反应溶液,随后将电容组件先后含浸该第一反应溶液及该第二反应溶液预定时间后,加热该经含浸的电容组件,使得电容组件中的(a)单体及(b)单体氧化聚合成聚合物。
因此,本发明的电解质材料调配物可视需要含有氧化剂,如采用“一液法” 以制备固态电容。此时,优选为将调配物储存于低温(如0℃)的环境下,以延长调配物的储存寿命。
在上述使用本发明的电解质材料调配物在固态电容中以提供电解质材料的应用中,所采用的溶剂可为任何可溶解(a)单体与(b)单体且视需要可溶解氧化剂,以及在氧化聚合反应条件下不会与(a)单体及(b)单体反应的惰性溶剂,例如包含,但不限于,水、醇类、苯类或其组合物,较佳为甲醇、乙醇、丙醇、正丁醇、第三丁醇、水或其组合物。
可用于(a)单体及(b)单体的氧化聚合反应的氧化剂并无特别限制,只要其可促使该氧化聚合反应进行。举例言之,氧化剂可选自以下群组,但不以此为限:碱金属过硫酸盐类、铵盐、过氧化物、有机酸的三价铁盐类及前述的组合。优选为对甲苯磺酸铁、过氧化物、硫酸铵盐、过硫酸铵盐、草酸铵盐、过氯酸铵盐、过氧化氢或其混合物。根据本发明的具体实施例,本发明所使用的氧化剂为对甲苯磺酸铁。
此外,当存在氧化剂时,本发明电解质材料调配物中的氧化剂的用量并无特殊限制,只要足以使(a)单体及(b)单体充分聚合即可。一般而言,以(a)单体及(b)单体的总重为100重量份计,该氧化剂的用量为约5重量份至约3000重量份、优选为约100重量份至约1000重量份、最优选为约100重量份至约300重量份。在本发明的部分实施方式中,以(a)单体及(b)单体的总重为100重量份计,是使用约110重量份至约140重量份的对甲苯磺酸铁。
因此,本发明另提供一种作为电解质材料的聚合物,其是由本发明的电解质材料调配物进行氧化聚合反应而得。本发明的聚合物为高聚合度的高分子结构,其分子量为约1000至约500000,优选为,分子量为约1000至约50000。本发明的聚合物的平均粒径为约10奈米至约500奈米,优选为,平均粒径为约10奈米至约300奈米,且粒径分布范围(跨度(span)值)为约0.1至约2。此外,本发明的聚合物在作为电解质材料时,其高聚合度的高分子结构能防止如漏电电流击穿阳极而产生的短路现象,且可良好附着于电极表面。再者,由于本发明的聚合物具有良好的耐高压性,故可使用于以耐电压能力相对较低的金属箔作为电极的电容器中,利用金属孔隙来提高电极面积、提高电容器的电容 量。
本发明另提供一种固态电容,包含一阳极、一形成于该阳极上的介电层、一阴极、以及一位于该介电层与该阴极间的固态电解质,其中,该固态电解质是前文所述的聚合物。本发明的固态电容能耐受高电压(高于50伏特),且同时具有高电容量特性。
参考图1,显示一供形成本发明的固态电容的电容组件1的一种实施方式的概略示意图。如附图所示,电容组件1是包含一经过蚀刻的金属箔(如铝箔、钽箔、铌箔等)作为阳极箔131,阳极箔131表面覆有一介电层(未画出),且阳极箔131是与阳极导线133电性相接;一金属箔作为阴极箔151,且阴极箔151是与阴极导线153电性相接;以及一隔离纸171介于阳极箔131与阴极箔151之间。将上述阳极膜131、阴极膜151及隔离纸171卷绕成圆筒状后,即得到电容组件1。通过前述“一液法”或“两液法”,将电容组件1含浸反应溶液,或先后含浸第一反应溶液与第二反应溶液后,部分热处理经含浸的电容组件1,以在阳极131及阴极151之间形成固态电解质,随后利用习知组装工序,即可制得本发明的固态电容。在本发明的固态电容中,阳极箔131及阴极箔151的数量并无特别限制,且阳极箔131与阴极箔151的数量可相同或不同;阳极导线133及阴极导线153的数量亦无特别限制,只要每一阳极箔131与阴极箔151皆有导线连接即可。此外,阳极箔131表面的介电层可透过预先氧化阳极箔131表面而形成、或另外由其它介电材料来提供。有关上述构件的材料及其制备方式,皆为本领域具有通常知识者基于本说明书揭露内容而可轻易完成者。
兹以下列具体实施例以进一步说明本发明,但所例示的实施例仅为说明目的并非用以限制本发明的范围。
制备电解质材料调配物
实施例1
将30克及2.6克溶于100克含40%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物1。
实施例2
将30克及5.3克溶于100克含45%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物2。
实施例3
将7.9克及30克溶于100克含50%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物3。
实施例4
将30克及2.6克溶于100克含40%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物4。
实施例5
将30克及5.3克溶于100克含45%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物5。
实施例6
将7.9克及30克溶于100克含50%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物6。
实施例7
将30克及2.6克溶于100克含40%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物7。
实施例8
将30克及5.3克溶于100克含45%对甲苯磺酸铁的乙醇溶液,制 得电解质材料调配物8。
实施例9
将7.9克及30克溶于100克含50%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物9。
实施例10
将30克及2.6克溶于100克含40%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物10。
实施例11
将30克及5.3克溶于100克含45%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物11。
实施例12
将7.9克及30克溶于100克含50%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物12。
实施例13
将30克及2.6克溶于100克含40%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物13。
实施例14
将30克及5.3克溶于100克含45%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物14。
实施例15
将7.9克及30克溶于100克含50%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物15。
实施例16
将30克及2.6克溶于100克含40%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物16。
实施例17
将30克及5.3克溶于100克含45%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物17。
实施例18
将7.9克及30克溶于100克含50%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物18。
实施例19
将30克及2.6克溶于100克含40%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物19。
实施例20
将30克及5.3克溶于100克含45%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物20。
实施例21
将7.9克及30克溶于100克含50%对甲苯磺酸铁的乙醇溶液,制得电解质材料调配物21。
实施例22
将30克溶于100克含40%对甲苯磺酸铁的乙醇溶液,制得比较电解质材料调配物22。
制备固态电容
分别以如下方式,使用电解质材料调配物1至21制备固态电容1至21及使用比较电解质材料调配物22制备比较固态电容22。将如附图1所示的电容组件1浸渍于选定的电解质材料调配物中5分钟,之后取出经浸渍的电容组件1,并于约25℃至约260℃的温度下加热聚合,以在经浸渍的电容组件1中形成固态电解质。测量固态电解质的粒径分布(以跨度值表示),并将结果记录于表1。接着,将含有固态电解质的电容器组件1,置于一具有底部的盒体,随后密封该盒体并露出导线,完成固态电容的制备。分别测量所制得的固态电容的各项性质,并将结果记录于表1。其中,所采用的量测仪器及方法分别如下:
电容量(capacitance)测量
使用HP4284ALCR表在温度20℃及频率120赫兹(Hz)下量测固态电容的电容量。
耐电压/火花电压测量
使用Chroma Model 11200电容漏电流/绝缘电阻表量测上固态电容的耐电压。
跨度值测量
使用HORIBA LA-950V2雷射粒径分析仪量测固态电容的固态电解质的跨度。
表1
由表1可知,由本发明的电解质材料调配物所聚合而成的固态电解质粒径分布极为均匀(跨度值<2),且所制得的固态电容(固态电容1至21)的火花电压(>50伏特)明显优于单纯使用3,4-亚乙基二氧噻吩制得的习知电容(比较固态电容22),同时具有良好的电容量。
上述实施例仅为例示性说明本发明的原理及其功效,并阐述本发明的技术特征,而非用于限制本发明的保护范畴。任何熟悉本技术者在不违背本发明的技术原理及精神下,可轻易完成的改变或安排,均属本发明所主张的范围。
Claims (8)
1.一种电解质材料调配物,其特征在于,包含(a)单体和(b)单体,所述(a)单体选自以下群组:
其中R4及R5各自独立为H、或经取代或未经取代的C1至C15烷基或烷氧基、或经取代或未经取代的C6至C15芳基;
所述(b)单体选自以下群组:
及前述的组合,其中R1、R2及R3各自独立为H、C1至C3烷基或烷氧基;
其中,以100重量份的(a)单体计,(b)单体的含量为5重量份至800重量份。
2.如权利要求1所述的材料调配物,其特征在于,还包含一选自以下群组的氧化剂:碱金属过硫酸盐类、铵盐、过氧化物、有机酸的三价铁盐类、含有机基团的无机酸及前述的组合。
3.如权利要求2所述的材料调配物,其特征在于,其中以100重量份的(a)单体及(b)单体的总重计,该氧化剂的含量为5重量份至3000重量份。
4.一种作为电解质材料的聚合物,其特征在于,其由如权利要求1至3中任一所述的材料调配物聚合而得。
5.如权利要求4所述的聚合物,其特征在于,其中该聚合物的分子量为1000至500000。
6.如权利要求4所述的聚合物,其特征在于,其中该聚合物的平均粒径为10奈米至500奈米。
7.如权利要求4所述的聚合物,其特征在于,其中该聚合物的粒径分布范围为0.1至2。
8.一种固态电容,其特征在于,包含:
一阳极;
一介电层,形成于所述阳极上;
一阴极;以及
一固态电解质,位于所述介电层与所述阴极之间;
其中,所述固态电解质是权利要求4至7中任一所述的聚合物。
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