CN100583329C - 复合烧结电极的电化学电容器及其制备方法 - Google Patents
复合烧结电极的电化学电容器及其制备方法 Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
一种新型的电化学电容器,其特点是电容器的正极使用复合烧结电极,负极使用大比表面积的多孔碳材料电极,以碱溶液作为电解质,正负极之间有可通过离子的电子绝缘隔膜,该电化学电容器具有较高的能量密度和功率密度,具有良好的应用前景。
Description
技术领域
本发明涉及一种使用复合烧结电极的电化学电容器及其制备方法,属于化工领域,可广泛应用于电子工业、交通运输、电力、矿冶等领域。
背景技术
电化学电容器是一类新型的电源元件,具有比传统电容器大10~100倍的电容量,比能量仅仅比二次电池低一个量级,可以提供较高的能量,在电子电路、工业控制等方面中得到广泛的应用,并部分取代了电解电容器。高比能量的电化学电容器比能量接近二次电池,寿命长,可以循环10万次以上,具有较高的比能量和比功率,可以作为变电站、供电站的高压开关电源,也可以用作电动工具和电动自行车储能装置,也可以部分替代电池作为计算机以及通讯系统的不间断电源。大型电化学电容器还是电动交通机车的备选能源之一,由于能够以大功率快速充放电,电化学电容器既可用作汽车起动、加速和爬坡时的辅助电源,又可作为车辆下坡、刹车时回收动能的蓄能器,从而可以使燃料电池和电动机的设计功率大为降低,在车辆行驶时这些能源装置可在最佳稳定功率下运行,节省燃料,延长使用寿命,还可有效地降低发动机的废气排放。
不同于传统的电容器,电化学电容器的高容量是通过以下两种途径实现的:一是采用大比表面积的电极材料,将电荷储存在电化学双电层中,即双电层储能原理;二是采用快速电化学反应储存电荷,如单层金属(氢)沉积、RuO2电化学反应等,即准电容储能原理,具有比双电层电容更高的比电容。
对于一般的化学电源,其充放电过程往往涉及活性物质相的变化,因而反应速度与电化学电容器相比较慢,并且循环中不可避免的有容量损失,寿命较短。与电池相比,电化学电容器具有更长的循环寿命、安全、无记忆等优点,更重要的是,电化学电容器具有电池所不具备的高功率连续充放电的性能,因此,电化学电容器是一种极有发展潜力的储能装置。
目前技术较为成熟的电化学电容器是以多孔活性炭作为电极材料的双电层电容器,其正负极均由多孔活性炭组成,如CN1160455,采用了活性炭粉末作电极的方法,另外还有使用炭纤维、炭凝胶等材料的电容器,由于这种电容器正负极采用相同的材料和结构,比能量不大,成本较高,使用受到很大限制,也不适合在电动车等大众化设备上使用。此外,研究表明活性炭的比容量与其比表面和孔隙结构有关,而这些因素不可能无限制提高材料的比容量,因此,利用高比表面材料获得大比容量的余地不大。另外,活性炭材料本身具有较高的接触电阻,影响了双电层电容器的功率性能的提高。
电化学准电容是准法拉第过程,比能量与电极材料的电化学反应性有关,可以大幅度提高材料的容量特性。具有较高法拉第准电容的材料,研究较多的是RuO2,如CN1345074A,使RuO2与活性炭复合材料构成电化学电容器。RuO2类虽然具有较高的比容量,同时也有很高的功率性能,但其高昂的价格限制了其商业化和进一步应用。利用某些过渡金属化合物的准电容特性,可以组成电化学电容器,具有较高的比能量,如CN2541938Y以烧结镍电极作为正极,与活性炭负极构成电化学电容器;CN1369886A,使用MnO2与活性炭构成电化学电容器等。但以上已有的专利,没有解决诸如充放电过程的副反应大、放电倍率难于提高以及循环使用过程中的容量衰减等问题。电化学过程中单一的活性材料组分一般都有缺陷,因而是以上问题没有能够解决的关键。
发明内容
本发明的目的在于提供一种电化学电容器及其制备方法,以抑制副反应的发生,提高电化学电容器的能量密度和功率特性,真正做到高性能、长寿命,本发明的技术方案如下:
电容器的正极使用复合烧结电极;电容器的负极使用大比表面积的多孔碳材料电极;以碱溶液作为电解质;正负极之间有可通过离子的电子绝缘隔膜。
电化学电容器的正极制备步骤如下:以导电剂、粘接剂、造孔剂、导电骨架,在800~1000℃烧结成微孔基板;以基板作为阴极在中性或微酸性盐溶液中电解,直到活性物质装填量达到要求;或将基板放在中性或微酸性盐溶液中浸渍,一段时间后取出淋干,再转入碱液中浸渍,浸渍后的极板水洗到中性,烘干,按以上步骤浸渍多次,直到活性物质装填量达到要求。导电骨架可以是镍箔、铁箔、镀镍钢带、镀镍切拉网等。将制得的电极和辅助电极一起在碱性电解液中化成;化成后的极板经水洗、干燥后直接应用;或在150~500℃温度下热处理后使用。本发明所述的中性或微酸性盐溶液中包含两种或两种以上的以下成分:镍、镉、钴、锌、铬、钡、锰、钒、铝、铁、铟、钛、钼、钌、钇、铋、锑、铅等。
本发明所述的多孔碳材料电极以以下一种或一种以上为主要活性物质:活性炭、活性炭纤维、活性炭布、活性炭毡、碳纳米管、碳气凝胶、活性玻璃态炭等。
本发明所述的电解质是NaOH、KOH、LiOH或其混合水溶液。
本发明所述的电子绝缘隔膜是下列材料之一:聚丙烯、尼龙、聚乙烯微孔膜、石棉纸或它们的复合材料等。
本发明制备的电化学电容器,寿命长、价格低,具有较高的能量密度和功率密度,能量利用效率高,可广泛应用于电力、交通、电子等行业。
具体实施方式
下面举三个实施例简要说明本发明电化学电容器的制备方法。
实施例1
电化学电容器正极的制备
以导电剂羰基镍粉和粘接剂CMC(羧甲基纤维素钠)以质量比1∶1混合,用多元醇和水调成浆料,用湿式刮浆方法均匀刮涂到打孔镀镍钢带上,在立式炉中连续干燥,得到烘干的镍基板。烘干的镍基板在烧结炉中,以还原气氛下1000℃烧结10分钟,得到烧结镍基板。烧结镍基板作为阴极在含镍、镉、钴盐的微酸性水溶液中电解,电解过程中控制镍、镉、钴生成氢氧化物沉淀共同沉积在基板的微孔中,同时不会析出金属。电解基板的活性物质填充量达到要求后,经刷洗、水洗到中性,在碱性电解液中作为正极与辅助电极一起进行化成。化成后的电极板经水洗、干燥即可作为成品。钴的存在可以提高氢氧化镍材料的导电性,提高电容器的倍率放电性能,而镉的加入可以有效改善电容器滥用时的性能劣化。
实施例2
电化学电容器多孔碳材料电极的制备
将活性炭、导电碳黑、CMC(羧甲基纤维素钠)、PTFE以质量比85∶12∶2∶1的比例混合,用水调成浆料,刮浆方法均匀刮涂到泡沫镍上,经干燥、辊压即可作为成品。
实施例3
电化学电容器的制备
取以上实施例1的正极和实施例2的负极裁成适当的极片,在极耳上焊接导电片,在装配夹上布好螺栓、隔膜等材料,将一片正极的导电片套在一边螺栓上,将隔膜折向一边,铺平拉紧,在另一边将一片负极的导电片套在螺栓上,使隔膜将两电极隔开。继续放以正极。以以上方式组成电极组。极板装配完成,经整理后放入电容器壳体中,调整极柱位置,将螺栓紧固,封口。加注电解液,加密封阀,预充电后即可应用。也可以在使用时才加注电解液,可以长期存放。本专利制备的电化学电容器比能量可以达到5Wh/kg,比功率可以达到2~3kW/kg,性能远远高于普通的炭/炭电化学电容器。
Claims (5)
1、一种电化学电容器的制备方法,该电化学电容器的正极为复合烧结电极,负极为高比表面积的多孔碳材料电极,以碱溶液作为电解质,正负极之间有可通过离子的电子绝缘隔膜,其特征在于:电容器的正极制备步骤如下:①以导电剂、粘接剂、造孔剂、导电骨架,在800~1000℃烧结成微孔基板;②以上基板作为阴极在中性或微酸性盐溶液中电解,溶液中包含两种或两种以上的以下成分:镍、镉、钴、锌、铬、钡、锰、钒、铝、铁、铟、钛、钼、钌、钇、铋、锑、铅,直到活性物质装填量达到要求;或将基板放在中性或微酸性盐溶液中浸渍,一段时间后取出淋干,再转入碱液中浸渍,浸渍后的极板水洗到中性,烘干,以上浸渍步骤重复多次,直到活性物质装填量达到要求;③将第②步制得的电极和辅助电极一起在碱性电解液中化成;④将化成后的极板经水洗、干燥后直接应用;或在150~500℃温度下热处理后使用。
2、根据权利要求1所述的电化学电容器的制备方法,其特征在于:多孔碳材料电极是以以下一种或一种以上为主要活性物质:活性炭、活性炭纤维、活性炭布、活性炭毡、碳纳米管、碳气凝胶、活性玻璃态炭。
3、根据权利要求1所述的电化学电容器的制备方法,其特征在于:电解质是NaOH、KOH、LiOH或其混合水溶液。
4、根据权利要求1所述的电化学电容器的制备方法,其特征在于:电子绝缘隔膜是下列材料之一:聚丙烯、尼龙、聚乙烯微孔膜、石棉纸或它们的复合材料。
5、根据权利要求2所述的电化学电容器的制备方法,其特征在于:导电骨架可以是镍箔、铁箔、镀镍钢带或镀镍切拉网。
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