CN1383168A - 采用凝胶聚合物电解质的聚合物超电容器及其制作方法 - Google Patents
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Abstract
采用凝胶聚合物电解质的聚合物超电容器及其制作方法,属于电子器件技术领域。本发明采用凝胶聚合物电解质,该电解质是以聚偏氟乙烯或偏氟乙烯-六氟丙烯共聚物为基体的锂离子聚合物电解质。其制备方法是在丙酮中加入偏氟乙烯-六氟丙烯共聚物颗粒配成溶液,再将0.5~2M/L的锂盐的碳酸乙烯酯-碳酸丙烯酯溶液加入到上述溶液中,充分混合,制成凝胶聚合物电解质溶液;将凝胶聚合物电解质溶液分别涂覆在已制作好的聚吡咯聚合物电极I和聚甲基噻吩或甲基噻吩-甲氧基噻吩共混物的聚合物电极II的表面,然后进行组装。该超电容器的比电容高,可达25F/g,具有良好的环境稳定性和使用寿命,不漏液,且比液体电解质超电容器更容易组装,对环境无污染。
Description
技术领域
本发明涉及一种超电容器,特别涉及以导电高分子为活性材料组成的超电容器的结构及其制备方法,属于电子器件技术领域。
背景技术
超电容器是以导电聚合物为电极组成的电容器,与传统电容器相比,超电容器具有非常高的电容量,此外还具有高的放电功率、快速充放电能力、长循环寿命等优点,若与电动汽车中的动力电池联用,可在启动和爬坡时快速提供大电流及大功率;在正常行驶时给电容器充电。
以导电聚合物为活性材料的超电容器比贵金属氧化物电极成本低,具有更大的发展前途和竞争力。其工作原理是:通过在电极上聚合物中发生快速可逆的n型或p型元素掺杂和去掺杂过程,即氧化还原过程,使聚合物达到很高的储存电荷密度。由于电荷可在整个聚合物材料的体积内储存,所以可以形成很高的法拉第准(赝)电容。另外还可通过分子设计和材料设计来进一步优化聚合物电极的性能。因而将会有很好的发展前景。现有技术中以导电高分子为活性材料的超电容器基本上有三种类型,I型超电容器是以两种相同的p型掺杂的导电聚合物为电极;II型的超电容器以两种不同的p型掺杂的导电聚合物为电极;III型超电容器中一个电极为p型掺杂的导电聚合物,另一个电极为n型掺杂的导电聚合物。
文献“Catia Arbizzani,et al Electrochemica Acta,41(1):21-26,1996”公开了一种以聚噻吩(PMTh)和聚吡咯(PPy)两种不同的p型掺杂的导电聚合物为电极的超电容器,是采用液体电解质的,液体型超电容器存在着不易封装及漏液问题。在“S.Panero A.Clemente Solid State Ionics 86-88(1996)1285-1285”中公开了一种采用质子或者锂离子导电的聚合物为电解质,但却是以两种相同的p型掺杂的导电聚合物为电极的I型超电容器。
发明内容
本发明的目的是提供一种采用凝胶聚合物电解质的聚合物超电容器及其制备方法,旨在简化聚合物超电容器的制作工艺,并克服漏液问题。
本发明是通过如下技术方案实现的:一种采用凝胶聚合物电解质的聚合物超电容器,以两种不同的p型掺杂的导电聚合物为电极,该电容器含有电流收集极I、导电聚合物电极I、电解质、导电聚合物电极II、电流收集极II,其特征在于:所述的电解质采用凝胶聚合物电解质,所述凝胶聚合物电解质采用聚偏氟乙烯或偏氟乙烯-六氟丙烯共聚物为基体的锂离子聚合物电解质。
本发明所述的超电容器的导电聚合物电极,其导电聚合物电极I采用聚吡咯,其导电聚合物电极II采用聚甲基噻吩或甲基噻吩-甲氧基噻吩共聚物。
一种制作如权利要求1所述聚合物超电容器的方法,该方法包括如下步骤:
(1)以不锈钢或碳纸为电流收集极,在其上分别制成聚吡咯导电聚合物电极I和聚甲基噻吩或甲基噻吩-甲氧基噻吩共聚物导电聚合物电极II;
(2)制备凝胶聚合物电解质:在丙酮中加入偏氟乙烯-六氟丙烯共聚物颗粒,将其完全溶解,然后再将0.5~2M/L的高氯酸锂的碳酸乙烯酯-碳酸丙烯酯(1∶1)溶液加入到偏氟乙烯-六氟丙烯共聚物的丙酮溶液中,使各组分充分混合,制成凝胶状聚合物电解质溶液;
(3)将制成的凝胶聚合物电解质溶液分别涂覆在已经制作好的导电聚合物电极I和导电聚合物电极II的一侧表面,在室温下使丙酮自然挥发,然后将两个电极粘合在一起;
以甲基噻吩-甲氧基噻吩共聚物制作导电聚合物电极II,所述甲基噻吩-甲氧基噻吩共聚物按如下方法制备:
以碳酸丙二酯作溶剂,以1~0.001M/L浓度的六氟磷酸四丁基銨(Bu)4NPF6为支持电解质,甲基噻吩和甲氧基噻吩(2∶1~15∶1)混合物的总浓度为0.002~0.5M/L,将体系保持在-10~25℃范围内,采用三电极法聚合,以不锈钢薄片或碳纸作工作电极和对电极,以银/氯化银电极为参比电极,然后充氮气10分钟,用恒电流(j=0.1~10mA/cm2)和循环伏安相结合的方法合成甲基噻吩-甲氧基噻吩的共聚物,总共聚合时间为600~20000s。
本发明聚合物超电容器的比电容高,可达25F/g,并具有良好的环境稳定性和使用寿命。由于本电容器中采用了凝胶聚合物电解质膜,故不存在漏液问题,而且比液体电解质超电容器更容易组装,对环境不会造成污染。
附图说明
图1为本发明的超电容器的结构示意图。
图2为采用两电极法在电压的扫描速率为0.004V/s时电容器的循环伏安曲线。
图3为采用两电极法在电压的扫描速率为0.01V/s时电容器的循环伏安曲线。
图4为I=0.002A下电容器的恒电流充放电曲线。
图5为I=0.0036A下电容器的恒电流充放电曲线。
图6为电容器的交流阻抗谱。
图7为电容器的阻抗-频率特性。
具体实施方式
图1表示出本发明凝胶聚合物电解质的聚合物超电容器的结构,包括电流收集I1、导电聚合物电极I2、凝胶聚合物电解质3、导电聚合物电极II4和电流收集极II5。其具体制备步骤如下:
①.导电聚合物电极1的制作
以碳酸丙二酯作溶剂,以1~0.001M/L浓度的六氟磷酸四丁基銨(Bu)4NPF6为支持电解质,吡咯的浓度为0.5~0.002M/L,将体系保持在-10~25℃范围内,采用三电极法聚合,以不锈钢薄片或碳纸作工作电极和对电极,以银/氯化银电极为参比电极,然后充氮气10分钟,用恒电流(j=0.1~10mA/cm2)和循环伏安相结合的方法合成聚吡咯,总共聚合时间为600~20000s。聚合后在-0.5V下去掺杂。
②.导电聚合物电极II的制作
以碳酸丙二酯作溶剂,以1~0.001M/L浓度的六氟磷酸四丁基銨(Bu)4NPF6为支持电解质,甲基噻吩的浓度为0.5~0.002M/L,将体系保持在0~25℃范围内,采用三电极法聚合,以不锈钢薄片或碳纸作工作电极和对电极,以银/氯化银电极为参比电极,然后充氮气10分钟,用恒电流(j=0.1~10mA/cm2)和循环伏安相结合的方法合成聚甲基噻吩,总共聚合时间为600~20000s。
③.另一种导电聚合物电极II的制作
以碳酸丙二酯作溶剂,以1~0.001M/L浓度的六氟磷酸四丁基銨(Bu)4NPF6为支持电解质,甲基噻吩和甲氧基噻吩(2∶1~15∶1)混合物的总浓度为0.5~0.002M/L,将体系保持在-10~25℃范围内,采用三电极法聚合,以不锈钢薄片或碳纸作工作电极和对电极,以银/氯化银电极为参比电极,然后充氮气10分钟,用恒电流(j=0.1~10mA/cm2)和循环伏安相结合的方法合成甲基噻吩-甲氧基噻吩的共聚物,总共聚合时间为600~20000s。
④.凝胶聚合物电解质的制作
丙酮中加入偏氟乙烯-六氟丙烯共聚物颗粒,在回流的条件下将其完全溶解,然后再将0.5~2M/L的高氯酸锂的碳酸乙烯酯-碳酸丙烯酯(1∶1)溶液加入到聚偏氟乙烯或偏氟乙烯-六氟丙烯共聚物的丙酮溶液中,并置于超声波振荡器中使各组分充分混合,制成凝胶状聚合物电解质。
⑤.本发明聚合物超电容器的制作
将上述凝胶状聚合物电解质溶液分别涂覆在已经制作好的导电聚合物电极I和导电聚合物电极II的一侧表面,在室温下使丙酮自然挥发,然后将两个电极按图1组装(即将涂有凝胶聚合物电解质的两个面粘合在一起),如果在电极制作时采用碳纸,则在三合一组装物的外侧,再分别压入一片薄的不锈钢网作为电流收集极,以组装成本发明的聚合物超电容器。
实施例1
①.合成聚甲基噻吩
以丙二醇碳酸酯作溶剂,支持电解质(Bu)4NPF6为0.02M/L,甲基噻吩的浓度为0.1M/L,将体系保持在5±2℃范围内,采用三电极法聚合,以不锈钢作工作电极和对电极,银/氯化银电极为参比电极,然后充氮气10分钟,恒电流(j=2mA/cm2)和循环伏安相结合的方法合成聚甲基噻吩。聚合时间为6000s。
②.聚吡咯
以丙二醇碳酸酯作溶剂,支持电解质(Bu)4NPF6为0.02M/L,吡咯的浓度为0.1M/L,将体系保持在0℃,采用三电极法聚合,以不锈钢作工作电极和对电极,银/氯化银电极为参比电极,然后充氮气10分钟,恒电流(j=2mA/cm2)和循环伏安相结合的方法合成聚吡咯,聚合时间为3000s,然后在-0.5V下去掺杂。
③.凝胶电解质的制作
在丙酮中加入偏氟乙烯-六氟丙烯共聚物颗粒,在回流的条件下将其完全溶解,然后再将1M/L的高氯酸锂的碳酸乙烯酯-碳酸丙烯酯(1∶1)溶液加入到偏氟乙烯-六氟丙烯共聚物的丙酮溶液中,用超声波振荡器使各组分充分混合。
④.电容器的制作
将上述溶液分别涂覆在已经制作好的两电极的一侧表面,室温下在密闭容器中将丙酮挥发,然后将两电极按图1组装。
⑤.电容器的电化学性能测试:
采用两电极法对组装好的电容器进行了循环伏安特性测试、阻抗测试、充放电测试。图2~图7表示出了本实施例的循环伏安特特性、阻抗、恒电流充放电测试曲线。
实施例2
①.合成甲基噻吩-甲氧基噻吩共聚物
以碳酸丙二酯作溶剂,以0.02M/L浓度的六氟磷酸四丁基銨(Bu)4NPF6为支持电解质,甲基噻吩和甲氧基噻吩(10∶1)混合物的总浓度为0.1M/L,将体系保持在5±2℃范围内,采用三电极法聚合,以不锈钢薄片或碳纸作工作电极和对电极,以银/氯化银电极为参比电极,然后充氮气10分钟,用恒电流(j=0.1~10mA/cm2)和循环伏安相结合的方法合成甲基噻吩-甲氧基噻吩的共聚物,总共聚合时间为6000s。
②.聚吡咯
以丙二醇碳酸酯作溶剂,支持电解质(Bu)4NPF6为0.02M/L,吡咯的浓度为0.1M/L,将体系保持在0℃范围内,采用三电极法聚合,以不锈钢作工作电极和对电极,银/氯化银电极为参比电极,然后充氮气10分钟,恒电流(j=2mA/cm2)和循环伏安相结合的方法合成聚吡咯,聚合时间为3000s,然后在-0.5V下去掺杂。
③.凝胶电解质的制作
在丙酮中加入聚偏氟乙烯颗粒,在回流的条件下将其完全溶解,然后再将1M/L的四氟磷酸锂的碳酸乙烯酯-碳酸丙烯酯(1∶1)溶液加入到聚偏氟乙烯的丙酮溶液中,用超声波振荡器使溶液充分混合。
④.电容器的制作
将上述溶液分别涂覆在已经制作好的两电极的一侧表面,室温下在密闭容器中将丙酮挥发,然后将两电极按上述图1组装。
⑤.电容器的电化学性能测试
采用两电极法对组装好的电容器分别进行了循环伏安特性测试、阻抗测试、充放电测试,与实施例1基本相同,但环境稳定性要好一些。
Claims (6)
1.一种采用凝胶聚合物电解质的聚合物超电容器,以两种不同的p型掺杂的导电聚合物为电极,该电容器由电流收集极I、导电聚合物电极I、电解质、导电聚合物电极II、电流收集极II组成,其特征在于:所述的电解质采用凝胶聚合物电解质,所述凝胶聚合物电解质采用聚偏氟乙烯或偏氟乙烯-六氟丙烯共聚物为基体的锂离子聚合物电解质。
2.按照权利要求1所述的聚合物超电容器,其特征在于导电聚合物电极I采用聚吡咯,导电聚合物电极II采用聚甲基噻吩。
3.按照权利要求1所述的聚合物超电容器,其特征在于:导电聚合物电极I采用聚吡咯,导电聚合物电极II采用甲基噻吩-甲氧基噻吩共聚物。
4.一种制作如权利要求1所述聚合物超电容器的方法,其特征在于该方法包括如下步骤:
(1)以不锈钢或碳纸为电流收集极,在其上分别制成聚吡咯导电聚合物电极I和聚甲基噻吩(或甲基噻吩-甲氧基噻吩共聚物)导电聚合物电极II;
(2)制备凝胶聚合物电解质:在丙酮中加入偏氟乙烯-六氟丙烯共聚物颗粒,使其完全溶解,然后将0.5~2M/L的锂盐的碳酸乙烯酯-碳酸丙烯酯(1∶1)溶液加入到偏氟乙烯-六氟丙烯共聚物的丙酮溶液中,使各组分充分混合,制成凝胶聚合物电解质溶液;
(3)将制成的凝胶聚合物电解质溶液分别涂覆在已经制作好的导电聚合物电极I和导电聚合物电极II的一侧表面,在室温下使丙酮自然挥发,然后将涂有凝胶聚合物电解质的两个电极的面粘合在一起;
5.按照权利要求4所述的方法,其特征在于:所述甲基噻吩-甲氧基噻吩共聚物按如下方法合成:
以碳酸丙二酯作溶剂,以1~0.001M/L浓度的六氟磷酸四丁基銨(Bu)4NPF6为支持电解质,甲基噻吩和甲氧基噻吩(其摩尔比2∶1~15∶1)混合物的总浓度为0.002~0.5M/L,将体系保持在-10~25℃范围内,采用三电极法聚合,以不锈钢薄片或碳纸作工作电极和对电极,以银/氯化银电极为参比电极,然后充氮气10分钟,用恒电流(j=0.1~10mA/cm2)和循环伏安相结合的方法合成甲基噻吩-甲氧基噻吩的共聚物,总共聚合时间为600~20000s。
6.按照权利要求4所述的方法,其特征在于:所述的锂盐为高氯酸锂或四氟硼酸锂。
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CN100453590C (zh) * | 2004-07-23 | 2009-01-21 | 上海南都能源科技有限公司 | 聚偏氟乙烯共聚物凝胶态电解质膜及其制备工艺 |
US7528896B2 (en) | 2003-01-17 | 2009-05-05 | Cbrite, Inc. | Display employing organic material |
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US8222077B2 (en) | 2006-11-07 | 2012-07-17 | Cbrite Inc. | Metal-insulator-metal (MIM) devices and their methods of fabrication |
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