CN106409520A - 一种锂离子混合电容器电极材料的制备方法及应用 - Google Patents
一种锂离子混合电容器电极材料的制备方法及应用 Download PDFInfo
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Classifications
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
一种锂离子混合电容器电极材料的制备方法，步骤是：将硫酸亚铁铵和亚氨基二乙酸的水溶液置于反应釜中，在一定温度下进行反应，生成前驱体Fe‑IDA；将洗涤、干燥后置于氩气保护的管式炉中，进行退火实验，得到负极材料Fe3O4@C；将上述负极材料在稀酸溶液中进行腐蚀，从而得到正极材料多孔碳；将正极、负极、隔膜置于纽扣电池中，加入六氟磷酸锂溶液作为电解液，封装后得到锂离子混合电容器。本发明采用一条路线制备出锂离子混合电容器的负极材料和正极材料，解决了制备时间长、成本高、正负极容量和体积的相容性等问题。本发明组装的新型锂离子混合电容器工作电压范围宽，性能优异，并且具有较高的能量密度和超高的功率密度。
Description
技术领域
本发明涉及一种锂离子混合电容器电极材料的制备方法及应用，属于电池和超级电容器技术领域。
背景技术
由于同时使用了锂离子电池和超级电容器的电极材料，锂离子混合电容器拥有电池和超级电容器的双重特性，具有比常规超级电容器能量密度大、比锂离子电池功率密度高的优点。目前常用的锂离子混合电容器的正极材料为活性炭、碳纳米管、石墨烯等双电层电容材料，负极材料为钛酸锂、金属氧化物、石墨等可进行脱嵌锂的材料。然而，所报道的锂离子混合电容器的正负极材料通常是分别制备，因而存在制备时间长、成本高、正负极容量和体积的相容性等问题而限制了商业化生产。
现有技术中，CN105679547A公开了一种铁酸镍基锂离子混合电容器及其制备方法，该方法将活性炭与石墨烯的混合材料作为正极材料，以乙醇分散碳材料，溶解硝酸铁、硝酸镍与尿素，通过溶剂热反应得到二元复合材料前驱体，对前驱体原位聚合苯胺得到铁酸镍基的三元复合材料，作为负极材料。该专利中使用了大量的苯胺，虽提高了电极材料的导电性，但苯胺是剧毒物质，在材料制备过程中对操作人员身体健康造成极大危害，对厂区周边空气和土壤造成严重污染，不利于环保。
文献(Zhang,Fan,et al."A high-performance supercapacitor-batteryhybrid energy storage device based on graphene-enhanced electrode materialswith ultrahigh energy density."Energy&Environmental Science,2013,6,1623-1632)中公开了一种Fe3O4/石墨烯复合材料与3D石墨烯所组装成的锂离子混合电容器。该混合电容器中Fe3O4/石墨烯复合材料首先需要采用传统的Hummer方法制备氧化石墨烯，所使用的3D石墨烯需要经过葡萄糖碳化，氢氧化钾活化过程才能得到，步骤繁琐，成本高，不适合大规模的工业化生产。
发明内容
本发明的目的是针对上述存在问题，提供一种锂离子混合电容器电极材料的制备方法，该方法克服现有技术中合成步骤简单、成本低、成分中不含有有毒物质。
本发明的技术方案：
一种锂离子混合电容器电极材料的制备方法，所述锂离子混合电容器电极材料包括负极材料Fe3O4@C和正极材料多孔碳，步骤如下：
(一)负极材料Fe3O4@C核壳纳米颗粒的制备
1)将摩尔比为(2～2.5):1的硫酸亚铁铵和亚氨基二乙酸加入超纯水中，配置硫酸亚铁铵水溶液的浓度为0.05-0.2mol/L，不断搅拌直至完全溶解，得到混合液；
2)将上述混合液转移到反应釜中，将反应釜置于鼓风干燥箱中在140-180℃下保温6-18小时，然后降至室温，得到前驱体Fe-IDA，洗涤干燥后备用；
3)将上述前驱体Fe-IDA置于管式炉中，以2-10℃/min升温速率加热至400-600℃并保温1-5小时，得到Fe3O4@C核壳纳米颗粒；
(二)正极材料多孔碳的制备
将制得的负极材料Fe3O4@C核壳纳米颗粒加入浓度为1-2mol/L的稀酸溶液中，所述稀酸溶液为稀盐酸、稀醋酸或稀磷酸，在80-90℃下保温5-12小时，将产物分别用水、乙醇洗涤干燥，得到多孔碳。
一种所制备的锂离子混合电容器电极材料的的应用，用于制备锂离子混合电容器，组装步骤如下：
所述锂离子混合电容器包括正极、负极、隔膜和电解液，将多孔碳和聚偏氟乙烯按质量比为9:1的比例调成浆液，涂覆与铝箔上，干燥后作为正极；将Fe3O4@C、乙炔黑和聚偏氟乙烯按照质量比为85:10:5的比例调成浆液，涂覆与铜箔上，干燥后作为负极；将正极、负极和商业化的Celgard隔膜放置于纽扣电池壳中，正极材料和负极材料的质量比为4:1，加入电解液，电解液为1mol/L的六氟磷酸锂溶解在碳酸乙烯酯、碳酸甲乙酯和碳酸二甲酯的混合溶剂中，其中上述三种混合溶剂的体积比为1:1:1，封装后得到锂离子混合电容器。
本发明的优点和有益效果是：
1)现有技术CN105679547A中，负极材料和正极材料是分别制备的，而本发明方法中负极材料和正极材料是采用的一条路线的合成方法，用稀酸腐蚀负极材料即可得到正极材料，方法简便，操作工艺容易，因而现有技术CN105679547A中电极材料的制备成本比本发明方法中的制备成本高。
2)现有技术CN105679547A在合成负极材料的过程中，加入了大量的苯胺，苯胺是剧毒物质，将在材料制备过程中对操作人员身体健康造成极大危害，对厂区周边空气和土壤造成严重污染，不利于环保。本发明的原材料中不含有毒物质，更为绿色环保。
3)与现有技术(Zhang,Fan,et al."A high-performance supercapacitor-battery hybrid energy storage device based on graphene-enhanced electrodematerials with ultrahigh energy density."Energy&Environmental Science,2013,6,1623-1632)相比，本发明所得的锂离子混合电容器的能量密度和功率密度都较高。
附图说明
图1为制备的Fe3O4@C核壳纳米颗粒的SEM和TEM图，图中：a为SEM图，b为TEM图。
图2为制备的多孔碳的SEM和TEM图，图中：a为SEM图，b为TEM图。
图3为制备的Fe3O4@C核壳纳米颗粒和多孔碳的XRD。
图4为锂离子混合电容器的Ragone图。
具体实施方式
下面结合实施例对本发明做进一步描述。
实施例：
一种锂离子混合电容器电极材料的制备方法，所述锂离子混合电容器电极材料包括负极材料Fe3O4@C和正极材料多孔碳，步骤如下：
(一)Fe3O4@C核壳纳米颗粒的制备
1)将摩尔比为2:1的硫酸亚铁铵和亚氨基二乙酸加入超纯水中，配置硫酸亚铁铵水溶液的浓度为0.05-0.2mol/L，不断搅拌直至完全溶解，得到混合液；
2)将上述混合液转移到反应釜中，将反应釜置于鼓风干燥箱中在160℃下保温12小时，然后降至室温，得到前驱体Fe-IDA，将产物洗涤干燥备用；
3)将上述前驱体Fe-IDA置于管式炉中，以2℃/min升温速率加热至500℃并保温2小时，得到Fe3O4@C核壳纳米颗粒。
图1为制备的Fe3O4@C核壳纳米颗粒的SEM图和TEM图，图中：a为SEM图，b为TEM图。图中表明：Fe3O4@C复合材料是由无数细小的纳米颗粒组成的纳米棒，其中每个纳米颗粒都由碳层的壳和四氧化三铁的核组成的。
(二)多孔碳的制备
将上述负极材料Fe3O4@C核壳纳米颗粒加入到浓度为1mol/L的稀盐酸溶液中，在80℃并保温12小时，将产物洗涤干燥，即可得到多孔碳。
图2为制备的多孔碳的SEM图和TEM图，图中：a为SEM图，b为TEM图。图中表明：多孔碳很好地保持了Fe3O4@C纳米棒的结构，与Fe3O4@C不同的是，多孔碳中的每个纳米颗粒都只有很薄的碳层组成。
图3为制备的Fe3O4@C核壳纳米颗粒和多孔碳的XRD。图中表明：Fe3O4@C复合物在25度左右有个大包峰，除此之外其他的衍射峰都可以归属为Fe3O4，表明制备的材料为Fe3O4@C复合物；与Fe3O4@C复合物相比，多孔碳只有25度的包峰，表明Fe3O4被完全洗掉，得到纯相的碳材料。
所制备的锂离子混合电容器电极材料的的应用，用于制备锂离子混合电容器，组装步骤如下：
所述的电容器包括正极、负极和电解液，其中将多孔碳和聚偏氟乙烯按照质量比为9:1的比例调成浆液，涂覆与铝箔上，干燥后作为正极；将Fe3O4@C、乙炔黑和聚偏氟乙烯按照质量比为85:10:5的比例调成浆液，涂覆与铜箔上，干燥后作为负极；将质量比为4:1的正极和负极，以及隔膜放置于纽扣电池中，加入1mol/L的六氟磷酸锂溶解在碳酸乙烯酯、碳酸甲乙酯和碳酸二甲酯的混合溶剂(体积比为1:1:1)作为电解液，封装后得到锂离子混合电容器。
图4为锂离子混合电容器的Ragone图。图中表明：在功率密度为39W kg-1时，能量密度高达185Wh kg-1；当功率密度高达28kW kg-1时，能量密度仍能保持在95Wh kg-1。
上述实施例中所用的原材料和设备均通过公知的途径获得，所用的操作工艺是本技术领域的技术人员所能掌握的。
Claims (2)
1.一种锂离子混合电容器电极材料的制备方法，其特征在于所述锂离子混合电容器电极材料包括负极材料Fe3O4@C和正极材料多孔碳，步骤如下：
(一)负极材料Fe3O4@C核壳纳米颗粒的制备
1)将摩尔比为(2～2.5):1的硫酸亚铁铵和亚氨基二乙酸加入超纯水中，配置硫酸亚铁铵水溶液的浓度为0.05-0.2mol/L，不断搅拌直至完全溶解，得到混合液；
2)将上述混合液转移到反应釜中，将反应釜置于鼓风干燥箱中在140-180℃下保温6-18小时，然后降至室温，得到前驱体Fe-IDA，洗涤干燥后备用；
3)将上述前驱体Fe-IDA置于管式炉中，以2-10℃/min升温速率加热至400-600℃并保温1-5小时，得到Fe3O4@C核壳纳米颗粒；
(二)正极材料多孔碳的制备
将制得的负极材料Fe3O4@C核壳纳米颗粒加入浓度为1-2mol/L的稀酸溶液中，所述稀酸溶液为稀盐酸、稀醋酸或稀磷酸，在80-90℃下保温5-12小时，将产物分别用水、乙醇洗涤干燥，得到多孔碳。
2.一种权利要求1所制备的锂离子混合电容器电极材料的的应用，其特征在于用于制备锂离子混合电容器，组装步骤如下：
所述锂离子混合电容器包括正极、负极、隔膜和电解液，将多孔碳和聚偏氟乙烯按质量比为9:1的比例调成浆液，涂覆与铝箔上，干燥后作为正极；将Fe3O4@C、乙炔黑和聚偏氟乙烯按照质量比为85:10:5的比例调成浆液，涂覆与铜箔上，干燥后作为负极；将正极、负极和商业化的Celgard隔膜放置于纽扣电池壳中，正极材料和负极材料的质量比为4:1，加入电解液，电解液为1mol/L的六氟磷酸锂溶解在碳酸乙烯酯、碳酸甲乙酯和碳酸二甲酯的混合溶剂中，其中上述三种混合溶剂的体积比为1:1:1，封装后得到锂离子混合电容器。
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