CN107804846A - 一种高比容量超级电容器 - Google Patents
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Abstract
本发明涉及一种高比容量超级电容器,属于电容器制备领域。该方法将榴莲壳炭化并活化,经植物和微生物复合改性,最后冷冻干燥制得高比容量超级电容器。本发明以榴莲壳为原料制备超级电容器,解决了传统碳材料超级电容器以不可再生的化石资源为原料,制备过程复杂耗时,成本昂贵,而且对环境有污染的问题,通过碱活化扩大生物炭孔径,提高离子传输率,增大比容量,再经带有含氧官能团和含氮官能团的植物和微生物复合改性,增加生物炭表面官能团,进一步扩大比容量,又弥补了生物质炭材料大多数都是微孔材料,不利用离子的传输,制得的超级电容器比容量小的缺陷,具有广阔的应用前景。
Description
技术领域
本发明涉及一种高比容量超级电容器,属于电容器制备领域。
背景技术
超级电容器是一种高储量和大功率密度的新型储能设备,在移动通讯、航天科技、汽车工程、电力系统以及微型电子等领域受到广泛的应用,已经成为了研究者关注的热点。碳材料由于其高比表面积、良好的导电性、稳定的化学性能,便宜的价格、较宽的工作温度范围等优点被广泛应用于超级电容器的电极材料。碳材料主要包括碳气凝胶、碳纳米管、微孔碳材料、有序介孔碳和分级孔道碳材料。但是,这些碳材料的制备过程复杂耗时,成本昂贵,而且对环境有污染。
近年来,由于化石资源的短缺,碳材料的发展和应用受到了限制。含有丰富的碳材料的生物质资源木材、森林废弃物、农业废弃物、水生植物、油料植物、动物粪便、城市和工业有机废弃物等为原料制备各种碳材料成为了研究者关注的重点。我国是典型的缺材少林国家,每年都有很多农业废物资源,如果可以利用废弃的生物质制备出高性能的生物质材料,并表现出良好的电化学性能,那么这些农业废弃物则可以变废为宝。
生物质材料因其来源丰富,成本低廉,绿色环保,可再生等有点成为双电层电容器的首选材料。生物质材料主要含有纤维素、半纤维素和木质素,它们都是制备微孔生物质碳材料的很好的原料。各种各样的生物质被用于制备生物质碳材料。但是制备的生物质碳大多数都是微孔材料,不利用离子的传输,因而对于电容的贡献甚微。也就是说,大量的微孔不适合离子的运输和存储。因此,大孔结构对于多孔碳材料也至关重要。
发明内容
本发明主要解决的技术问题:针对目前传统碳材料超级电容器多是以不可再生的化石资源为原料,制备过程复杂耗时,成本昂贵,而且对环境有污染,而生物质碳材料大多数都是微孔材料,不利于离子的传输,制得的超级电容器比容量小的缺陷,提供了一种利用榴莲壳制备高比容量超级电容器的方法。该方法将榴莲壳炭化并活化,经植物和微生物复合改性,最后冷冻干燥制得高比容量超级电容器。本发明以榴莲壳为原料制备超级电容器,解决了传统碳材料超级电容器以不可再生的化石资源为原料,制备过程复杂耗时,成本昂贵,而且对环境有污染的问题,通过碱活化扩大生物炭孔径,提高离子传输率,增大比容量,再经带有含氧官能团和含氮官能团的植物和微生物复合改性,增加生物炭表面官能团,进一步扩大比容量,又弥补了生物质炭材料大多数都是微孔材料,不利用离子的传输,制得的超级电容器比容量小的缺陷,具有广阔的应用前景。
为了解决上述技术问题,本发明所采用的技术方案是:
(1)称取1~2kg榴莲壳自然晾晒1~2周,将晒干的榴莲壳放入气流粉碎机中粉碎后过60目标准筛,将过筛后的榴莲壳碎块放入炭化炉中,向炉中通入氮气直至置换出所有空气,以10℃/min速率程序升温至400~500℃保温炭化1~2h,得到炭化预制体;
(2)将上述得到的炭化预制体移入烧杯,向杯中加入浓度为0.5mol/L氢氧化钾溶液直至将炭化预制体完全浸没,放置在摇床上振荡活化过夜,过滤后将炭化预制体再次放入炭化炉,在氮气氛围下于700~800℃二次炭化2~3h,得到活化生物炭;
(3)称取2~3kg龙芽草去除叶片留下根茎,用去离子水洗涤3~5遍后放入石臼中,用石杵捣碎研磨30~40min得到糊状龙芽草浆,按质量比为1:2将得到的龙芽草浆和上述活化生物炭混合均匀得混合物;
(4)将上述混合物转入陶瓷发酵罐中,加入混合物总质量1~3%的偶氮二异丁腈,搅拌混合5~10min后按接种量为8%向罐中接入产黄纤维单胞菌,将发酵罐移入恒温箱,在28~32℃下保温发酵改性12~16天;
(5)发酵结束后取出发酵产物,放入高压蒸汽灭菌器中在0.10~0.15MPa和120~122℃下灭菌10~15min,灭菌结束后向发酵产物中加入等体积的去离子水,移入超声振荡仪以200~300W功率超声处理20~30min得混合液;
(6)待超声完毕,将混合液用卧式离心机以3000~4000r/min转速离心处理10~15min,分离得到下层黑色沉淀,将沉淀物放入真空冻干机中冻干后,即得高比容量超级电容器。
本发明的物理性质:本发明制得的高比容量超级电容器比表面积达到1950~2100m2/g,在1A/g的电流密度下比容量达到350~370F/g,在20A/g的电流密度下比容量仍然可达240~260F/g,具有广阔的应用前景。
本发明的有益效果是:
(1)本发明制得的高比容量超级电容器以生物质为原材料,成本低廉,制备工艺简单,对环境物任何污染;
(2)本发明制得的高比容量超级电容器比容量大,1A/g的电流密度下比容量达到350~370F/g,在20A/g的电流密度下比容量仍然可达240~260F/g。
具体实施方式
称取1~2kg榴莲壳自然晾晒1~2周,将晒干的榴莲壳放入气流粉碎机中粉碎后过60目标准筛,将过筛后的榴莲壳碎块放入炭化炉中,向炉中通入氮气直至置换出所有空气,以10℃/min速率程序升温至400~500℃保温炭化1~2h,得到炭化预制体;将上述得到的炭化预制体移入烧杯,向杯中加入浓度为0.5mol/L氢氧化钾溶液直至将炭化预制体完全浸没,放置在摇床上振荡活化过夜,过滤后将炭化预制体再次放入炭化炉,在氮气氛围下于700~800℃二次炭化2~3h,得到活化生物炭;称取2~3kg龙芽草去除叶片留下根茎,用去离子水洗涤3~5遍后放入石臼中,用石杵捣碎研磨30~40min得到糊状龙芽草浆,按质量比为1:2将得到的龙芽草浆和上述活化生物炭混合均匀得混合物;将上述混合物转入陶瓷发酵罐中,加入混合物总质量1~3%的偶氮二异丁腈,搅拌混合5~10min后按接种量为8%向罐中接入产黄纤维单胞菌,将发酵罐移入恒温箱,在28~32℃下保温发酵改性12~16天;发酵结束后取出发酵产物,放入高压蒸汽灭菌器中在0.10~0.15MPa和120~122℃下灭菌10~15min,灭菌结束后向发酵产物中加入等体积的去离子水,移入超声振荡仪以200~300W功率超声处理20~30min得混合液;待超声完毕,将混合液用卧式离心机以3000~4000r/min转速离心处理10~15min,分离得到下层黑色沉淀,将沉淀物放入真空冻干机中冻干后,即得高比容量超级电容器。
实例1
称取1kg榴莲壳自然晾晒1周,将晒干的榴莲壳放入气流粉碎机中粉碎后过60目标准筛,将过筛后的榴莲壳碎块放入炭化炉中,向炉中通入氮气直至置换出所有空气,以10℃/min速率程序升温至400℃保温炭化1h,得到炭化预制体;将上述得到的炭化预制体移入烧杯,向杯中加入浓度为0.5mol/L氢氧化钾溶液直至将炭化预制体完全浸没,放置在摇床上振荡活化过夜,过滤后将炭化预制体再次放入炭化炉,在氮气氛围下于700℃二次炭化2h,得到活化生物炭;称取2kg龙芽草去除叶片留下根茎,用去离子水洗涤3遍后放入石臼中,用石杵捣碎研磨30min得到糊状龙芽草浆,按质量比为1:2将得到的龙芽草浆和上述活化生物炭混合均匀得混合物;将上述混合物转入陶瓷发酵罐中,加入混合物总质量1%的偶氮二异丁腈,搅拌混合5min后按接种量为8%向罐中接入产黄纤维单胞菌,将发酵罐移入恒温箱,在28℃下保温发酵改性12天;发酵结束后取出发酵产物,放入高压蒸汽灭菌器中在0.10MPa和120℃下灭菌10min,灭菌结束后向发酵产物中加入等体积的去离子水,移入超声振荡仪以200W功率超声处理20min得混合液;待超声完毕,将混合液用卧式离心机以3000r/min转速离心处理10min,分离得到下层黑色沉淀,将沉淀物放入真空冻干机中冻干后,即得高比容量超级电容器。
本发明制得的高比容量超级电容器比表面积达到1950m2/g,在1A/g的电流密度下比容量达到350F/g,在20A/g的电流密度下比容量仍然可达240F/g,具有广阔的应用前景。
实例2
称取1kg榴莲壳自然晾晒2周,将晒干的榴莲壳放入气流粉碎机中粉碎后过60目标准筛,将过筛后的榴莲壳碎块放入炭化炉中,向炉中通入氮气直至置换出所有空气,以10℃/min速率程序升温至450℃保温炭化1h,得到炭化预制体;将上述得到的炭化预制体移入烧杯,向杯中加入浓度为0.5mol/L氢氧化钾溶液直至将炭化预制体完全浸没,放置在摇床上振荡活化过夜,过滤后将炭化预制体再次放入炭化炉,在氮气氛围下于750℃二次炭化3h,得到活化生物炭;称取2kg龙芽草去除叶片留下根茎,用去离子水洗涤4遍后放入石臼中,用石杵捣碎研磨35min得到糊状龙芽草浆,按质量比为1:2将得到的龙芽草浆和上述活化生物炭混合均匀得混合物;将上述混合物转入陶瓷发酵罐中,加入混合物总质量2%的偶氮二异丁腈,搅拌混合8min后按接种量为8%向罐中接入产黄纤维单胞菌,将发酵罐移入恒温箱,在30℃下保温发酵改性14天;发酵结束后取出发酵产物,放入高压蒸汽灭菌器中在0.13MPa和121℃下灭菌13min,灭菌结束后向发酵产物中加入等体积的去离子水,移入超声振荡仪以250W功率超声处理25min得混合液;待超声完毕,将混合液用卧式离心机以3500r/min转速离心处理13min,分离得到下层黑色沉淀,将沉淀物放入真空冻干机中冻干后,即得高比容量超级电容器。
本发明制得的高比容量超级电容器比表面积达到2000m2/g,在1A/g的电流密度下比容量达到360F/g,在20A/g的电流密度下比容量仍然可达250F/g,具有广阔的应用前景。
实例3
称取2kg榴莲壳自然晾晒2周,将晒干的榴莲壳放入气流粉碎机中粉碎后过60目标准筛,将过筛后的榴莲壳碎块放入炭化炉中,向炉中通入氮气直至置换出所有空气,以10℃/min速率程序升温至500℃保温炭化2h,得到炭化预制体;将上述得到的炭化预制体移入烧杯,向杯中加入浓度为0.5mol/L氢氧化钾溶液直至将炭化预制体完全浸没,放置在摇床上振荡活化过夜,过滤后将炭化预制体再次放入炭化炉,在氮气氛围下于800℃二次炭化3h,得到活化生物炭;称取3kg龙芽草去除叶片留下根茎,用去离子水洗涤5遍后放入石臼中,用石杵捣碎研磨40min得到糊状龙芽草浆,按质量比为1:2将得到的龙芽草浆和上述活化生物炭混合均匀得混合物;将上述混合物转入陶瓷发酵罐中,加入混合物总质量3%的偶氮二异丁腈,搅拌混合10min后按接种量为8%向罐中接入产黄纤维单胞菌,将发酵罐移入恒温箱,在32℃下保温发酵改性16天;发酵结束后取出发酵产物,放入高压蒸汽灭菌器中在0.15MPa和122℃下灭菌15min,灭菌结束后向发酵产物中加入等体积的去离子水,移入超声振荡仪以300W功率超声处理30min得混合液;待超声完毕,将混合液用卧式离心机以4000r/min转速离心处理15min,分离得到下层黑色沉淀,将沉淀物放入真空冻干机中冻干后,即得高比容量超级电容器。
本发明制得的高比容量超级电容器比表面积达到2100m2/g,在1A/g的电流密度下比容量达到370F/g,在20A/g的电流密度下比容量仍然可达260F/g,具有广阔的应用前景。
Claims (1)
1.一种高比容量超级电容器,其利用榴莲壳制备得到,其特征在于具体制备步骤为:
称取1kg榴莲壳自然晾晒1周,将晒干的榴莲壳放入气流粉碎机中粉碎后过60目标准筛,将过筛后的榴莲壳碎块放入炭化炉中,向炉中通入氮气直至置换出所有空气,以10℃/min速率程序升温至400℃保温炭化1h,得到炭化预制体;
将上述得到的炭化预制体移入烧杯,向杯中加入浓度为0.5mol/L氢氧化钾溶液直至将炭化预制体完全浸没,放置在摇床上振荡活化过夜,过滤后将炭化预制体再次放入炭化炉,在氮气氛围下于700℃二次炭化2h,得到活化生物炭;
称取2kg龙芽草去除叶片留下根茎,用去离子水洗涤3遍后放入石臼中,用石杵捣碎研磨30min得到糊状龙芽草浆,按质量比为1:2将得到的龙芽草浆和上述活化生物炭混合均匀得混合物;
将上述混合物转入陶瓷发酵罐中,加入混合物总质量1%的偶氮二异丁腈,搅拌混合5min后按接种量为8%向罐中接入产黄纤维单胞菌,将发酵罐移入恒温箱,在28℃下保温发酵改性12天;
发酵结束后取出发酵产物,放入高压蒸汽灭菌器中在0.10MPa和120℃下灭菌10min,灭菌结束后向发酵产物中加入等体积的去离子水,移入超声振荡仪以200W功率超声处理20min得混合液;
待超声完毕,将混合液用卧式离心机以3000r/min转速离心处理10min,分离得到下层黑色沉淀,将沉淀物放入真空冻干机中冻干后,即得高比容量超级电容器。
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