CN110217793A - 一种通过锰矿强化储能效率的秸秆基活性炭超级电容器电极材料的制备方法 - Google Patents
一种通过锰矿强化储能效率的秸秆基活性炭超级电容器电极材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种通过锰矿强化储能效率的秸秆基活性炭超级电容器电极材料的制备方法,是将秸秆与锰矿混合后,进行高温碳化和活化,所得活化产物再经酸浸泡、水洗、烘干,即获得用作超级电容器电极材料的活性炭。本发明利用廉价易得的锰矿和秸秆混合煅烧来优化秸秆基电容器的电化学性能,不仅工艺条件简单而且大大提高了秸秆基活性炭的电化学性能;本发明所得活性炭结构稳定、孔隙发达,具有较高的比电容和循环稳定性,是一种相对理想的超级电容器电极材料。
Description
技术领域
本发明涉及电化学领域,具体涉及一种秸秆基活性炭超级电容器电极材料的制备方法。
背景技术
由于生态平衡遭到破坏,能源危机和环境污染问题已经成为影响当今世界可持续发展的重大瓶颈性难题。目前世界上可利用能源除了煤、石油和天然气外,还有水力、风力和农业废弃物等。其中,小麦秸秆是世界上广泛分布的一种可再生农业废弃物,对其进行综合处理以实现农业废弃物在各领域的工业化应用,可以缓解能源危机、环境污染,同时提高农业综合效益,是目前各国科研人员研究的热点问题。
开发新型高效电能的储存和利用方法成为能源发展和利用的重要工作。超级电容器是一种能够快速充放电的新型功率型能源储存电子元器件,它具有高功率和长寿命的特点,填补了普通电容器与电池之间的比能量与比功率空白。它还具有安全度高、使用范围宽的优点,能够应用到多个领域,目前已受到广泛关注。因此,对超级电容器的研究具有重要的现实意义。
众所周知,电极材料是影响超级电容器性能的关键因素,所以寻找一种优异的电极材料是当前研究的重要方向。活性炭由于具有丰富的孔隙结构、巨大的比表面积及稳定的化学性质成为应用最多的电极材料。而秸秆中含有大量的木质素和纤维素,木质素和纤维素可以作为制备微孔生物质碳材料很好的原材料,因此把秸秆作为超级电容器电极制备的原材料不仅可以有效减少秸秆的不合理利用对环境的污染,还能变废为宝创造经济效益。近年来,国内外许多学者对用玉米秸秆、稻草秸秆、小麦秸秆等制备活性炭进行了大量研究,但对秸秆基活性炭的性能优化效果却不甚理想。因此,如何有效优化秸秆基活性炭的电化学性能成为目前关注的重点问题。
发明内容
本发明提供了一种通过锰矿强化储能效率的秸秆基活性炭超级电容器电极材料的制备方法,旨在可以有效制备出一种结构稳定、导电性高、孔隙发达的高性能电极材料。
为解决技术问题,本发明采用如下技术方案:
一种通过锰矿强化储能效率的秸秆基活性炭超级电容器电极材料的制备方法,其特点在于:是将秸秆与锰矿混合后,进行高温碳化和活化,所得活化产物再经酸浸泡、水洗、烘干,即获得用作超级电容器电极材料的活性炭。具体是按如下步骤进行:
(1)将秸秆在80-100℃烘干4-5h,粉碎过40-100目筛,获得秸秆颗粒备用;
(2)将所述秸秆颗粒与锰矿粉末按质量比1:0.2-0.5混合,获得混合物料;
(3)将所述混合物料置于高温管式炉中,在惰性气体保护下,以2-15℃/min的升温速率升温至350-600℃,恒温碳化0.5-2h,然后停止加热,继续在惰性气体保护下冷却至室温,取出并研磨成粉状,获得碳化料粉末;
(4)将所述碳化料粉末与活化剂按质量比1:1-4混合,然后加入与碳化料粉末质量体积比为1g:30~150mL的去离子水,超声分散均匀,再在80℃下水浴加热10-12h;
所得产物放入干燥箱中80-100℃下干燥2-3h,再置于高温管式炉中,在惰性气体保护下,以2-15℃/min的升温速率升至650-900℃,恒温活化0.5-2h,然后停止加热,继续在惰性气体保护下冷却至室温,获得活化产物;
(5)将所述活化产物置于浓酸中,超声浸泡10-30min,然后用80℃去离子水洗涤至中性,再将产物置于烘箱中80-100℃下干燥10-12h,最后过200-400目筛,即获得用作超级电容器电极材料的活性炭。
进一步地:将所述活性炭与导电剂、粘结剂按质量比7-9:1-2:1-2混合,滴加适量有机溶剂并搅拌均匀,获得涂覆液;用丝网印刷板将所得涂覆液均匀涂于集流体上,90-100℃下真空干燥12-14h,最后通过压片机在10-15MPa下压片10-30s,即制得超级电容器电极片。更进一步地:所述导电剂为乙炔黑、炭黑或石墨,优选为乙炔黑;所述粘结剂为PTFE或PVDF,优选为PTFE;所述有机溶剂为无水乙醇或N-甲基吡咯烷酮,优选为N-甲基毗咯烷酮;所述集流体为铜箔、铝箔、泡沫镍或碳纸,优选为泡沫镍。
进一步地,所述秸秆可以为水稻秸秆、小麦秸秆、油菜秸秆或者玉米秸秆。
进一步地,所述锰矿为二氧化锰矿、天然水锰矿、褐锰矿、软锰矿、硬锰矿和黑锰矿中的至少一种。
进一步地,步骤(3)和步骤(4)所述惰性气体为高纯氮气、高纯氩气或二氧化碳,优选为高纯氮气。
进一步地,步骤(4)所述活化剂为氢氧化钾、氢氧化钠、磷酸或者氯化锌中的至少一种的固体粉末,优选为分析纯氢氧化钾固体粉末。
进一步地,步骤(5)中所述浓酸为浓硝酸或浓盐酸,优选为浓盐酸;所述浓酸的质量浓度为20-37.5%。
本发明通过在秸秆中加入锰矿,高温煅烧条件下MnO2与秸秆中的碳发生反应,生成Mn2O3和CO,实现氧原子的掺杂,进而促使氧化还原反应的发生,产生赝电容,从而提高超级电容器的电化学性能。
与已有技术相比,本发明的有益效果体现在:
1、空白秸秆制备超级电容器的比电容为168.0Fg-1,而本发明利用锰矿与秸秆混合制备的超级电容器比电容最高达到了224.5Fg-1,相比空白秸秆比电容提高了33.6%。
2、通过本发明的方法所得活性炭结构稳定、孔隙发达(具有微中孔相结合的孔隙结构、较高的比表面积),具有较高的比电容和循环稳定性,是一种相对理想的超级电容器电极材料。
3、本发明添加的锰矿廉价易得,大大节约了成本,且无需预处理,操作方法简单可行,节能环保,后处理工艺简单,重复性高。
附图说明
图1为本发明实施例1所得活性炭样品AC-400-Mn的FESEM图像,其中a、b对应不同放大倍数;
图2为本发明实施例1所得活性炭样品AC-400-Mn和AC-400-0的低温N2吸附脱附等温线(a)和孔体积分布(b)。
具体实施方式
下面通过具体实施方式对本发明的方法进行说明,此部分的描述仅为解释性和示范性,所描述的实例仅仅是本发明的一部分实例,而不是全部的实例,而且本发明并不局限于此。
实施例1
本实施例按如下步骤制备活性炭:
(1)将收集到的秸秆在80℃烘干5h,粉碎过40目筛,获得秸秆颗粒备用;
(2)将5g秸秆颗粒与1.5g二氧化锰矿粉末混合均匀,获得混合物料;
(3)将混合物料置于高温管式炉中,在惰性气体氮气保护下,以5℃/min的升温速率升温至400℃,恒温碳化1h,然后停止加热,继续在氮气保护下冷却至室温,取出并研磨成粉状,获得碳化料粉末;
(4)将2g碳化料粉末与6g固体粉末KOH混合,然后加入200mL的去离子水,超声分散均匀,再在80℃下水浴加热10h;
所得产物放入干燥箱中90℃下干燥3h,再置于高温管式炉中,在惰性气体保护下,以5℃/min的升温速率升至750℃,恒温活化2h,然后停止加热,继续在惰性气体保护下冷却至室温,获得活化产物;
(5)将活化产物置于36.5g/L的浓盐酸中,用额定功率为100W的超声机超声浸泡15min,然后用80℃去离子水洗涤至中性,再将产物置于烘箱中100℃下干燥10h,最后过200目筛,即获得用作超级电容器电极材料的活性炭,记为AC-400-Mn。
为进行对比,制备不加锰矿的空白对照样品,标记为AC-400-0,制备方法与AC-400-Mn相同,区别仅在于步骤(2)中不加二氧化锰矿粉末。
图1为样品AC-400-Mn在不同放大倍数下的FESEM图像,从图中可清晰得看出材料表面有大量的通道,显示出活性炭有序的孔结构。
图2为活性炭样品AC-400-Mn和AC-400-0的低温N2吸附脱附等温线(a)和孔体积分布(b)。相对压力0.01以下陡峭的吸附曲线表明,微孔对表面积的贡献最大。由图(a)可见,活性炭样品AC-400-0的低温N2吸附脱附等温线具有IUPCA-I型形状,在中等分压(P/P0=0.4)以上的N2吸附量几乎没有增加,表明N2分子已经几乎完全填满微孔,活性炭主要以微孔为主,存在少量中孔。活性炭样品AC-400-0的比表面积较低,孔隙结构较不发达,微孔孔径集中在0.5-1.5nm之间。当加入二氧化锰矿之后,活性炭AC-400-Mn的N2吸附脱附曲线在中等分压(P/P0=0.4)以上的N2吸附量有所增加,存在回滞环,表明样品存在中孔,比表面积明显增加,达到1559m2g-1,其中微孔面积为916m2g-1、中孔面积为642m2g-1,活性炭AC-400-Mn存在大量的微孔和中孔,为微/中孔复合材料。丰富的多孔结构和活性炭高的比表面积可以作为离子交换的信道,因此有望作为电极材料用于超级电容器。
综上,经测试,本实施例所得活性炭AC-400-Mn的比表面积1559m2g-1、总孔体积1.00cm3g-1,孔径分布较均匀,以中孔和微孔分布为主。而空白对照AC-400-0的比表面积为1380m2g-1、总孔体积0.80cm3g-1,孔径以微孔为主。
将步骤(5)所得活性炭与导电剂乙炔黑和粘结剂PTFE按质量比8:1:1混合并搅拌均匀,获得涂覆液;用丝网印刷板将所得涂覆液均匀涂于面积为1cm2集流体泡沫镍上,100℃下真空干燥12h,最后通过压片机在12MPa下压片30s,即制得超级电容器电极片。
采用三电极体系,电解液为6M KOH溶液,在电化学工作站CHI660上对本实施例所得超级电容器电极片进行测试。经测试,本实施例所得电极片对应不同扫速下的循环伏安曲线呈类矩形状,表明其是典型碳材料的双电层电容器,进行充放电测试,发现曲线呈对称的三角形,说明发生了双电层的电荷转移反应,在电流密度为1Ag-1时,活性炭材料对应的比电容为224.5Fg-1,相比空白秸秆制备的活性炭其比电容提高约33.6%。
实施例2
本实施例按如下步骤制备活性炭:
(1)将收集到的秸秆在80℃烘干5h,粉碎过40目筛,获得秸秆颗粒备用;
(2)将5g秸秆颗粒与2g二氧化锰矿粉末混合均匀,获得混合物料;
(3)将混合物料置于高温管式炉中,在惰性气体氮气保护下,以5℃/min的升温速率升温至500℃,恒温碳化1h,然后停止加热,继续在氮气保护下冷却至室温,取出并研磨成粉状,获得碳化料粉末;
(4)将2g碳化料粉末与8g固体粉末KOH混合,然后加入200mL的去离子水,超声分散均匀,再在80℃下水浴加热10h;
所得产物放入干燥箱中90℃下干燥3h,再置于高温管式炉中,在惰性气体保护下,以5℃/min的升温速率升至850℃,恒温活化2h,然后停止加热,继续在惰性气体保护下冷却至室温,获得活化产物;
(5)将活化产物置于36.5g/L的浓盐酸中,用额定功率为100W的超声机超声浸泡15min,然后用80℃去离子水洗涤至中性,再将产物置于烘箱中100℃下干燥10h,最后过200目筛,即获得用作超级电容器电极材料的活性炭。
经测试,本实例所得活性炭的比表面积1046m2g-1、总孔体积0.72cm3g-1,孔径分布均匀,以中孔和微孔分布为主。
将步骤(5)所得活性炭与导电剂乙炔黑和粘结剂PTFE按质量比8:1:1混合并搅拌均匀,获得涂覆液;用丝网印刷板将所得涂覆液均匀涂于面积为1cm2集流体泡沫镍上,100℃下真空干燥12h,最后通过压片机在12MPa下压片30s,即制得超级电容器电极片。
采用三电极体系,电解液为6M KOH溶液,在电化学工作站CHI660上对本实施例所得超级电容器电极片进行测试。经测试,本实施例所得电极片对应不同扫速下的循环伏安曲线呈类矩形状,表明其是典型碳材料的双电层电容器,进行充放电测试,发现曲线呈对称的三角形,说明发生了双电层的电荷转移反应,在电流密度为1Ag-1时,活性炭材料对应的比电容为214.3Fg-1,相比空白秸秆制备活性炭其比电容提高约27.6%。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种通过锰矿强化储能效率的秸秆基活性炭超级电容器电极材料的制备方法,其特征在于:是将秸秆与锰矿混合后,进行高温碳化和活化,所得活化产物再经酸浸泡、水洗、烘干,即获得用作超级电容器电极材料的活性炭。
2.根据权利要求1所述的制备方法,其特征在于,是按如下步骤进行:
(1)将秸秆在80-100℃烘干4-5h,粉碎过40-100目筛,获得秸秆颗粒备用;
(2)将所述秸秆颗粒与锰矿粉末按质量比1:0.2-0.5混合,获得混合物料;
(3)将所述混合物料置于高温管式炉中,在惰性气体保护下,以2-15℃/min的升温速率升温至350-600℃,恒温碳化0.5-2h,然后停止加热,继续在惰性气体保护下冷却至室温,取出并研磨成粉状,获得碳化料粉末;
(4)将所述碳化料粉末与活化剂按质量比1:1-4混合,然后加入与碳化料粉末质量体积比为1g:30~150mL的去离子水,超声分散均匀,再在80℃下水浴加热10-12h;
所得产物放入干燥箱中80-100℃下干燥2-3h,再置于高温管式炉中,在惰性气体保护下,以2-15℃/min的升温速率升至650-900℃,恒温活化0.5-2h,然后停止加热,继续在惰性气体保护下冷却至室温,获得活化产物;
(5)将所述活化产物置于浓酸中,超声浸泡10-30min,然后用80℃去离子水洗涤至中性,再将产物置于烘箱中80-100℃下干燥10-12h,最后过200-400目筛,即获得用作超级电容器电极材料的活性炭。
3.根据权利要求1或2所述的制备方法,其特征在于:将所述活性炭与导电剂、粘结剂按质量比7-9:1-2:1-2混合,滴加适量有机溶剂并搅拌均匀,获得涂覆液;用丝网印刷板将所得涂覆液均匀涂于集流体上,90-100℃下真空干燥12-14h,最后通过压片机在10-15MPa下压片10-30s,即制得超级电容器电极片。
4.根据权利要求1或2所述的制备方法,其特征在于:所述秸秆为水稻秸秆、小麦秸秆、油菜秸秆或者玉米秸秆。
5.根据权利要求1或2所述的制备方法,其特征在于:所述锰矿为二氧化锰矿、天然水锰矿、褐锰矿、软锰矿、硬锰矿和黑锰矿中的至少一种。
6.根据权利要求2所述的制备方法,其特征在于:步骤(3)和步骤(4)所述惰性气体为高纯氮气、高纯氩气或二氧化碳。
7.根据权利要求2所述的制备方法,其特征在于:步骤(4)所述活化剂为氢氧化钾、氢氧化钠、磷酸或者氯化锌中的至少一种。
8.根据权利要求2所述的制备方法,其特征在于:步骤(5)中所述浓酸为浓硝酸或浓盐酸;所述浓酸的质量浓度为20-37.5%。
9.根据权利要求3所述的制备方法,其特征在于:所述导电剂为乙炔黑、炭黑或石墨,所述粘结剂为PTFE或PVDF,所述有机溶剂为无水乙醇或N-甲基吡咯烷酮,所述集流体为铜箔、铝箔、泡沫镍或碳纸。
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CN115295319A (zh) * | 2022-08-30 | 2022-11-04 | 百色学院 | 一种基于电解锰渣的多元掺杂锰铁炭复合电极材料及其制备方法 |
CN115744900A (zh) * | 2022-11-29 | 2023-03-07 | 淮阴工学院 | 一种生物质活性炭基电极材料的制备方法及应用 |
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CN115295319A (zh) * | 2022-08-30 | 2022-11-04 | 百色学院 | 一种基于电解锰渣的多元掺杂锰铁炭复合电极材料及其制备方法 |
CN115295319B (zh) * | 2022-08-30 | 2024-03-01 | 百色学院 | 一种基于电解锰渣的多元掺杂锰铁炭复合电极材料及其制备方法 |
CN115744900A (zh) * | 2022-11-29 | 2023-03-07 | 淮阴工学院 | 一种生物质活性炭基电极材料的制备方法及应用 |
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Application publication date: 20190910 |