CN104851609A - 一种高化学稳定性的秸秆基超级电容器电极及其制备方法 - Google Patents
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Abstract
本发明公开了一种高化学稳定性的秸秆基超级电容器电极,其特征在于,由下列重量份的原料制成:改性秸秆复合材料85-95、磷酸铁锂2-4、醋酸锌1-2、硝酸镁1-2、硅微球2-3、聚偏氟乙烯1-2、N-甲基-2-吡咯烷酮3-5、去离子水适量;本发明通过对作物秸秆炭化、活化和掺杂改性,制备出高活性、高比表面积的炭,添加的磷酸铁锂具有高的能量密度,安全性好,对人体无毒,并且充电速度快,寿命长,和活性炭相互协同作用,具有很高的化学稳定性和能量密度,性能优异。
Description
技术领域
本发明涉及化学能源材料领域,特别是一种高化学稳定性的秸秆基超级电容器电极及其制备方法。
背景技术
超级电容器是一种介于传统电容器和二次电池之间的电化学储能装 置,主要包括双电层电容和法拉第准电容(也称为赝电容)。双电层电容的原理是德国物理学家亥姆霍兹于1853年提出的界面双电层理论,即通过活性材料和电解液界面上的电荷分离过程产生静电电容进行储能。相比于法拉第准电容,双电层电容在电极和电解液表面没有化学反应,具有更快的充放电速度,更高的功率密度,更好的循环稳定性,以及更长久的充放电寿命。超级电容器一般采用具有较大比表面积的多孔炭结构作为储能活性材料。但是一直以来阻碍活性炭应用发展的最大问题是高昂的生产价格,所以国内外的研究工作集中在如何利用价廉易得的废弃生物质能源来制备具有高比表面积的木质活性炭。
我国是农业大国,伴随着各种农作物成熟后秸秆产量更是多达7亿多吨,除去将其用作燃料、建筑材料、饲料和肥料以及发电外,仍有60%的无法有效利用而遭废弃,不仅造成了大量的生物质能源浪费,也对环境造成了一定的影响。所以本发明利用农作物秸秆进行炭化、活化等步骤制成活性炭,作为电极的材料,但是缺点就是能量密度不高,针对这一情况添加的磷酸铁锂具有高的能量密度,安全性好,对人体无毒,并且充电速度快,寿命长,和活性炭相互协同作用,具有很高的化学稳定性和能量密度,性能优异。
发明内容
本发明的目的是提供一种高化学稳定性的秸秆基超级电容器电极及其制备方法。
为了实现本发明的目的,本发明通过以下方案实施:
一种高化学稳定性的秸秆基超级电容器电极,由下列重量份的原料制成:改性秸秆复合材料85-95、磷酸铁锂2-4、醋酸锌1-2、硝酸镁1-2、硅微球2-3、聚偏氟乙烯1-2、N-甲基-2-吡咯烷酮3-5、去离子水适量;
所述改性秸秆复合材料是由下列重量份的原料制成:秸秆100-120、稀盐酸溶液30-50、氯化锌30-50、甲基三乙氧基硅烷1-2、钛酸锰1-2、导电炭黑2-4、石墨烯2-4、煅烧高岭土15-25、过硫酸钾0.5-0.8、超细玻璃纤维0.5-1;制备方法是(1)将秸秆粉碎成8-20目,用水清洗干净后在100-120°C下干燥至恒重;(2)将秸秆原料与60%的氯化锌按照1:2-3的配比混合,搅拌均匀,浸渍24小时后放入马弗炉中,在600-700°C温度下活化1小时,然后经水洗、过滤、干燥得到活性炭备用;(3)将煅烧高岭土和活性炭加到稀盐酸溶液中,于室温下浸泡8-12小时,过滤,固体用蒸馏水洗涤至中性,滤液无氯离子检出,真空干燥后研磨粉碎过200-300目筛;(4)将步骤(3)的产物和蒸馏水按照粉体重量:0.1:30-50的比例混合均匀,加热至40-50°C,加入过硫酸钾、甲基三乙氧基硅烷,搅拌均匀,再加入其余剩余物质搅拌3-5小时,反应结束后经抽滤、干燥制得改性秸秆复合材料。
本发明所述一种高化学稳定性的秸秆基超级电容器电极,由以下具体的步骤制成:将聚偏氟乙烯加到N-甲基-2-吡咯烷酮中,高速搅拌形成粘稠的液体,再加入称量好的磷酸铁锂、醋酸锌、硝酸镁、硅微球充分搅拌0.5-1小时,再加入改性秸秆复合材料和适量的去离子水,先高速搅拌1-2小时,再转移到胶磨机中低速研磨得到200-400目的浆料,再将浆料均匀的涂布在集流体上,在温度100-110°C下真空干燥8-12小时,取出后在10MPa的压力下进行压片,裁剪后再次放入真空干燥箱内90-100°C温度下烘干至恒重即可。
本发明的优点是:本发明通过对作物秸秆炭化、活化和掺杂改性,制备出高活性、高比表面积的炭,添加的磷酸铁锂具有高的能量密度,安全性好,对人体无毒,并且充电速度快,寿命长,和活性炭相互协同作用,具有很高的化学稳定性和能量密度,性能优异。
具体实施方案
下面通过具体实例对本发明进行详细说明。
一种高化学稳定性的秸秆基超级电容器电极,由下列重量份(公斤)的原料制成:改性秸秆复合材料90、磷酸铁锂3、醋酸锌1、硝酸镁2、硅微球3、聚偏氟乙烯2、N-甲基-2-吡咯烷酮5、去离子水适量;
所述改性秸秆复合材料是由下列重量份(公斤)的原料制成:秸秆100、稀盐酸溶液39、氯化锌35、甲基三乙氧基硅烷1、钛酸锰2、导电炭黑4、石墨烯3、煅烧高岭土20、过硫酸钾0.7、超细玻璃纤维0.8;制备方法是(1)将秸秆粉碎成8-20目,用水清洗干净后在100-120°C下干燥至恒重;(2)将秸秆原料与60%的氯化锌按照1:2-3的配比混合,搅拌均匀,浸渍24小时后放入马弗炉中,在600-700°C温度下活化1小时,然后经水洗、过滤、干燥得到活性炭备用;(3)将煅烧高岭土和活性炭加到稀盐酸溶液中,于室温下浸泡8-12小时,过滤,固体用蒸馏水洗涤至中性,滤液无氯离子检出,真空干燥后研磨粉碎过200-300目筛;(4)将步骤(3)的产物和蒸馏水按照粉体重量:0.1:30-50的比例混合均匀,加热至40-50°C,加入过硫酸钾、甲基三乙氧基硅烷,搅拌均匀,再加入其余剩余物质搅拌3-5小时,反应结束后经抽滤、干燥制得改性秸秆复合材料。
本发明所述一种高化学稳定性的秸秆基超级电容器电极,由以下具体的步骤制成:将聚偏氟乙烯加到N-甲基-2-吡咯烷酮中,高速搅拌形成粘稠的液体,再加入称量好的磷酸铁锂、醋酸锌、硝酸镁、硅微球充分搅拌0.5-1小时,再加入改性秸秆复合材料和适量的去离子水,先高速搅拌1-2小时,再转移到胶磨机中低速研磨得到200-400目的浆料,再将浆料均匀的涂布在集流体上,在温度100-110°C下真空干燥8-12小时,取出后在10MPa的压力下进行压片,裁剪后再次放入真空干燥箱内90-100°C温度下烘干至恒重即可。
以所述实施例中制备的电极为工作电极,铝箔为集电极,聚四氟乙烯为隔膜,1.0M三乙基甲基铵四氟硼酸盐的乙腈溶液为电解液,在1.2-2.5V的范围内,在恒流(5mA)下进行循环测试,容量:1.69F,内阻:1.7Ω·m,循环容量保持率(%):98.3。
Claims (2)
1.一种高化学稳定性的秸秆基超级电容器电极,其特征在于,由下列重量份的原料制成:改性秸秆复合材料85-95、磷酸铁锂2-4、醋酸锌1-2、硝酸镁1-2、硅微球2-3、聚偏氟乙烯1-2、N-甲基-2-吡咯烷酮3-5、去离子水适量;
所述改性秸秆复合材料是由下列重量份的原料制成:秸秆100-120、稀盐酸溶液30-50、氯化锌30-50、甲基三乙氧基硅烷1-2、钛酸锰1-2、导电炭黑2-4、石墨烯2-4、煅烧高岭土15-25、过硫酸钾0.5-0.8、超细玻璃纤维0.5-1;制备方法是(1)将秸秆粉碎成8-20目,用水清洗干净后在100-120°C下干燥至恒重;(2)将秸秆原料与60%的氯化锌按照1:2-3的配比混合,搅拌均匀,浸渍24小时后放入马弗炉中,在600-700°C温度下活化1小时,然后经水洗、过滤、干燥得到活性炭备用;(3)将煅烧高岭土和活性炭加到稀盐酸溶液中,于室温下浸泡8-12小时,过滤,固体用蒸馏水洗涤至中性,滤液无氯离子检出,真空干燥后研磨粉碎过200-300目筛;(4)将步骤(3)的产物和蒸馏水按照粉体重量:0.1:30-50的比例混合均匀,加热至40-50°C,加入过硫酸钾、甲基三乙氧基硅烷,搅拌均匀,再加入其余剩余物质搅拌3-5小时,反应结束后经抽滤、干燥制得改性秸秆复合材料。
2.根据权利要求1所述一种高化学稳定性的秸秆基超级电容器电极,其特征在于,由以下具体的步骤制成:将聚偏氟乙烯加到N-甲基-2-吡咯烷酮中,高速搅拌形成粘稠的液体,再加入称量好的磷酸铁锂、醋酸锌、硝酸镁、硅微球充分搅拌0.5-1小时,再加入改性秸秆复合材料和适量的去离子水,先高速搅拌1-2小时,再转移到胶磨机中低速研磨得到200-400目的浆料,再将浆料均匀的涂布在集流体上,在温度100-110°C下真空干燥8-12小时,取出后在10MPa的压力下进行压片,裁剪后再次放入真空干燥箱内90-100°C温度下烘干至恒重即可。
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CN102786052A (zh) * | 2012-07-16 | 2012-11-21 | 太仓市联林活性炭厂 | 一种稻壳脱硅制备活性炭的方法 |
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US20030068550A1 (en) * | 2001-10-01 | 2003-04-10 | Katsuhiko Naoi | Electrode material and applications therefor |
CN101162789A (zh) * | 2007-11-16 | 2008-04-16 | 山东神工海特电子科技有限公司 | 1.5v的充电电容电池 |
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