CN108365232A - 一种针刺状柔性空气电极材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种针刺状柔性空气电极材料的制备方法,将乙酸镍、乙酸钴和硫代乙酰胺加入到去离子水中搅拌形成均匀混合溶液,再将混合溶液和碳布进行水热反应,反应结束后冷却至室温后取出产物,获得生长有针刺状CoNi2S4/CP。本发明通过在碳布(CP)上生长的针刺状CoNi2S4的无粘结剂阴极来制造柔性阴极,避免使用聚合物粘结剂导致的副产物生成。
Description
技术领域
本发明涉及电极领域,具体涉及一种针刺状柔性空气电极材料及其制备方法。
背景技术
由于其轻便,可弯曲,坚固,便携带,可卷曲和可折叠等特殊优势,全球对柔性电子器件的需求持续快速增长。为了实现消费产品到汽车,航空航天和医疗行业等行业的进一步应用,灵活的能量储存与转换设备被认为是关键的必需组件之一。然而,目前的传统电源无法集成到柔性设备中,并且这些电源的低理论能量密度本质上限制了它们在下一代柔性器件中的应用。幸运的是,可充电的锂-氧(Li-O2)电池由于其理论能量密度极高(约3600Wh/kg),成为最有希望的电化学储能技术之一。尽管开发灵活的Li-O2电池理论上满足了对高能量密度的柔性电池的迫切需求,但该技术尚处于起步阶段,必须先克服众多科技挑战。首先,碳阴极的腐蚀及其促进电解质的分解导致碳阴极钝化和电池过早死亡。其次,金属泡沫和碳纸等高导电性集电器是不灵活的。因此,迫切需要设计和制造机械稳定的,电化学稳定的和高效的组件,并且创建优异的柔性电池构造和结构设计。
发明内容
针对上述问题,本发明的目的在于提供一种针刺状柔性空气电极材料及其制备方法。本发明通过在碳布(CP)上生长的针刺状CoNi2S4的无粘结剂阴极来制造柔性阴极,避免使用聚合物粘结剂导致的副产物生成。
本发明通过下述技术方案实现:
一种针刺状柔性空气电极材料的制备方法,将乙酸镍、乙酸钴和硫代乙酰胺加入到去离子水中搅拌形成均匀混合溶液,再将混合溶液和碳布进行水热反应,反应结束后冷却至室温后取出产物,获得生长有针刺状CoNi2S4/CP。
水热反应的温度为200~220摄氏度。
水热反应的时间为6~6.5h。
乙酸镍、乙酸钴和硫代乙酰胺的摩尔比为2:1:3~6。
乙酸镍、乙酸钴和硫代乙酰胺的摩尔比为2:1:6。
搅拌时间为30~45min。
碳布的清理为依次用乙醇和去离子水超声清洗30~45min。
如前述的制备方法得到的针刺状柔性空气电极材料。
本发明是用针刺状CoNi2S4的无粘结剂阴极来制造柔性阴极,避免使用聚合物粘结剂导致的副产物生成,实现更稳定和可逆的Li-O2电池,该电极还具有优异的机械强度和优异的循环稳定性。
本发明制得的电极材料的电化学性能:1)首次充放电性能:具有CoNi2S4/CP阴极的Li-O2电池在200mA/g的电流密度下,提供~8000mAh/g的高放电容量。2)倍率性能:具有CoNi2S4/CP阴极的Li-O2电池分别在不同电流密度下测试其倍率性能,当电流密度恢复到初始电流密度时,截止电压几乎没有衰减,表明具有良好的倍率性和可恢复性。3)循环性能:具有CoNi2S4/CP阴极的Li-O2电池在200mA/g的电流密度下稳定且可逆循环50次,并且无明显的电压变化,循环性能良好。
本发明中水热反应的温度不能低于200摄氏度,反应时间不能低于6小时。
本发明与现有技术相比,具有如下的优点和有益效果:
1、本发明中的针刺状柔性电极结构具有较大的比表面积,更多的催化活性位点,还有效地促进氧气和电解质的传输。
2、本发明的电极材料避免了由传统粘接剂制备的电极所涉及的副反应,从而避免了电极反应中副产物的形成,具有高度的化学稳定性,具有良好的可循环性。
3、本发明的一体化电极不仅可以应用于锂空气电池阴极中,也能运用到其他柔性电子储能器件中。
附图说明
此处所说明的附图用来提供对本发明实施例的进一步理解,构成本申请的一部分,并不构成对本发明实施例的限定。在附图中:
图1为实施例1所提供的针刺状柔性电极结构SEM图;
图2为实施例1所提供的针刺状柔性电极结构TEM图;
图3为实施例1所提供的针刺状柔性电极结构BET图;
图4为实施例1所提供的针刺状柔性电极结构的XRD图;
图5为实施例1所提供的针刺状柔性电极结构作为锂空气电极材料的首次充放电图;
图6为实施例1所提供的针刺状柔性电极结构作为锂空气电极材料的倍率性能图;
图7为实施例1所提供的针刺状柔性电极结构作为锂空气电极材料的循环性能图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,下面结合实施例和附图,对本发明作进一步的详细说明,本发明的示意性实施方式及其说明仅用于解释本发明,并不作为对本发明的限定。
实施例1
1)碳布预处理:
将商品碳布用乙醇和去离子水分别超声清洗30min,干燥待用。
2)CoNi2S4/CP的合成:将6mmol乙酸镍,3mmol乙酸钴,和18mmol硫代乙酰胺加入到30ml去离子水中搅拌30min形成均匀混合溶液,随后将混合溶液和碳布(CP)转移到100ml的高压反应釜中,于200℃反应6h。待水热反应后,在室温下取出CP,并用乙醇和去离子水洗涤数次后干燥,最后获得生长有针刺状CoNi2S4的CP(CoNi2S4/CP)。
本发明制得的电极的形貌如图1、2所示,活性表面积显着增加(如BET图3),提供大量的反应活性位点。其XRD如图4所示。电化学性能:1)首次充放电性能:具有CoNi2S4/CP阴极的Li-O2电池在200mA/g的电流密度下,提供~8000mAh/g的高放电容量。(如图5)。2)倍率性能,如图6所示:具有CoNi2S4/CP阴极的Li-O2电池分别在不同电流密度下测试其倍率性能,当电流密度恢复到初始电流密度时,截止电压几乎没有衰减,表明具有良好的倍率性和可恢复性。3)循环性能:具有CoNi2S4/CP阴极的Li-O2电池在200mA/g的电流密度下稳定且可逆循环50次,并且无明显的电压变化(如图7),循环性能良好。
实施例2
1)碳布预处理:
将商品碳布用乙醇和去离子水分别超声清洗30min,干燥待用。
2)CoNi2S4/CP的合成:将6mmol乙酸镍,3mmol乙酸钴,和12mmol硫代乙酰胺加入到30ml去离子水中搅拌30min形成均匀混合溶液,随后将混合溶液和碳布(CP)转移到100ml的高压反应釜中,于220℃反应6.5h。待水热反应后,在室温下取出CP,并用乙醇和去离子水洗涤数次后干燥,最后获得生长有针刺状CoNi2S4的CP(CoNi2S4/CP)。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种针刺状柔性空气电极材料的制备方法,其特征在于,将乙酸镍、乙酸钴和硫代乙酰胺加入到去离子水中搅拌形成均匀混合溶液,再将混合溶液和碳布进行水热反应,反应结束后冷却至室温后取出产物,获得生长有针刺状CoNi2S4/CP。
2.根据权利要求1所述的针刺状柔性空气电极材料的制备方法,其特征在于,水热反应的温度为200~220摄氏度。
3.根据权利要求1所述的针刺状柔性空气电极材料的制备方法,其特征在于,水热反应的时间为6~6.5h。
4.根据权利要求1所述的针刺状柔性空气电极材料的制备方法,其特征在于,乙酸镍、乙酸钴和硫代乙酰胺的摩尔比为2:1:3~6。
5.根据权利要求1所述的针刺状柔性空气电极材料的制备方法,其特征在于,乙酸镍、乙酸钴和硫代乙酰胺的摩尔比为2:1:6。
6.根据权利要求1所述的针刺状柔性空气电极材料的制备方法,其特征在于,搅拌时间为30~45min。
7.根据权利要求1所述的针刺状柔性空气电极材料的制备方法,其特征在于,碳布的清理为依次用乙醇和去离子水超声清洗30~45min。
8.根据权利要求1-7所述的制备方法得到的针刺状柔性空气电极材料。
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CN110299510A (zh) * | 2019-07-11 | 2019-10-01 | 青岛科技大学 | 一种以导电碳布为基底的双金属硫化物的制备及其在锂离子电池负极方面的应用 |
CN114371202A (zh) * | 2020-10-14 | 2022-04-19 | 东华大学 | 一种碳纤维复合材料及其制备方法和应用 |
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CN107010676B (zh) * | 2017-05-08 | 2018-06-19 | 浙江师范大学 | 一种用于超级电容器电极材料硫化钴镍纳米片的简便制备方法 |
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CN109786628A (zh) * | 2019-03-20 | 2019-05-21 | 广西师范大学 | 一种钴镍双金属硫化物/碳纸复合材料的制备方法及其应用 |
CN110299510A (zh) * | 2019-07-11 | 2019-10-01 | 青岛科技大学 | 一种以导电碳布为基底的双金属硫化物的制备及其在锂离子电池负极方面的应用 |
CN114371202A (zh) * | 2020-10-14 | 2022-04-19 | 东华大学 | 一种碳纤维复合材料及其制备方法和应用 |
CN114371202B (zh) * | 2020-10-14 | 2023-05-02 | 东华大学 | 一种碳纤维复合材料及其制备方法和应用 |
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