CN112614985A - 一种水系锌离子电池及正极的制备方法 - Google Patents
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
一种水系锌离子电池及正极制备方法,涉及锌离子电池的技术领域。所述锌离子电池由正极、负极、介于正负极之间的隔膜和电解液组成,所述正极由多金属钒酸盐复合材料、导电剂、粘结剂组成。将多金属钒酸盐复合材料、导电碳、粘结剂,按照一定质量比配制成混合浆料,搅拌后制备成水系锌离子电池电极浆料;再将水系锌离子电池电极浆料涂覆在集流体上,干燥后得到水系锌离子电池的正极极片。本发明的金属钒酸盐复合正极材料在电化学测试过程中表现出优良的稳定性和较高的可逆容量,在水系锌离子电池领域中有着较大的应用潜力。
Description
技术领域
本发明涉及水系锌离子电池技术领域,具体涉及基于多金属钒酸盐的锌离子电池正极材料的制备方法。
背景技术
目前,能源危机和环境污染是人类面临的两大挑战。随着对环保要求的不断增高,人们渴望生产出高能量密度且成本低的大规模储能设备,这种需求刺激了各种能量储存系统的快速发展。作为最有前途的能源存储技术之一,锌离子可充电电池近来备受关注。首先,锌离子电池具有很高的理论容量(820 mAh g–1),这为替代锂离子电池提供了理论基础。一方面,作为锌离子电池阳极材料的金属锌有着很大的自然丰度,这意味着较低的成本。另外,金属锌的冶炼储存难度也远远低于锂,这也有益于进一步降低成本。另一方面,锌离子电池采用温和的水系电解液,相比于锂离子电池采用的有机系电解液,水系电解液更加安全环保,不会发生着火爆炸等安全事故。由于水系电解液安全的特性,锌离子电池对环境几乎没有负担,即使随意弃置也不会造成环境污染。
但是,目前为止锌离子电池的开发仍然处于初步阶段。这是因为缺少合适的正极材料。目前,锌离子电池的正极材料主要有钒基材料、锰基材料和普鲁士蓝类材料。这些材料合成工艺复杂,成本高昂,因此极大地限制了锌离子电池的发展。在这样的背景下,寻找一种具有高容量,高能量密度且制备简单成本低廉的锌离子电池正极材料是迫在眉睫的。
发明内容
针对背景技术中所指出的问题及现有技术存在的不足,本发明的目的是提供一种基于多金属钒酸盐的复合正极材料的构建方法,有助于构建高性能水系锌离子电池体系。
本发明的技术方案是:
一种水系锌离子电池,所述锌离子电池由正极、负极、介于正负极之间的隔膜和电解液组成,所述正极由多金属钒酸盐复合材料、导电剂、粘结剂组成。
优选的是,本发明的负极材料为锌片、锌粉、电镀锌、泡沫锌或锌单质材料中的一种。
优选的是,本发明的膈膜选自无纺布、玻璃纤维、聚酰胺、聚对苯二甲酸酯、聚酰亚胺、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚丙乙烯、聚四氟乙烯、聚偏氟乙烯、聚碳酸酯中的一种或多种。
优选的是,本发明的电解液包括可溶性锌盐。
优选的是,本发明的可溶性锌盐为硫酸锌、氯化锌、硝酸锌、乙酸锌、氟化锌、六氟酸锌、三氟甲磺酸锌中至少一种。
基于本发明的水系锌离子电池的正极制备方法,将多金属钒酸盐复合材料、导电碳、粘结剂,按照一定质量比配制成混合浆料,搅拌后制备成水系锌离子电池电极浆料;再将水系锌离子电池电极浆料涂覆在集流体上,干燥后得到水系锌离子电池的正极极片。
优选的是,本发明的集流体是不锈钢箔,不锈钢网,碳布,钛箔中的一种或几种。
与现有技术相比,本发明具有如下有益效果:
1、本发明的多金属钒酸盐复合材料制备过程简单,成本低廉、对设备要求低,反应条件温和。
2、本发明的多金属钒酸盐复合材料应用于水系锌离子电池正极材料中表现出优异的电化学性能。
附图说明
图1是实施例1制得的多金属钒酸盐(V19)作为水系锌离子电池正极材料的周期-容量图。
图2是实施例2制得的多金属钒酸盐复合材料(V19@PDA)作为水系锌离子电池正极材料的周期-容量图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
一种水系锌离子电池,所述锌离子电池由正极、负极、介于正负极之间的隔膜和电解液组成,所述正极由多金属钒酸盐复合材料、导电剂、粘结剂组成。负极材料为锌片、锌粉、电镀锌、泡沫锌或锌单质材料中的一种。
本发明的膈膜选自无纺布、玻璃纤维、聚酰胺、聚对苯二甲酸酯、聚酰亚胺、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚丙乙烯、聚四氟乙烯、聚偏氟乙烯、聚碳酸酯中的一种或多种。
本发明的电解液包括可溶性锌盐。可溶性锌盐为硫酸锌、氯化锌、硝酸锌、乙酸锌、氟化锌、六氟酸锌、三氟甲磺酸锌中至少一种。
基于本发明的水系锌离子电池的正极制备方法,将多金属钒酸盐复合材料、导电碳、粘结剂,按照一定质量比配制成混合浆料,搅拌后制备成水系锌离子电池电极浆料;再将水系锌离子电池电极浆料涂覆在集流体上,干燥后得到水系锌离子电池的正极极片。本发明的集流体是不锈钢箔,不锈钢网,碳布,钛箔中的一种或几种。
实施例1:多金属钒酸盐(NH4)8[V19O41(OH)9]•11H2O (下文中以V19代指) 的制备和在水系锌离子电池中的应用。
将8g NH4VO3溶于250ml,70-80℃,PH=5-6的水溶液(10%的H2SO4调节),加入1.4g硫酸肼。溶液的颜色由黄色变成黑色。将混合物在室温下搅拌10-30分钟,用10%的H2SO4将溶液PH调至5-6,随后将溶液在60-70℃油浴中加热5-10小时,过滤得到黑色晶体。洗涤,干燥。得到化合物V19。
将V19与乙炔黑和PTFE以7:2:1的质量比混合,加入适量N-甲基吡咯烷制备成电极浆料,充分混合后将电极浆料均匀涂抹到的不锈钢片上,真空干燥制成电极片。使用2.5mol/L Zn(CF3SO3)2溶液作为电解液,组装CR-2032型纽扣电池。
如图1所示,用电池测试系统对组装的电池进行循环性能测试,测试电压范围为0.2-1.6 V,电流密度为2000 mA/g,对电池进行充放电循环。
V19在作为水系锌离子电池阳极材料时表现出了良好的电化学性能,在2000 mA/g的电流密度下,首周放电容量约为310.97 mAh/g,首周库伦效率91.4%,在之后的几圈循环内,库伦效率迅速上升到98%以上,这表明电极表面已形成稳定的SEI膜。在后来的循环中,V19的可逆容量稳定在250-300 mAh/g。这表明这V19在水系锌离子电池方面具有良好的应用潜力。
实施例2:多金属钒酸盐复合材料V19@PDA的制备和在水系锌离子电池中的应用。
根据实施例1合成V19作为前体材料,将0.05克多巴胺添加到20 mL 浓度为2 mM的V19水溶液中。将混合溶液连续搅拌1小时后将转移到特氟龙高压釜中,在150-170 ℃下热处理16-20小时。冷却至室温后,在反应釜的底部和侧壁获得黑色产物即为V19@PDA复合材料。最后,将V19@PDA复合材料进行洗涤,并在120-160 ℃下干燥。
将V19@PDA复合材料与乙炔黑和PTFE以7:2:1的质量比混合,加入适量N-甲基吡咯烷制备成电极浆料,充分混合后将电极浆料均匀涂抹到的不锈钢片上,真空干燥制成电极片。使用2.5 mol/L Zn(CF3SO3)2溶液作为电解液,组装CR-2032型纽扣电池。
如图2所示,用电池测试系统对组装的电池进行循环性能测试,测试电压范围为0.2-1.6 V,电流密度为2000 mA/g,对电池进行充放电循环。
V19@PDA复合材料在作为水系锌离子电池阳极材料时表现出了良好的电化学性能,在2000 mA/g的电流密度下,首周放电容量约为76.92 mAh/g,首周库伦效率为112.0%,在之后的几圈循环内,库伦效率迅速下降到98%,这表明电极表面已形成稳定的SEI膜。在后来的循环中,V19@PDA复合材料的可逆容量稳定在140-200 mAh/g。这表明这V19@PDA复合材料在水系锌离子电池方面具有良好的应用潜力。
本发明的多金属钒酸盐复合正极材料合成方法简单,成本低廉,安全环保,是非常理想的水系锌离子电池正极材料。本发明的金属钒酸盐复合正极材料在电化学测试过程中表现出优良的稳定性和较高的可逆容量,在水系锌离子电池领域中有着较大的应用潜力。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (7)
1.一种水系锌离子电池,其特征在于所述锌离子电池由正极、负极、介于正负极之间的隔膜和电解液组成,所述正极由多金属钒酸盐复合材料、导电剂、粘结剂组成。
2.根据权利要求1所述的水系锌离子电池,其特征在于上述负极材料为锌片、锌粉、电镀锌、泡沫锌或锌单质材料中的一种。
3.根据权利要求1所述的水系锌离子电池,其特征在于上述膈膜选自无纺布、玻璃纤维、聚酰胺、聚对苯二甲酸酯、聚酰亚胺、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚丙乙烯、聚四氟乙烯、聚偏氟乙烯、聚碳酸酯中的一种或多种。
4.根据权利要求1所述的水系锌离子电池,其特征在于上述电解液包括可溶性锌盐。
5.根据权利要求1所述的水系锌离子电池,其特征在于上述可溶性锌盐为硫酸锌、氯化锌、硝酸锌、乙酸锌、氟化锌、六氟酸锌、三氟甲磺酸锌中至少一种。
6.基于权利要求1所述的水系锌离子电池的正极制备方法,其特征在于将上述多金属钒酸盐复合材料、导电碳、粘结剂,按照一定质量比配制成混合浆料,搅拌后制备成水系锌离子电池电极浆料;再将水系锌离子电池电极浆料涂覆在集流体上,干燥后得到水系锌离子电池的正极极片。
7.根据权利要求1所述的水系锌离子电池的正极制备方法,其特征在于上述集流体是不锈钢箔,不锈钢网,碳布,钛箔中的一种或几种。
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