CN113012948A - 一种用于锌离子储能器件的锌碳复合电极材料的制备方法 - Google Patents
一种用于锌离子储能器件的锌碳复合电极材料的制备方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004146 energy storage Methods 0.000 title claims abstract description 22
- 239000007772 electrode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 238000000227 grinding Methods 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
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- 229910052799 carbon Inorganic materials 0.000 claims description 24
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- 230000001351 cycling effect Effects 0.000 abstract description 7
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- 238000012360 testing method Methods 0.000 description 9
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- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明提供一种用于锌离子储能器件的锌碳复合电极材料的制备方法,包括以下步骤:制备锌碳复合负极材料、制备电极浆料、制得电池电极,本发明所提出的锌碳复合负极材料,可以增强锌离子储能器件的容量,并增强器件的循环稳定性,可拓展性强,能够显著改善锌离子储能器件的性能,增加能量密度并延长使用寿命,易于大规模推广。
Description
技术领域
本发明涉及电极材料领域,特别涉及一种用于锌离子储能器件的锌碳复合电极材料的制备方法。
背景技术
常见的水系锌离子电池和锌离子电容器中常用纯锌箔作为负极使用。但纯锌箔负极价格昂贵且表面易发生副反应和枝晶生长,存在电化学性能不稳定和使用寿命短的问题。如果要进一步提高器件的功率密度或是使器件在更长的周期中循环时,在大电流刺激下或是多次的循环后,锌枝晶和惰性副产物的大量生成就成为了不可忽视的重要问题。
而且锌枝晶的形成会增加负极的表面积,提高析氢速率;发生在负极表面的析氢反应会使得OH-浓度升高,引起局部pH值变化,这些生成的OH-将参与反应并形成电化学惰性的腐蚀副产物沉积在负极表面;负极表面的惰性腐蚀副产物可导致表面不均匀并加重电极极化,反过来促进枝晶的形成。因此,锌枝晶的大量出现有可能会造成使器件寿命减少和容量下降的恶性循环形成。
发明内容
鉴以此,本发明提出一种用于锌离子储能器件的锌碳复合电极材料的制备方法,来解决上述问题,
本发明的技术方案是这样实现的:一种用于锌离子储能器件的锌碳复合电极材料的制备方法,包括以下步骤:
S1、制备锌碳复合负极材料:锌粉颗粒与粉末状碳添加剂材料进行研磨,所述研磨方式为机械研磨或手工研磨,研磨结束后将样品置于真空干燥箱中干燥,干燥温度为100~130℃,干燥时间2~8h,得到锌碳复合负极材料;
S2、制备电极浆料:将上述锌碳复合负极材料和聚四氟乙烯(PTFE)依比例混合均匀,所述锌碳复合负极材料所占质量比为85~95%,所述聚四氟乙烯所占质量比为5~15%,制得电极浆料;
S3、将上述电极浆料压制为厚度150~300μm的薄片,放入电热恒温烘箱中干燥,所述干燥温度为60~120℃,干燥时间为1~8h;
S4、将上述薄片中用冲片机剪裁成直径8~12mm的圆片,并移入真空干燥箱中进行干燥,干燥温度为100~130℃,干燥时间为10~15h;
S5、将上述干燥好的圆片压至不锈钢网集流体上即可作为扣式电池电极使用。
进一步的,所述S1步骤中碳添加剂材料和锌粉材料分别占除粘结剂外的电极浆料质量的1~10%和90~99%。
进一步的,所述S1步骤中碳添加剂其特征为粉末状碳材料或碳粉末分散液,粉末状碳材料粒径为10nm~200μm,包括科琴黑、乙炔黑、生物质碳、石墨碳、石墨烯、碳纳米管。
进一步的,所述S1步骤中纯锌粉末,纯度高于90%,形貌为球形颗粒或类球形颗粒,锌粉材料的粒径为1~30μm。
进一步的,所述S1步骤中机械研磨方式所用球料比为20:1。
进一步的,所述S1步骤中机械研磨为行星式球磨机,球磨速度控制在200~600rpm,研磨时间为2~4h。
进一步的,所述S1步骤中手工研磨的研磨时间为10~180min。
与现有技术相比,本发明的有益效果是:
本发明所提出的锌碳复合负极材料,可以增强锌离子储能器件的容量,并增强器件的循环稳定性。可使用锌粉为储能器件提供电化学活性基础,锌粉的造价远低于纯锌箔;使用的锌碳复合电极在被组装成锌离子混合电容器后,可以提供308.75F/g的首圈放电比容量,在经过500次1A/g恒电流充放电测试后,可以保持85.83%的容量;
除此之外,本方法制备流程简单,可拓展性强,能够显著改善锌离子储能器件的性能,增加能量密度并延长使用寿命,易于大规模推广。
附图说明
图1本发明实施例2得到的锌碳复合电极的扫描电镜图
图2中Zn是用作对比的纯锌箔-活性炭电容器在不同电流密度下的循环性能对比图。
图2中KB@Zn-1%是例1中的锌碳复合电极-活性炭电容器在不同电流密度下的循环性能对比图。
图2中KB@Zn-10%是例2中的锌碳复合电极-活性炭电容器在不同电流密度下的循环性能对比图。
图2中AC@Zn-10%是例3中的锌碳复合电极-活性炭电容器在不同电流密度下的循环性能对比图。
具体实施方式
为了更好理解本发明技术内容,下面提供具体实施例,对本发明做进一步的说明。
本发明实施例所用的实验方法如无特殊说明,均为常规方法。
本发明实施例所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1
一种用于锌离子储能器件的锌碳复合电极材料的制备方法,包括以下步骤:
S1、制备锌碳复合负极材料:锌粉颗粒与粉末状碳添加剂材料进行研磨,碳添加剂材料和锌粉材料分别占除粘结剂外的电极浆料质量的1%和94%,碳添加剂为科琴黑粒径为10nmμm,锌粉颗粒为类球形颗粒,粒径为1μm,所述研磨方式为手工研磨,研磨时间为10min,研磨结束后将样品置于真空干燥箱中干燥,干燥温度为100℃,干燥时间2h,得到锌碳复合负极材料;
S2、制备电极浆料:将上述锌碳复合负极材料和聚四氟乙烯(PTFE)依比例混合均匀,所述锌碳复合负极材料所占质量比为85%,所述聚四氟乙烯所占质量比为15%,制得电极浆料;
S3、将上述电极浆料压制为厚度150μm的薄片,放入电热恒温烘箱中干燥,所述干燥温度为60℃,干燥时间为1h;
S4、将上述薄片中用冲片机剪裁成直径8mm的圆片,并移入真空干燥箱中进行干燥,干燥温度为100℃,干燥时间为10h;
S5、将上述干燥好的圆片压至不锈钢网集流体上即可作为扣式电池电极,与活性炭正极材料极片、2M硫酸锌溶液共同组装成CR2025扣式电池以测试电化学性能。
实施例2
一种用于锌离子储能器件的锌碳复合电极材料的制备方法,包括以下步骤:
S1、制备锌碳复合负极材料:锌粉颗粒与粉末状碳添加剂材料进行研磨,碳添加剂材料和锌粉材料分别占除粘结剂外的电极浆料质量的10%和90%,碳添加剂为科琴黑粒径为200μm,锌粉颗粒为类球形颗粒,粒径为30μm,所述研磨方式为手工研磨,研磨时间为180min,研磨结束后将样品置于真空干燥箱中干燥,干燥温度为130℃,干燥时间8h,得到锌碳复合负极材料;
S2、制备电极浆料:将上述锌碳复合负极材料和聚四氟乙烯(PTFE)依比例混合均匀,所述锌碳复合负极材料所占质量比为95%,所述聚四氟乙烯所占质量比为5%,制得电极浆料;
S3、将上述电极浆料压制为厚度300μm的薄片,放入电热恒温烘箱中干燥,所述干燥温度为120℃,干燥时间为8h;
S4、将上述薄片中用冲片机剪裁成直径8~12mm的圆片,并移入真空干燥箱中进行干燥,干燥温度为120℃,干燥时间为15h;
S5、将上述干燥好的圆片压至不锈钢网集流体上即可作为扣式电池电极,与活性炭正极材料极片、2M硫酸锌溶液共同组装成CR2025扣式电池以测试电化学性能。
实施例3
一种用于锌离子储能器件的锌碳复合电极材料的制备方法,包括以下步骤:
S1、制备锌碳复合负极材料:锌粉颗粒与粉末状碳添加剂材料进行研磨,碳添加剂材料和锌粉材料分别占除粘结剂外的电极浆料质量的10%和90%,碳添加剂为生物质碳粒径为100μm,锌粉颗粒为类球形颗粒,粒径为25μm,所述研磨方式为行星式球磨机研磨,球磨速度控制在400rpm,研磨时间为3h,研磨结束后将样品置于真空干燥箱中干燥,干燥温度为120℃,干燥时间8h,得到锌碳复合负极材料;
S2、制备电极浆料:将上述锌碳复合负极材料和聚四氟乙烯(PTFE)依比例混合均匀,所述锌碳复合负极材料所占质量比为95%,所述聚四氟乙烯所占质量比为5%,制得电极浆料;
S3、将上述电极浆料压制为厚度200μm的薄片,放入电热恒温烘箱中干燥,所述干燥温度为120℃,干燥时间为8h;
S4、将上述薄片中用冲片机剪裁成直径10mm的圆片,并移入真空干燥箱中进行干燥,干燥温度为120℃,干燥时间为8h;
S5、将上述干燥好的圆片压至不锈钢网集流体上即可作为扣式电池电极,与活性炭正极材料极片、2M硫酸锌溶液共同组装成CR2025扣式电池以测试电化学性能。
表1为图2中4种样品在1A/g的电流密度下循环500圈所得到的恒电流充放电循环测试结果
表1
如表1,本发明所提出的锌碳复合负极材料,可以增强锌离子储能器件的容量,并增强器件的循环稳定性。用作对比的纯锌电极在被组装成锌离子混合电容器后,可以提供228.75F/g的首圈放电比容量,在经过500次1A/g恒电流充放电测试后,可以保持80.94%的容量。本发明例1所使用的锌碳复合电极在被组装成锌离子混合电容器后,可以提供285F/g的首圈放电比容量,在经过500次1A/g恒电流充放电测试后,可以保持83.78%的容量。本发明例2所使用的锌碳复合电极在被组装成锌离子混合电容器后,可以提供308.75F/g的首圈放电比容量,在经过500次1A/g恒电流充放电测试后,可以保持85.83%的容量。本发明例3所使用的锌碳复合电极在被组装成锌离子混合电容器后,可以提供306.25F/g的首圈放电比容量,在经过500次1A/g恒电流充放电测试后,可以保持85.30%的容量。
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、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种用于锌离子储能器件的锌碳复合电极材料的制备方法,其特征在于:包括以下步骤:
S1、制备锌碳复合负极材料:锌粉颗粒与粉末状碳添加剂材料进行研磨,所述研磨方式为机械研磨或手工研磨,研磨结束后将样品置于真空干燥箱中干燥,干燥温度为100~130℃,干燥时间2~8h,得到锌碳复合负极材料;
S2、制备电极浆料:将上述锌碳复合负极材料和聚四氟乙烯混合均匀,所述锌碳复合负极材料所占质量比为85~95%,所述聚四氟乙烯所占质量比为5~15%,制得电极浆料;
S3、将上述电极浆料压制为厚度150~300μm的薄片,放入电热恒温烘箱中干燥,所述干燥温度为60~120℃,干燥时间为1~8h;
S4、将上述薄片中用冲片机剪裁成直径8~12mm的圆片,并移入真空干燥箱中进行干燥,干燥温度为100~130℃,干燥时间为10~15h;
S5、将上述干燥好的圆片压至不锈钢网集流体上即可作为扣式电池电极使用。
2.如权利要求1所述的一种用于锌离子储能器件的锌碳复合电极材料的制备方法,其特征在于:所述S1步骤中碳添加剂材料和锌粉材料分别占除粘结剂外的电极浆料质量的1~10%和90~99%。
3.如权利要求1所述的一种用于锌离子储能器件的锌碳复合电极材料的制备方法,其特征在于:所述S1步骤中碳添加剂其特征为粉末状碳材料或碳粉末分散液,粉末状碳材料粒径为10nm~200μm,包括科琴黑、乙炔黑、生物质碳、石墨碳、石墨烯、碳纳米管。
4.如权利要求1所述的一种用于锌离子储能器件的锌碳复合电极材料的制备方法,其特征在于:所述S1步骤中纯锌粉末,纯度高于90%,形貌为球形颗粒或类球形颗粒,锌粉材料的粒径为1~30μm。
5.如权利要求1所述的一种用于锌离子储能器件的锌碳复合电极材料的制备方法,其特征在于:所述S1步骤中机械研磨方式所用球料比为20:1。
6.如权利要求1所述的一种用于锌离子储能器件的锌碳复合电极材料的制备方法,其特征在于:所述S1步骤中机械研磨为行星式球磨机,球磨速度控制在200~600rpm,研磨时间为2~4h。
7.如权利要求1所述的一种用于锌离子储能器件的锌碳复合电极材料的制备方法,其特征在于:所述S1步骤中手工研磨的研磨时间为10~180min。
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