CN104904040A - 用于Li-S电池的阴极材料以及该阴极材料、由该阴极材料构成的阴极和包含该阴极的Li-S电池的制备方法 - Google Patents

用于Li-S电池的阴极材料以及该阴极材料、由该阴极材料构成的阴极和包含该阴极的Li-S电池的制备方法 Download PDF

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CN104904040A
CN104904040A CN201280077418.1A CN201280077418A CN104904040A CN 104904040 A CN104904040 A CN 104904040A CN 201280077418 A CN201280077418 A CN 201280077418A CN 104904040 A CN104904040 A CN 104904040A
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acrylonitrile
cathode material
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王久林
尹力超
杨军
赵娜红
周龙捷
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Robert Bosch GmbH
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Abstract

本发明提供用于Li-S电池的阴极材料。所述阴极材料包含去氢丙烯腈基聚合物、硫和GNS（石墨烯纳米层），其中所述阴极材料颗粒为球状的，去氢丙烯腈基聚合物的含量为20-79wt%，硫的含量为20-79wt%和GNS的含量为1-30wt%。还提供制备阴极材料、由所述阴极材料构成的阴极和包含所述阴极的Li-S电池的方法。

Description

用于Li-S电池的阴极材料以及该阴极材料、由该阴极材料构成的阴极和包含该阴极的Li-S电池的制备方法
技术领域
本发明涉及可重复充电的锂-硫(Li-S)电池的阴极材料以及形成所述阴极材料的方法。
背景技术
锂离子电池为具有非常高能量密度的可重复充电电池。锂-硫电池的理论比能量密度为2600Wh/kg，其对于电池来说为最高的能量密度之一。由于Li-S电池更高的能量密度和更低的成本，使其可接替锂离子电池。
对于可重复充电锂电池来说，元素硫为具有高理论比容量和比能量密度的有前途的阴极材料。但在Li-S电池中不能单独使用硫作为所述阴极材料，这归应于它的高电阻率和多硫化物在有机电解质溶液中的高溶解度，其导致所述活性材料的低的利用率、低的库仑效率和所述硫电极的短的循环寿命。
国际专利申请号PCT/CN2011/073598公开了Li-S电池的阴极材料以及形成所述阴极材料的方法。所述阴极材料包含丙烯腈基聚合物、硫和石墨烯。所述国际专利申请号还提出了制备Li-S电池的阴极材料的方法，其包括：分散10-30重量份的丙烯腈基聚合物于30-1000重量份的水中，向所述混合物中添加0.1-5重量份的石墨烯，添加20-200重量份的硫，和在惰性气氛下将由此获得的丙烯腈基聚合物/硫/氧化石墨烯的混合物加热至200-400℃的温度之前均质化所述混合物并保持所述温度1-20小时，以便获得阴极材料。
另一件国际专利申请号PCT/CN2010/077530公开了Li-S电池的阴极材料。用于Li-S电池的所述阴极材料包含去氢丙烯腈共聚物、硫和碳纳米管，其中这些组分的重量百分比如下：20％≤去氢丙烯腈共聚物≤70％，20％≤硫≤80％，0％≤碳纳米管≤20％。所述国际专利申请还提出了制备Li-S电池的阴极材料的方法，其包括：在球磨机中混合碳纳米管和丙烯腈共聚物，其中乙醇被用作为分散剂；添加硫于所述球磨机中并进一步混合；在真空下干燥所述混合物以去除乙醇；在惰性气氛下热处理并保压(dwelling)所述混合物；和在周围环境温度下冷却，以便获得阴极材料。
但是，如在所述国际专利申请号PCT/CN2010/077530的图1中所示的，可以看到所述阴极材料部分为非规则颗粒。为了得到高覆盖率的电极膜，存在对于具有更好颗粒形态的材料以及简单形成具有更高密度的电极膜的需要以进一步改善所述Li-S电池的工业化。
发明内容
根据上文所述，本发明的目的之一为提供用于Li-S电池的高效的阴极材料以及制备所述阴极材料的方法。
本发明的另一个目的为提供用于Li-S电池的高效的阴极。
本发明的还有一个目的为提供具有良好充电和放电性能的高效Li-S电池。
在一个方面中，本发明提供用于Li-S电池的阴极材料，其包含去氢丙烯腈基聚合物、硫和GNS(石墨烯纳米层)，其中所述阴极材料颗粒为球状的，去氢丙烯腈基聚合物含量为20-79wt％，优选地50-55wt％，硫的含量为20-79wt％，优选地45-50wt％，和GNS的含量为1-30wt％，优选地3-10wt％。
优选地，所述阴极材料的粒径分布具有在1-30μm范围内的单峰特性。
在本发明中，所述丙烯腈基聚合物起着包封硫的聚合物基底的作用。优选地，所述丙烯腈基聚合物包含丙烯腈共聚物和具有50,000-300,000范围的分子量的丙烯腈均聚物。
丙烯腈共聚物指的是含有丙烯腈单元的共聚物。丙烯腈均聚物指的是聚丙烯腈。优选地，所述丙烯腈共聚物选自包含丙烯腈-丁二烯共聚物、丙烯腈-氯乙烯共聚物、丙烯腈-丙烯酸甲酯共聚物、丙烯腈-甲基丙烯酸甲酯共聚物或丙烯腈-苯乙烯共聚物的群组，并且在所述丙烯腈共聚物中的丙烯腈单元的摩尔百分比为90％-99％。
在另一个方面中，本发明提供由上文所述阴极材料构成的阴极。
在还有一个方面中，本发明提供包含上文所述阴极的Li-S电池。具体地，所述Li-S电池可包含锂阳极，由根据本发明所述的阴极材料构成的阴极和电解质。
在又一个方面中，本发明提供制备用于Li-S电池的阴极材料的方法，其包括以下步骤：
分散0.05-0.2重量份的石墨烯纳米层于水中；
均质化所述分散体，优选地，通过声波处理所述分散体；
添加1-2重量份的具有10nm-500nm粒径范围的丙烯腈基聚合物，优选地，所述丙烯腈基聚合物具有40nm-200nm的粒径范围。
优选地通过声波处理所述悬浮液使所述悬浮液均质化；并且通过喷雾干燥法干燥所述均质悬浮液以得到具有1-20μm粒径范围的球状二级颗粒；
通过捣锤将5-20重量份的硫与所得的球状二级颗粒混合；
在保护性气氛中加热所述混合物；以及
在周围环境温度下冷却以获得所述阴极材料，其具有球状的阴极材料颗粒。
所述保护性气氛可为惰性气氛或氮气气氛。
优选地，在200-400℃的温度下加热所述混合物。加热所述混合物1-20小时。
优选地，所述阴极材料的粒径分布具有在1-30μm范围内的单峰特性。
优选地，所述丙烯腈基聚合物包含丙烯腈共聚物和具有50,000-300,000范围的分子量的丙烯腈均聚物。
优选地，所述丙烯腈共聚物选自包含丙烯腈-丁二烯共聚物、丙烯腈-氯乙烯共聚物、丙烯腈-丙烯酸甲酯共聚物、丙烯腈-甲基丙烯酸甲酯共聚物或丙烯腈-苯乙烯共聚物的群组，并且在所述丙烯腈共聚物中的丙烯腈单元的摩尔百分比为90％-99％。
所述球状三元复合材料，其具有去氢丙烯腈基聚合物嵌入的硫和均匀分布在以上二元材料中的GNS的结构，其显著增加所述硫的利用率，循环寿命和功率特性。
在200-400℃下，丙烯腈基聚合物与元素硫反应以形成聚合物基底，其中硫可以纳米级或甚至在分子水平上被嵌入。这种特殊结构确保了硫材料的高电化学活性；并且在实用电池中所述硫的利用率超过90％。
通过这种特殊结构另外得以改善的是：经由在聚合物基底和硫以及多硫化物之间的强烈的相互作用有效地抑制了多硫化物、放电产物的溶解。向所述聚合物/硫复合材料中添加石墨烯纳米层(良好的导电体)显著增加了所述阴极材料的导电性。
由于所述阴极材料的所述球形，其可优于现有技术被更好地附着在所述电极膜上并且更难从所述电极膜上脱落。因此，压实密度(特别是阴极密度)高于现有技术并由此改善含由本发明所述阴极材料构成的所述阴极的所述Li-S电池的效率。
所述球状三元复合材料，其具有聚合物嵌入的硫和均匀分布在以上二元材料中的GNS的结构，其显著增加所述硫的利用率、循环寿命和功率特性。
附图说明
本发明上述和其它的目的、特征和优点将从如在附图中所说明的优选实施方案的下列更为具体的描述中变得显而易见，其中：
图1显示由实例1获得的所述阴极材料的SEM图像；
图2显示由实例1获得的所述阴极材料的粒径分布；
图3显示由实例2获得的所述阴极材料的SEM图像；
图4显示分别由比较实例获得的所述阴极材料的SEM图像；
图5显示包含由所述阴极材料构成的所述阴极的所述Li-S电池的循环稳定性，所述阴极材料分别由实例1和比较实例获得；
图6显示包含由所述阴极材料构成的所述阴极的所述Li-S电池的倍率性能，所述阴极材料分别由实例1和比较实例获得，其中C表示放电率(discharge power rate)。例如，1C代表1-小时放电和10C代表0.1-小时放电；以及
图7显示包含由自实例2获得的所述阴极材料构成的所述阴极的所述Li-S电池的循环稳定性。
具体实施方式
虽然本发明涵盖各种修改和备选的构造，但本发明的实施例在附图中示出并将在下文中被详述。但应理解，具体的描述和附图并不旨在限制本发明于所公开的具体形式。相反地，其旨在使请求保护的本发明的范围包括所有的修改和备选的构造，它们都落入如在所附权利要求中表述的本发明的范围内。
若没有另外说明，本文提及的所有出版物、专利申请、专利和其它的参考文献将为全部目的而以整体引用的方式结合在本文中，如同全部被阐述的那样。
根据本发明的Li-S电池可包含锂阳极、由实例1/2所述的阴极材料构成的阴极和电解质。
所述比较电池可包含锂阳极、由比较实例的所述阴极材料构成的阴极和电解质。
可通过以下步骤制备石墨烯纳米层：添加氧化石墨于水中并加热所述溶液或添加氧化石墨于水中并添加还原剂于所述溶液中。所述还原剂可例如选自水合肼、硼氢化钠、硼氢化钾、葡萄糖和氨水、多硫化钠。
实例1：根据本发明的所述阴极材料的制备
将0.1g的GNS加入作为分散剂的足够的水中。声波处理所述分散体。向所述GNS的水悬浮液中添加具有10nm-500nm粒径范围的1g聚丙烯腈。进一步声波处理所述混合悬浮液并然后通过喷雾干燥法将其干燥以去除水。由此得到含GNS和聚丙烯腈的并且具有1-20μm粒径范围的球状二级颗粒。
通过捣锤将8g硫与所述获得的二级颗粒混合。在300℃下在氩保护气氛中加热所述集合混合物5小时以得到如在图1中所示的具有1-20μm粒径的目标球状阴极材料颗粒。如在图2中所示的，所述粒径分布显示出在1-30μm范围内的单峰特性。主要的粒径分布在5-15μm的范围内。
所述球状三元复合材料含有48wt％去氢聚丙烯腈、47wt％硫和5wt％GNS。
比较实例
将0.1g的GNS加入作为分散剂的足够的水中。声波处理所述分散体。向所述GNS的水悬浮液中添加具有10nm-500nm粒径范围的1g聚丙烯腈。进一步声波处理所述混合悬浮液并然后通过加热法将其干燥，在加热过程中在80℃下干燥所述悬浮液以去除水。
通过捣锤将8g硫与所述获得的二元复合材料混合。在300℃下在氩保护气氛中加热所述集合混合物5小时以得到比较的阴极材料颗粒。如在图4中所示的，所述复合材料颗粒为非规则的。
图5显示包含由所述阴极材料构成的所述阴极的所述Li-S电池的循环稳定性，所述阴极材料分别由实例1和比较实例获得。图6显示包含由所述阴极材料构成的所述阴极的所述Li-S电池的倍率性能，所述阴极材料分别由实例1和比较实例获得。
如在图5中所示的，包含由自实例1获得的所述阴极材料构成的所述阴极的所述Li-S电池展现出863mAh/g的第一放电容量和680mAh/g的可逆容量，高于86％的活性材料的利用率，估计最多500的循环寿命(80％保持率)。包含由比较实例的阴极材料构成的所述阴极的所述Li-S电池具有相似的第一放电容量和充电容量以及相似的活性材料的利用率，却仅具有估计最多300的循环寿命(80％保持率)。
当由实例1获得的所述阴极材料在10C下放电时，对于实例1可释放高达331.5mAh/g的容量，如在图6中所示的，包含由比较实例的阴极材料构成的所述阴极的所述Li-S电池在8C的更小的倍率下才可释放出相似的容量。
如在图5和图6中所示的，这些测量结果显示，根据本发明的所述Li-S电池的循环稳定性比包含由根据比较实例所制备的阴极材料构成的阴极的Li-S电池要长，并且根据本发明的所述Li-S电池的所述电能倍率性能(power rate performance)要优于包含由根据比较实例所制备的阴极材料构成的阴极的Li-S电池。
实例2：根据本发明的所述阴极材料的制备
将0.1g的GNS加入作为分散剂的足够的水中。声波处理所述分散体。向所述GNS的水悬浮液中添加具有10nm-500nm粒径范围的1g丙烯腈-苯乙烯共聚物。进一步声波处理所述混合悬浮液并然后通过喷雾干燥法将其干燥以去除水。由此得到含GNS和丙烯腈-苯乙烯共聚物的并且具有1-20μm粒径范围的球状二级颗粒。
通过捣锤将8g硫与所述获得的二级颗粒混合。在300℃下在氩保护气氛中加热所述集合混合物5小时以得到具有1-20μm粒径的目标球状阴极材料颗粒，如在图3中所示。
所述球状三元复合材料含有50wt％去氢丙烯腈-苯乙烯共聚物、47wt％硫和3wt％GNS。
图6显示包含由自实例2获得的所述阴极材料构成的所述阴极的所述Li-S电池的循环稳定性。如在图6中所示的，包含由自实例2获得的所述阴极材料构成的所述阴极的所述Li-S电池显示出895mAh/g的第一放电容量和655mAh/g的可逆容量，高于83％的活性材料的利用率，估计最多200的循环寿命(80％保持率)。
应注意，以上所述的实施方案为本发明的示例性说明，而不是用来限制本发明的，可由本领域的技术人员设计替代实施方案，其并不背离下述权利要求的范围。诸如“含有(contain)”、“含有(containing)”、“包含(comprise)”和“包含(comprising)”的措辞不排除存在的却未被列入本说明书和权利要求中的单元和步骤。

Claims (12)

1.一种用于Li-S电池的阴极材料，其包含去氢丙烯腈基聚合物、硫和石墨烯纳米层(GNS)，其中所述阴极材料颗粒为球状的，去氢丙烯腈基聚合物的含量为20-79wt％，硫的含量为20-79wt％和GNS的含量为1-30wt％。
2.根据权利要求1的用于Li-S电池的阴极材料，其中所述阴极材料的粒径分布具有在1-30μm范围内的单峰特性。
3.根据权利要求1的用于Li-S电池的阴极材料，其中所述去氢丙烯腈基聚合物包含丙烯腈共聚物和具有50,000-300,000范围的分子量的丙烯腈均聚物。
4.根据权利要求3的用于Li-S电池的阴极材料，其中所述丙烯腈共聚物选自包含丙烯腈-丁二烯共聚物、丙烯腈-氯乙烯共聚物、丙烯腈-丙烯酸甲酯共聚物、丙烯腈-甲基丙烯酸甲酯共聚物或丙烯腈-苯乙烯共聚物的群组，并且在所述丙烯腈共聚物中的丙烯腈单元的摩尔百分比为90％-99％。
5.一种阴极，其由根据之前权利要求中的任何一项所述的阴极材料构成。
6.一种Li-S电池，其包含根据权利要求5所述的阴极。
7.制备用于Li-S电池的阴极材料的方法，其包括以下步骤：
分散0.05-0.2重量份的石墨烯纳米层于水中；
均质化所述分散体；
添加1-2重量份的具有10nm-500nm范围的粒径的丙烯腈基聚合物；
均质化所述悬浮液并通过喷雾干燥法干燥所述均质悬浮液以获得具有1-20μm范围的粒径的球状二级颗粒；
通过捣锤将5-20重量份的硫与所得球状二级颗粒混合；
在保护性气氛中加热所述混合物；以及
在周围环境温度下冷却以获得具有球形阴极材料颗粒的所述阴极材料。
8.根据权利要求7所述的方法，其中在200-400℃的温度下加热所述混合物。
9.根据权利要求8所述的方法，其中加热所述混合物1-20小时。
10.根据权利要求7所述的方法，其中所述阴极材料的粒径分布具有在1-30μm范围内的单峰特性。
11.根据权利要求7所述的方法，其中所述丙烯腈基聚合物为包含丙烯腈共聚物和具有50,000-300,000范围的分子量的丙烯腈均聚物的丙烯腈聚合物。
12.根据权利要求11所述的方法，其中所述丙烯腈共聚物选自包含丙烯腈-丁二烯共聚物、丙烯腈-氯乙烯共聚物、丙烯腈-丙烯酸甲酯共聚物、丙烯腈-甲基丙烯酸甲酯共聚物或丙烯腈-苯乙烯共聚物的群组，并且在所述丙烯腈共聚物中的丙烯腈单元的摩尔百分比为90％-99％。
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