CN113201808A - 一种多孔纤维硅氧负极复合材料及其制备方法 - Google Patents
一种多孔纤维硅氧负极复合材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及锂离子电池技术领域,尤其涉及一种多孔纤维硅氧负极复合材料及其制备方法。该制备方法包括:将SiOx在惰性气氛下进行球磨获得球磨SiOx;将球磨SiOx、碳前驱体、钛前驱体和造孔剂按比例加入溶剂中搅拌均匀获得前驱体纺丝液,并进行纺丝获得前驱体纤维薄膜;将所述前驱体纤维薄膜经过稳定化处理和碳化处理,获得多孔纤维硅氧负极SiOx@TiO2/C复合材料。本发明制备方法简单环保,工艺中各项反应条件易控制产率高,且复合材料具有良好的导电性以及界面稳定性,具有较高的容量、良好的循环性能和倍率性能,可用于锂离子电池负极材料。
Description
技术领域
本发明涉及锂离子电池技术领域,尤其涉及一种多孔纤维硅氧负极复合材料及其制备方法。
背景技术
锂离子电池(LIBs)具有比能量密度高、循环寿命长、无记忆效应等优点,被广泛应用于便携电子设备和新能源汽车上。然而,传统的石墨负极材料(理论比容量低,372mAh g-1)难以满足下一代高能量密度锂离子电池的需求。硅的理论比容量高(3579mAh g-1)、反应电位适中(~0.4V)且资源丰富(地壳中第二丰富的元素),是极具应用潜力的新一代高容量锂离子电池负极材料之一。但是,由于在充放电过程中硅合金化反应而产生的巨大体积变化(~320%),硅负极会产生颗粒粉化、电极结构破坏及界面稳定性恶化等问题,严重制约了其商业化应用。
因此,人们将目光转向了体积膨胀较小的SiOx材料,但是SiOx也面临着导电性差、不可忽略的体积膨胀的问题。研究人员已提出各种方法对氧化亚硅进行改性,比如球磨法、化学气相沉积法,溶胶凝胶法等。因此,开发一种解决SiOx导电性差以及体积膨胀的问题的技术材料迫在眉睫。
发明内容
针对现有技术存在的上述问题,本发明通过静电纺丝法对SiOx进行碳包覆和二氧化钛包覆,再通过稳定化处理和高温碳化处理获得多孔纤维结构,该纤维结构可以避免断裂问题,且对于压力和体积形变具有良好的适应性,由于活性物质和导电网络、集流体之间会存在更好的接触往往具有更好的导电性,同时也可以降低电解液和电极之间的界面阻抗,可用于锂粒子电池负极材料。
为实现上述发明目的,本发明提供了多孔纤维硅氧负极复合材料的制备方法,具体包括:
将SiOx在惰性气氛下进行球磨获得球磨SiOx;
将球磨SiOx、碳前驱体、钛前驱体和造孔剂加入溶剂中搅拌均匀获得前驱体纺丝液,并进行纺丝获得前驱体纤维薄膜;
将所述前驱体纤维薄膜在空气气氛、100-300℃条件下进行稳定化处理后,置于惰性气氛下进行碳化处理,获得多孔纤维状的SiOx@TiO2/C复合材料。
进一步的,所述球磨过程中球料比为20-30:1,转速为700-900rpm,球磨时间为3-5h。
进一步的,所述纺丝液中各原料及其质量百分含量为:
球磨SiOx 1~10wt%,碳前驱体5~15wt%,钛前驱体5~25wt%,造孔剂1~10wt%,其余量为溶剂。
进一步的,所述碳前驱体为聚乙烯基吡咯烷酮、聚丙烯腈、聚乙烯醇缩丁醛、聚乙烯醇、左旋聚乳酸、聚丙烯酸中的至少一种;
所述钛前驱体为钛酸异丙酯、硫酸氧钛、钛酸四丁酯、偏钛酸、四氯化钛中的至少一种;
所述造孔剂为聚乙二醇、聚甲基丙烯酸甲酯和聚苯乙烯中的至少一种;
所述溶剂为乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二氯甲烷、二甲基亚砜的至少一种。
进一步的,所述纺丝过程的工艺参数为:
针头内径为0.3~2.0mm,纺丝电压为8~20kV,纺丝液的流速为0.03~0.15mmmin-1,接收距离为10~20cm,以及纺丝时间为6~15h。
进一步的,所述稳定化处理的升温速度为2~10℃min-1,稳定化保温时间为0.5~3h。
进一步的,所述碳化处理的升温速度为5~10℃min-1,碳化处理温度为500-800℃,处理时间为2-5h。
基于同一发明构思的,本发明还提供了一种多孔纤维状SiOx@TiO2/C复合材料,所述复合材料由上述制备方法制备获得。
有益效果:
(1)本发明多孔纤维多孔纤维硅氧负极(SiOx@TiO2/C)复合材料复合材料的制备方法简单环保,工艺中各项反应条件易控制,制备成本低廉,制备时间短,产率高,利于批量大规模生产。
(2)本发明的多孔纤维SiOx@TiO2/C复合材料以碳纤维为基体,SiOx可以依附或者嵌入碳纤维里面,同时生成的纳米TiO2粒子可以包覆在材料的表面,且纤维含有孔结构。该复合材料有效地提高了材料的导电性以及界面稳定性,具有较高的容量、良好的循环性能和倍率性能,以其作为负极材料的锂离子电池具有优良的比容量、倍率性能和循环性能。
附图说明
图1是本发明实施例1提供的多孔纤维SiOx@TiO2/C复合材料的SEM图。
图2是本发明实施例1提供的球磨SiOx和多孔纤维SiOx@TiO2/C复合材料的XRD图。
图3是本发明实施例1提供的多孔纤维SiOx@TiO2/C复合材料作为锂电负极材料在0.1Ag-1的电流密度下的首次充放电曲线。
图4是本发明实施例1提供的多孔纤维SiOx@TiO2/C复合材料作为锂电负极材料在0.1Ag-1活化三圈、0.4Ag-1循环100圈的循环稳定性曲线。
图5是本发明实施例2提供的多孔纤维SiOx@TiO2/C复合材料的SEM图。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚,下面将结合具体实施例进行详细描述,但本发明的保护范围并不限于以下具体实施例。
除非另有定义,下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的,并不是旨在限制本发明的保护范围。
除非另有特别说明,本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
实施例1
按20:1的球料比将SiOx装入球磨罐,在惰性气氛下按400rpm的转速球磨4h后获得材料球磨SiOx(M-SiOx)。
配制以乙醇为溶剂的纺丝液,其中,纺丝液中各种原料的配比为:聚乙烯基吡咯烷酮的质量分数为6.3wt%,钛酸异丙酯的质量分数为11.8wt%,M-SiOx的质量分数为6.3wt%,聚乙二醇的质量分数为3.2wt%。
将上述纺丝液进行静电纺丝,纺丝条件为:针头内径为0.7mm,纺丝电压为12kV,纺丝液的流速为0.1mm min-1,接收距离为15cm,以及纺丝时间为10h,得到前驱体纤维薄膜。
然后将前驱体纤维薄膜在空气气氛、250℃下对前驱体纤维薄膜进行稳定化,其中升温速率为3℃min-1,保温时间为1h。
最后,将经过稳定化处理的纤维薄膜在氩气气氛、650℃下进行碳化处理,其中升温速率为5℃min-1,碳化时间为3h,得到SiOx@TiO2/C复合材料。
在制备扣式电池时,将目标材料、导电剂Super P和粘结剂海藻酸钠按7:2:1的质量比混合配成浆料均匀地涂覆到铜箔集流体上得到电极片。80℃真空干燥箱12h。将极片切成直径12mm的小圆片。采用金属锂片(直径14mm)为对电极、玻璃纤维(GF/A)为隔膜和LiPF6/EC+DEC(体积比为1:1)/VC+FEC(质量分数分别为2%和10%)的有机溶液为电解液。电池的组装在充满氩气的手套箱中进行,按自下往上的顺序依次放置电池负极壳、锂片、隔膜、极片、电解液、垫片、弹片和电池正极壳,组装好的电池用纽扣电池封口机进行密封。采用恒流充放电模式,电压范围为0.01~2.0V。在上海辰华电化学工作站进行循环伏安测试,扫描速度为0.1mV s-1。
实施例2:
由实施例1中所述方法制备出材料M-SiOx。
配制以N,N-二甲基甲酰胺为溶剂的纺丝液,其中,纺丝液中各种原料的配比为:聚丙烯腈的质量分数为6.1wt%,硫酸氧钛的质量分数为12.1wt%,M-SiOx的质量分数为3.0wt%,聚甲基丙烯酸甲酯的质量分数为3.1wt%。
接下来将上述纺丝液进行静电纺丝,纺丝条件为:纺丝针头内径为1mm,纺丝电压为15kV,纺丝液的流速为0.08mm min-1,接收距离为15cm,以及纺丝时间为12h,得到前驱体纤维薄膜。
然后将前驱体纤维薄膜在空气气氛、250℃下对前驱体纤维薄膜进行稳定化,其中升温速率为1℃min-1,保温时间为0.5h。
最后,将经过稳定化处理的纤维薄膜在氩气气氛、650℃下进行碳化处理,其中升温速率为5℃min-1,碳化时间为5h,得到SiOx@TiO2/C复合材料。
材料涂片和扣式电池的制备及电化学性能测试同实施例1。
实施例3
由实施例1中所述方法制备出材料M-SiOx。
配制以二氯甲烷为溶剂的纺丝液,其中,纺丝液中各种原料的配比为:聚乙烯醇缩丁醛的质量分数为9.6wt%,钛酸四丁酯的质量分数为15.5wt%,M-SiOx的质量分数为4.8wt%,聚苯乙烯的质量分数为4.8wt%。
接下来将上述纺丝液进行静电纺丝,纺丝条件为:针头内径为1.5mm,纺丝电压为18kV,纺丝液的流速为0.12mm min-1,接收距离为20cm,以及纺丝时间为8h,得到前驱体纤维薄膜。
然后将前驱体纤维薄膜在空气气氛、250℃下对前驱体纤维薄膜进行稳定化,其中升温速率为2℃min-1,保温时间为1.5h。
最后,将经过稳定化处理的纤维薄膜在氩气气氛、650℃下进行碳化处理,其中升温速率为3℃min-1,碳化时间为4h,得到SiOx@TiO2/C复合材料。
材料涂片和扣式电池的制备及电化学性能测试同实施例1。
以实施例1和实施例2获得的SiOx@TiO2/C复合材料进行表征和测试。参见图1,从图1可以看出,经过高温碳化后,材料含有微小的孔,纤维形貌保持较为完整,并且裸露着的M-SiOx很少,说明M-SiOx与碳纤维复合的效果很好。参见图2,从图2可以看出,M-SiOx为无定型结构,而SiOx@TiO2/C材料在25°出现了尖锐的衍射峰,这与了锐钛矿型二氧化钛(JPCDSNo.21-1272)的(101)晶面是相一致的,说明形成了锐钛矿型的二氧化钛晶体。然而晶体碳的衍射峰并没有观察到,说明形成的碳为非晶碳。参见图3,从图3可以看出,SiOx@TiO2/C在0.1Ag-1的电流密度下的首次充电比容量为1125.1mAh g-1,首次库伦效率为68.8%。参见图4,从图4可以看出,在0.4Ag-1的电流密度下循环100圈后的充电比容量为855.0mAh g-1,对应的容量保持率分别为89.5%(对比于第四圈的充电比容量),说明SiOx@TiO2/C复合材料拥有出色的循环稳定性。参见图5,从图5可以看出,SiOx@TiO2/C复合材料为多孔纤维结构,大部分直径在800nm左右,且表面较为粗糙。
以上所述实施例,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明的技术范围内,根据本发明的技术方案及其构思加以等同替换或改变,都应涵盖在本发明的保护范围内。
Claims (8)
1.一种多孔纤维硅氧负极复合材料的制备方法,其特征在于,具体包括以下步骤:
将SiOx在惰性气氛下进行球磨获得球磨SiOx;
将球磨SiOx、碳前驱体、钛前驱体和造孔剂加入溶剂中搅拌均匀获得前驱体纺丝液,并进行纺丝获得前驱体纤维薄膜;
将所述前驱体纤维薄膜在空气气氛、100-300℃条件下进行稳定化处理后,置于惰性气氛下进行碳化处理,获得多孔纤维状的SiOx@TiO2/C复合材料。
2.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法,其特征在于,所述球磨过程中球料比为20-30:1,转速为700-900rpm,球磨时间为3-5h。
3.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法,其特征在于,所述纺丝液中各原料及其质量百分含量为:
球磨SiOx 1~10wt%,碳前驱体5~15wt%,钛前驱体5~25wt%,造孔剂1~10wt%,其余量为溶剂。
4.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法,其特征在于,所述碳前驱体为聚乙烯基吡咯烷酮、聚丙烯腈、聚乙烯醇缩丁醛、聚乙烯醇、左旋聚乳酸、聚丙烯酸中的至少一种;
所述钛前驱体为钛酸异丙酯、硫酸氧钛、钛酸四丁酯、偏钛酸、四氯化钛中的至少一种;
所述造孔剂为聚乙二醇、聚甲基丙烯酸甲酯和聚苯乙烯中的至少一种;
所述溶剂为乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二氯甲烷、二甲基亚砜的至少一种。
5.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法,其特征在于,所述纺丝过程的工艺参数为:
针头内径为0.3~2.0mm,纺丝电压为8~20kV,纺丝液的流速为0.03~0.15mm min-1,接收距离为10~20cm,以及纺丝时间为6~15h。
6.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法,其特征在于,所述稳定化处理的升温速度为2~10℃ min-1,稳定化保温时间为0.5~3h。
7.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法,其特征在于,所述碳化处理的升温速度为5~10℃ min-1,碳化处理温度为500-800℃,处理时间为2-5h。
8.一种多孔纤维硅氧负极复合材料,其特征在于,所述复合材料由权利要求1-7任意所述的制备方法制备获得。
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