CN114075717B - 一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法及其应用 - Google Patents

一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法及其应用 Download PDF

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CN114075717B
CN114075717B CN202111330237.2A CN202111330237A CN114075717B CN 114075717 B CN114075717 B CN 114075717B CN 202111330237 A CN202111330237 A CN 202111330237A CN 114075717 B CN114075717 B CN 114075717B
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黄昊
吴爱民
孙伟
刘佳
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Dalian University of Technology
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Abstract

本发明涉及一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法及其应用，将所得该负极材料应用在锂离子电池技术领域。将高分子聚合物、碳黑、磷化锡纳米粒子加入到有机溶剂中，搅拌溶剂得到胶体溶液；通过静电纺丝方法得到磷化锡/碳黑复合材料，经过简单的预烧、碳化过程得到磷化锡/碳黑纳米纤维自支撑负极材料。该方法工艺简单、生产周期短、产品均匀性好可适用于工业化生产。本发明应用于锂离子电池负极材料在以0.5A g‑1电流密度下经过300圈循环后，其可逆容量保持在528mAh/g。

Description

一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的 方法及其应用
技术领域
本发明具体涉及一种静电纺丝制备磷化锡/碳黑纳米纤维的制备方法，及其作为锂离子电池负极材料在锂离子电池领域的应用。
背景技术
随着移动设备和新能源汽车等行业的蓬勃发展，储能设备的需求量也大幅度增长。锂离子电池由于具有高能量密度、长使用寿命以及良好的倍率性能等特性成为储能设备的主流方向。目前商业化的锂离子电池一般采用石墨作为负极材料，然而石墨较低的能量密度(372mAh g-1)，难以满足当今社会对电池高能量密度的要求。传统铜箔基涂覆浆料的工艺中，铜箔自重会降低锂离子电池的能量密度。为了实现低成本，高能量转换效率和能量密度的目标，无集流体、高性能电化学储能技术已经成为目前的研究热点。
随着研究的发展，金属磷化物(如NixPy、CoP、FexPy和SnxPy)具有能量密度高，原材料来源丰富，嵌锂电位低等优点而受到了广泛关注。其中Sn4P3作为锂离子电池负极材料时，其理论比容量高达1255mAh g-1，是传统石墨负极的三倍以上。然而Sn4P3存在导电性差的缺点，在嵌锂和脱锂的过程中会产生巨大的体积变化(353％)，导致电极粉化以及SEI膜破裂，从而严重降低循环寿命。针对上述问题，国内外相关研究工作的解决策略主要体现在，采用各种方法将Sn4P3与高导电性、非活性的碳材料或金属复合，从而缓解体积膨胀问题，改善循环稳定性，提高倍率性能。如公开号CN106602020A的中国专利公开了一种Sn4P3/C复合材料的制备方法，该方法将红磷和金属锡球磨20h制备磷化锡；再将磷化锡与石墨球磨40h得到Sn4P3/C复合材料，在0.1A/g电流密度下，首次放电容量为1224mAh g-1，经过50次循环后比容量为750mAhg-1。但是该方法存在制备效率低，形貌不均匀，容量衰减快等问题。另有Ran等人(Journal of Power Sources 461(2020)228116)采用静电纺丝的方法制备Sn@多孔碳，再用后期磷化的方法制备Sn4P3@多孔碳作为自支撑负极材料。但是该方法中的锡源来自静电纺丝过程中的锡盐碳化，存在纳米粒子粒径、形貌难以调控的问题，在热处理过程中容易造成纳米粒子团聚。相比于金属集流体，用碳纤维做自支撑电极导电性低，会影响整体的电化学性能。
发明内容
有鉴于此，针对现有技术不足以及改进需求，本发明提供一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法。该负极材料具有能量密度高、循环稳定的优点。
为了实现上述目的，本发明采用的技术方案如下：
一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法，包括以下步骤：
1)前驱体纺丝液的配制
将高分子聚合物、磷化锡纳米粒子、碳黑加入到有机溶剂中，搅拌溶解，得到均匀的前驱体纺丝胶体溶液；
2)静电纺丝法制备磷化锡/碳黑纳米复合纤维膜
以步骤1)得到的前驱体纺丝胶体溶液进行静电纺丝，得到磷化锡/碳黑纳米复合纤维膜；
3)磷化锡/碳黑纳米纤维自支撑负极材料制备
将步骤2)制备的磷化锡/碳黑纳米复合纤维膜置于空气环境中预烧后，在惰性气体环境中碳化，得到磷化锡/碳黑纳米纤维自支撑负极材料。
所述的步骤1)中高分子聚合物为聚丙烯腈、聚甲基丙烯酸甲酯或聚乙烯吡咯烷酮等，分子量为50～150万。
所述步骤1)中的纳米磷化锡粒径为10～500nm；可以通过但不限于如下方法制备得到：高能球磨法、溶剂热法、直流电弧等离子体蒸发法等其中任意一种。
所述的步骤1)中有机溶剂为N,N-二甲基甲酰胺、乙醇或丙酮等其中任意一种。
所述的步骤1)中碳黑为科琴黑、super P、导电石墨等等其中任意一种或几种复合。
所述的步骤1)中，高分子聚合物在有机溶剂中的浓度为0.05～0.2g/ml；磷化锡纳米粒子有机溶剂中的浓度为0.05～0.3g/ml；碳黑在有机溶剂中的浓度为 0.01～0.05g/ml。
优选的，当高分子聚合物为聚丙烯腈，溶剂为N,N-二甲基甲酰胺，碳黑为科琴黑，所述步骤1)中聚丙烯腈的添加量为每毫升N,N-二甲基甲酰胺配比 0.05～0.2g聚丙烯腈；所述聚丙烯腈、磷化锡纳米粒子、科琴黑的质量比为 1:0.8～2:0.05～0.2。
所述步骤1)中搅拌参数为：15～35℃下搅拌24小时。
所述步骤2)中静电纺丝参数为：纺丝针头与金属收集器之间距离为8～15cm，纺丝电压为13～18KV，给液速度为0.6～1.5mL/h，环境温度15～35℃，相对湿度为20～40％；金属收集器的自转速度为400～800r/min。
所述步骤2)中预烧条件为升温至200～300℃保温1～4小时；惰性气体为氩气、氮气或氦气的一种或两种以上混合；碳化条件为500～800℃保温2～8小时。
一种用静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的应用，将上述磷化锡/碳黑纳米纤维自支撑负极材料在80～120℃条件下真空干燥10～24h，依据电池规格冲压或裁剪出不同尺寸的电极片。
本发明的有益效果为：
(1)本发明采用两步法将纳米磷化锡负载到碳纤维上，可以精确调控纳米粒子的粒径、形貌，碳纤维可以缓解电化学反应过程中体积膨胀，防止结构崩塌。
(2)本发明通过添加碳黑作为分散剂和导电剂，能够有效解决纳米粒子在胶体里团聚问题，并且进一步提高纳米纤维导电率。
(3)本发明所制备的磷化锡/碳黑纳米纤维自支撑负极材料，采用无集流体自支撑设计，可以有效降低电池自重，从根本上提高锂离子电池能量密度。在锂离子电池半电池测试中表现出高储锂容量以及良好的循环稳定性。
(4)本发明工艺简单，无需锂离子电池材料制备中的调浆、涂布工艺，且生产周期短、成本低廉、产品均匀性好，可适用于工业化生产。
附图说明
图1是实施例1合成磷化锡/碳黑纳米纤维的XRD图。
图2是实施例1合成磷化锡/碳黑纳米纤维的SEM图。
图3是实施例1合成磷化锡/碳黑纳米纤维的XPS图，其中，(a)为Sn 3d； (b)为P2p。
图4是实施例1合成磷化锡/碳黑纳米纤维组装扣式电池在0.5A/g电流密度下的循环性能图。
具体实施方式
实施例1
在装有10mL N-N二甲基甲酰胺烧杯中，加入0.8g磷化锡纳米粒子、0.1g 科琴黑及1g分子量为130万的聚丙烯腈，磁力搅拌24h形成均一分散溶液。其中磷化锡纳米粒子采用直流电弧等离子体法制备，粒径为200nm。
将溶液加入到10mL针管中，调整针头距圆筒收集器间距离为12cm，圆筒收集器转速为500r/min，纺丝电压为16KV，给液速度为1.0ml/h，空气湿度25％，环境温度20℃。
将纺丝产物置于管式炉内，在空气气氛下2℃/min升温到250℃保温2h进行预烧，再在氩气气氛下5℃/min升温到600℃保温4h进行碳化，之后冷却至室温得到磷化锡/碳黑纳米纤维自支撑负极材料。
本实施例所制备的磷化锡/碳黑纳米自支撑纤维负极材料的XRD图谱如图1 所示。由图1可知，该负极材料为无定形态。图2为磷化锡/碳黑纳米纤维自支撑负极材料的SEM图，可知磷化锡均匀负载在纳米纤维上。图3为该负极材料的XPS图谱，可知该负极材料的分峰与纯磷化锡一致，说明在热处理过程中，晶态磷化锡进行了非晶化转变。
将所制得的磷化锡/碳黑纳米自支撑纤维负极材料冲压成14mm圆片，在氩气气氛手套箱中装配电池；其中电解液为1mol/L的LiPF6溶液，溶剂为体积比 1:1碳酸聚乙烯酯(EC)与碳酸二乙酯(DC)，同时添加体积比为10％氟代碳酸乙烯酯(FEC)作为电解液添加剂。以聚丙烯作为隔膜，锂片作为对电极组成 CR2025扣式半电池。
图4为本发明制得磷化锡/碳黑纳米纤维自支撑负极材料用于锂离子半电池测试时所得的循环性能图。由图4可知，在室温下，0.01～3V电压范围内，以 0.5A g-1电流密度进行充放电测试，首次可逆比容量为567mAh/g，在经过300 圈循环后，其可逆容量保持在528mAh/g，容量保持率高达93％。
实施例2
在装有10mL丙酮烧杯中，加入3g磷化锡纳米粒子、0.5g super P及0.5g 分子量为50万的聚甲基丙烯酸甲酯，磁力搅拌24h形成均一分散溶液。其中磷化锡纳米粒子采用高能球磨法制备，粒径为500nm。将溶液加入到10mL针管中，调整针头距圆筒收集器间距离为15cm，圆筒收集器转速为400r/min，纺丝电压为18KV，给液速度为1.5ml/h，环境湿度28％，环境温度24℃。
将纺丝产物置于管式炉内，在空气气氛下2℃/min升温到200℃保温4h进行预烧，再在氮气气氛下5℃/min升温到800℃保温2h进行碳化，之后冷却至室温得到所需要的负极材料。
实施例3
在装有10mL乙醇烧杯中，加入1.5g磷化锡纳米粒子、0.3g导电石墨及2g 分子量为150万的聚乙烯吡咯烷酮，磁力搅拌24h形成均一分散溶液。其中磷化锡纳米粒子采用溶剂热法制备，粒径为25nm。
将溶液加入到10mL针管中，调整针头距圆筒收集器间距离为8cm，圆筒收集器转速为800r/min，纺丝电压为13KV，给液速度为0.6ml/h，空气湿度为27％，环境温度23℃。
将纺丝产物置于管式炉内，在空气气氛下2℃/min升温到300℃保温1h进行预烧，再在氩气气氛下5℃/min升温到500℃保温8h进行碳化，之后冷却至室温得到所需要的负极材料。

Claims (7)

1.一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法，其特征在于，包括以下步骤：
1)前驱体纺丝液的配制
将高分子聚合物、磷化锡纳米粒子、碳黑加入到有机溶剂中，搅拌溶解，得到均匀的前驱体纺丝胶体溶液；
2)静电纺丝法制备磷化锡/碳黑纳米复合纤维膜
以步骤1)得到的前驱体纺丝胶体溶液进行静电纺丝，得到磷化锡/碳黑纳米复合纤维膜；
3)磷化锡/碳黑纳米纤维自支撑负极材料制备
将步骤2)制备的磷化锡/碳黑纳米复合纤维膜置于空气环境中预烧后，在惰性气体环境中碳化，得到磷化锡/碳黑纳米纤维自支撑负极材料。
2.根据权利要求1所述的一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法，其特征在于，步骤1)中：
高分子聚合物在有机溶剂中的浓度为0.05～0.2g/ml；磷化锡纳米粒子在有机溶剂中的浓度为0.05～0.3g/ml；碳黑在有机溶剂中的浓度为0.01～0.05g/ml；
搅拌参数为：15～35℃下搅拌24小时。
3.根据权利要求1所述的一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法，其特征在于，步骤1)中：
高分子聚合物为聚丙烯腈、聚甲基丙烯酸甲酯或聚乙烯吡咯烷酮，分子量为50～150万；
有机溶剂为N,N-二甲基甲酰胺、乙醇或丙酮；
碳黑为科琴黑、super P或导电石墨中的一种或两种以上组合；
纳米磷化锡粒径为10～500nm；可以通过如下方法制备得到：高能球磨法、溶剂热法或直流电弧等离子体蒸发法。
4.根据权利要求1所述的一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法，其特征在于，步骤2)中，静电纺丝的技术参数如下：
纺丝针头与金属收集器之间距离为8～15cm；纺丝电压为13～18KV；给液速度为0.6～1.5mL/h；环境湿度20～40％；环境温度15～35℃；金属收集器的自转速度为400～800r/min。
5.根据权利要求3所述的一种静电纺丝制备磷化锡/碳黑纳米纤维负极材料的方法，其特征在于，当高分子聚合物为聚丙烯腈，溶剂为N,N-二甲基甲酰胺，所述步骤1)中聚丙烯腈的添加量为每毫升N,N-二甲基甲酰胺配比0.05～0.2g聚丙烯腈；所述聚丙烯腈、磷化锡纳米粒子、科琴黑的质量比为1:0.8～2:0.05～0.2。
6.根据权利要求1所述的一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的方法，其特征在于，所述步骤3)中预烧条件为升温至200～300℃保温1～4小时；惰性气体为氩气、氮气或氦气的一种或两种以上混合；高温碳化条件为500～800℃保温2～8小时。
7.采用权利要求1-6任一所述的方法制得的一种静电纺丝制备磷化锡/碳黑纳米纤维自支撑负极材料的应用，将磷化锡/碳黑纳米纤维自支撑负极材料在80～120℃条件下真空干燥10～24h，依据电池规格冲压或裁剪出不同尺寸的电极片。
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