CN104303339A - 二次电池的阳极材料及其制备方法 - Google Patents

二次电池的阳极材料及其制备方法 Download PDF

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CN104303339A
CN104303339A CN201280072727.XA CN201280072727A CN104303339A CN 104303339 A CN104303339 A CN 104303339A CN 201280072727 A CN201280072727 A CN 201280072727A CN 104303339 A CN104303339 A CN 104303339A
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姜允圭
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Abstract

本发明涉及二次电池的阳极材料，更具体地涉及使用氧化硅(SiOx)的二次电池阳极材料，及其制备方法。提供了一种二次电池的阳极材料，所述阳极材料通过制备SiOx和碳材料，混合所述SiOx和碳材料，形成SiOx-碳(SiOx-C)复合物以及进行热处理而形成。

Description

二次电池的阳极材料及其制备方法
技术领域
本公开涉及二次电池的阳极材料，更具体地涉及使用氧化硅的二次电池阳极材料，及其制备方法。
背景技术
由于近年来化石燃料消耗和全球变暖的问题，锁定新能源成为国际性问题。因此，可再生能源和能量存储的研发以提高能量的有效利用变得日益重要。
特别地，在车辆工业领域，由于化石燃料的即将耗尽，电动汽车的发展是急需的。但是，在使用常规锂二次电池的情况下，单次电池充电时驾驶车辆行驶超过200km的相对长距离可能是有问题的。常规锂二次电池也不适合存储可再生能源产生的电力的长期能量存储系统。
为了解决该问题，必须发展新的高容量高输出材料和新的技术设计。具体地，由于阴极材料的研发受到限制，新阳极材料的研发已受到极大关注。
可以使用基于石墨的材料作为二次电池的阳极材料。但是，使用这种基于石墨的材料可能得到相对低的容量(理论容量：约372mAh/g,约830mAh/ml；实际容量:约330mAh/g)，因此，开发容量大于或等于500mAh/g的阳极材料变得日益重要，以代替制备高容量锂二次电池时的基于石墨的材料。
硅(Si)基材料正成为能替代基于石墨的材料的新型阳极材料。使用这种Si基材料的二次电池的最大的优点是大容量，其单位体积是使用基于石墨的材料的二次电池的大约4倍，单位质量是使用基于石墨的材料的二次电池的大约10倍。同样，对于形成含有LiCoO2,LiMn2O4等的这类电池的情况，电池电压约为3.4V，比常规电池的3.7V仅低0.3V。因此，如果制得的阳极材料相对于充放电稳定，这类二次电池的另一个优点是可以立即商业化。但是，Si基材料作为阳极材料还可能存在与锂反应之后重量和体积方面的问题，这是由于Si基材料与锂反应之后体积变化很大，而基于石墨的材料与锂反应之后体积变化小。
一个避免与锂(Li)反应之后Si材料体积膨胀的方法是Sanyo研发的使用具有柱形结构的Si基材料作为电极的方法，所述Si基材料的体积可以通过控制其形式而膨胀。已知该方法包括通过向集流器基材上经物理沉积施加Si柱形结构来形成电极。据报道，该方法中柱形结构中的Si基材料的容量大于3000mAh/g，适当的初始效率为96％。
但是，与Li反应导致的体积膨胀将柱形结构的长度(或厚度)以及柱形结构的宽度从6μm变为17μm，然后反过来变为11μm。在形成柱形结构的电极方法效率，以及柱形结构部分中Li浓度梯度和用由铜(Cu)形成的集流器形成第二产物方面存在这类问题。同时，一直在进行对控制结构形式，例如微多孔的纳米纤维、管、棒等的方法的研究。但是，这种方法的可用性是不明确的。
同时，对于使用钛(Ti)基材料，例如氧化锂钛(Li4Ti5O12:LTO)的情况，在与Li反应期间，LTO仅显示微小的体积变化(0.1-0.2％)。LTO的晶格中零应变，在输出、寿命延长和稳定性方面表现优异。但是，LTO也有缺点，它与石墨相比电势较高，容量较低。
同时，除了Si和Ti材料之外，对于氧化硅(SiOx)材料的兴趣逐渐增加。氧化硅具有约1000mAh/g的高容量，但表现为体积膨胀方面的缺点，事实上当形成配混材料时使用大量相对昂贵的SiOx。
因此，为了使其可用于需要高容量的车辆，例如混合动力车(HV)，插入式混合动力电动车(PHEV)等，迫切需要发展用于二次电池的具有低体积膨胀和稳定电势的价格相对较低的SiOx基阳极材料。
同时提供相关技术文献1-3。专利文献1涉及一种通过形成多孔碳来形成二次电池的高容量阳极材料的方法，但专利文献1未公开使用SiOx作为阳极材料的技术。专利文献2涉及使用有机溶剂涂覆硅基材料和碳材料的技术，但专利文献2公开的湿方法可用性低并且方法不方便。专利文献3涉及使用气体等离子体制备硅－碳复合体的技术。根据该技术，硅－碳复合体通过以下方法制备：使用喷涂法在基于石墨或基于焦炭的碳颗粒表面通过气体等离子体活化硅前体。该技术使用相对昂贵的等离子体，因此可用性低。
(专利文献1)韩国专利申请公开第2011-0053027号
(专利文献2)韩国专利申请公开第2011-0046076号
(专利文献3)韩国专利第0761000号
发明内容
技术问题
本公开的一个方面提供二次电池的阳极材料及其制备方法，所述阳极材料使用相对便宜的氧化硅，所述氧化硅可具有高输出容量，即使与锂反应时也可抑制体积膨胀。
技术方案
根据本公开的一个方面，提供了一种制备二次电池的阳极材料的方法，其包括：制备氧化硅(SiOx)和碳材料；通过以15:1-7:3的重量比混合所述SiOx和碳材料并进行固态反应形成SiOx-碳(SiOx-C)复合物；以及以1-10℃/分钟的升温速率在SiOx-C复合物上进行热处理至800-1000℃，持续30分钟至3小时，以1-10℃/分钟的冷却速率进行冷却。
根据本发明的另一方面，提供了一种二次电池的阳极材料，所述阳极材料由SiOx-碳(SiOx-C)复合物形成，其中氧化硅(SiOx)颗粒表面被碳材料涂覆。
有益效果
根据本公开的示例性实施方式，提供了高容量的二次电池阳极材料，其不仅可用于IT材料，也可用于电动车辆。具体地，提供一种可抑制与Li反应时体积膨胀的阳极材料，从而制备能稳定使用的二次电池，其可用性高。
附图说明
图1A和1B是分别是在本公开的示例性实施方式中，涂覆沥青基(pitch-based)碳纤维之前和之后观察到的颗粒的电子显微照片；
图2是描述在本公开的示例性实施方式中涂覆之前和之后的颗粒得到的x-射线衍射(XRD)结果的图；以及
图3显示本发明示例性实施方式的电化学性质的实验结果。
具体实施方式
下面将更详细地描述本公开的实施方式。
详细描述本公开示例性实施方式中制备二次电池阳极材料的方法。
制备氧化硅(SiOx)和碳材料。
本公开的示例性实施方式中使用的SiOx不受任何具体类型或其制备方法的限制。
可以使用通过以下方法制备的氧化硅：将四氯化硅(SiCl4)和乙二醇以10:90-70:30的重量比混合，在其50-300℃的温度下搅拌2-72小时，最后将得到的凝胶在500-1000℃的温度下进行热处理。
碳材料的类型没有特别限制，碳材料的例子包括沥青基碳纤维、碳纳米管(CNT)、碳纳米纤维(CNF)、石墨烯和石墨等。
SiOx-碳(SiOx-C)复合物可以通过将SiOx和碳材料混合并进行固态反应而形成。
SiOx和碳材料混合的重量比为15:1-7:3。当SiOx和碳材料的重量比小于15:1时，复合物中SiOx的量不足，导致最终电化学反应中锂(Li)的嵌入反应(intercalation)不能平稳进行。当SiOx和碳材料的重量比大于7：3时，最终复合物中SiOx的量过大，导致碳材料的体积膨胀不能平稳进行。
可以通过球磨方法进行固态反应。可通过将SiOx和碳材料的混合物用直径为1-100mm的氧化锆球进行球磨来形成SiOx-C复合物。
所述球磨法可以50-500rpm的转速进行2-15小时。当球磨以低于50rpm的速度进行时，复合物的混合不能平稳进行，不能适当地形成复合物。当球磨速度快于500rpm时，SiOx由于高能量水平而被损毁坏或由于过多施加其上的压力而熔融，导致SiOx转化为二氧化硅(SiO2)的风险。
当球磨持续时间小于2小时时，不能适当地形成复合物，当球磨持续时间超过15小时时，对形成复合物的进一步效果可能相对不明显。
以上形成的复合物可以进行热处理。
热处理可以在惰性气体环境下进行。惰性气体包括氩气、氮气和氢气等。
热处理可以以1-10℃/分钟的升温速率在800-1000℃下进行30分钟至3小时，然后以1-10℃/分钟的冷却速率进行冷却。
当热处理温度低于800℃时，脱氧化反应不能顺利进行，不能适当地形成碳基质。当热处理温度高于1000℃时，高温扩散反应可使得SiOx碳化物通过与氧反应形成一氧化碳(CO)，不能适当地形成复合物。
同时，当升温速率和冷却速率低于1℃/分钟时，由于热处理时间过长生产率可能降低，当升温速率和冷却速率大于10℃/分钟时，快速的温度变化可能导致脱氧化反应不充分。
热处理可以进行30分钟至3小时，以使SiOx-C复合物的碳组分围绕SiOx粉末颗粒的表面并抑制SiOx氧化。
更优选地，SiOx-C复合物可以5℃/分钟的升温速率加热至900℃，持续1小时，然后以5℃/分钟的冷却速率冷却。
以下将详细描述本公开的示例性实施方式的二次电池的阳极材料。
本公开的实施方式的二次电池阳极材料可以是SiOx-C复合物颗粒，其SiOx表面涂覆有碳材料。
SiOx-C复合物可具有SiOx颗粒分散在碳材料上的结构，SiOx和碳材料形成芯-壳结构的结构，或球形SiOx颗粒被碳颗粒围绕的结构。
SiOx颗粒的平均直径可以是10-50nm。如果SiOx颗粒相对较小，其与Si和Li的反应性可能增加，因此，通常SiOx颗粒的最小可能粒径是优选的。但是，形成其中SiOx颗粒平均直径小于10nm的SiOx-C复合物稍有难度，难以实现本公开的目的。同时，当SiOx颗粒的平均直径大于50nm时，可能不易分散SiOx颗粒，因此，其平均颗粒直径不能超过50nm。
发明实施方式
下面将更详细地描述本公开的示例性实施方式。提供这些实施方式以使本公开完整充分，不应理解为限制本发明的范围。
实施例
制备重量比为10：2的氧化硅(SiOx)和沥青基碳纤维，将其放入体积为50ml并包含直径为5mm的10个氧化锆球的宽口烧瓶中。将所述宽口烧瓶放入球磨机，以100rpm的速率进行低能球磨12小时，以得到SiOx-碳(SiOx-C)复合物。
将SiOx-C复合物放入氧化铝坩埚，在氩气环境中使用电炉进行热处理。温度以5℃/分钟的速率升至900℃，在900℃维持1小时，然后以5℃/分钟的速率降至室温，以形成二次电池阳极材料的最终产物。
由上述方法形成的SiOx-C粉末示于图1和图2，分别是电子显微照片和采用x-射线衍射(XRD)观察到的晶体结构结果的图。
图1A显示在SiOx-C复合物之前形成SiOx，图1B显示根据本发明示例性实施方式的SiOx-C颗粒。如图1所示，示例性实施方式的SiOx-C颗粒的纳米粒径为30nm-50nm，其基质结构被碳覆盖。
图2显示涂覆之前和之后SiOx粉末的XRD观察结果，以显示本公开示例性实施方式制备的粉末晶体化。如图2所示，SiOx保持原始一氧化硅的晶体结构(甚至在涂覆之后)，未显示碳晶体化，因此可以看出适当地形成了SiOx-C复合物。
图3是显示本公开示例性实施方式中制备的二次电池阳极材料的电化学性质的评价结果的图表。
评价尺寸为1.4875cm2的阳极的电化学特性，所述阳极通过以下方法形成：向铜集流器的一个表面上施加阳极浆料，在约130℃的温度下将其干燥2小时，其中所述阳极浆料通过以下方式制备：使用SiOx-C复合物作为阳极活性材料，科琴黑()作为导电剂以及聚偏二氟乙烯(PVdF)作为粘合剂，以90:2:8的重量比混合，然后与溶剂N-甲基-2-吡咯烷酮(NMP)混合。
使用锂金属箔作为阴极。将聚烯烃隔膜插入两个电极之间之后，注入电解质以形成硬币型半电池，将其用于进行充放电测试。结果如图3所示。
图3A和3B显示0.01-1.5V范围内的充放电测试结果。1325mAh/g时(第一次循环中SiOx的容量)的体积膨胀得到抑制，第二次循环之后容量维持在约630mAh/g，因此，计算得到的效率为约50％。可以看出SiOx具有高容量，是已有碳材料的大约2倍。
同时，图3C显示0.01-1.5V范围内半电池的寿命特性结果，具有安全寿命。如图3C所示，即使在10次充放电循环之后，容量仍保持为大于或等于600mAh/g。对于Si基氧化物和金属Si的情况，由于2次充放电循环后的快速体积膨胀，无法鉴定寿命特性。但在本公开的示例性实施方式中，碳抑制SiOx的氧化，从而得到长寿命。
综上所述，根据本公开的示例性实施方式，将SiOx和碳材料形成SiOx-C复合体使得基质中的碳能抑制SiOx和氧之间的反应，并抑制SiOx中二氧化硅(SiO2)的反应，从而改进Si金属与Li的反应性。同样，可以看出SiOx的晶粒边界中存在足够的空间以确保Li的嵌入，即使在重复操作的情况下，稳定的晶粒边界能使Li嵌入和脱嵌。

Claims (10)

1.一种制备二次电池阳极材料的方法，所述方法包括：
制备氧化硅(SiOx)和碳材料；
通过以15:1-7:3的重量比混合SiOx和碳材料并进行固态反应形成SiOx-碳(SiOx-C)复合物；以及
以1-10℃/分钟的升温速率在800-1000℃下对SiOx-C复合物进行热处理30分钟至3小时，以1-10℃/分钟的冷却速率进行冷却。
2.如权利要求1所述的制备二次电池阳极材料的方法，其特征在于，所述SiOx通过以下方法制备：以10:90-70:30的重量比混合四氯化碳(SiCl4)和乙二醇，在50-300℃的温度下搅拌2-72小时，以及在500-1000℃的温度下热处理得到的凝胶。
3.如权利要求1所述的制备二次电池阳极材料的方法，其特征在于，所述碳材料选自下组中的一种或多种：沥青基碳纤维、碳纳米管(CNT)、碳纳米纤维(CNF)、石墨烯和石墨。
4.如权利要求1所述的制备二次电池阳极材料的方法，其特征在于，所述固态反应通过使用直径为1-100mm的氧化锆球的球磨法进行。
5.如权利要求3所述的制备二次电池阳极材料的方法，其特征在于，所述球磨法以50-500rpm的速率进行2-15小时。
6.如权利要求1所述的制备二次电池阳极材料的方法，其特征在于，以5℃/分钟的升温速率升至900℃热处理1小时，以及
以5℃/分钟的冷却速率进行冷却。
7.由SiOx-碳(SiOx-C)复合物形成的二次电池阳极材料，其中氧化硅(SiOx)颗粒的表面涂覆有碳材料。
8.如权利要求7所述的二次电池阳极材料，其特征在于，所述SiOx-C复合物包括以下结构中的至少一种：SiOx颗粒分散在碳材料上的结构，SiOx颗粒和碳材料形成芯－壳结构的结构，SiOx颗粒被所述碳材料围绕的结构。
9.如权利要求7所述的二次电池阳极材料，其特征在于，所述SiOx颗粒的平均粒径为10-50nm。
10.如权利要求7所述的二次电池阳极材料，其特征在于，所述碳材料选自下组中的一种或多种：沥青基碳纤维、碳纳米管(CNT)、碳纳米纤维(CNF)、石墨烯和石墨。
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