CN116281943A - 无定形硅基负极材料的制备方法及应用 - Google Patents
无定形硅基负极材料的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种无定形硅基负极材料的制备方法，具体包括如下步骤：步骤1，将多孔碳基体置于回转炉中，通入保护气体和硅源气体的混合气在多孔碳基体内部沉积纳米硅，得到生长纳米硅的多孔碳基体；步骤2，将步骤1所得的纳米硅生长的多孔碳基体置于回转炉中，在保护气体和有机气源的混合气氛中进行化学化学气相沉积，对纳米硅生长的多孔碳基体进行软碳包覆，得到硅基负极材料。本发明通过调控全流程中氢气流量以控制硅颗粒生长程度和结晶性，从而制备具有高容量、高首效和低膨胀的硅基负极材料。
Description
技术领域
本发明属于锂离子电池材料技术领域，涉及一种无定形硅基负极材料的制备方法。
背景技术
近年来，随着大规模用电设备的应用，人们对电池续航时间、快充和安全性能提出了更高的要求。硅负极材料由于比容量高、原料来源广等优点而受到广泛关注。但是，硅材料在充放电过程中巨大的体积膨胀，严重影响了电极材料在循环过程中的稳定性，造成电池容量快速衰减。目前，无定形化是降低硅材料体积膨胀的有效手段。
发明内容
本发明的目的是提供一种无定形硅基负极材料的制备方法，该方法通过调控全流程中氢气流量以控制硅颗粒生长程度和结晶性，从而制备具有高容量、高首效和低膨胀的硅基负极材料。
本发明所采用的技术方案是，无定形硅基负极材料的制备方法，具体包括如下步骤：
步骤1，将多孔碳基体置于回转炉中，通入保护气体和硅源气体的混合气在多孔碳基体内部沉积纳米硅，得到生长纳米硅的多孔碳基体；
步骤2，将步骤1所得的纳米硅生长的多孔碳基体置于回转炉中，在保护气体和有机气源的混合气氛中进行化学化学气相沉积，对纳米硅生长的多孔碳基体进行软碳包覆，得到硅基负极材料。
本发明的特点还在于：
步骤1中，保护气体和硅源气体的混合比例1:1-9:1，保护气体中氢气与其他保护气体的比例1:1-1:5，混合气体流量为10-50L/h，加热温度为500-900℃，保温时间为1-10h。
步骤1中，保护气体为氢气和氮气或氢气和氩气的混合气体，氢气和氮气或氩气的混合比例1:1-1:5；硅源气体为硅烷、二硅烷、三硅烷、四硅烷、氯硅烷和六氯硅烷中的至少一种。
步骤2中，保护气体和有机气源的混合比例1:1-9:1，混合气体流量为10-50L/h，加热温度为500-900℃，保温时间为2-6h。
步骤2中，保护气体为氢气和氮气或氢气和氩气的混合气体，氢气和氮气或氩气的混合比例1:1-1:5；有机气源为乙炔、丙烷、环己烷、甲烷和苯中的至少一种。
步骤1中，多孔碳比表面积为100-2000m2/g，孔容为0.3-2.5cm3/g，平均孔径为2-500nm。
本发明的有益效果是，本发明以多孔碳为化学气相沉积(Chemical VaporDeposition，CVD)生长硅颗粒的基体，并在表面包覆软碳制备出硅碳负极材料。在化学气相沉积和软碳包覆过程中通入氢气并控制混合气体流量抑制硅颗粒长大和结晶，有效降低硅材料在循环过程中的体积膨胀，提高材料的电化学性能。此外，多孔碳基体提供电子通道，同时抑制硅材料在循环过程中的体积膨胀，多孔碳和硅颗粒表面包覆的软碳可降低材料比表面积，提高材料首次库伦效率。
附图说明
图1是本发明无定形硅基负极材料的制备方法的流程图；
图2是本发明无定形硅基负极材料的制备方法实施例1、2和对比例1的XRD图。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明无定形硅基负极材料的制备方法，如图1所示，具体包括如下步骤：
步骤1，将多孔碳基体置于回转炉中，通入保护气体和硅源气体的混合气在多孔碳基体内部沉积纳米硅，得到生长纳米硅的多孔碳基体。
步骤1，保护气体和硅源气体的混合比例1:1-9:1，混合气体流量为10-50L/h，加热温度为500-900℃，保温时间为1-10h。
步骤1，保护气体为氢气和氮气或氢气和氩气的混合气体，氢气和氮气或氩气的混合比例1:1-1:5。
硅源气体为硅烷、二硅烷、三硅烷、四硅烷、氯硅烷和六氯硅烷中的至少一种，优选硅烷。
步骤2，将纳米硅生长的多孔碳基体置于回转炉中，在保护气体和有机气源的混合气氛中进行化学化学气相沉积，对纳米硅生长的多孔碳基体进行软碳包覆，得到硅基负极材料。
步骤2，保护气体和有机气源的混合比例1:1-9:1，混合气体流量为10-50L/h，加热温度为500-900℃，保温时间为2-6h。
步骤2，保护气体为氢气和氮气或氢气和氩气的混合气体，氢气和氮气或氩气的混合比例1:1-1:5。
有机气源为乙炔、丙烷、环己烷、甲烷和苯中的至少一种，优选乙炔。
多孔碳可选用商业活性炭或通过以下方式制得，例如采用SiO2、碳酸钙、聚苯乙烯、KOH、ZnCl2等为造孔剂，以酚醛树脂、沥青、蔗糖、二乙烯苯等为碳源，碳源和造孔剂混合后经高温碳化去除造孔剂，通过控制造孔剂和碳源比例控制多孔碳的孔容、比表和孔径。
多孔碳比表面积为100-2000m2/g，孔容为0.3-2.5cm3/g，平均孔径为2-500nm。
步骤2中，保护气体和硅源气体及有机气源的混合比例为1:1-9:1。
如果保护气体比例低于1:1，此时保护气体量过少，将无法抑制在全流程中硅颗粒的长大和晶化行为，循环过程中材料膨胀增大。如果保护气体比例高于9:1，硅源气体过少，多孔碳内硅颗粒沉积量不足，材料制备效率低。
本发明以上制备的硅基负极材料，可以用作锂电池负极材料中的活性物质，用于制备锂电池负极极片。
本发明实施例中提供的活性物质制备锂离子电池负极材料，然后组装纽扣式锂离子电池，组装锂离子电池所用的原料均相同，其中，正极为锂片，集流体为铜箔，组装完毕后测试各组锂离子电池的首次充电比容量和首次库伦效率。
多孔碳孔容、比表和孔径测试方法：采用BET比表面积测试仪。
纳米硅颗粒结晶性测试方法：采用X射线衍射仪进行测试。
硅基负极材料膨胀率测试方法：采用上述方法制备CR2032型扣式电池，用蓝电测试系统对电池进行充放电测试，第二次循环满电后在手套箱中拆解扣电，测量极片厚度。膨胀率计算方法：(循环后极片厚度-循环前极片厚度)/循环前极片厚度×100％。
实施例1
(1)将40gKOH溶于1L去离子水中，待其完全溶解后加入20g沥青，搅拌30min后置于烘箱中，干燥后的粉末置于管式炉中在900℃惰性气氛下热处理2h，将收集到的黑色粉末在盐酸浓度为1mol/L反应2h，随后用乙醇和去离子水分别冲洗3次，抽滤干燥得到多孔碳。
(2)将步骤1中得到的多孔碳放入回转炉中，氮气气氛下加热至500℃，通入15％硅烷/70％氩气/15％氢气的混合气体10h，其混合气体的流量为20L/h，停止通入硅烷气体后，进一步升温至750℃，通入20％乙炔/80％氮气的混合气体30min，混合气体的通入量为30L/h，冷却至室温后，得到最终的硅基负极材料。
实施例2
与实施例1相比，前后分别通入50％硅烷/25％氩气/25％氢气的混合气体10h和50％乙炔/50％氮气的混合气体30min，其它步骤相同。
实施例3
与实施例1相比，前后分别通入10％硅烷/15％氩气/75％氢气的混合气体10h和10％乙炔/90％氮气的混合气体30min，其它步骤相同。
实施例4
(1)将商业活性炭20g置于1mol/L HF溶液中搅拌6h后在烘箱中干燥，随后用乙醇和去离子水分别冲洗3次，抽滤干燥得到多孔碳。
(2)将步骤1中得到的多孔碳放入回转炉中，氮气气氛下加热至650℃，通入10％硅烷/65％氩气/25％氢气的混合气体6h，其混合气体的流量为30L/h，停止通入硅烷气体后，进一步升温至700℃，通入15％氢气/25％乙炔/60％氮气的混合气体4h，混合气体的通入量为20L/h，冷却至室温后，得到最终的硅基负极材料。
对比例1
将4g粒径为50nm的硅颗粒加入到1L乙醇溶液中超声分散1h，然后加入5g实施例1中制备的多孔碳和1.4g沥青进行混合搅拌1h，将上述分散液置于烘箱中蒸干得到硅碳复合材料前驱体，将制备得到的前驱体在惰性气氛下800℃处理2h后制得硅碳负极材料。分别对实施例1-4提供的和对比例1提供的硅碳负极材料进行性能测试。
表1多孔碳参数及电化学性能测试结果
从表1和图2可以看出，采用本发明在硅烷沉积和软碳包覆过程中合理控制混合气源中各部分的比例及通入氢气的流量，可有效控制硅碳负极材料中硅的结晶性，并且极片的膨胀率降低明显。当通入过多的保护气体后，材料容量和首效明显降低，但仍然具有较低的膨胀率。实施例4所采用的商业活性炭采用本发明提供的方法制备得到的硅碳负极材料同样具有较低的极片膨胀率。
本发明无定形硅基负极材料的制备方法，是以多孔碳为硅源化学气相沉积的基体，通过控制化学气相沉积过程中的混合气源比例、流量和时间等参数，制备出无定形硅碳负极材料。在该制备方法中，通过在混合气源中掺入一定量的氢气，可有效抑制硅晶粒的长大和晶化，即使在较高温度下进行软碳包覆后硅晶粒仍然呈现无定形态。与传统硅碳负极材料相比，本发明制备的硅碳负极材料在电化学循环测试中具有更低的体积膨胀，更利于电池使用过程中的安全性和稳定性。
本发明以具有高比表面积的多孔碳为基体诱导硅源气体负载硅于多孔碳孔隙内，随后在多孔碳和纳米硅表面包覆软碳，通过调控全流程中氢气流量以控制硅颗粒生长程度和结晶性，从而制备具有高容量、高首效和低膨胀的硅基负极材料。
Claims (7)
1.无定形硅基负极材料的制备方法，其特征在于：具体包括如下步骤：
步骤1，将多孔碳基体置于回转炉中，通入保护气体和硅源气体的混合气在多孔碳基体内部沉积纳米硅，得到生长纳米硅的多孔碳基体；
步骤2，将步骤1所得的纳米硅生长的多孔碳基体置于回转炉中，在保护气体和有机气源的混合气氛中进行化学化学气相沉积，对纳米硅生长的多孔碳基体进行软碳包覆，得到硅基负极材料。
2.根据权利要求1所述的无定形硅基负极材料的制备方法，其特征在于：所述步骤1中，保护气体和硅源气体的混合比例1:1-9:1，保护气体中氢气与其他保护气体的比例1:1-1:5，混合气体流量为10-50L/h，加热温度为500-900℃，保温时间为1-10h。
3.根据权利要求2所述的无定形硅基负极材料的制备方法，其特征在于：所述步骤1中，保护气体为氢气和氮气或氢气和氩气的混合气体，氢气和氮气或氩气的混合比例1:1-1:5；硅源气体为硅烷、二硅烷、三硅烷、四硅烷、氯硅烷和六氯硅烷中的至少一种。
4.根据权利要求1所述的无定形硅基负极材料的制备方法，其特征在于：所述步骤2中，保护气体和有机气源的混合比例1:1-9:1，混合气体流量为10-50L/h，加热温度为500-900℃，保温时间为2-6h。
5.根据权利要求4所述的无定形硅基负极材料的制备方法，其特征在于：所述步骤2中，保护气体为氢气和氮气或氢气和氩气的混合气体，氢气和氮气或氩气的混合比例1:1-1:5；有机气源为乙炔、丙烷、环己烷、甲烷和苯中的至少一种。
6.根据权利要求1所述的无定形硅基负极材料的制备方法，其特征在于：所述步骤1中，多孔碳比表面积为100-2000m2/g，孔容为0.3-2.5cm3/g，平均孔径为2-500nm。
7.根据权利要求1所述的无定形硅基负极材料的制备方法制备的无定形硅基负极材料的用途，用作锂电池负极材料中的活性物质，用于制备锂电池负极极片。
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| CN116613299A (zh) * | 2023-07-17 | 2023-08-18 | 浙江锂宸新材料科技有限公司 | 一种新型硅碳负极材料的制备方法及其产品 |
| CN116895747A (zh) * | 2023-07-11 | 2023-10-17 | 广东凯金新能源科技股份有限公司 | 磷掺杂硅碳复合材料及其制备方法、及二次电池 |
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| CN116495731A (zh) * | 2023-06-30 | 2023-07-28 | 北京壹金新能源科技有限公司 | 多孔碳微球、制备方法及应用和硅碳负极材料 |
| CN116895747A (zh) * | 2023-07-11 | 2023-10-17 | 广东凯金新能源科技股份有限公司 | 磷掺杂硅碳复合材料及其制备方法、及二次电池 |
| CN116613299A (zh) * | 2023-07-17 | 2023-08-18 | 浙江锂宸新材料科技有限公司 | 一种新型硅碳负极材料的制备方法及其产品 |
| CN116613299B (zh) * | 2023-07-17 | 2023-11-24 | 浙江锂宸新材料科技有限公司 | 一种硅碳负极材料的制备方法及其产品 |
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