CN116262670A - 一种氮化硅陶瓷多孔流延膜在用作锂离子电池隔膜中的应用 - Google Patents

一种氮化硅陶瓷多孔流延膜在用作锂离子电池隔膜中的应用 Download PDF

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CN116262670A
CN116262670A CN202111524657.4A CN202111524657A CN116262670A CN 116262670 A CN116262670 A CN 116262670A CN 202111524657 A CN202111524657 A CN 202111524657A CN 116262670 A CN116262670 A CN 116262670A
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silicon nitride
powder
sintering aid
use according
sintering
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张景贤
张桢祺
孔乐川
段于森
戴金荣
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Shanghai Caoyang Second Middle School Affiliated School
SHANGHAI WENLAI MIDDLE SCHOOL
Shanghai Institute of Ceramics of CAS
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SHANGHAI WENLAI MIDDLE SCHOOL
Shanghai Institute of Ceramics of CAS
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Abstract

本发明涉及一种氮化硅陶瓷多孔流延膜在用作锂离子电池隔膜中的应用。所述氮化硅陶瓷多孔流延膜的孔径小于200nm，优选为小于100nm，孔隙率为40～60%，厚度为0.05～0.2mm，抗弯强度为100～150MPa。

Description

一种氮化硅陶瓷多孔流延膜在用作锂离子电池隔膜中的应用
技术领域
本发明涉及一种氮化硅陶瓷多孔流延膜在用作锂离子电池隔膜中的应用，属于陶瓷材料的制备工艺和应用领域。
背景技术
目前，锂离子电池已经成为人们生活中不可或缺的一部分。但是，关于其使用过程中发生***的情形也屡见不鲜。锂离子电池的***起火主要是由于短路引起的，而短路则主要与电池充放电过程中生成锂枝晶、刺破隔膜有关，因而抑制锂枝晶生长并刺破隔膜是防止锂离子电池***的重要途径。
当前，商品化的锂电池隔膜材料主要采用聚乙烯PE、聚丙烯PP微孔膜等，主要的隔膜材料产品有单层PP、单层PE、PP+陶瓷涂覆、PE+陶瓷涂覆、双层PP/PE、双层PP/PP和三层PP/PE/PP等。CN102437302A公开了一种陶瓷涂覆的聚烯烃微孔薄膜用作锂离子电池隔膜。然而，无论是传统的聚合物隔膜，还是经过涂层处理的聚合物隔膜，都因为强度较低而无法避免被锂枝晶刺穿，虽然涂层可以改善聚合物隔膜抗锂枝晶刺穿的能力，但是仍然无法达到良好的抗刺穿效果。
发明内容
针对上述问题，本发明基于流延成型的思路，提供了一种氮化硅陶瓷多孔流延膜用作锂离子电池隔膜。
具体来说，本发明提供了一种氮化硅陶瓷多孔流延膜在用作锂离子电池隔膜中的应用，所述氮化硅陶瓷多孔流延膜的孔径小于200nm，优选为小于100nm，孔隙率为40～60％，厚度为0.05～0.2mm，抗弯强度为100～150MPa。
陶瓷材料具有机械强度高、硬度高、耐腐蚀、性能稳定等多重优势，采用陶瓷材料作为锂离子电池隔膜，有望防止锂枝晶刺穿，进而防止短路，提高锂离子电池的安全性。本发明采用孔径小于200nm，优选为小于100nm，孔隙率为40～60％，厚度为0.05～0.2mm的氮化硅陶瓷多孔流延膜作为锂离子电池隔膜，不仅具有孔径分布窄的优势，而且该孔隙率的隔膜一方面在保证锂离子自由穿梭的同时保持材料较高的容量和电化学性能，另一方面通过对材料上的气孔孔径、气孔率进行综合控制能够确保隔膜的拉伸强度、抗刺穿强度，可以保证锂枝晶不会穿透隔膜，也不会从多孔中穿出。
较佳地，所述氮化硅陶瓷多孔流延膜的制备方法包括：将氮化硅粉体和硅粉体的混合粉体以及烧结助剂分散于有机溶剂中，一次球磨后加入分散剂、粘结剂、塑性剂进行二次球磨制得流延用浆料，采用所述流延用浆料进行流延成膜，干燥、脱粘后，在含有氮气的气氛中进行氮化烧结，制得所述氮化硅陶瓷多孔流延膜。
较佳地，所述混合粉体中氮化硅粉体和硅粉体的质量比为1：(0.25～4)；所述混合粉体的粒径为1～50μm，优选为1～20μm。
本发明采用流延法制备氮化硅陶瓷隔膜，可以自由控制隔膜厚度，且无需基层支撑。采用氮化硅粉体和硅粉体的混合粉体为混合原料，控制原料粉体的粒径为1～50μm。一方面，粗颗粒的粉体烧结活性较低，有利于烧结后保留气孔结构；另一方面，硅粉体在后续氮化烧结过程中原位形成氮化硅晶粒、进一步相变生成beta相柱状晶，通过柱状晶之间相互搭接形成空隙，在高温长时间烧结作用下，也能促使氮化生成的beta相氮化硅晶粒充分发育，生成氮化硅柱状晶粒相互搭接的结构，从而在保证陶瓷高气孔率的前提下，提高材料的力学性能。此外，与国内外常用的有机膜材料相比，工艺更加简单、可靠，材料力学性能优异，大大降低了生产成本，为氮化硅隔离膜的应用创造了有利条件。
较佳地，所述烧结助剂由第一烧结助剂和第二烧结助剂组成，所述第一烧结助剂选自由Al2O3、AlN、CaO、MgO、SiO2组成的组，所述第二烧结助剂为Y2O3；第一烧结助剂和第二烧结助剂的质量比为3:5～8。
较佳地，所述有机溶剂由选自乙醇、甲醇、异丙醇、正丙醇、正丁醇、异丁醇、叔丁醇中的至少一种第一溶剂，以及选自丁酮、甲苯、正己烷、和二甲苯中的至少一种第二溶剂组成，所述第一溶剂和第二溶剂的质量比选择为二者的共沸组成。两种溶剂选择的主要目的在于调整挥发速度、浆料溶解性以及分散性等性能，其质量比可以选择为溶剂的共沸组成。
较佳地，所述一次球磨和/或二次球磨的时间为12～72小时。所述球磨可以采用常规球磨方式与工艺进行。
较佳地，所述分散剂为三油酸甘油酯、磷酸酯、蓖麻油、鲱鱼油、抗坏血酸和松油醇中的至少一种；所述粘结剂为聚乙烯醇缩丁醛PVB和/或聚甲基丙烯酸甲酯PMMA；所述塑性剂为邻苯二甲酸二丁酯DBP和/或邻苯二甲酸二丁卞酯BBP。
较佳地，所述混合粉体、烧结助剂、有机溶剂、分散剂、粘结剂和塑性剂的质量比为100：(3～5)：(40～48)：(1～2)：(6～10)：(6～20)。
较佳地，所述脱粘的温度为400～1000℃，时间为6～72小时。
较佳地，所述氮化烧结的温度为1600～1950℃，保温时间为1～24小时，升温速率为1～20℃/分钟；所述含有氮气的气氛为纯氮气气氛，或者氮气与氢气的混合气氛。
附图说明
图1为采用本发明实施例1制备的氮化硅多孔膜作为电池隔膜的Li/Si3N4/Li电池在室温、3.0mA·cm-2@3.0mAh·cm-2的电压-时间曲线。
图2为采用现有的聚合物膜作为电池隔膜的Li/聚合物隔膜/Li电池在室温、3.0mA·cm-2@3.0mAh·cm-2的电压-时间曲线。
具体实施方式
以下通过实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
针对前述问题，本发明基于长期氮化硅流延成型的研究，提出了一种流延成型制备氮化硅多孔膜用作锂电池隔膜来抑制锂枝晶的思路，所述氮化硅隔膜主要通过制备流动性可控的氮化硅/硅浆料，并进一步将氮化硅/硅浆料流延成型来实现，所述的氮化硅/硅陶瓷浆料以非水基溶剂为介质。
首先，本发明以氮化硅粉体和硅粉体的混合粉体为原料，并控制原料粉体的粒径为1～50μm，优选为1～20μm。氮化硅本身抗拉伸性能、抗弯折性能优异，适于用作隔膜材料。在可选的实施例中，所述混合粉体中氮化硅粉体和硅粉体的质量比为1：(0.25～4)。
本发明采用流延法制备氮化硅陶瓷隔膜，可以自由控制隔膜厚度，且无需基层支撑。采用氮化硅粉体和硅粉体的混合粉体为混合原料，控制原料粉体的粒径为1～50μm。一方面，粗颗粒的粉体烧结活性较低，有利于烧结后保留气孔结构；另一方面，硅粉体在后续氮化烧结过程中原位形成氮化硅晶粒、进一步相变生成beta相柱状晶，通过柱状晶之间相互搭接形成空隙，在高温长时间的烧结作用下，也能促使氮化生成的beta相氮化硅晶粒充分发育，生成氮化硅柱状晶粒相互搭接的结构，从而在保证陶瓷高气孔率的前提下，提高材料的力学性能。此外，与国内外常用的有机膜材料相比，工艺更加简单、可靠，材料力学性能优异，大大降低了生产成本，为氮化硅隔离膜的应用创造了有力条件。
在原料粉体中混入烧结助剂粉体，加入有机溶剂进行球磨。烧结助剂可选用混合烧结助剂，例如由Al2O3、AlN、CaO、MgO、SiO2中的一种和Y2O3组成，前者和后者的比例可为3:5～8。
有机溶剂可由选自乙醇、甲醇、异丙醇、正丙醇、正丁醇、异丁醇、叔丁醇中的至少一种第一溶剂，以及选自丁酮、甲苯、正己烷、和二甲苯中的至少一种第二溶剂组成，第一溶剂和第二溶剂的质量比可以选择为二者的共沸组成。
一次球磨后加入分散剂、粘结剂、塑性剂进行二次球磨制得流延用浆料。分散剂为三油酸甘油酯、磷酸酯、蓖麻油、鲱鱼油、抗坏血酸和松油醇中的至少一种；粘结剂可为聚乙烯醇缩丁醛和/或聚甲基丙烯酸甲酯；塑性剂可以为邻苯二甲酸二丁酯DBP和/或邻苯二甲酸二丁卞酯BBP。
所述混合粉体、烧结助剂、有机溶剂、分散剂、粘结剂和塑性剂的质量比为100：(3～5)：(40～48)：(1～2)：(6～10)：(6～20)，所得浆料的固含量可为20vol％～40vol％。
接着，采用所得浆料进行流延成膜，干燥、脱粘、以及在含有氮气的气氛中进行氮化烧结，制得氮化硅陶瓷多孔流延膜。
所述氮化烧结的温度为1600～1950℃，保温时间为1～24小时，升温速率可为1～20℃/分钟。高温长时间烧结的作用是促使氮化生成的beta相氮化硅晶粒充分发育，生成氮化硅柱状晶粒相互搭接的结构，从而在保证陶瓷高气孔率的前提下，提高材料的力学性能。
所述含有氮气的气氛可以是纯氮气气氛，或者包含部分氢气。
所述干燥可为自然干燥，或者室温～80℃下进行。
所述脱粘的温度为400～1000℃，时间为6～72h。
所得氮化硅多孔膜的孔径小于200nm，优选为小于100nm，孔隙率为40～60％，厚度为0.05～0.2mm，抗弯强度为100～150MPa。
陶瓷材料机械强度高、硬度高、耐腐蚀、性能稳定，本发明采用孔径小于200nm，优选为小于100nm，孔隙率为40～60％，厚度为0.05～0.2mm的氮化硅陶瓷多孔流延膜作为锂离子电池隔膜，孔径分布窄。一方面，能够保证锂离子自由穿梭、保持材料较高的容量和电化学性能；另一方面，通过对材料的气孔孔径、气孔率进行综合控制进而可确保隔膜的拉伸强度、抗刺穿强度，也可以保证锂枝晶不会穿透隔膜，也不会从多孔中穿出。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。若无特殊说明，下述实施例中氮化硅粉体和硅粉体的混合粉体粒径一般为1～20μm。
实施例1
将40g氮化硅(粒径1微米)粉体、10g硅(粒径5微米)粉体和1.5g氧化铝(粒径0.8微米)、氧化钇(粒径3微米)组成的烧结助剂(质量比3：5)粉体，添加在20g乙醇/丁酮溶剂体系(乙醇和丁酮质量比为66：34)中，球磨24h。采用1g三油酸甘油酯作为分散剂，球磨后加入3gPVB为粘结剂，3gDBP为塑性剂，再次球磨48小时后脱泡，然后进行流延成型(素坯膜厚0.12mm)。陶瓷膜经自然干燥后，在600℃脱粘炉中脱粘720分钟，然后以5℃/分钟升温到1800℃，氮气气氛中保温2h完成烧结，得到氮化硅隔膜，其孔隙率为46％，孔径小于等于0.10微米，膜厚0.1mm，抗弯强度为133MPa。
实施例2
将35g氮化硅(粒径2微米)、15g硅(粒径8微米)粉体和1.8g氧化铝(粒径0.8微米)、氧化钇(粒径3微米)组成的烧结助剂(质量比3：5)粉体，添加在24g乙醇/甲苯溶剂体系(乙醇和甲苯质量比为2：1)中，球磨24h。采用1g磷酸酯作为分散剂，球磨后加入3g PVB为粘结剂，3g DBP为塑性剂，再次球磨60小时后脱泡，然后进行流延成型(素坯膜厚0.15mm)。陶瓷膜经自然干燥后，在600℃脱粘炉中脱粘8h。然后以6℃/分钟升温到1800℃，氮气气氛中保温6h完成烧结，得到氮化硅隔膜，其孔隙率为48％，孔径小于等于0.12微米，膜厚0.12mm，抗弯强度为134MPa。
实施例3
将30g氮化硅(粒径3微米)、20g硅(粒径10微米)粉体和2.0g氧化铝(粒径0.8微米)、氧化钇(粒径3微米)组成的烧结助剂(质量比3：6)粉体，添加在20g乙醇/正己烷溶剂体系(乙醇和正己烷质量比为3：1)中，球磨24h。采用0.5g蓖麻油作为分散剂，球磨后加入5gPVB为粘结剂，5g DBP为塑性剂，再次球磨50小时后脱泡，然后进行流延成型(素坯膜厚0.20mm)。陶瓷膜经自然干燥后，在600℃脱粘炉中脱粘12h。然后以5℃/分钟升温到1800℃，氮气气氛中保温12h完成烧结，得到氮化硅隔膜，其孔隙率为49％，孔径小于等于0.13微米，膜厚0.16mm，抗弯强度为129MPa。
实施例4
将25g氮化硅(粒径5微米)、25g硅(粒径15微米)粉体和2.2g氧化钙(粒径1微米)、氧化钇(粒径3微米)组成的烧结助剂(质量比3：7)粉体，添加在21g甲醇/丁酮溶剂体系(丁酮和甲醇质量比为2：5)中，球磨36h。采用1g抗坏血酸作为分散剂，球磨后加入5g PVB为粘结剂，5g BBP为塑性剂，再次球磨60小时后脱泡，然后进行流延成型(素坯膜厚0.18mm)。陶瓷膜经自然干燥后，在600℃脱粘炉中脱粘16h，然后以5℃/分钟升温到1650℃，氮气气氛中保温18h完成烧结，得到氮化硅隔膜，其孔隙率为53％，孔径小于等于0.15微米，膜厚0.15mm，抗弯强度为126MPa。
实施例5
将20g氮化硅(粒径5微米)、30g硅(粒径15微米)粉体和2.4g二氧化硅(粒径2微米)、氧化钇(粒径3微米)组成的烧结助剂(质量比3：8)粉体，添加在24g正丙醇/二甲苯溶剂体系(二甲苯和正丙醇质量比为2：1)中，球磨24h。采用0.8g三油酸甘油酯作为分散剂，球磨后加入5g PVB为粘结剂，5g BBP为塑性剂，再次球磨50小时后脱泡，然后进行流延成型(素坯膜厚0.2mm)。陶瓷膜经自然干燥后，在600℃脱粘炉中脱粘20h。然后以3℃/分钟升温到1800℃，氮气气氛中保温24h完成烧结，得到氮化硅隔膜，其孔隙率为55％，孔径小于等于0.15微米，膜厚0.16mm，抗弯强度为133Pa。
实施例6
将15g氮化硅(粒径2微米)粉体、35g硅(粒径20微米)粉体和1.5g氧化铝(粒径0.8微米)、氧化钇(粒径3微米)组成的烧结助剂(质量比3：5)粉体，添加在24g乙醇/丁酮溶剂体系(乙醇和丁酮质量比为66：34)中，球磨24h。采用1g三油酸甘油酯作为分散剂，球磨后加入3g PVB为粘结剂，3g DBP为塑性剂，再次球磨48小时后脱泡，然后进行流延成型(素坯膜厚0.15mm)。陶瓷膜经自然干燥后，在600℃脱粘炉中脱粘720分钟，然后以5℃/分钟升温到1850℃，氮气气氛中保温2h完成烧结，得到氮化硅隔膜，其孔隙率为46％，孔径小于等于0.12微米，膜厚0.12mm，抗弯强度为128MPa。
实施例7
将10g氮化硅(粒径3微米)粉体、40g硅(粒径20微米)粉体和2.0g氧化铝(粒径0.8微米)、氧化钇(粒径3微米)组成的烧结助剂(质量比3：5)粉体，添加在24g乙醇/丁酮溶剂体系(乙醇和丁酮质量比为66：34)中，球磨24h。采用1g三油酸甘油酯作为分散剂，球磨后加入4g PVB为粘结剂，4gDBP为塑性剂，再次球磨48小时后脱泡，然后进行流延成型(素坯膜厚0.15mm)。陶瓷膜经自然干燥后，在600℃脱粘炉中脱粘12h，然后以5℃/分钟升温到1850℃，氮气气氛中保温6h完成烧结，得到氮化硅隔膜，其孔隙率为49％，孔径小于等于0.15微米，膜厚0.13mm，抗弯强度为127MPa。
实施例8
将25g氮化硅(粒径5微米)粉体、25g硅(粒径20微米)粉体和1.5g氧化铝(粒径0.8微米)、氧化钇(粒径3微米)组成的烧结助剂(质量比3：5)粉体，添加在22g乙醇/丁酮溶剂体系(乙醇和丁酮质量比为66：34)中，球磨24h。采用1g三油酸甘油酯作为分散剂，球磨后加入5g PVB为粘结剂，5g DBP为塑性剂，再次球磨48小时后脱泡，然后进行流延成型(素坯膜厚0.16mm)。陶瓷膜经自然干燥后，在600℃脱粘炉中脱粘24h，然后以5℃/分钟升温到1850℃，氮气气氛中保温12h完成烧结，得到氮化硅隔膜，其孔隙率为53％，孔径小于0.18微米，膜厚0.12mm，抗弯强度为128MPa。
上述实施例中相关原料、制备工艺以及隔膜相关物性指标整理如下表1：
Figure BDA0003409697470000071
。
为了研究本发明提供的氮化硅膜抑制锂枝晶的性能，分别对采用本发明实施例1制备的氮化硅多孔膜作为电池隔膜的Li/Si3N4/Li电池以及采用现有的聚合物膜作为电池隔膜的Li/聚合物隔膜/Li电池进行室温、3.0mA·cm-2@3.0mAh·cm-2的循环电压-时间曲线测试。图1示出了采用本发明实施例1制备的氮化硅多孔膜作为电池隔膜的Li/Si3N4/Li电池在室温、3.0mA·cm-2@3.0mAh·cm-2的电压-时间曲线；图2示出了采用现有的聚合物膜作为电池隔膜的Li/聚合物隔膜/Li电池在室温、3.0mA·cm-2@3.0mAh·cm-2的电压-时间曲线。从图1、2可以看出，使用氮化硅陶瓷隔膜的锂金属对称电池在较大面容量3.0mAh/cm2的情况下，与同样条件下采用聚合物隔膜制备的电池(对比组)相比，采用氮化硅陶瓷隔膜制备的电池使用寿命从50小时增加到2000小时以上，抑制锂枝晶效果明显。这体现了氮化硅陶瓷隔膜较高的机械强度、合理的孔径分布能够确保锂金属表面枝晶被抑制，进而能够确保锂金属负极在循环过程中良好的机械稳定性。

Claims (10)

1.一种氮化硅陶瓷多孔流延膜在用作锂离子电池隔膜中的应用，其特征在于，所述氮化硅陶瓷多孔流延膜的孔径小于200nm，优选为小于100nm，孔隙率为40～60%，厚度为0.05～0.2mm，抗弯强度为100～150MPa。
2.根据权利要求1所述的应用，其特征在于，所述氮化硅陶瓷多孔流延膜的制备方法包括：将氮化硅粉体和硅粉体的混合粉体以及烧结助剂分散于有机溶剂中，一次球磨后加入分散剂、粘结剂、塑性剂进行二次球磨制得流延用浆料，采用所述流延用浆料进行流延成膜，干燥、脱粘后，在含有氮气的气氛中进行氮化烧结，制得所述氮化硅陶瓷多孔流延膜。
3.根据权利要求2所述的应用，其特征在于，所述混合粉体中氮化硅粉体和硅粉体的质量比为1：（0.25～4）；所述混合粉体的粒径为1～50μm，优选为1～20μm。
4.根据权利要求2或3所述的应用，其特征在于，所述烧结助剂由第一烧结助剂和第二烧结助剂组成，所述第一烧结助剂选自由 Al2O3、AlN、CaO、MgO、SiO2组成的组，所述第二烧结助剂为Y2O3；第一烧结助剂和第二烧结助剂的质量比为3:5～8。
5.根据权利要求2至4中任一项所述的应用，其特征在于，所述有机溶剂由选自乙醇、甲醇、异丙醇、正丙醇、正丁醇、异丁醇、叔丁醇中的至少一种第一溶剂，以及选自丁酮、甲苯、正己烷、和二甲苯中的至少一种第二溶剂组成，所述第一溶剂和第二溶剂的质量比选择为二者的共沸组成。
6.根据权利要求2至5中任一项所述的应用，其特征在于，所述一次球磨和/或二次球磨的时间为12～72小时。
7.根据权利要求2至6中任一项所述的应用，其特征在于，所述分散剂为三油酸甘油酯、磷酸酯、蓖麻油、鲱鱼油、抗坏血酸和松油醇中的至少一种；所述粘结剂为聚乙烯醇缩丁醛PVB和/或聚甲基丙烯酸甲酯PMMA；所述塑性剂为邻苯二甲酸二丁酯DBP和/或邻苯二甲酸二丁卞酯BBP。
8.根据权利要求2至7中任一项所述的应用，其特征在于，所述混合粉体、烧结助剂、有机溶剂、分散剂、粘结剂和塑性剂的质量比为100：（3～5）：（40～48）：（1～2）：（6～10）：（6～20）。
9.根据权利要求2至8中任一项所述的应用，其特征在于，所述脱粘的温度为400～1000℃，时间为6～72小时。
10.根据权利要求2至9中任一项所述的应用，其特征在于，所述氮化烧结的温度为1600～1950℃，保温时间为1～24小时，升温速率为1～20℃/分钟；所述含有氮气的气氛为纯氮气气氛，或者氮气与氢气的混合气氛。
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