CN115466116A - 一种多孔锂镧锆氧固体电解质片及其制备方法和应用 - Google Patents
一种多孔锂镧锆氧固体电解质片及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种多孔锂镧锆氧固体电解质片及其制备方法和应用,由以下步骤组成:将锂镧锆氧固体电解质粉体与溶剂、分散剂混合后进行球磨,得到第一球磨浆料;将第一球磨浆料与塑化剂、粘结剂混合后进行第二次球磨,得到第二球磨浆料;利用第二球磨浆料流延成膜,干燥后得到多孔锂镧锆氧前驱体,最后经过热处理得到厚度为微米级的多孔锂镧锆氧固体电解质片;锂镧锆氧固体电解质粉体、溶剂、分散剂、塑化剂和粘结剂的质量比为100:(100~150):(5.5~10):(7.5~12):(7.5~10)。本发明固体电解质片内部具有均匀、连续且贯通的孔隙结构,有利于制备三维结构有机/无机复合固体电解质时聚合物电解质的完全填充。
Description
技术领域
本发明涉及固体电解质材料技术领域,具体涉及一种多孔锂镧锆氧固体电解质片及其制备方法和应用。
背景技术
目前已经商业化使用的锂离子电池包含两类:采用液态电解质的传统锂离子电池和采用凝胶态电解质的锂离子电池。由于这两类锂离子电池中均使用了易燃、易腐蚀、易泄露的有机液态电解质,使得锂离子电池存在潜在的安全隐患,且随着三元高电压正极材料的大规模应用,更加剧了锂离子电池的不稳定性。此外,液态电解质在低温下会发生液固转化,导致离子电导率显著降低,因而也不能满足低温应用要求。
为解决上述传统锂离子电池存在的安全性和高低温应用问题并进一步提高能量密度,以固体电解质取代电解液而形成的全固态锂电池逐渐成为当前的研究热点。其中三维结构有机/无机复合固体电解质能通过构筑双连续的离子传输通道,弥补无机固体电解质和聚合物固体电解质各自的局限性,集成二者优点,同时具有高离子电导率、宽电化学窗口、良好的电化学稳定性和热稳定性、与金属锂负极兼容性好等诸多优点而受到广泛关注。
制备三维结构有机/无机复合固体电解质的难点之一在于多孔无机固体电解质骨架的构筑,它需要有连续贯通的内部孔隙结构以实现聚合物电解质的完全填充、足够的机械强度防止在加工过程中碎裂、优良的电化学性能等。目前多采用模板法或3D打印制备用于复合固体电解质的多孔无机固体电解质骨架,这两种方法制备工艺较为复杂且成本相对较高,难以实现工业化应用;其它方法如固相合成法或流延成型法,通常是以提高电解质膜致密度为目标,难以形成连续且贯通的孔隙结构。
发明内容
本发明的目的在于克服上述技术不足,提供一种多孔锂镧锆氧固体电解质片及其制备方法和应用,解决现有技术中多孔无机固体电解质骨架难以形成连续贯通的内部孔隙结构的技术问题。
为达到上述技术目的,本发明的技术方案提供一种多孔锂镧锆氧固体电解质片的制备方法:
由以下步骤组成:
(a)将锂镧锆氧固体电解质粉体与溶剂、分散剂混合后进行球磨,得到第一球磨浆料;
(b)将第一球磨浆料与塑化剂、粘结剂混合后进行第二次球磨,得到第二球磨浆料;
(c)利用第二球磨浆料流延成膜,干燥后得到多孔锂镧锆氧前驱体,最后经过热处理得到厚度为微米级的多孔锂镧锆氧固体电解质片;
其中,锂镧锆氧固体电解质粉体、溶剂、分散剂、塑化剂和粘结剂的质量比为100:(100~150):(5.5~10):(7.5~12):(7.5~10)。
进一步地,锂镧锆氧固体电解质为Li7La3Zr2O12或其元素掺杂物,掺杂元素包括Al、Ga或Ta。
进一步地,锂镧锆氧固体电解质粉体的平均粒径不超过20μm。
进一步地,所述溶剂选自乙醇、丁酮、甲乙酮、三氯乙烯、甲苯和二甲苯中的任意一种或几种,所述分散剂选自蓖麻油、磷酸脂、乙氧基化合物、鱼油和KD-1分散剂中的任意一种;所述塑化剂选自聚乙二醇、邻苯二甲酸脂类化合物和乙二醇中的任意一种;所述粘接剂选自聚乙烯醇缩丁醛、聚丙烯酸甲酯和乙基纤维素中的任意一种。
进一步地,流延成膜是将第二球磨浆料除泡后经流延机流延成膜。
进一步地,步骤(c)干燥是在60~120℃环境中干燥6~48h。
进一步地,步骤(c)热处理是在保护气氛下,以10~30℃/min的升温速率从室温升至1000~1200℃保温1~6h,再随炉冷却至室温。
如上制备方法制得的多孔锂镧锆氧固体电解质片。
进一步地,多孔锂镧锆氧固体电解质片的孔径在0.5~2.5μm之间。
如上多孔锂镧锆氧固体电解质片作为三维结构有机/无机复合固体电解质的骨架中的应用。
与现有技术相比,本发明的有益效果包括:
(1)无需通过切割打磨即可得到厚度为微米级的多孔锂镧锆氧固体电解质片,且厚度均匀可控,适用于规模化生产;(2)前驱体中的有机组分在两次球磨过程中均匀分散在坯体中,同时充当了造孔剂的作用,使得最后烧制得到的多孔锂镧锆氧固体电解质片内部具有均匀、连续且贯通的孔隙结构,有利于制备三维结构有机/无机复合固体电解质时聚合物电解质的完全填充;(3)本发明可通过调控有机添加剂含量及烧结工艺步骤实现多孔LLZO电解质膜孔隙率的精确调控,且工艺简单,成本较低;(4)本发明多孔锂镧锆氧固体电解质片作为三维结构有机/无机复合固体电解质的骨架,与有机物复合时,电导率能够提升一个数量级。
附图说明
图1为本发明实施例1制得的多孔锂镧锆氧固体电解质片的实物照片;
图2为实施例1中1100℃烧结所得多孔锂镧锆氧固体电解质片的断面微观形貌图。
图3为不同烧结温度下制得的多孔锂镧固体电解质片的X射线衍射图;
图4为不同烧结温度下制得的多孔锂镧锆氧固体电解质片的交流阻抗谱。
图5为多孔LLZO与丁二腈塑晶固体电解质复合的阻抗谱。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明提供一种用于三维结构有机/无机复合固体电解质的多孔锂镧锆氧固体电解质片的制备方法,包括以下步骤:
(a)将锂镧锆氧固体电解质粉体与溶剂、分散剂混合后进行球磨,得到第一次球磨浆料;
(b)将第一次球磨浆料与塑化剂、粘结剂混合后进行第二次球磨,得到第二次球磨浆料;
(c)利用第二次球磨浆料流延成膜,干燥后得到多孔锂镧锆氧前驱体,最后经过热处理得到厚度为微米级的多孔锂镧锆氧固体电解质片。
进一步的,锂镧锆氧固体电解质为无掺杂的Li7La3Zr2O12(LLZO)或其元素掺杂物,掺杂元素如Al、Ga、Ta;LLZO粉体使用前需进行研磨过筛处理,制成平均粒径不超过20μm的粉体。
进一步的,溶剂选自乙醇、丁酮、甲乙酮、三氯乙烯、甲苯、二甲苯中的任意一种或几种,分散剂选自蓖麻油、磷酸脂、乙氧基化合物、鱼油、KD-1分散剂中的任意一种;塑化剂选自聚乙二醇、邻苯二甲酸脂类化合物、乙二醇中的任意一种;粘接剂选自聚乙烯醇缩丁醛、聚丙烯酸甲脂、乙基纤维素中的任意一种。
进一步的,第一次球磨时LLZO固体电解质粉体与分散剂、溶剂的质量比为100:(5.5~10):(100~150),第二次球磨时加入的塑化剂、粘结剂与LLZO固体电解质粉体的质量比为(7.5~12):(7.5~10):100。
进一步的,第二次球磨浆料除泡后经流延机流延成膜,接着将所得湿膜置于60~120℃环境中干燥6~48h,
进一步的,烧结具体过程为:在保护气氛下,以10~30℃/min的升温速率将膜坯从室温升至1000~1200℃,保温1~6h,然后随炉冷却至室温。
进一步的,多孔锂镧锆氧固体电解质片厚度为50-500μm。
本发明在采用流延法制备多孔锂镧锆氧前驱体的过程中,充分发挥流延成型工艺的优点,同时特意提高了所加入的分散剂、塑化剂和粘结剂等有机物的比例,能在提高锂镧锆氧粉体分散均匀性和浆料稳定性的同时,使有机物组分在最后的热处理过程中充当造孔剂,无需排胶过程,从而使固体电解质片内部形成均匀连续贯通的孔结构。本发明是一种设备简单、工艺稳定、生产效率高、易于工业化生产的多孔无机固体电解质膜制备方法,并由此获得了厚度可控、性能优良的微米级多孔锂镧锆氧固体电解质膜材料,可以用于三维结构有机/无机复合固体电解质的无机骨架。
下面通过具体的实施例对本发明做进一步详细说明。
实施例1
将石榴石型固体电解质Li6.25Al0.25La3Zr2O12粉体放入玛瑙研钵中,手动研磨30min,过500目筛。称取6g过筛后的粉体,加入氧化锆球磨罐中,再加入乙醇和丁酮各3g以及蓖麻油0.33g,以300r/min的转速球磨12h。第一次球磨完成后再加入塑化剂邻苯二甲酸二丁酯(DBP)和粘接剂聚乙烯醇缩丁醛(PVB)各0.45g,以300r/min的转速继续球磨24h,得到稳定且分散均匀的流延浆料。以流延浆料为原料在流延机上流延成型,控制刮刀高度为500μm,所得湿膜在80℃下真空干燥24h,得到可加工性能良好的前驱体。裁剪成直径18mm的圆片,置于氧化铝坩埚中并转入马弗炉,以10℃/min的升温速率升至1100℃,保温4h后随炉冷却随炉冷却,所得成品即为本发明多孔锂镧锆氧固体电解质片,其实物照片如图1所示,微观形貌如图2所示。
如图1所示,本发明制得的多孔锂镧锆氧固体电解质片为膜片状固体电解质,整体呈现均匀的半透明状,表明合成了多孔结构的锂镧锆氧固体电解质片。
由图2可知,通过本发明流延成型工艺制备的多孔LLZO固体电解质膜内部存在连通的孔隙结构,这为制备复合固体电解质时聚合物电解质的填入提供了有利条件。
实施例2
将石榴石型固体电解质Li7La3Zr2O12粉体放入玛瑙研钵中,手动研磨60min,过300目筛。称取6g过筛后的粉体,加入氧化锆球磨罐中,再加入乙醇和甲苯各4.5g以及KD-1分散剂0.42g,以400r/min的转速球磨18h。第一次球磨完成后再加入塑化剂邻苯二甲酸丁基苄酯(BBP)和粘接剂PVB各0.6g,以400r/min的转速继续球磨18h,得到稳定且分散均匀的流延浆料。以流延浆料为原料在流延机上流延成型,控制刮刀高度为400μm,所得湿膜在100℃下真空干燥20h,得到可加工性能良好的流延坯体。裁剪成直径18mm的圆片,置于氧化铝坩埚中并转入箱式炉中,以20℃/min的升温速率升至1200℃,保温2h后随炉冷却,所得成品即为本发明多孔锂镧锆氧固体电解质片。
实施例3
将石榴石型固体电解质Li6.4La3Zr1.4Ta0.6O12粉体放入玛瑙研钵中,手动研磨45min,过300目筛。称取6g过筛后的粉体,加入氧化锆球磨罐中,再加入三氯乙烯9.0g以及鱼油0.5g,以200r/min的转速球磨24h。第一次球磨完成后再加入塑化剂聚乙二醇0.7g、粘接剂聚丙烯酸甲酯0.6g,以300r/min的转速继续球磨24h,得到稳定且分散均匀的流延浆料。以流延浆料为原料在流延机上流延成型,控制刮刀高度为400μm,所得湿膜在80℃下真空干燥24h,得到可加工性能良好的流延坯体。裁剪成直径20mm的圆片,置于氧化铝坩埚中并转入马弗炉,按15℃/min的升温速率升至1000℃,保温6h后随炉冷却,所得成品即为本发明多孔锂镧锆氧固体电解质片。
实施例4
为充分研究烧结温度对多孔LLZO固体电解质片的影响,按照实施例1的方法分别在1200℃、1150℃和1100℃烧结得到了多孔锂镧锆氧固体电解质片,并对其进行了X射线衍射实验,结果如图3所示。
由图3可知,流延成型过程中所加有机添加剂对固体电解质的物相无影响,在1100℃、1150℃和1200℃烧结所得多孔LLZO固体电解质膜,其物相均为纯立方相。
由图4可知,不同烧结温度对所得固体电解质的锂离子电导率有较大影响;本发明优选烧结温度为1200℃,烧结时间为12h。其多孔LLZO固体电解质电导率可达1.94*10-5S/cm。
对比例1
增加排胶步骤:将原片先在600℃保温2h,随炉冷却后再置于氧化铝坩埚中并转入马弗炉烧结,其它条件同实施例1。
结果发现,增加了排胶步骤,使得有机物排出,无法形成贯通均匀的孔道。
对比例2
在有氮气保护下,其他条件同实施例3。
结果发现,会少部分有机物残留在固体电解质内部,相较于直接空气烧结,难以完全除去有机物。
应用例
将丁二腈加热融化,并加入0.1g双三氟甲基磺酸亚酰胺锂。再将实施例4得到的多孔LLZO固体电解质,浸入到丁二腈溶液中。待充分接触后,取出LLZO/SN复合固体电解质。通过抛光,除去复合固体电解质表面的丁二腈,其阻抗谱如图5所示;测试其电导率为1.2*10- 4S/cm。
本发明提供了一种用于三维结构有机/无机复合固体电解质的多孔锂镧锆氧固体电解质片的制备方法,具体为通过流延法制备厚度为微米级的多孔锂镧锆氧固体电解质片。本发明在采用流延法制备多孔锂镧锆氧前驱体的过程中所加入的分散剂、塑化剂和粘结剂等有机物组分同时充当造孔剂,所得前驱体经过短时间热处理,无需进一步打磨成型,即可形成厚度为50~500μm的多孔锂镧锆氧固体电解质片。与现有方法相比,本发明具有成本低、设备简单、易于工业化等优点,所得膜产品厚度可控、内部孔隙均匀连续贯通,可实现孔隙率的精确调控。
以上所述本发明的具体实施方式,并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形,均应包含在本发明权利要求的保护范围内。
Claims (10)
1.一种多孔锂镧锆氧固体电解质片的制备方法,其特征在于,由以下步骤组成:
(a)将锂镧锆氧固体电解质粉体与溶剂、分散剂混合后进行球磨,得到第一球磨浆料;
(b)将第一球磨浆料与塑化剂、粘结剂混合后进行第二次球磨,得到第二球磨浆料;
(c)利用第二球磨浆料流延成膜,干燥后得到多孔锂镧锆氧前驱体,最后经过热处理得到厚度为微米级的多孔锂镧锆氧固体电解质片;
其中,锂镧锆氧固体电解质粉体、溶剂、分散剂、塑化剂和粘结剂的质量比为100:(100~150):(5.5~10):(7.5~12):(7.5~10)。
2.根据权利要求1所述的多孔锂镧锆氧固体电解质片的制备方法,其特征在于,所述锂镧锆氧固体电解质为Li7La3Zr2O12或其元素掺杂物,掺杂元素包括Al、Ga或Ta。
3.根据权利要求1所述的多孔锂镧锆氧固体电解质片的制备方法,其特征在于,锂镧锆氧固体电解质粉体的平均粒径不超过20μm。
4.根据权利要求1所述的多孔锂镧锆氧固体电解质片的制备方法,其特征在于,所述溶剂选自乙醇、丁酮、甲乙酮、三氯乙烯、甲苯和二甲苯中的任意一种或几种,所述分散剂选自蓖麻油、磷酸脂、乙氧基化合物、鱼油和KD-1分散剂中的任意一种;所述塑化剂选自聚乙二醇、邻苯二甲酸脂类化合物和乙二醇中的任意一种;所述粘接剂选自聚乙烯醇缩丁醛、聚丙烯酸甲酯和乙基纤维素中的任意一种。
5.根据权利要求1所述的多孔锂镧锆氧固体电解质片的制备方法,其特征在于,流延成膜是将第二球磨浆料除泡后经流延机流延成膜。
6.根据权利要求1所述的多孔锂镧锆氧固体电解质片的制备方法,其特征在于,步骤(c)干燥是在60~120℃环境中干燥6~48h。
7.根据权利要求1所述的多孔锂镧锆氧固体电解质片的制备方法,其特征在于,步骤(c)热处理是在保护气氛下,以10~30℃/min的升温速率从室温升至1000~1200℃保温1~6h,再随炉冷却至室温。
8.如权利要求1-7任一项所述制备方法制得的多孔锂镧锆氧固体电解质片。
9.根据权利要求8所述的多孔锂镧锆氧固体电解质片,其特征在于,所述多孔锂镧锆氧固体电解质片的孔径在0.5~2.5μm之间。
10.如权利要求8所述的多孔锂镧锆氧固体电解质片作为三维结构有机/无机复合固体电解质的骨架中的应用。
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