CN113745656A - 一种聚异氰尿酸酯基阻燃凝胶聚合物电解质及其制备方法 - Google Patents
一种聚异氰尿酸酯基阻燃凝胶聚合物电解质及其制备方法 Download PDFInfo
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 45
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 23
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims abstract description 3
- UCBVELLBUAKUNE-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)NC(=O)N(CC=C)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 claims abstract description 3
- JCUMQTAAEUDUPK-UHFFFAOYSA-N 3-[3-(2-carboxyethyl)-2,4,6-trioxo-1,3,5-triazinan-1-yl]propanoic acid Chemical compound OC(=O)CCN1C(=O)NC(=O)N(CCC(O)=O)C1=O JCUMQTAAEUDUPK-UHFFFAOYSA-N 0.000 claims abstract description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
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- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
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- 238000005303 weighing Methods 0.000 description 1
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
本发明公开了一种聚异氰尿酸酯基阻燃凝胶聚合物电解质及其制备方法,所述聚合物电解质以异氰尿酸酯基单体材料和锂盐为原料制备而成,其中:异氰尿酸酯基单体材料为异氰尿酸二烯丙基丙酯、异氰尿酸三烯丙酯、异氰尿酸三缩水甘油酯、双(2‑羧乙基)异氰尿酸酯,三(2‑丙烯酰氧乙基)异氰尿酸酯中的一种或多种;锂盐选自双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、双草酸硼酸锂、二氟草酸硼酸锂、六氟磷酸锂、四氟硼酸锂中的至少一种。本发明利用异氰尿酸酯基有机单体聚合形成网络,通过本身异氰尿酸酯基的热稳定性、原位构筑具有阻燃效果的凝胶聚合物电解质材料,制备工艺简单可控,操作简便,所得产品性能优良,安全、便于大规模的工业化生产。
Description
技术领域
本发明属于准固态锂离子电池技术领域,涉及一种聚异氰尿酸酯基阻燃凝胶聚合物电解质及其制备方法。
背景技术
锂离子电池具有能量密度高、无记忆效应、自放电小、循环寿命长等优点,是21世纪电动汽车和电子产品的主要动力来源。然而,商用锂离子电池存在大量的安全隐患,如短路或局部过热等,导致事故频发,阻碍了其在相关领域的进一步发展。一般认为锂离子电池的安全问题与液体电解液密切相关,液体电解液容易被点燃,引起热失控甚至爆炸。而凝胶聚合物电解质可以减少电解液的用量,避免电解液的泄漏,并为锂金属电池提供良好的界面相容性和良好的电化学稳定性。
然而目前常用的凝胶聚合物电解质由于较大含量绝缘性聚合物的添加,存在离子电导率降低过大、电极浸润性差使得正负极界面恶化的严重问题;同时由于含有大量的有机电解液,仍然存在着火等安全隐患。因此,设计一种安全环保、阻燃,同时兼顾电化学性能的凝胶态聚合物电解质是目前电解质研究的重点。
发明内容
本发明的目的是提供一种聚异氰尿酸酯基阻燃凝胶聚合物电解质及其制备方法,基于多网络结构的凝胶聚合物电解质,一方面使得电解液固化减少漏液隐患同时具有阻燃效果进一步提升其安全性能,另一方面高液相成分保持了良好的界面相容性,改善界面电阻,进一步提高锂离子电池的电化学性能。
本发明的目的是通过以下技术方案实现的:
一种聚异氰尿酸酯基阻燃凝胶聚合物电解质,以异氰尿酸酯基单体材料和锂盐为原料制备而成,其中:所述异氰尿酸酯基单体材料能聚合得到异氰尿酸酯基聚合物,异氰尿酸酯基单体材料为异氰尿酸二烯丙基丙酯、异氰尿酸三烯丙酯、异氰尿酸三缩水甘油酯、双(2-羧乙基)异氰尿酸酯,三(2-丙烯酰氧乙基)异氰尿酸酯中的一种或多种;当锂离子电池正极材料为Li Ni0.8Co0.1Mn0.1O2和高压LiCoO2时,异氰尿酸酯基单体材料优选为三(2-丙烯酰氧乙基)异氰尿酸酯;所述凝胶聚合物电解质中,异氰尿酸酯基单体材料的质量分数为1~50wt%,优选地,异氰尿酸酯基单体材料的质量分数为3~20wt%,进一步优选为5~15wt%;所述锂盐选自双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、双草酸硼酸锂、二氟草酸硼酸锂、六氟磷酸锂、四氟硼酸锂中的至少一种;所述锂盐占异氰尿酸酯基单体材料和锂盐总质量的60~90%。
一种上述聚异氰尿酸酯基阻燃凝胶聚合物电解质的制备方法,包括如下步骤:
步骤一、前驱体溶液制备:在具有保护气氛氩气且氧含量和水含量均小于0.1ppm的环境下,将异氰尿酸酯基单体材料溶解于含有锂离子的锂离子电池电解液体系中,充分搅拌,随后加入自由基引发剂化合物,得到凝胶聚合物电解质前驱体溶液,其中:所述锂离子电解液溶剂体系由碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸丙酸酯中的一种或者多种组成,优选为碳酸乙烯酯和碳酸二甲酯混合溶剂,碳酸乙烯酯与碳酸二甲酯的体积比为3:7;所述自由基引发剂化合物选自偶氮二异丁腈、过氧化苯甲酰、偶氮二异庚腈、叔丁基过氧化氢、偶氮二异丁酸二甲酯、过氧化苯甲酸叔丁酯中的至少一种,优选为偶氮二异丁腈;所述自由基引发剂化合物的加入量为异氰尿酸酯基单体材料的0.01~1wt%,优选为0.5wt%;
步骤二、固化成膜:在锂离子电池注液过程中,将步骤一中的前驱体溶液滴加在多孔支撑材料上,直接装配成电池,随后将装配好的电池置于烘箱中进行原位热聚合,其中:多孔支撑材料选自聚乙烯、聚丙烯、聚丙烯腈、聚(偏氟乙烯-六氟乙烯)、聚甲基丙烯酸甲酯、聚酰亚胺中单一或多种成分组成的多孔膜,优选为聚丙烯;原位热聚合的温度为40~70℃,优选为50~60℃,时间为0.5~4h,优选为1h。
本发明中,当锂离子电池正极材料为Li Ni0.8Co0.1Mn0.1O2,载量为2mg·cm-1,所用异氰尿酸酯基有机单体为三(2-丙烯酰氧乙基)异氰尿酸酯时,所得产品在0.5C下的充放电循环200次后,容量保持率为75~80%;当锂离子电池正极材料为LiCoO2,载量为5mg·cm-1,所用异氰尿酸酯基有机单体为三(2-丙烯酰氧乙基)异氰尿酸酯时,所得产品在1C下的充放电循环300次后,容量保持率为75~80%。
本发明利用异氰尿酸酯基有机单体聚合形成网络,通过本身异氰尿酸酯基的热稳定性、原位构筑具有阻燃效果的凝胶聚合物电解质材料,相比于现有技术,具有如下优点:
1、本发明的制备方法主要是通过含异氰尿酸酯基有机单体聚合后形成聚合物网络结构,同时本身含有的三嗪结构具有热稳定性,进一步提升凝胶聚合物电解质的阻燃性能。
2、本发明获得的多网络结构凝胶聚合物电解质具有近液体电解液的高离子电导率,同时提高了锂离子迁移率,改善了聚合物电解质与正负极接触电阻大,接触界面相容性差的问题。
3、本发明引入的异氰尿酸酯基单体可在负极侧产生丰富的氮化物,形成有机无机复合的界面膜,利于锂离子的快速传输和均匀沉积,同时聚异氰尿酸酯基分子的高抗氧化性可以保证电解质在正极侧高电压下的稳定。
4、本发明凝胶聚合物电解质组分设计合理,制备工艺简单可控,操作简便,聚合物材料用量较少,成本廉价,所得产品性能优良,安全、便于大规模的工业化生产。
附图说明
图1为实施例1中凝胶聚合物电解质的电导率测试图;
图2为实施例2中凝胶聚合物电解质的燃烧实验图;
图3为实施例3中凝胶聚合物电解质的电化学窗口测试图;
图4为实施例4中液态以及凝胶聚合物电解质LiCoO2电池电化学性能图;
图5为实施例5中液态以及凝胶聚合物电解质NCM811电池电化学性能图。
具体实施方式
下面结合实施例对本发明的技术方案作进一步的说明,但并不局限于此,凡是对本发明技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,均应涵盖在本发明的保护范围中。
实施例1
准确称取0.1g三(2-丙烯酰氧乙基)异氰尿酸酯溶于碳酸乙烯酯与碳酸二甲酯比例为3:7的电解液体系当中,锂盐为双三氟甲烷磺酰亚胺锂(双三氟甲烷磺酰亚胺锂的用量为0.230g),在氩气保护气氛下搅拌10min后,在混合液当中加入0.001g偶氮二异丁腈引发剂,继续搅拌得到凝胶聚合物电解质前驱体溶液。
在氩气保护且水含量和氧含量均小于0.1ppm的手套箱中,将制得的前驱体溶液注入Celgard 2500隔膜,并选取两个不锈钢片为阻塞电极装配成扣式电池,之后将电池置于60℃下加热1h进行原位聚合。采用电化学工作站对上述装配的不锈钢片对称电池进行阻抗谱测试,凝胶聚合物电解质测得的锂离子电导率为1.09×10-3S/cm。
实施例2
将实施例1中的前驱体溶液加热固化,得到阻燃型凝胶聚合物电解质材料。进行燃烧实验,发现置于火焰上,凝胶电解质中的液态电解液发生燃烧,离开火焰之后,凝胶聚合物电解质火焰熄灭。说明制得的凝胶固态电解质具有很好的阻燃效果。
实施例3
在氩气保护且水含量和氧含量均小于0.1ppm的手套箱中,将实施例1制得的前驱体溶液注入Celgard 2500隔膜,并选取两个锂片装配成对称电池,之后将电池置于60℃下加热1h进行原位聚合。采用电化学工作站对上述装配的锂对称电池进行稳态电流极化测试以及极化前后阻抗谱测试,测得锂离子迁移数为0.544。采用相同电解液装配的锂对称电池测得的锂离子迁移数为0.276。
实施例4
选用化学通式为LiCoO2的高压钴酸锂正极材料作为正极,锂片作为负极,在氩气保护且水含量和氧含量均小于0.1ppm的手套箱中,将实施例1制得的前驱体溶液注入Celgard 2500电解质膜当中,装配成锂金属电池,之后将电池置于60℃下加热1h进行原位聚合得到凝胶聚合物电解质电池。作为对比,采用相同有机电解液装配液态锂金属电池,将上述装配的两种锂金属电池在1C倍率下进行恒电流充放测试,测试电压区间为3.0~4.4V,测得的凝胶高压钴酸锂锂金属电池初始放电比容量为169.03 mAh/g,能够稳定循环300圈,容量保持率为78%,而装配的液态锂离子电池初始放电比容量为169.53 mAh/g,循环300圈后容量保持率仅为60%。
实施例5
选用NCM811作为正极,锂片作为负极,在氩气保护且水含量和氧含量均小于0.1ppm的手套箱中,将实施例1制得的前驱体溶液注入Celgard 2500当中,装配成NCM811/锂金属电池,之后将电池置于60℃下加热1h进行原位聚合得到凝胶聚合物电解质电池。作为对比,采用相同有机电解液装配液态NCM811/锂金属电池,将上述装配的两种NCM811/锂金属电池在1C倍率下进行恒电流充放测试,测试电压区间为3.0~4.3V,测得的凝胶NCM811/锂金属电池初始放电比容量为153.2m Ah/g,能够稳定循环200圈,容量保持率为78.5%,而装配的液态锂离子电池初始放电比容量为155.1m Ah/g,循环200圈后容量保持率仅为44.1%。
Claims (10)
1.一种聚异氰尿酸酯基阻燃凝胶聚合物电解质,其特征在于所述聚合物电解质以异氰尿酸酯基单体材料和锂盐为原料制备而成,其中:所述异氰尿酸酯基单体材料为异氰尿酸二烯丙基丙酯、异氰尿酸三烯丙酯、异氰尿酸三缩水甘油酯、双(2-羧乙基)异氰尿酸酯,三(2-丙烯酰氧乙基)异氰尿酸酯中的一种或多种;所述锂盐选自双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、双草酸硼酸锂、二氟草酸硼酸锂、六氟磷酸锂、四氟硼酸锂中的至少一种;所述凝胶聚合物电解质中,异氰尿酸酯基单体材料的质量分数为1~50wt%。
2.根据权利要求1所述的聚异氰尿酸酯基阻燃凝胶聚合物电解质,其特征在于所述异氰尿酸酯基单体材料的质量分数为3~20wt%,进一步优选为5~15wt%。
3.根据权利要求1或2所述的聚异氰尿酸酯基阻燃凝胶聚合物电解质,其特征在于所述异氰尿酸酯基单体材料为三(2-丙烯酰氧乙基)异氰尿酸酯。
4.根据权利要求1所述的聚异氰尿酸酯基阻燃凝胶聚合物电解质,其特征在于所述锂盐占异氰尿酸酯基单体材料和锂盐总质量的60~90%。
5.一种权利要求1-4任一项所述聚异氰尿酸酯基阻燃凝胶聚合物电解质的制备方法,其特征在于所述方法包括如下步骤:
步骤一、前驱体溶液制备:在具有保护气氛氩气且氧含量和水含量均小于0.1ppm的环境下,将异氰尿酸酯基单体材料溶解于含有锂离子的锂离子电池电解液体系中,充分搅拌,随后加入自由基引发剂化合物,得到凝胶聚合物电解质前驱体溶液;
步骤二、固化成膜:在锂离子电池注液过程中,将步骤一中的前驱体溶液滴加在多孔支撑材料上,直接装配成电池,随后将装配好的电池置于烘箱中进行原位热聚合。
6.根据权利要求5所述的聚异氰尿酸酯基阻燃凝胶聚合物电解质的制备方法,其特征在于所述锂离子电解液溶剂体系由碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸丙酸酯中的一种或者多种组成,优选为碳酸乙烯酯和碳酸二甲酯混合溶剂,碳酸乙烯酯与碳酸二甲酯的体积比为3:7。
7.根据权利要求5所述的聚异氰尿酸酯基阻燃凝胶聚合物电解质的制备方法,其特征在于所述自由基引发剂化合物选自偶氮二异丁腈、过氧化苯甲酰、偶氮二异庚腈、叔丁基过氧化氢、偶氮二异丁酸二甲酯、过氧化苯甲酸叔丁酯中的至少一种,优选为偶氮二异丁腈。
8.根据权利要求5所述的聚异氰尿酸酯基阻燃凝胶聚合物电解质的制备方法,其特征在于所述自由基引发剂化合物的加入量为异氰尿酸酯基单体材料的0.01~1wt%,优选为0.5wt%。
9.根据权利要求5所述的聚异氰尿酸酯基阻燃凝胶聚合物电解质的制备方法,其特征在于所述多孔支撑材料选自聚乙烯、聚丙烯、聚丙烯腈、聚(偏氟乙烯-六氟乙烯)、聚甲基丙烯酸甲酯、聚酰亚胺中单一或多种成分组成的多孔膜,优选为聚丙烯。
10.根据权利要求5所述的聚异氰尿酸酯基阻燃凝胶聚合物电解质的制备方法,其特征在于所述原位热聚合的温度为40~70℃,优选为50~60℃,时间为0.5~4h,优选为1h。
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