CN114006036A - 一种非对称凝胶聚合物电解质及其制备方法和应用 - Google Patents
一种非对称凝胶聚合物电解质及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种非对称凝胶聚合物电解质及其制备方法和应用,其解决了现有电池中正极不稳定和负极锂枝晶生长的技术问题,本发明提供的非对称凝胶聚合物电解质为非对称结构,其一侧含有铁电性陶瓷微粒,另一侧含有聚多巴胺包覆的铁电性陶瓷微粒;其基体为聚(偏二氟乙烯‑co‑六氟丙烯)、聚偏二氟乙烯、聚丙烯腈、聚氧乙烯/聚乙烯醇共混物之一种或其混合物;所述铁电性陶瓷微粒为钛酸钡、钛酸铅、钛酸锶之一种或其混合物。本发明同时提供了其制备方法和应用。本发明可用于电池材料领域。
Description
技术领域
本发明涉及一种电池材料,具体地说,涉及一种非对称凝胶聚合物电解质及其制备方法和应用。
背景技术
目前,质量轻便、环境友好、放电比容量高的锂、钠离子电池已被广泛应用到便携式电子设备以及电动汽车等领域。以往对锂、钠离子电池的研究主要集中于液态电解质,虽然能够达到锂、钠离子电池使用的要求,但是液态电解质仍然存在很多安全隐患,如电解液易泄露、有机溶剂毒性大、沸点低、易挥发甚至燃烧,电解液与正负极材料发生副反应导致容量衰减严重等。使用金属作为负极时可以达到更高的能量密度,但是使用液态电解液会产生大量枝晶,而枝晶生长刺穿隔膜造成电池短路会带来严重的安全问题,正极材料中的活性物质也会溶解穿梭到负极造成容量下降。使用全固态电解质存在电极与电解质界面接触不良的问题,此外,全固态电解质的离子电导率较低,难以满足电池的应用要求。凝胶聚合物电解质结合了液态电解质离子电导率高以及固态电解质安全性高的优点,可以得到更加广泛的应用。
凝胶聚合物电解质要获得实际应用必须达到以下条件:较高的离子电导率和离子迁移数、宽的电化学稳定窗口、优异的电化学稳定性及耐热性,高效简单的制备工艺。凝胶聚合物电解质骨架需要具备多孔结构以及一定的机械强度,静电纺丝技术工艺简单、便于操作,通过静电纺丝技术制备的纳米纤维膜具有大量微孔结构,可以吸附电解液变成凝胶态获得更高的电化学性能。可采用静电纺丝技术制备凝胶电解质的聚合物有PVDF-HFP、PAN、PEO、PVA等,但是纯的聚合物力学性能较低,离子电导率较低,难以满足电池的应用要求。因此,常采用加入无机陶瓷纳米颗粒或聚合物共混等方法来提高电解质的各项性能。
发明内容
本发明就是为了解决现有电池中正极不稳定和负极锂枝晶生长的技术问题,提供一种掺杂不同填料的具备多功能的非对称凝胶聚合物电解质及其制备方法和应用。
为此,本发明提供一种非对称凝胶聚合物电解质,其为非对称结构,其一侧含有铁电性陶瓷微粒,另一侧含有聚多巴胺包覆的铁电性陶瓷微粒;其基体为聚(偏二氟乙烯-co-六氟丙烯)(PVDF-HFP)、聚偏二氟乙烯(PVDF)、聚丙烯腈(PAN)、聚氧乙烯/聚乙烯醇共混物(PEO/PVA)可以静电纺丝的、利于离子迁移的聚合物或其混合物;铁电性陶瓷微粒可以是钛酸钡(BaTiO3)、钛酸铅(PbTiO3)、钛酸锶(SrTiO3)具有铁电性的微粒或其混合物。
优选的,所述非对称凝胶聚合物电解质所用电解液为所述非对称凝胶聚合物电解质所用电解液为酯类或醚类溶剂电解液。
优选的,所述非对称凝胶聚合物电解质所用电解液为六氟磷酸锂溶于碳酸乙烯酯和碳酸二甲酯的电解液、六氟磷酸钠溶于碳酸乙烯酯和碳酸二乙酯的电解液,或双三氟甲烷磺酰亚胺锂溶于1,3-二氧戊环和二甲醚的电解液。
本发明同时提供一种非对称凝胶聚合物电解质的制备方法,其包括如下步骤:(1)配置弱碱性缓冲液;(2)在所述步骤(1)中获得的弱碱性缓冲液中使用多巴胺盐酸盐在铁电性陶瓷微粒表面进行聚合反应,获得聚多巴胺包覆的铁电性陶瓷微球;(3)将铁电性陶瓷微粒与所述步骤(2)获得的聚多巴胺包覆的铁电性陶瓷微粒分别与聚合物共混分散于溶剂中,分别制备两种不同的聚合物纺丝液;(4)通过连续静电纺丝技术制得非对称电解质聚合物骨架纤维膜,其由两层组成,一层含有铁电性陶瓷微粒,另一层含有聚多巴胺包覆的铁电性陶瓷微粒;(5)将所述步骤(4)获得的非对称电解质聚合物骨架纤维膜滴加电解液,静置后使纤维膜凝胶化,制得非对称凝胶聚合物电解质,该电解质一侧含有铁电性陶瓷微粒,另一侧含有聚多巴胺包覆的铁电性陶瓷微粒。
优选的,所述步骤(1)中配置的弱碱性缓冲液为羟甲基氨基甲烷缓冲液,pH值优选为7.5~9。
优选的,所述步骤(2)中,铁电性陶瓷微粒的粒径为30~100nm。
优选的,所述步骤(2)中,聚合物包覆微球时,将铁电性陶瓷微粒均匀地分散至缓冲液中,浓度为4.5~5.5g/L。
优选的,所述步骤(2)中,聚合物包覆过程如下:在铁电性陶瓷微粒分散液中加入浓度为0.2~0.5g/L的多巴胺盐酸盐,超声分散均匀,搅拌反应2~3h,用去离子水离心洗涤后,将沉淀再次分散到乙醇中,真空抽滤,得到的产物在室温干燥后研磨,获得聚多巴胺包覆铁电性陶瓷微粒。
优选的,所述步骤(3)中,将占溶剂质量比为1.36wt%~2.4wt%的铁电性陶瓷微粒、聚多巴胺包覆后的铁电性陶瓷微粒分别超声分散到溶剂中,分散均匀后加入占溶剂质量比为17%~20%的聚合物,水浴中加热磁力搅拌获得两种纺丝液。
本发明还提供一种非对称凝胶聚合物电解质作为电池材料中的应用。
本发明具有以下有益效果:
本发明从结构设计出发,设计了一种掺杂无机纳米颗粒的非对称的凝胶聚合物电解质,该电解质骨架通过连续静电纺丝技术制备而成,纤维膜骨架材料吸附电解液后变成凝胶态即可使用于锂、钠电池。该电解质骨架材料由两层掺杂不同填料的聚合物纤维膜组成,组装电池时,掺杂无机纳米颗粒的一侧靠近正极可以稳定正极-电解质界面,减少正极活性物质溶出,改善电池的循环性能并且可用于更高的电压;掺杂多巴胺包覆无机纳米颗粒的一侧靠近负极,一方面可以防止无机纳米颗粒与锂金属之间发生反应,另一方面聚多巴胺具有一定的电解液亲和性,可以在负极一侧形成稳定的SEI膜,缓解枝晶的生长。本发明首次将聚多巴胺包覆后的纳米颗粒纺入纳米纤维中,提高了颗粒与基体的结合能力,使得纤维膜的力学性能得到提升。最终制得的凝胶电解质具有较高的离子电导率和离子迁移数,较宽的电化学稳定窗口,高压下优异的倍率性能和循环性能。
本发明设计的非对称凝胶聚合物电解质针对正负极存在的不同问题添加不同的功能性纳米颗粒,既可以解决正极结构不稳定以及界面问题,又可以在负极形成稳定有效的CEI层,抑制枝晶的生长。
本发明得到的非对称凝胶聚合物电解质,其离子电导率可以达到5.23×10-3S cm-1,电化学稳定窗口可以大于4.5V,骨架力学强度可以达到7MPa以上,以三元高压正极材料NCM811为正极组装成电池在0.5C下循环可以获得较高的理论比容量,库伦效率为98%以上,具有优异的倍率性能。
具体实施方式
下面结合实施例对本发明做进一步描述。
除特别说明外,本发明所用的所有原料、试剂、设备和仪器等均可在市场上购买到或者自行制备得到。离子电导率和电化学稳定窗口都是用电化学工作站测试计算得到,倍率性能和循环性能是组装成全电池在蓝电测试系统上测试得到。
实施例1
(1)配制pH为7.5的Tris缓冲液;
(2)将0.45g BTO分散到100ml Tris缓冲液中,分散均匀后加入0.02g DA·HCl,反应3h,用去离子水离心洗涤3次,将沉淀分散到乙醇中,真空抽滤,得到的产物室温干燥后研磨,获得包覆厚度约为4nm的PDA@BTO;
(3)将占溶剂1.36wt%的BTO、PDA@BTO分别超声分散到DMF/丙酮(v:v,1:1)混合溶剂中,分散均匀后分别加入占溶剂质量比为17wt%的PVDF-HFP,在45℃水浴中磁力搅拌12h,使PVDF-HFP完全溶解获得两种纺丝液;
(4)通过连续静电纺丝制备得到非对称多孔纳米纤维膜,该纤维膜中一层含有BTO,另一层含有PDA@BTO,将该纤维膜真空干燥除去多余溶剂;
(5)将干燥后的非对称纤维膜裁成直径为19mm的小圆片,滴加电解液使其凝胶化并静置使其活化制得非对称凝胶聚合物电解质。该操作在充满氩气的手套箱中进行。所用电解液为1M六氟磷酸锂溶于碳酸乙烯酯和碳酸二甲酯体积比1:1并添加5%的氟化碳酸乙烯酯(1MLiPF6,EC:DMC=1:1,5%FEC)的电解液;
该非对称凝胶聚合物电解质的离子电导率为4.32×10-3S cm-1,电化学稳定窗口为4.5V,用锂片和NCM811组装成全电池在0.5C下循环的初始放电比容量为189mAh g-1,库伦效率保持在98%以上,电池循环50圈后的锂片形貌仍然光滑平整。
实施例2
(1)配制pH为8.5的Tris缓冲液;
(2)将0.55g BTO分散到100ml Tris缓冲液中,分散均匀后加入0.05g DA·HCl,反应2.5h,用去离子水离心洗涤3次,将沉淀分散到乙醇中,真空抽滤,得到的产物室温干燥后研磨,获得包覆厚度约为5nm的PDA@BTO;
(3)将占溶剂2.4wt%的BTO、PDA@BTO分别超声分散到DMF/丙酮(v:v,1:1)混合溶剂中,分散均匀后分别加入占溶剂质量比为20wt%的PVDF-HFP,在45℃水浴中磁力搅拌12h,使PVDF-HFP完全溶解获得两种纺丝液;
(4)通过连续静电纺丝制备得到非对称多孔纳米纤维膜,该纤维膜中一层含有BTO,另一层含有PDA@BTO,将该纤维膜真空干燥除去多余溶剂;
(5)将干燥后的非对称纤维膜裁成直径为19mm的小圆片,滴加电解液使其凝胶化并静置使其活化制得非对称凝胶聚合物电解质。该操作在充满氩气的手套箱中进行。所用电解液为1M六氟磷酸锂溶于碳酸乙烯酯和碳酸二甲酯体积比1:1并添加5%的氟化碳酸乙烯酯(1MLiPF6,EC:DMC=1:1,5%FEC)的电解液;
该非对称凝胶聚合物电解质的离子电导率为5.23×10-3S cm-1,电化学稳定窗口为4.5V,用锂片和NCM811组装成全电池在0.5C下循环的初始放电比容量为196mAh g-1,库伦效率保持在98%以上,电池循环50圈后的锂片形貌仍然光滑平整。
实施例3
(1)配制pH为9的Tris缓冲液;
(2)将0.5g BTO分散到100ml Tris缓冲液中,分散均匀后加入0.03g DA·HCl,反应2h,用去离子水离心洗涤3次,将沉淀分散到乙醇中,真空抽滤,得到的产物室温干燥后研磨,获得包覆厚度约为4nm的PDA@BTO;
(3)将占溶剂1.8wt%的BTO、PDA@BTO分别超声分散到DMF/丙酮(v:v,1:1)混合溶剂中,分散均匀后分别加入占溶剂质量比为18wt%的PVDF-HFP,在45℃水浴中磁力搅拌12h,使PVDF-HFP完全溶解获得两种纺丝液;
(4)通过连续静电纺丝制备得到非对称多孔纳米纤维膜,该纤维膜中一层含有BTO,另一层含有PDA@BTO,将该纤维膜真空干燥除去多余溶剂;
(5)将干燥后的非对称纤维膜裁成直径为19mm的小圆片,滴加电解液使其凝胶化并静置使其活化制得非对称凝胶聚合物电解质。该操作在充满氩气的手套箱中进行。所用电解液为1M六氟磷酸锂溶于碳酸乙烯酯和碳酸二甲酯体积比1:1并添加5%的氟化碳酸乙烯酯(1MLiPF6,EC:DMC=1:1,5%FEC)的电解液;
该非对称凝胶聚合物电解质的离子电导率为4.68×10-3S cm-1,电化学稳定窗口为4.5V,用锂片和NCM811组装成全电池在0.5C下循环的初始放电比容量为192mAh g-1,库伦效率保持在98%以上,电池循环50圈后的锂片形貌仍然光滑平整。
实施例4
(1)配制pH为8.5的Tris缓冲液;
(2)将0.5g BTO分散到100ml Tris缓冲液中,分散均匀后加入0.05g DA·HCl,反应2h,用去离子水离心洗涤3次,将沉淀分散到乙醇中,真空抽滤,得到的产物室温干燥后研磨,获得包覆厚度约为5nm的PDA@BTO;
(3)将占溶剂1.8wt%的BTO、PDA@BTO分别超声分散到DMF/丙酮(v:v,1:1)混合溶剂中,分散均匀后分别加入占溶剂质量比为18wt%的PVDF-HFP,在45℃水浴中磁力搅拌12h,使PVDF-HFP完全溶解获得两种纺丝液;
(4)通过连续静电纺丝制备得到非对称多孔纳米纤维膜,该纤维膜中一层含有BTO,另一层含有PDA@BTO,将该纤维膜真空干燥除去多余溶剂;
(5)将干燥后的非对称纤维膜裁成直径为19mm的小圆片,滴加电解液使其凝胶化并静置使其活化制得非对称凝胶聚合物电解质。该操作在充满氩气的手套箱中进行。所用电解液为1M六氟磷酸钠溶于碳酸乙烯酯和碳酸二乙酯体积比1:1(1M NaPF6,EC:DEC=1:1)的电解液。
该非对称凝胶聚合物电解质的离子电导率为3×10-3S cm-1,电化学稳定窗口为4.2V,用钠金属和磷酸钒钠组装成全电池在0.2C下循环的初始放电比容量为110mAh g-1,库伦效率保持在98%以上,电池循环50圈后的钠片形貌仍然光滑平整。
实施例5
(1)配制pH为8.5的Tris缓冲液;
(2)将0.5g BTO分散到100ml Tris缓冲液中,分散均匀后加入0.05g DA·HCl,反应2h,用去离子水离心洗涤3次,将沉淀分散到乙醇中,真空抽滤,得到的产物室温干燥后研磨,获得包覆厚度约为5nm的PDA@BTO;
(3)将占溶剂1.8wt%的BTO、PDA@BTO分别超声分散到DMF中,分散均匀后分别加入占溶剂质量比为18wt%的PAN,在45℃水浴中磁力搅拌12h,使PAN完全溶解获得两种纺丝液;
(4)通过连续静电纺丝制备得到非对称多孔纳米纤维膜,该纤维膜中一层含有BTO,另一层含有PDA@BTO,将该纤维膜真空干燥除去多余溶剂;
(5)将干燥后的非对称纤维膜裁成直径为19mm的小圆片,滴加电解液使其凝胶化并静置使其活化制得非对称凝胶聚合物电解质。该操作在充满氩气的手套箱中进行。所用电解液为1M双三氟甲烷黄酰亚胺锂溶于1,3-二氧戊环和二甲醚体积比2:1(1M LiTFSI,DOL:DME=2:1)的电解液。
该非对称凝胶聚合物电解质的离子电导率为4.72×10-3S cm-1,电化学稳定窗口为4.5V,用锂片和NCM811组装成全电池在0.5C下循环的初始放电比容量为193mAh g-1,库伦效率保持在98%以上,电池循环50圈后的锂片形貌仍然光滑平整。
对比例1
(1)将占溶剂2.4wt%的BTO超声分散到DMF/丙酮(v:v,1:1)混合溶剂中,分散均匀后加入占溶剂质量比为20wt%的PVDF-HFP,在45℃水浴中磁力搅拌12h,使PVDF-HFP完全溶解获得纺丝液;
(2)通过静电纺丝制备得到多孔纳米纤维膜,该纤维膜中含有BTO,将该纤维膜真空干燥除去多余溶剂;
(3)将干燥后的纤维膜裁成直径为19mm的小圆片,滴加电解液使其凝胶化并静置使其活化制得凝胶聚合物电解质。该操作在充满氩气的手套箱中进行。所用电解液为1M六氟磷酸锂溶于碳酸乙烯酯和碳酸二甲酯体积比1:1并添加5%的氟化碳酸乙烯酯(1MLiPF6,EC:DMC=1:1,5%FEC)的电解液;
该凝胶聚合物电解质的离子电导率为5×10-3S cm-1,电化学稳定窗口为4.5V,用锂片和NCM811组装成全电池在0.5C下循环的初始放电比容量为189mAh g-1,库伦效率保持在98%以上,但是电池循环50圈后的锂片形貌粗糙。
对比例2
(1)将占溶剂质量比为20wt%的PVDF-HFP,在45℃水浴中磁力搅拌12h,使PVDF-HFP完全溶解获得纺丝液;
(2)通过静电纺丝制备得到多孔纳米纤维膜,将该纤维膜真空干燥除去多余溶剂;
(3)将干燥后的纤维膜裁成直径为19mm的小圆片,滴加电解液使其凝胶化并静置使其活化制得凝胶聚合物电解质。该操作在充满氩气的手套箱中进行。所用电解液为1M六氟磷酸锂溶于碳酸乙烯酯和碳酸二甲酯体积比1:1并添加5%的氟化碳酸乙烯酯(1MLiPF6,EC:DMC=1:1,5%FEC)的电解液;
该凝胶聚合物电解质的离子电导率仅为3.45×10-3S cm-1,电化学稳定窗口为4.5V,用锂片和NCM811组装成全电池在0.5C下循环的初始放电比容量为187mAh g-1,库伦效率保持在98%以上,但是电池循环50圈后的锂片形貌粗糙。
惟以上所述者,仅为本发明的具体实施例而已,当不能以此限定本发明实施的范围,故其等同组件的置换,或依本发明专利保护范围所作的等同变化与修改,皆应仍属本发明权利要求书涵盖之范畴。
Claims (10)
1.一种非对称凝胶聚合物电解质,其特征是,其为非对称结构,其一侧含有铁电性陶瓷微粒,另一侧含有聚多巴胺包覆的铁电性陶瓷微粒;其基体为聚(偏二氟乙烯-co-六氟丙烯)、聚偏二氟乙烯、聚丙烯腈、聚氧乙烯/聚乙烯醇共混物之一种或其混合物;所述铁电性陶瓷微粒为钛酸钡、钛酸铅、钛酸锶之一种或其混合物。
2.根据权利要求1所述的非对称凝胶聚合物电解质,其特征在于,所述非对称凝胶聚合物电解质所用电解液为酯类或醚类溶剂电解液。
3.根据权利要求2所述的非对称凝胶聚合物电解质,其特征在于,所述非对称凝胶聚合物电解质所用电解液为六氟磷酸锂溶于碳酸乙烯酯和碳酸二甲酯的电解液、六氟磷酸钠溶于碳酸乙烯酯和碳酸二乙酯的电解液,或双三氟甲烷磺酰亚胺锂溶于1,3-二氧戊环和二甲醚的电解液。
4.如权利要求1所述的非对称凝胶聚合物电解质的制备方法,其特征是,包括如下步骤:
(1)配置弱碱性缓冲液;
(2)在所述步骤(1)中获得的弱碱性缓冲液中使用多巴胺盐酸盐在铁电性陶瓷微粒表面进行聚合反应,获得聚多巴胺包覆的铁电性陶瓷微球;
(3)将铁电性陶瓷微粒与所述步骤(2)获得的聚多巴胺包覆的铁电性陶瓷微粒分别与聚合物共混分散于溶剂中,分别制备两种不同的聚合物纺丝液;
(4)通过连续静电纺丝技术制得非对称电解质聚合物骨架纤维膜,其由两层组成,一层含有铁电性陶瓷微粒,另一层含有聚多巴胺包覆的铁电性陶瓷微粒;
(5)将所述步骤(4)获得的非对称电解质聚合物骨架纤维膜滴加电解液,静置后使纤维膜凝胶化,制得非对称凝胶聚合物电解质,该电解质一侧含有铁电性陶瓷微粒,另一侧含有聚多巴胺包覆的铁电性陶瓷微粒。
5.根据权利要求4所述的非对称凝胶聚合物电解质的制备方法,其特征在于,所述步骤(1)中配置的弱碱性缓冲液为羟甲基氨基甲烷缓冲液,pH值范围为7.5~9。
6.根据权利要求4所述的非对称凝胶聚合物电解质的制备方法,其特征在于,所述步骤(2)中,铁电性陶瓷微粒的粒径为30~100nm。
7.根据权利要求4所述的非对称凝胶聚合物电解质的制备方法,其特征在于,所述步骤(2)中,聚合物包覆微球时,将铁电性陶瓷微粒均匀地分散至缓冲液中,浓度为3~6g/L。
8.根据权利要求4所述的非对称凝胶聚合物电解质的制备方法,其特征在于,所述步骤(2)中,聚合物包覆过程如下:在铁电性陶瓷微粒分散液中加入占铁电性陶瓷微粒质量分数为3%~10%的多巴胺盐酸盐,超声分散均匀,搅拌反应2~6h,用去离子水离心洗涤后,将沉淀再次分散到乙醇中,真空抽滤,得到的产物在室温干燥后研磨,获得包覆厚度为2~10nm的聚多巴胺包覆铁电性陶瓷微粒。
9.根据权利要求4所述的非对称凝胶聚合物电解质的制备方法,其特征在于,所述步骤(3)中,将占溶剂质量比为0.8wt%~4.5wt%的铁电性陶瓷微粒、聚多巴胺包覆后的铁电性陶瓷微粒分别超声分散到溶剂中,分散均匀后加入占溶剂质量比为16%~22%的聚合物,在45~70℃水浴中磁力搅拌6~12h获得两种纺丝液。
10.如权利要求1所述的非对称凝胶聚合物电解质作为电池材料中的应用。
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