CN106935904A - 一种基于功能化硼酸锂盐的锂单离子传导聚合物电解质 - Google Patents
一种基于功能化硼酸锂盐的锂单离子传导聚合物电解质 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
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- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 26
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- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
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- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 4
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明公开了一种基于功能化硼酸锂盐的锂单离子传导聚合物电解质。由含有双键的功能化硼酸锂盐与含有巯基的化合物进行烯‑巯点击反应、或者由含有双键的功能化硼酸锂盐与同时与含有巯基的化合物和含有双键的聚醚进行多元烯‑巯点击反应，制成线性或网络状的全固态或者凝胶电解质。本发明制备的锂单离子传导聚合物电解质具有合成简单易行、原料便宜易得、室温电导率高、锂离子迁移数高、电化学窗口宽等优点，用本发明提供的电解质组装的锂电池安全性好，倍率性能好，循环寿命高且稳定。
Description
技术领域
本发明属于锂离子电池电解质领域，涉及锂单离子传导聚合物电解质及其制备方法。更具体的，涉及一种基于功能化硼酸锂盐的锂单离子传导聚合物电解质。
背景技术
随着智能手机、智能移动设备、电动汽车、混合动力汽车的快速发展，对锂电池的能量密度，安全性能要求越来越高。电解质作为锂电池的一个重要组成部分，对电池性能有重要影响。理想的电解质要求具有离子电导率高，锂离子迁移数高，电化学窗口宽，热稳定性好、机械强度高、安全性好等特性。
传统的锂离子电池使用的是液体电解质，通常由有机液体与锂盐组成。而这些有机液体如碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、乙烯碳酸酯(EC)等是易燃易爆物质，在锂离子电池的使用中存在诸多安全隐患(如燃烧、***、泄漏等)。
聚合物电解质由具有离子传导能力的聚合物与锂盐复合而成，比液体电解质具有更好的安全性，而且可以同时作为电解质和隔膜使用。但是一般聚合物电解质是双离子导体，即锂离子和阴离子在充放电过程都会迁移。但是由于锂离子与聚合物有络合，迁移速率比阴离子慢很多，由锂离子所传递的电流低至只占五分之一，相应的锂离子迁移数通常在0.2～0.5之间。且阴离子与电极没有反应，在电极处累积造成浓差极化，会造成阻抗增大，阻碍锂离子的传导，降低电池的能量效率。
锂单离子传导聚合物电解质是指将锂盐中的阴离子固定到高分子链上，高分子链由于分子量和体积巨大而迁移困难，这样就限制了阴离子的移动，仅有锂离子发生迁移，离子迁移数理论上可以接近1。
现在国内外锂单离子传导聚合物电解质的研究工作很多，但是多存在合成步骤繁琐、室温电导率较低、机械强度和成膜性能较差等问题。
发明内容
本发明的目的在于克服现有技术的不足，用简单易行、低成本的方法制备离子电导率高、离子迁移数高的锂单离子传导聚合物电解质。
本发明的上述目的通过以下技术方法来解决：一种基于功能化硼酸锂盐的锂单离子传导聚合物电解质，由含有双键的功能化硼酸锂盐与含有巯基的化合物进行烯-巯点击反应、或者由含有双键的功能化硼酸锂盐与同时与含有巯基的化合物和含有双键的聚醚在增塑剂中进行多元烯-巯点击反应，制成线性或网络状的全固态或者凝胶电解质。
本发明的基于功能化硼酸锂盐的锂单离子传导聚合物电解质，其制备方法为原位反应生成或者反应完成之后再成膜进行应用。
优选地，上述含有双键的功能化硼酸锂盐的结构如式(Ⅰ)所示：
其中，所述R1,R2相同或者不同，均选自C1～C4的直链饱和烷烃；
优选地，上述的含有巯基的化合物的分子内有1～5个巯基。
优选地，上述的含有双键的聚醚的分子内有1～5个双键。
优选地，上述的烯-巯点击反应，其使用的引发剂为光引发剂或者热引发剂。
进一步地，上述的增塑剂为碳酸酯类溶剂、醚类溶剂或酯类溶剂。
进一步地，本发明提供的基于功能化硼酸锂盐的锂单离子传导聚合物电解质可以作为锂离子二次电池的电解质使用。
进一步地，本发明提供的基于功能化硼酸锂盐的锂单离子传导聚合物电解质作为锂离子二次电池中正极和负极之间的隔膜使用。
进一步地，本发明提供的基于功能化硼酸锂盐的锂单离子传导聚合物电解质可以作为锂离子二次电池的正极材料的粘结剂使用。
与现有技术相比，本发明具有如下有益效果：本发明制备的锂单离子传导聚合物电解质具有合成简单易行、原料便宜易得、室温电导率高、锂离子迁移数高、电化学窗口宽等优点，用本发明提供的电解质组装的锂电池安全性好，倍率性能好，循环寿命高且稳定。
附图说明
图1为以基于功能化硼酸锂盐的锂单离子传导聚合物为粘结剂和凝胶电解质的磷酸铁锂电池性能图。
具体实施方式
实施例1-5为锂单离子传导聚合物电解质的制备
实施例1：基于烯丙基丙二酸硼酸锂凝胶电解质(碳酸丙烯酯为增塑剂)的制备(电解质1)
以下操作都在手套箱中进行，在小玻璃瓶中加入烯丙基丙二酸硼酸锂(LiBAMB)(5.00mmol，1.50g)、季戊四醇四-3-巯基丙酸酯(2.50mmol，0.8540mL)、DMPA(0.50mmol，0.1281g)及碳酸丙烯酯5.0mL。搅拌溶解后倒于矩形的聚四氟乙烯模具中(7*10cm)，装入封口袋中，拿出手套箱在水平的桌面上放置，用365nm紫外光照射2h。然后放入手套箱中用直径15mm的裁孔器裁出直径15mm的膜，装在纽扣电池中进行交联阻抗、循环伏安、离子迁移数的测定。
实施例2：基于烯丙基丙二酸硼酸锂凝胶电解质(碳酸二乙酯为溶剂和增塑剂)的制备(电解质2)
除了溶剂和增塑剂改为碳酸二乙酯之外，用和在实施例1中一样的方法制备聚合物电解质。
实施例3：基于烯丙基丙二酸硼酸锂凝胶电解质(γ-丁内酯为溶剂和增塑剂)的制备(电解质3)
除了溶剂和增塑剂改为γ-丁内酯之外，用和在实施例1中一样的方法制备聚合物电解质。
实施例4：基于烯丙基丙二酸硼酸锂凝胶电解质(三甘醇二甲醚为增塑剂)的制备(电解质4)
以下操作都在手套箱中进行，在小玻璃瓶中加入烯丙基丙二酸硼酸锂(LiBAMB)(1.25mmol，0.375g)、季戊四醇四-3-巯基丙酸酯(1.25mmol，477mL)、聚乙二醇双丙烯酸酯400(1.25mmol，0.50g)、DMPA(0.50mmol，0.0645g)及三甘醇二甲醚5.0mL。搅拌溶解后倒于矩形的聚四氟乙烯模具中(7*10cm)，装入封口袋中，拿出手套箱在水平的桌面上放置，用365nm紫外光照射2h。然后放入手套箱中用直径15mm的裁孔器裁出直径15mm的膜，装在纽扣电池中进行交联阻抗、循环伏安、离子迁移数的测定。
实施例5：基于烯丙基丙二酸硼酸锂全固态电解质的制备(电解质5)的制备
以下操作都在手套箱中进行，在小玻璃瓶中加入烯丙基丙二酸硼酸锂(LiBAMB)(5.00mmol，1.50g)、3,6-二氧-1,8-辛二硫醇(5.00mmol，0.8540mL)、DMPA(0.50mmol，0.1281g)及碳酸丙烯酯5.0mL。搅拌溶解后倒于矩形的聚四氟乙烯模具中(7*10cm)，装入封口袋中，拿出手套箱在水平的桌面上放置，用365nm紫外光照射2h。然后放入80℃烘箱中成膜，后在80℃真空烘箱高真空干燥24h。然后放入手套箱中用直径15mm的裁孔器裁出直径15mm的膜，装在纽扣电池中进行交联阻抗、循环伏安、离子迁移数的测定。
实施例6：以基于功能化硼酸锂盐的锂单离子传导聚合物为粘结剂和凝胶电解质的磷酸铁锂电池
以下操作都在手套箱中进行，在小玻璃瓶中加入烯丙基丙二酸硼酸锂(LiBAMB)(2.50mmol，0.75g)、季戊四醇四-3-巯基丙酸酯(1.25mmol，0.427mL)、DMPA(0.25mmol，0.0645g)及碳酸丙烯酯5.0mL。搅拌溶解后加入6.0g磷酸铁锂，1.5g super P，充分搅拌之后刮涂于铝箔上，用365nm紫外光照射2h。然后放入手套箱中用直径12mm的裁孔器裁出直径12mm的正极片。
将实施例1合成的电解质膜1夹于制备的磷酸铁锂正极片与金属锂负极之间，组装成磷酸铁锂电池进行充放电实验，性能如图1所示。从图1中可以看出用本发明提供的电解质组装的锂电池容量高，倍率性能好，库伦效率高，容量保持率好。
实施例1-5的单离子传导聚合物电解质的性能测试的结果列于表1中。
表1单离子聚合物电解质1-5的性能测试结果(20℃)
Claims (7)
1.一种基于功能化硼酸锂盐的锂单离子传导聚合物电解质，其特征在于由含有双键的功能化硼酸锂盐与含有巯基的化合物进行烯-巯点击反应、或者由含有双键的功能化硼酸锂盐与同时与含有巯基的化合物和含有双键的聚醚在增塑剂中进行多元烯-巯点击反应，制成线性或网络状的全固态或者凝胶电解质。
2.根据权利要求1所述的基于功能化硼酸锂盐的锂单离子传导聚合物电解质，其特征在于所述含有双键的功能化硼酸锂盐的结构如式(Ⅰ)所示：
其中，所述R1,R2相同或者不同，均选自C1～C4的直链饱和烷烃。
3.根据权利要求1所述的基于功能化硼酸锂盐的锂单离子传导聚合物电解质，其特征在于所述含有巯基的化合物的分子内有1～5个巯基。
4.根据权利要求1所述的基于功能化硼酸锂盐的锂单离子传导聚合物电解质，其特征在于所述含有双键的聚醚的分子内有1～5个双键。
5.根据权利要求1所述的基于功能化硼酸锂盐的锂单离子传导聚合物电解质，其特征在于所述的多元烯-巯点击反应，使用的引发剂为光引发剂或者热引发剂。
6.根据权利要求1所述的基于功能化硼酸锂盐的锂单离子传导聚合物电解质，其特征在于所述的增塑剂为碳酸酯类溶剂、醚类溶剂或酯类溶剂。
7.权利要求1所述的基于功能化硼酸锂盐的锂单离子传导聚合物电解质在制备锂离子二次电池电解质、锂离子二次电池中正极和负极之间的隔膜、或者锂离子二次电池的正极材料的粘结剂中的应用。
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