CN116836381B - 一种稳定的固体电解质膜及其制备方法 - Google Patents
一种稳定的固体电解质膜及其制备方法 Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 25
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 125000000129 anionic group Chemical group 0.000 claims description 4
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- 238000006555 catalytic reaction Methods 0.000 claims description 3
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- 239000003999 initiator Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 3
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- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
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- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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Abstract
本发明公开了一种稳定的固体电解质膜及其制备方法,属于聚离子液体领域。首次合成了一种聚离子液体,该聚离子液体同时包含了氨基和碳氯键。氨基和碳氯键在加热条件下反应形成交联网络,形成稳定的聚合物薄膜,并具有很好的导电性。该电解质膜的优点是具有较高的离子电导率,且随温度的升高而升高,作为聚离子液体电解质膜具有应用于固态锂电池的潜力,除此之外,相比于传统有机电解液,聚离子液体电解质膜安全性高,组装便捷。
Description
技术领域
本发明属于聚离子液体领域。具体涉及一种稳定的固体电解质膜及其制备方法。
背景技术
固体聚合物电解质(Solid polymer electrolyte,SPE),又称为离子导电聚合物(Ion-conducting polymer)。固体聚合物电解质的研究始于1973年Wright等人对聚氧化乙烯(PEO)与碱金属离子络合物导电性的发现。1979年,法国Armand等报道了PEO碱金属盐络合物在40~60℃时离子电导率达10-5S/cm,且具有良好的成膜性,可用作锂离子电池电解质。固体聚合物电解质在电子、医疗、空间技术、电致显色、光电学、传感器等方面有着广泛的应用。由于它具有质轻、成膜性好、黏弹性和稳定性均较好等优点,使这一研究有了迅速发展。然而,Li+需通过与PEO链段间的“络合-解络合”作用形成离子导通, SPE在室温下的结晶结构使Li+运动受禁,仅在温度高于玻璃化转变温度(Tg)时达到理想的电导率水平,但高温时接近液体的状态并不利于其作为锂离子电池隔膜的应用。因此,现阶段的研究主要集中在改善PEO的微观结构,在保证SPE优良安全性与循环寿命的同时,降低其结晶度。Prabakaran等以PEO与PVDF-HFP为混合基体,通过溶液浇铸法制备了含不同锂盐的聚合物混合电解质,指出无定型PVDF-HFP可以大幅增加PEO/PVDF-HFP混合物中非晶区域的比例,所制备SPE的电导率最高可达8.20×10–4S/cm。总体来说,提高电解质电导率有两种途径:抑制聚合物链的结晶;提高载离子浓度。聚离子液体具有高离子传导性、高稳定性、低蒸汽透过率、低氧气透过率等优点,因此在能源领域具有广泛的应用前景。
发明内容
为了解决现有技术中存在的问题,本发明提供了一种聚离子液体及其制备方法,该方法制备的固体电解质膜具有优越的导电稳定性。
用环氧氯丙烷作为原始材料,在无水1,2-二氯乙烷-无水乙醇体系中,以无水四氯化锡为引发剂,在三氟乙酸催化下进行阳离子开环聚合,合成聚环氧氯丙烷(PECH)。然后通过PECH与氨基咪唑反应,进一步通过离子置换后采用“一锅法”制得电解质交联膜。
本发明提供一种聚离子液体,所述聚离子液体同时包含了氨基和碳氯键,该聚离子液体的结构式为:
其中X= Br、 PF6、CH3COO或NTf2阴离子基团。
本发明提供一种稳定的固体电解质膜,将上述聚离子液体加热,形成所述稳定的固体电解质膜。
进一步,具体步骤为:用环氧氯丙烷作为原始材料,在无水1,2-二氯乙烷-无水乙醇体系中,以无水四氯化锡为引发剂,在三氟乙酸催化下进行阳离子开环聚合,合成聚环氧氯丙烷(PECH);然后通过聚环氧氯丙烷与氨基咪唑反应,制备反离子为Cl-的聚离子液体,然后进一步通过离子交换制备具有不同反离子的聚离子液体,进一步加热制得所述固体电解质膜。
进一步,离子交换时所用的溶液为NaBr、NaNTf2、NaPF6或CH3COONa。
进一步,具体合成路线为:
X= Br、 PF6、CH3COO或NTf2阴离子基团。
本发明有益效果:
1、本发明合成的一种聚离子液体,具有聚氧化乙烯主链,同时在聚合物侧链部分引入氨基咪唑阳离子和不同的阴离子。一方面,该聚离子液体保留了聚氧化乙烯结构的特点,同时因为引入阴阳离子,形成的聚合物电解质能够克服聚氧乙烯结晶的缺点,并有利于离子传导,更有利提高导电性。另一方面,在聚合物侧链中保留了氨基和碳氯键,该聚合物电解质通过加热能够发生交联反应,有利于制备稳定的聚合物电解质,具有优越的导电稳定性。
2、基于聚离子液体的粘度较高和导电性较低,我们制备了同时包含了氨基和碳氯键的聚离子液体并使氨基和碳氯键反应在加热条件下形成交联网络,形成稳定的聚合物薄膜,具有较高的离子电导率,且随温度的升高而升高,作为聚离子液体电解质膜具有应用于固态锂电池的潜力,除此之外,相比于传统有机电解液,聚离子液体电解质膜安全性高,组装便捷。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
聚环氧氯丙烷上接氨基咪唑
预先将1 mmolPECH (数均分子量500)、100 ml史莱克瓶及磁子在真空干燥箱中烘干并自然冷却,称取一定量PECH加入烧瓶中,将烧瓶置于加热套中进行烘烤,边抽真空边烘烤,之后用氩气置换烧瓶内气体,抽真空-充氩气反复3-4次,使烧瓶均匀受热以除去PECH中残留的溶剂至无气泡,此时PECH呈黄色透明状,最后在充氩气条件下撤去加热套。在烧瓶中室温下搅拌滴加0.9 mmol 1-(3-氨丙基)咪唑,滴加完毕后,继续搅拌20 min,将烧瓶转移至80℃油浴锅中,磁力搅拌10 h,混合溶液呈橙色。反应完毕后,将反应产物用无水乙醇溶解后转移至250 ml锥形瓶中,在乙醚中沉降若干次,至TLC检测上清液不显紫外,以除去未接上的氨基咪唑,旋蒸除去挥发性溶剂,40℃下真空干燥24 h,得到最终聚合物产物PIL,为橙色粘稠状液体。
实施例2
聚离子液体中阴离子的置换
取一定量的实施例1中最终得到的聚合物PIL于50 mL烧瓶中,加水将其溶解,室温下磁力搅拌,称取LiBr加水溶解,边搅拌边滴加LiBr溶液(聚离子液体与LiBr的摩尔比为1:2),滴加完毕后,将烧瓶转移至40℃油浴锅中搅拌48 h。反应结束后,把实验所得的混合溶液转移到透析袋中,让混合溶液在去离子水中进行透析,以洗去小分子物质,用硝酸银溶液检验至洗出液无白色沉淀,证明产物洗涤干净,最后使用冻干机冷冻干燥将混合溶液中的水除去,得到阴离子置换后的聚离子液体PIL-Br。
实施例3
PIL-Br电导率的测试
把实施例2得到的PIL-Br溶解在乙醇中,在磨具中制备成1 mm聚合物薄膜,然后将薄膜放置在60度烘箱中加热24 h,制得稳定得交联聚合物薄膜。取出后将其裁制成直径为16 mm的圆状电解质膜,装进纽扣电池,本文采用的锂离子电池型号是 CR2025 扣式电池,将聚离子液体电解质膜夹在LiFePO4正极与锂片之间,测试其电导率。
随着温度的逐步升高,固态聚电解质膜的离子电导率随之升高,在温度为30℃时,其离子电导率为1.26×10-4S.cm-1,当我们把温度上升到100℃,其离子电导率为1.59×10- 3S.cm-1,明显提升了大于一个数量级。随着温度的逐渐升高,该聚离子液体电解质膜的离子电导率呈现逐渐增大的趋势。此外,在接近高温的100℃条件下,该膜的离子电导率表现出理想的性能。
实施例4
PIL-NTF电导率的测试
同实施例2的步骤,NaNTf2进行离子置换,得到得到阴离子置换后的聚离子液体PIL-NTF,同实施例3测量其电导率。
随着温度的逐步升高,固态聚电解质膜的离子电导率随之升高,在温度为30℃时,其离子电导率为1.56×10-4S.cm-1,当我们把温度上升到100℃,其离子电导率为1.84×10- 3S.cm-1,明显提升了大于一个数量级。随着温度的逐渐升高,该聚离子液体电解质膜的离子电导率呈现逐渐增大的趋势。此外,在接近高温的100℃条件下,该膜的离子电导率表现出理想的性能。
实施例5
PIL-CH3COO-电导率的测试
同实施例2的步骤,CH3COONa进行离子置换,得到阴离子置换后的聚离子液体PIL-CH3COO-,同实施例3测量其电导率。
随着温度的逐步升高,固态聚电解质膜的离子电导率随之升高,在温度为30℃时,其离子电导率为1.32×10-4S.cm-1,当我们把温度上升到100℃,其离子电导率为1.61×10- 2S.cm-1,明显提升了大于一个数量级。随着温度的逐渐升高,该聚离子液体电解质膜的离子电导率呈现逐渐增大的趋势。此外,在接近高温的100℃条件下,该膜的离子电导率表现出理想的性能。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (3)
1.一种稳定的固体电解质膜,其特征在于,将聚离子液体加热,形成所述稳定的固体电解质膜;所述聚离子液体同时包含了氨基和碳氯键,该聚离子液体的结构式为:
;
其中X= Br、 PF6、CH3COO或NTf2阴离子基团;具体步骤为:用环氧氯丙烷作为原始材料,在无水1,2-二氯乙烷-无水乙醇体系中,以无水四氯化锡为引发剂,在三氟乙酸催化下进行阳离子开环聚合,合成聚环氧氯丙烷(PECH);然后通过聚环氧氯丙烷与氨基咪唑反应,制备反离子为Cl-的聚离子液体,然后进一步通过离子交换制备具有不同反离子的聚离子液体,进一步加热制得所述固体电解质膜。
2.如权利要求1所述的一种稳定的固体电解质膜的制备方法,其特征在于,离子交换时所用的溶液为NaBr、NaNTf2、NaPF6或CH3COONa。
3.如权利要求2所述的一种稳定的固体电解质膜的制备方法,其特征在于,具体合成路线为:
;
X= Br、 PF6、CH3COO或NTf2阴离子基团。
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