CN115312966B - 共价有机框架基半固态电解质复合隔膜、制备方法及其应用 - Google Patents
共价有机框架基半固态电解质复合隔膜、制备方法及其应用 Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 47
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 19
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- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
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Abstract
本发明公开了一种共价有机框架基半固态电解质复合隔膜、制备方法及其应用。所述的共价有机框架基半固态电解质复合隔膜是采用真空抽滤工艺将长烷基链修饰的共价有机框架材料复合到聚乙烯底膜两侧上,然后采用涂布工艺在膜两侧涂布聚偏氟乙烯‑六氟丙烯共聚物制备而成。本发明的共价有机框架基半固态电解质复合隔膜具有优异的锂离子传导效果和锂枝晶抑制效果,其组装的锂离子电池具有良好的电池循环稳定性和优异的充放电比容量。
Description
技术领域
本发明属于共价有机框架材料领域,涉及一种共价有机框架基半固态电解质复合隔膜、制备方法及其在锂离子电池中的应用。
背景技术
液态锂离子电池较低的能量密度和安全问题已经无法满足大规模储能***日益增长的需求。作为一种低成本的替代品,固态锂金属电池由于其高能量密度和良好的安全性,显示出巨大的竞争优势和广泛的应用前景。然而,固态电解质往往具有较低的离子电导率,固态电解质与电极之间较差的界面相容性和较差的稳定性会导致电化学性能不断恶化。目前,通常采用无机陶瓷材料和有机聚合物制备的固态电解质,无法高效实现锂离子传导和锂枝晶的抑制。如何设计超薄的复合型半固态锂离子电池的电解质隔膜仍是一项挑战。
共价有机框架(COFs)材料是由轻质元素(C、N、O等)组成的多孔有机框架材料,但是COFs一般都是固体粉末,难以加工为薄膜。文献使用含有PVDF-HFP层的复合膜,其组装的液态磷酸铁锂电池循环50圈后比容量已经降低到100mAh/g以下,循环稳定性差(Int.J.Hydrogen Energy,2017,42,10,6862-6875)。
发明内容
本发明的目的在于提供一种共价有机框架基半固态电解质复合隔膜、制备方法及其在锂离子电池中的应用,以解决锂枝晶抑制,实现高效循环和高比容量。
实现本发明目的的技术方案如下:
共价有机框架基半固态电解质复合隔膜的制备方法,包括以下步骤:
步骤1,在长烷基链修饰的共价有机框架材料中加入有机溶剂作为辅助剂,球磨12~48h,将球磨后的混合液静置,取上清液,得到长烷基链修饰的共价有机框架纳米片分散液;
步骤2,以聚乙烯膜为基膜,对长烷基链修饰的共价有机框架纳米片分散液进行真空抽滤,抽滤完后加入乙醇进行抽滤清洗,最后真空干燥,得到长烷基链修饰的共价有机框架复合隔膜;
步骤3,依次在长烷基链修饰的共价有机框架复合隔膜的两面均匀涂布聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)的丙酮/水溶液,涂布厚度为2~50μm,待有机溶剂挥发后干燥,得到共价有机框架基半固态电解质复合隔膜。
优选地,步骤1中,有机溶剂为N-甲基吡咯烷酮、二甲基甲酰胺或乙腈,更优选为N-甲基吡咯烷酮。
优选地,步骤1中,球磨转速为300~600rpm,更优选为400rpm;球磨时间为6~48h,更优选为24h。
优选地,步骤2中,聚乙烯膜的孔径为50~200nm,更优选为100nm。
优选地,步骤2中,真空抽滤后形成的复合隔膜中,共价有机框架纳米片层的厚度为2~15μm,更优选为5μm。
优选地,步骤2中,真空抽滤过程中,采用的真空度为0.1MPa。
优选地,步骤2中,真空干燥温度为60~80℃,干燥时间为10h以上。
优选地,步骤3中,聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)的丙酮/水溶液中,聚偏氟乙烯-六氟丙烯共聚物的浓度为5~15%,丙酮和水的质量比为9:1~6:1。
优选地,步骤3中,干燥温度为80~90℃,干燥时间为4~12h。
本发明所述的长烷基链修饰的共价有机框架材料是由三羟基均苯三甲醛中的三个醛和长烷基链修饰的胺基化合物(NH2NH-C16)的两个酰胺基连接形成-C=C-NH-NH-共价键而合成的六边形拓扑结构,其结构式如下:
本发明所述的长烷基链修饰的共价有机框架材料的制备方法,包括以下步骤:
将三羟基均苯三甲醛和长烷基链修饰的胺基化合物加入到均三甲苯/1,4-二氧六环溶液中,超声溶解后加入醋酸,再次超声溶解分散成悬浊液,将悬浊液进行液氮冷冻、抽真空、脱气处理,在真空状态下,使用火焰枪进行封管,之后在120±20℃下反应48~168h,得到粗产物,将粗产物洗涤干净后抽滤,用四氢呋喃和氯仿进行索氏提取,最后真空干燥,得到长烷基链修饰的共价有机框架材料,所述的均三甲苯/1,4-二氧六环溶液中,均三甲苯和1,4-二氧六环的体积比为1:7~7:1。
本发明所述的长烷基链修饰的胺基化合物的结构式如下:
本发明所述的三羟基均苯三甲醛的结构式如下:
优选地,三羟基均苯三甲醛和长烷基链修饰的胺基化合物的摩尔比为2:3。
优选地,液氮冷冻、抽真空、脱气处理的次数为3次以上。
优选地,三羟基均苯三甲醛的浓度为0.3~3mol/L,长烷基链修饰的胺基化合物的浓度为0.2~2mol/L。
优选地,醋酸浓度为3~12mol/L,更优选为6mol/L。
优选地,反应温度为120℃,反应时间为72h。
优选地,将粗产物依次用二氯甲烷、乙酸乙酯、甲醇、丙酮洗涤干净。
进一步地,本发明提供上述共价有机框架基半固态电解质复合隔膜在半固态锂离子电池中的应用。
本发明所述的半固态锂离子电池为本领域常见的半固态锂离子电池,例如磷酸铁锂电池、镍钴锰三元锂电池等。
与现有技术相比,本发明具有以下优点:
(1)本发明的共价有机框架基半固态电解质复合隔膜,采用纳米片复合的结构可以极大地降低隔膜厚度,厚度降至~15μm,为超薄复合隔膜,同时最外层均匀的PVDF-HFP层丰富的氟元素有利于锂离子均匀穿梭和抑制锂枝晶的形成。在1mA/cm2的电流密度下可以稳定循环900多小时,且电压趋势在逐步减小,说明内阻在逐步减小,具有优异的锂枝晶抑制效果。
(2)本发明的共价有机框架基半固态电解质复合隔膜具有丰富的人造孔洞结构,其有序的纳米级孔道可实现锂离子传导,有利于电解液的存储以实现半固态锂离子电池的循环稳定性和抑制容量衰减保持高比容量。其组装的磷酸铁锂电池稳定循环65圈,比容量为130mAh/g;其组装的镍钴锰三元锂电池稳定循环50圈,比容量为125mAh/g。
附图说明
图1为长烷基链修饰的共价有机框架材料的XRD图;
图2为共价有机框架基半固态电解质复合隔膜的红外光谱图;
图3为共价有机框架基半固态电解质复合隔膜的表面SEM图;
图4为共价有机框架基半固态电解质复合隔膜组装成的锂锂对称电池的循环性能图;
图5为共价有机框架基半固态电解质复合隔膜组装成的磷酸铁锂电池的循环图;
图6为共价有机框架基半固态电解质复合隔膜组装成的镍钴锰三元锂电池的循环图。
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,以下通过实施例,并结合附图,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用以解释本发明,并不用于限定本发明。以做出若干变形和改进,这些都属于本发明的保护范围。
下述实施例中,采用的聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)的丙酮/水溶液,配制方法如下:按质量比PVDF-HFP:丙酮:水=1:8:1,将PVDF-HFP、丙酮和水混合搅拌12小时直至形成无气泡的混合溶液,得到聚偏氟乙烯-六氟丙烯共聚物的丙酮/水溶液。
本发明所述的NH2NH-C16可商业购买获得,也可自行制备,具体合成路线如下:
具体步骤如下:
(1)化合物1c:将1mmol化合物1a,3mmol化合物1b和1mmol K2CO3加入30mlDMF中,在N2的保护气氛下65℃反应48个小时,反应结束后,用二氯甲烷萃取,饱和食盐水洗涤,无水硫酸钠干燥,真空旋干除溶剂,使用柱层析分离提纯,得到化合物1c;
(2)NH2NH-C16:将化合物1c和水合肼加入15ml乙醇溶液中反应12个小时,低温冰冻后直接过滤,将白色固体用石油醚溶剂洗涤多次可得目标单体NH2NH-C16。
实施例1
(1)长烷基链修饰的共价有机框架材料(COF-C16),是由三羟基均苯三甲醛和NH2NH-C16通过席夫碱反应形成的有机框架结构,其结构如下所示:
NH2NH-C16的结构如下所示:
COF-C16的制备方法,具体步骤如下:
在玻璃安瓿(体积约20mL,体长18cm,颈长9cm)中装入三羟基均苯三甲醛(21.0mg,0.1mmol)、NH2NH-C16(101.3mg,0.15mmol)和均三甲苯/1,4-二氧六环(3:1,v/v,4mL)。然后,将安瓿浸入超声波浴中5分钟;随后加入0.4mL的6.0mol L-1乙酸水溶液,将安瓿浸入超声波浴中2分钟。将混合物超声处理2分钟以获得均匀分散体。然后将管在77K下用液氮浴快速冷冻,并通过三个冷冻泵-解冻循环脱气,在真空下密封,并在120℃下加热3天。将安瓿瓶颈折断,离心分离黄色凝胶状产物,用丙酮(3×10mL)洗涤,在无水丙酮中浸泡12h,80℃真空干燥12h,得COF-C16,为黄色胶体粉末。反应式如下所示:
(2)将100mg的COF-C16胶体粉末加入到聚四氟乙烯的球磨罐中,然后加入15颗直径为5mm的玛瑙球磨珠,加入20mL的N-甲基吡咯烷酮,在300rpm的转速下球磨24h,球磨完毕后静置,取上清液为分散良好的COF-C16纳米片溶液。
(3)选用孔径为100nm的聚乙烯膜作为真空抽滤装置底膜,然后将20mL分散良好的COF-C16纳米片溶液滴加在底膜上,在0.1MPa真空度的条件下抽滤,等待溶剂抽滤完,加入10mL乙醇溶剂进行抽滤清洗,然后在50℃的真空烘箱中烘干溶剂,得到COF-C16复合隔膜。
(4)将真空抽滤后的COF-C16复合隔膜平铺在平台上,将配制好的聚偏氟乙烯-六氟丙烯共聚物溶液滴加在膜上,用调节为5μm高度的刮刀匀速刮一次,待溶剂挥发后,在另一面进行同样涂布操作,有机溶剂挥发后,放入到90℃烘箱烘干8h后,得到共价有机框架基半固态电解质复合隔膜。
实施例2
将共价有机框架基半固态电解质复合隔膜以电池隔膜的形式加入锂锂称电池中,电池装配在手套箱中完成。测试电池的循环稳定性,具体实施方法如下:将电池放入恒温箱内,在0.1mA/cm2的电流密度下用蓝电***测进行锂锂称电池的循环稳定性测试。
实施例3
将共价有机框架基半固态电解质复合隔膜作为磷酸铁锂电池的隔膜,半固态锂电池的组装在手套箱中完成。测试电池的充放电曲线,具体实施方法如下:将电池放入洁净恒温箱内,在2.7~3.8V的电压范围内,0.1C的充放电倍率条件下使用蓝电***测得电池的充放电曲线。充放电曲线表明该电池具有良好循环稳定性和高的比容量保持。
实施例4
将共价有机框架基半固态电解质复合隔膜作为镍钴锰三元锂电池的隔膜,半固态锂电池的组装在手套箱中完成。测试电池的充放电曲线,具体实施方法如下:将电池放入洁净恒温箱内,在3.0~4.2V的电压范围内,0.1C的充放电倍率条件下使用蓝电***测得电池的充放电曲线。测试电池的充放电曲线,充放电曲线表明该电池具有良好循环稳定性和高的比容量保持。
图1为长烷基链修饰的共价有机框架材料的XRD图,可以证明共价有机框架材料的结晶性。
图2为共价有机框架基半固态电解质复合隔膜的红外光谱图,可以证明复合膜最外层的有效官能团的存在(C-F键的存在)。
图3为共价有机框架基半固态电解质复合隔膜的表面SEM图,可以证明复合隔膜表面均匀的人造孔径,有助于电解液的吸附和储存。
图4为共价有机框架基半固态电解质复合隔膜组装成的锂锂对称电池的循环性能图,复合膜具有优异的锂枝晶抑制效果,在1mA/cm2的电流密度下可以稳定循环900多小时,且电压趋势在逐步减小说明内阻在逐步减小,具有优异的锂枝晶抑制效果。
图5为共价有机框架基半固态电解质复合隔膜组装成的磷酸铁锂电池的循环图,可以证明用共价有机框架基半固态电解质复合隔膜组装成的半固态电池具有良好的循环稳定性(65圈)和高的比容量(130mAh/g)。
图6为共价有机框架基半固态电解质复合隔膜组装成的镍钴锰三元锂电池的循环图,可以证明共价有机框架基半固态电解质复合隔膜组装成的半固态电池具有良好的循环稳定性(50圈)和高的比容量(125mAh/g)。
Claims (10)
1.共价有机框架基半固态电解质复合隔膜的制备方法,其特征在于,包括以下步骤:
步骤1,在长烷基链修饰的共价有机框架材料中加入有机溶剂作为辅助剂,球磨12~48h,将球磨后的混合液静置,取上清液,得到长烷基链修饰的共价有机框架纳米片分散液,所述的长烷基链修饰的共价有机框架材料的结构式如下:
,
通过以下步骤制备:
将三羟基均苯三甲醛和长烷基链修饰的胺基化合物加入到均三甲苯/1,4-二氧六环溶液中,超声溶解后加入醋酸,再次超声溶解分散成悬浊液,将悬浊液进行液氮冷冻、抽真空、脱气处理,在真空状态下,使用火焰枪进行封管,之后在120±20℃下反应48~168 h,得到粗产物,将粗产物洗涤干净后抽滤,用四氢呋喃和氯仿进行索氏提取,最后真空干燥,得到长烷基链修饰的共价有机框架材料,所述的均三甲苯/1,4-二氧六环溶液中,均三甲苯和1,4-二氧六环的体积比为1:7~7:1,
所述的长烷基链修饰的胺基化合物的结构式如下:
,
所述的三羟基均苯三甲醛的结构式如下:
;
步骤2,以聚乙烯膜为真空抽滤装置的底膜,对长烷基链修饰的共价有机框架纳米片分散液进行真空抽滤,抽滤完后加入乙醇进行抽滤清洗,最后真空干燥,得到长烷基链修饰的共价有机框架复合隔膜;
步骤3,依次在长烷基链修饰的共价有机框架复合隔膜的两面均匀涂布聚偏氟乙烯-六氟丙烯共聚物的丙酮/水溶液,涂布厚度为2~50µm,待有机溶剂挥发后干燥,得到共价有机框架基半固态电解质复合隔膜。
2. 根据权利要求1所述的制备方法,其特征在于,步骤1中,有机溶剂为N-甲基吡咯烷酮、二甲基甲酰胺或乙腈;球磨转速为300~600rpm;球磨时间为6~48 h。
3. 根据权利要求1所述的制备方法,其特征在于,步骤2中,聚乙烯膜的孔径为50~200nm;真空抽滤后形成的复合隔膜中,共价有机框架纳米片层的厚度为2~15 µm;真空抽滤过程中,采用的真空度为0.1MPa;真空干燥温度为60~80℃,干燥时间为10h以上。
4.根据权利要求1所述的制备方法,其特征在于,步骤3中,聚偏氟乙烯-六氟丙烯共聚物的丙酮/水溶液中,聚偏氟乙烯-六氟丙烯共聚物的浓度为5~15%,丙酮和水的质量比为9:1~6:1;干燥温度为80~90℃,干燥时间为4~12h。
5.根据权利要求1所述的制备方法,其特征在于,步骤1长烷基链修饰的共价有机框架材料的制备步骤中,三羟基均苯三甲醛和长烷基链修饰的胺基化合物的摩尔比为2:3,液氮冷冻、抽真空、脱气处理的次数为3次以上。
6.根据权利要求1所述的制备方法,其特征在于,步骤1长烷基链修饰的共价有机框架材料的制备步骤中,三羟基均苯三甲醛的浓度为0.3~3mol/L,长烷基链修饰的胺基化合物的浓度为0.2~2mol/L,醋酸浓度为3~12mol/L。
7. 根据权利要求1所述的制备方法,其特征在于,步骤1长烷基链修饰的共价有机框架材料的制备步骤中,反应温度为120℃,反应时间为72 h;将粗产物依次用二氯甲烷、乙酸乙酯、甲醇和丙酮洗涤干净。
8.根据权利要求1~7任一所述的制备方法制得的共价有机框架基半固态电解质复合隔膜。
9.根据权利要求8所述的共价有机框架基半固态电解质复合隔膜在半固态锂离子电池中的应用。
10.根据权利要求9所述的应用,其特征在于,所述的半固态锂离子电池为磷酸铁锂电池或镍钴锰三元锂电池。
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