CN111916628A - 一种锂离子电池隔膜及其制备方法 - Google Patents
一种锂离子电池隔膜及其制备方法 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 13
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OKHOYBDWRWLTEF-UHFFFAOYSA-N 1,1-dichloroethene;1,1,2-trifluoroethene Chemical group ClC(Cl)=C.FC=C(F)F OKHOYBDWRWLTEF-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
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- 229920001519 homopolymer Polymers 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
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- 239000004408 titanium dioxide Substances 0.000 claims description 2
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- 230000009477 glass transition Effects 0.000 abstract description 3
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 10
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及锂离子电池隔膜及其制备方法,旨在提供一种锂离子电池隔膜及其制备方法。是在隔膜基材的至少一侧表面上涂覆有聚合物涂层,该聚合物涂层包括第一聚合物和第二聚合物,前者为磺化聚芳醚酮;后者是PVDF、PVDF‑HFP、PVDF‑TrFE、PAN、PEG或PMMA中的至少一种。本发明有利于改善锂离子在隔膜中的传导性能,制得的复合隔膜具有较好的润湿性。按磺化度不同,玻璃化转变温度可达198~240℃,降低隔膜发生严重热收缩的风险,使电池的安全性得到保障。组分相容性较好,共混构成的聚合物涂层组成均一、性质稳定。制备工艺简单,控制条件少。涂覆浆料采用低沸点溶剂,干燥过程所需时间短、能耗低,蒸发的溶剂可冷凝回收,绿色环保。
Description
技术领域
本发明属于电池隔膜技术领域,具体涉及一种锂离子电池隔膜及其制备方法。
背景技术
锂离子二次电池是被广泛应用的储能设备,具有能量密度高、循环寿命长、无记忆效应等优点。近年来,移动电子产品的迭代和新能源电动交通工具的发展对锂电池的容量、充放电速率与安全性提出了更高的要求。隔膜是锂电池中的重要部件,用于分隔电池两极,同时允许锂离子在两极间快速移动,对电池的性能产生了重要影响,尤其是安全性与电性能两方面。
传统的锂电池隔膜为单层或多层复合的聚烯烃隔膜,具有较高的机械强度,并能在温度达到或略低于熔点时发生热闭孔,阻止电池内部电化学反应继续进行。但在温度高于熔点的环境下,聚烯烃隔膜会发生严重的热收缩,其中聚乙烯(PE)的熔点范围为 132-135℃,聚丙烯(PP)熔点范围为147-176℃。同时,电解液对聚烯烃隔膜的润湿性差,导致电解液分布不均匀,进而造成电池中极化电压的局部差异,最终加剧充放电过程中锂晶枝的生长。隔膜热收缩与锂晶枝的生长是导致电池内部短路,进而造成热失控的主要因素,对电池的安全性造成了严重的威胁。此外,聚烯烃隔膜本体不具备离子导电能力,锂离子通过隔膜的孔隙进行传递,离子电导率受到限制。
现有解决隔膜热收缩问题、改善隔膜润湿性和提高电导率的方法主要有以下三类:一类方案采用性能更加优异的新型聚合物代替聚烯烃,通过静电纺丝、相分离等方法制备性能更佳的隔膜。所用的新型聚合物往往具有刚性较强的主链或强极性基团,前者使聚合物具有更高的玻璃化转变温度,保证隔膜的耐热性;后者与锂盐、电解液间的相互作用强烈,有利于提高隔膜的润湿性,并促进锂盐解离,增大锂离子的有效浓度。专利 CN108134034 A公开了一种由聚(偏二氟乙烯-六氟丙烯)(PVDF-HFP)制备的锂电池隔膜,由于PVDF-HFP中含有大量强极性的C-F基团,该隔膜能够在极性电解液溶胀,具有极强的持液、保液能力,并提供较高的离子电导率。但PVDF-HFP的机械性能不理想,在锂电池卷绕、装配、以及日常使用过程中易破损,存在较大安全隐患。同时该隔膜的耐热性能有待提高。文献[Lingyi Kong,Yurong Yan,Zhiming Qiu,Zhiqiang Zhou, Jiqing Hu,Journal ofMembrane Science.549(2018)321-331]报道了一种的氟化聚酰亚胺 (FPI)隔膜。该聚合物同时具备含芳环的刚性主链与含氟侧基,所得的隔膜具有优秀的耐热性与润湿性,并使电池的离子电导率有所提高。但该聚合物不溶于常见低沸点溶剂,文中采用N,N’-二甲基乙酰胺(DMAc)作溶剂,通过静电纺丝法将FPI的浓溶液制备成膜,并在150℃下真空干燥除去溶剂,其制备方法严重限制了隔膜的生产能力。
另一类方案是通过表面接枝、表面涂覆等方法对现有隔膜表面进行修饰,使其性能满足应用需要。其中,表面接枝是通过高能射线、高能粒子束或臭氧活化等方式处理,将具备优异性能的聚合物、陶瓷颗粒、单体或官能团接枝到基膜表面的技术,这种方法得到的改性隔膜与表面材料结合紧密,性能稳定,但由于设备、能耗与生产效率的限制,难以实现大规模工业化的生产。表面涂覆方法在改善聚烯烃隔膜性能的同时,保留了热闭孔能力,且设备要求较低,工艺相对简单,能够应用于规模化的连续生产过程,是目前商业改性隔膜的主要生产方式。进行表面涂覆的材料主要包括耐热聚合物、润湿性优异的聚合物与陶瓷颗粒。文献[Lianyuan He,Teng Qiu,Chunjie Xie,Xinlin Tuo,Journal of AppliedPolymer Science.135(2018)46697]报道了一种通过静电纺丝法将聚对苯二甲酰对苯二胺(PPTA)纳米纤维涂覆在聚丙烯基膜表面得到的PPTA/PP复合隔膜。所述的隔膜在200℃下处理1h未见明显收缩,且明显改善了聚烯烃隔膜的润湿性能。但PPTA纳米纤维的制备工艺复杂,隔膜的生产能力受到严重制约。专利CN 105489819 A公开了一种锂离子电池陶瓷隔膜用浆料。浆料在聚烯烃表面涂覆得到一种陶瓷纳米颗粒涂覆的锂电池隔膜,纳米颗粒通过粘结剂固定在基膜表面。陶瓷颗粒涂层能够有效地强化隔膜的机械强度和耐热性能,并改善其润湿性。但该技术方案存在以下不足:陶瓷纳米颗粒与聚烯烃基膜结合不紧密,长期使用中纳米颗粒易脱落,不仅使隔膜难以维持在高温下的尺寸稳定性,还会对电池的寿命和性能造成不良影响。
第三类方案是采用共混方法对聚合物进行改性,使其性能得到提高。美国专利US20190245182公开了一种由聚烯烃隔膜、陶瓷涂层和聚合物涂层组成的复合锂电池隔膜,其中陶瓷涂层用于强化隔膜的机械强度与耐热性,聚合物涂层用于改善隔膜润湿性并减少陶瓷颗粒脱落。该技术方案在聚合物涂层中加入陶瓷颗粒共混,以提高隔膜的离子电导率。但聚合物涂层中混合的陶瓷颗粒分布不均匀,且会堵塞部分微孔,导致隔膜性能不够稳定。
为了满足当前锂离子电池的安全性与电性能要求,亟需一种耐热性、润湿性好,具备优秀的离子导电能力,且制备工艺简单的锂电池隔膜。
发明内容
本发明要解决的技术问题是,克服现有技术中的不足,提供一种性能优异、制备工艺相对简单的锂离子电池隔膜及其制备方法。该隔膜具有较好的润湿性、耐热性能,并使离子电导率进一步提高,从而解决上述背景技术中提出的锂离子电池的电性能及安全性能的问题。
为了实现上述目的,本发明的解决方案是:
提供一种锂离子电池隔膜,包括隔膜基材;在隔膜基材的至少一侧表面上涂覆有聚合物涂层,该聚合物涂层包括第一聚合物和第二聚合物,两者质量比为1.0∶1.0~10.0;
所述第一聚合物为磺化聚芳醚酮(SPAEK-6F);所述第二聚合物是聚偏氟乙烯均聚物(PVDF)、聚(偏氟乙烯-六氟丙烯)(PVDF-HFP)、聚(偏氯乙烯-三氟乙烯)(PVDF-TrFE)、聚丙烯腈(PAN)、聚乙二醇(PEG)或聚甲基丙烯酸甲酯(PMMA) 中的至少一种。
本发明中,所述磺化聚芳醚酮是H型磺化聚芳醚酮、Na型磺化聚芳醚酮或Li型磺化聚芳醚酮中的至少一种;其磺化度为30%~60%,重均分子量为1.6×106~2.8×106g/mol。
本发明中,所述隔膜基材的厚度为5~25μm,聚合物涂层的厚度为0.2~3.0μm。
本发明中,所述隔膜基材是聚乙烯隔膜、聚丙烯隔膜、PP/PE/PP复合隔膜、聚酰亚胺膜或无纺布中的任意一种;或者是具有陶瓷颗粒涂层的上述隔膜中的任意一种。
本发明中,所述陶瓷颗粒涂层是由下述一种或几种陶瓷颗粒组成的:氧化铝、勃姆石、二氧化钛、二氧化硅、二氧化锆、二氧化锡、氢氧化镁、氧化镁、氧化锌或硫酸钡。
本发明进一步提供了前述锂离子电池隔膜的制备方法,包括以下步骤:
(1)称取质量份为0.7~3.9份的第一聚合物、3.9~7.0份的第二聚合物、8.0~9.8份造孔剂和100~120份的溶剂,混合均匀;在40~60℃下加热搅拌60~240min,充分溶解后过滤,得到用于涂覆隔膜基材的共混浆料;
(2)将共混浆料均匀涂覆在隔膜基材单侧或两侧的表面上,在60~80℃下干燥后,制得具有聚合物涂层的锂离子电池隔膜。
本发明中,所述溶剂是丙酮、二氯甲烷、甲酸、四氢呋喃中的至少一种,所述造孔剂是乙醇、正丙醇、环己烷、去离子水、碳酸二甲酯或碳酸氢铵中的至少一种。
本发明中,所述涂覆的方法是凹版涂覆、狭缝涂覆、喷涂式涂布或浸涂式涂布中的任意一种。
与现有技术相比,本发明的有益效果在于:
1、本发明所用第一聚合物磺化聚芳醚酮SPAEK-6F含有的磺酸根基团为其提供了离子导电能力,有利于改善锂离子在隔膜中的传导性能。同时强极性基团-CF3与电解液间的相互作用强,制得的复合隔膜具有较好的润湿性。
2、本发明所用第一聚合物磺化聚芳醚酮SPAEK-6F具有刚性较强的主链,按磺化度不同,玻璃化转变温度可达198~240℃。在聚合物涂层中加入SPAEK-6F共混有利于强化隔膜的耐热性能,降低隔膜发生严重热收缩的风险,使电池的安全性得到保障。
3、第一聚合物磺化聚芳醚酮SPEAK-6F与第二聚合物PVDF等相容性较好,共混构成的聚合物涂层组成均一、性质稳定。
4、本发明所述复合隔膜制备工艺简单,控制条件少。此外,所述的涂覆浆料采用低沸点溶剂,干燥过程所需时间短、能耗低,蒸发的溶剂可冷凝回收,绿色环保。
附图说明
图1为本发明所涉及的Li型磺化聚芳醚酮聚合物的分子结构式。
图2为本发明所述的锂电池隔膜截面形貌电子扫描显像图(SEM图)。
具体实施方式
以下实施例是仅为更进一步具体说明本发明,在不违反本发明的主旨下,本发明应不限于以下实施例具体明示的内容。
实施例1
(1)称取磺化度为60%的Li型SPAEK-6F 1.6kg,PVDF-HFP 6.3kg,碳酸二甲酯9.8kg,丙酮100.0kg并混合,于40℃下搅拌4h,经过滤得到混合溶液,即为涂覆浆料。
(2)采用浸涂方法将浆料涂布在基膜两侧,涂布厚度为50μm。所述基膜为具有Al2O3颗粒涂层的聚乙烯隔膜,其中陶瓷层厚度为2μm,聚乙烯层厚度为7μm,隔膜孔隙率为48%。
(3)涂布后的隔膜在60℃下干燥40min,得到SPAEK-6F与PVDF-HFP共混物涂覆的复合隔膜,单侧涂层厚度为0.8μm。
实施例2
(1)称取磺化度为60%的Li型SPAEK-6F 3.9kg,PAN 3.9kg,碳酸氢铵8.9kg,甲酸120.0kg并混合,于60℃下搅拌1h,经过滤得到混合溶液,即为涂覆浆料。
(2)采用狭缝涂覆方法将浆料涂布在基膜一侧,涂布厚度为50μm。所述基膜为具有Al2O3颗粒涂层的聚丙烯隔膜,其中陶瓷层厚度为2μm,聚乙烯层厚度为7μm,隔膜孔隙率为48%。
(3)涂布后的隔膜在80℃下干燥0.5h,得到SPAEK-6F与PVDF-HFP共混物涂覆的复合隔膜,单侧涂层厚度为0.8μm。
实施例3
本实施例与实施例1不同的是,步骤(1)中所用的第一聚合物H型SPAEK-6F为3.9kg,第二聚合物PMMA为3.9kg,造孔剂为去离子水8.0kg;步骤(2)中所用的基膜为厚度25μm的PE/PP/PE复合隔膜,孔隙率为42%,其他步骤和参数与实施例1相同。
实施例4
本实施例与实施例1不同的是,步骤(1)中所用的造孔剂为正丙醇9.6kg,溶剂为四氢呋喃112kg,于50℃下搅拌2h;步骤(2)中所用的涂覆方法为凹版涂覆,基膜为厚度12μm的聚酰亚胺隔膜,其孔隙率为47%;步骤(3)中所用的干燥条件为70℃下干燥1h。
实施例5
本实施例与实施例1不同的是,步骤(1)中所用的聚合物为磺化度为60%的Li型SPAEK-6F 3.2kg,PVDF-HFP 4.6kg,其他步骤和参数与实施例1相同。
实施例6
本实施例与实施例1不同的是,步骤(1)中所用的聚合物为磺化度为60%的Li型SPAEK-6F 0.7kg,PVDF-HFP 7.0kg,其他步骤和参数与实施例1相同。
实施例7
本实施例与实施例1不同的是,步骤(1)中所用的磺化聚芳醚酮为磺化度为40%的Li型SPAEK-6F 1.6kg,其他步骤和参数与实施例1相同。
实施例8
本实施例与实施例1不同的是,步骤(1)中所用的磺化聚芳醚酮为磺化度为30%的Li型SPAEK-6F 1.6kg,其他步骤和参数与实施例1相同。
实施例9
本实施例与实施例1不同的是,步骤(2)中所用的涂布厚度为20μm,得到的复合隔膜单侧涂层厚度为0.2μm,其他步骤和参数与实施例1相同。
实施例10
本实施例与实施例1不同的是,步骤(2)中所用的涂布厚度为60μm,得到的复合隔膜单侧涂层厚度为3.0μm,其他步骤和参数与实施例1相同。
实施例11
本实施例与实施例1不同的是,步骤(2)中所用的基膜为聚乙烯隔膜,所述聚乙烯隔膜厚度为5μm,孔隙率为44%,其他步骤和参数与实施例1相同。
对比例1
本对比例与实施例1不同的是,步骤(1)中不添加磺化聚芳醚酮,所用的聚合物为PVDF-HFP 7.7kg,其他步骤和参数与实施例1相同。
对比例2
本对比例采用未经涂覆的聚乙烯隔膜,隔膜厚度为9μm,孔隙率为44%。
按上述方案制备隔膜,对制得隔膜的厚度、热收缩率、与电解液的接触角以及由其电池的离子电导率进行测试,结果如下所示。其中组装的电池以LiFePO4正极,Li为负极,电解液采用1mol/LLiPF6-碳酸乙烯酯(EC)/碳酸甲乙酯(EMC)/碳酸二甲酯(DMC)(体积比1:1:1)。
表1
从以上实施例及对比例数据可以看出,本发明中具有聚合物涂层的复合隔膜具有较好的润湿性,在高温下的尺寸稳定性得到有效的提高,并有利于锂离子的传导。同时,增大SPAEK-6F的磺化度或在共混中所占的比例,有利于耐热性能和离子电导率的提高。
上述实施例用来解释说明本发明,而不是对本发明进行限制,在本发明的精神和权利要求的保护范围内,对本发明作出的任何修改和改变,都落入本发明的保护范围。
Claims (8)
1.一种锂离子电池隔膜,包括隔膜基材;其特征在于,在隔膜基材的至少一侧表面上涂覆有聚合物涂层,该聚合物涂层包括第一聚合物和第二聚合物,两者质量比为1.0∶1.0~10.0;
所述第一聚合物为磺化聚芳醚酮;所述第二聚合物是聚偏氟乙烯均聚物、聚(偏氟乙烯-六氟丙烯)、聚(偏氯乙烯-三氟乙烯)、聚丙烯腈、聚乙二醇或聚甲基丙烯酸甲酯中的至少一种。
2.根据权利要求1所述的锂离子电池隔膜,其特征在于,所述磺化聚芳醚酮是H型磺化聚芳醚酮、Na型磺化聚芳醚酮或Li型磺化聚芳醚酮中的至少一种;其磺化度为30%~60%,重均分子量为1.6×106~2.8×106g/mol。
3.根据权利要求1所述的锂离子电池隔膜,其特征在于,所述隔膜基材的厚度为5~25μm,聚合物涂层的厚度为0.2~3.0μm。
4.根据权利要求1所述的锂离子电池隔膜,其特征在于,所述隔膜基材是聚乙烯隔膜、聚丙烯隔膜、PP/PE/PP复合隔膜、聚酰亚胺膜或无纺布中的任意一种;或者是具有陶瓷颗粒涂层的上述隔膜中的任意一种。
5.根据权利要求4所述的锂离子电池隔膜,其特征在于,所述陶瓷颗粒涂层是由下述一种或几种陶瓷颗粒组成的:氧化铝、勃姆石、二氧化钛、二氧化硅、二氧化锆、二氧化锡、氢氧化镁、氧化镁、氧化锌或硫酸钡。
6.权利要求1所述锂离子电池隔膜的制备方法,其特征在于,包括以下步骤:
(1)称取质量份为0.7~3.9份的第一聚合物、3.9~7.0份的第二聚合物、8.0~9.8份造孔剂和100~120份的溶剂,混合均匀;在40~60℃下加热搅拌60~240min,充分溶解后过滤,得到用于涂覆隔膜基材的共混浆料;
(2)将共混浆料均匀涂覆在隔膜基材单侧或两侧的表面上,在60~80℃下干燥后,制得具有聚合物涂层的锂离子电池隔膜。
7.根据权利要求6所述的方法,其特征在于,所述溶剂是丙酮、二氯甲烷、甲酸、四氢呋喃中的至少一种;所述造孔剂是乙醇、正丙醇、环己烷、去离子水、碳酸二甲酯或碳酸氢铵中的至少一种。
8.根据权利要求6所述的方法,其特征在于,所述涂覆的方法是凹版涂覆、狭缝涂覆、喷涂式涂布或浸涂式涂布中的任意一种。
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