CN114171789A - 一种聚合物固体电解质及其制备方法和应用 - Google Patents
一种聚合物固体电解质及其制备方法和应用 Download PDFInfo
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- CN114171789A CN114171789A CN202111438745.2A CN202111438745A CN114171789A CN 114171789 A CN114171789 A CN 114171789A CN 202111438745 A CN202111438745 A CN 202111438745A CN 114171789 A CN114171789 A CN 114171789A
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- electrolyte
- carbonate
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- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 26
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- VERMEZLHWFHDLK-UHFFFAOYSA-N tetrahydroxybenzene Natural products OC1=CC=C(O)C(O)=C1O VERMEZLHWFHDLK-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
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- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims 1
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- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 claims 1
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- 101150058243 Lipf gene Proteins 0.000 description 1
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- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
本发明提供了一种聚合物固体电解质及其制备方法和应用;聚合物固体电解质由聚合物和锂盐组成;本发明还公开了聚合物固体电解质的制备方法及应用。本发明合物电解质电化学窗口较宽,含有柔性链段和苯环刚性结构,既保证了电解质的可塑性,同时又增大了机械强度;柔性连段含有大量醚氧键,能够传导锂离子,而刚性结构中包含氟、三氟甲基、磺酰亚胺等电子离域性较强的基团,能够促进锂离子的解离,能提升离子电导率;同时,该聚合物电解质为聚阴离子型单离子导体,具有较高的锂离子迁移数。
Description
技术领域
本发明属于锂离子电池领域,具体涉及一种聚合物固体电解质及其制备方法和应用。
背景技术
随着锂离子电池技术的飞速发展,其应用场景也在不断拓展,比如:航空航天、储能、动力电池、3C、可穿戴产品等方方面面。随着其应用场景的拓展,锂离子电池暴露的问题也在不断增多,起火爆炸等现象也是屡见不鲜。因此人们对锂离子电池的性能提出了更高、更严苛的要求:低成本、高安全、高能量密度、长寿命等;于是,技术不断地更新,固态锂电池诞生了,现基于PEO(聚环氧乙烷)的聚合物固态电池已经进入商业化应用阶段。
PEO聚合物固态电池具有高安全、高能量密度等优点,且PEO聚合物固态电解质的界面兼容性好、化学稳定性好、可塑性强;但是由于PEO本身的结构问题,其室温下易结晶,导致PEO聚合物固态电解质的室温离子电导率较低(10-7S/cm量级),且其电化学窗口较窄(3.8V vs.Li/Li+)、锂离子迁移数也不高、机械性能也较差,难以满足如今严苛标准下的使用需求。
发明内容
本发明的目的是提供了一种聚合物固体电解质及其制备方法和应用。
本发明是通过以下技术方案实现的:
本发明涉及种聚合物固体电解质,由聚合物和锂盐组成,其特征在于,所述聚合物具有如下结构通式:
其中,
m为1-1000的整数;
通式中的R1、R2分别为以下结构中的至少一种:
通式中的R3、R4分别为如下结构各种的至少一种:
通式中的R5为如下结构中的至少一种:
所述锂盐为六氟磷酸锂(LiPF6)、双草酸硼酸锂(LiBOB)、二氟磷酸锂(LiPO2F2)、二氟草酸硼酸锂(LiDOFB)、双(氟磺酰)亚胺锂(LiFSI)、双(三氟甲基磺酰)亚胺锂(LiTFSI)、三氟甲磺酸锂(LiOTf)、四氟硼酸锂(LiBF4)、高氯酸锂(LiClO4)、(氟磺酰)三氟甲基磺酰亚胺锂(LiFTFSI)、四氯铝酸锂(LiAlCl4)、六氟砷酸锂(LiAsF6)中的至少一种。
优选地,所述聚合物中醚氧和锂盐的摩尔比为(1-100):1。
优选地,所述聚合物中醚氧和锂盐的摩尔比为(10-20):1。
本发明还是还涉及前述聚合物固体电解质的制备方法,包括以下步骤:
步骤1,取四甲氧基硼锂和含R5结构的四羟基苯,加入反应器中(惰性气氛),加入适量溶剂,室温下搅拌1-4h;其中,四甲氧基硼锂和含R5结构的四羟基苯的摩尔比为1:1;
步骤2,加热至40-100℃,搅拌反应1-10h,制得前驱体;
步骤3,加入R1、R2所对应的一元醇和R3、R4对应的一元羧酸或酯,保持加热,继续搅拌反应1-10h;其中,一元醇和四甲氧基硼锂的摩尔比为1-2:1000,一元羧酸和四甲氧基硼锂的摩尔比为1-2:1000;
步骤4,抽真空,直至溶剂和反应副产物全部除去,即制得聚合物;
步骤5,取所述聚合物和所述锂盐加热40-120℃混合均匀,即制得所述聚合物电解质。
优选地,所述溶剂为去离子水、乙醚、甲醇、苯、甲苯、二甲苯、氯仿、二硫化碳、乙腈、丙酮、N,N-二甲基吡咯烷酮、N,N-二甲基甲酰胺中的一种或多种。
本发明还涉及前述聚合物电解质的应用,所述聚合物电解质与有机溶剂、无机填料及其他聚合物中的至少一种进行复合,得到复合电解质。
优选地,所述有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、γ-丁内酯、二氧五环、四氢呋喃、二甲基三幅乙酰胺、二甲基亚砜中的至少一种。
优选地,所述无机填料氧化物固体电解质、硫化物固体电解质、氧化亚硅、二氧化硅、氧化钛、氧化锆、氧化铝、勃姆石中的至少一种。
优选地,所述其他聚合物为聚偏二氟乙烯、聚偏二氟乙烯-六氟丙烯共聚物、聚丙烯酸、聚丙烯腈、聚甲基丙烯碳酸甲酯、聚环氧乙烷、聚乙烯、聚丙烯、聚酰胺、聚酰亚胺、聚乙烯醇、聚乙烯缩丁醛中的至少一种。
优选地,所述聚合物电解质用于制备锂离子电池或金属锂电池。
本发明具有以下优点:
(1)本发明提供了一种聚合物固态电解质,该聚合物固态电解质的离子电导率较高,电化学窗口教宽,锂离子迁移数较大,且机械性能优秀。
(2)本发明合物电解质电化学窗口较宽,含有柔性链段和苯环刚性结构,既保证了电解质的可塑性,同时又增大了机械强度;柔性连段含有大量醚氧键,能够传导锂离子,而刚性结构中包含氟、三氟甲基、磺酰亚胺等电子离域性较强的基团,能够促进锂离子的解离,能提升离子电导率;同时,该聚合物电解质为聚阴离子型单离子导体,具有较高的锂离子迁移数。
附图说明
图1是本发明实施例1的聚合物P1结构式图;
图2是本发明实施例1的聚合物电解质的室温EIS曲线图;
图3是本发明实施例1的聚合物电解质的室温CV曲线图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。应当指出的是,以下的实施实例只是对本发明的进一步说明,但本发明的保护范围并不限于以下实施例。
实施例1
本实施例所涉及的聚合物结构如图1所示,含有该聚合物的电解质制备方法如下:
步骤1,取1mol四甲氧基硼锂和1mol的含(CF3)(SO2)(C6H4)(0C2H4)O-结构的四羟基苯,加入反应器中(惰性气氛),加入1000g乙醚作溶剂,室温下搅拌3h;
步骤2,加热至40℃,搅拌反应8h,制得前驱体;
步骤3,加入1mol乙二醇单甲醚、1mol乳酸甲酯、1mol甲氧基乙酸、1mol乙酰氧基乙酸,保持加热,继续搅拌反应10h;
步骤4,抽真空,直至溶剂和反应副产物甲醇全部除去,即制得聚合物P1;
步骤5,将3g聚合物P1和0.8g LiTFSI,加热60℃混合均匀,倒在干净的平板玻璃上,冷却至室温,制得厚度为0.48mm的聚合物电解质膜SPE1。
将制备得到的聚合物电解质膜SPE1冲成φ16mm的圆片,组装成锂/SPE1/锂的扣式电池进行室温交流阻抗(EIS)和锂离子迁移数测试;组装成锂/SPE1/不锈钢的扣式电池进行室温循环伏安测试(CV)。
交流阻抗图谱见图2,经计算得出其室温离子电导率为3*10-5S/cm;循环伏安测试结果见图3,其电化学窗口5V以上,经计算其室温锂离子迁移数为0.83。
实施例2
本实施例聚合物电解质制备方法如下:
步骤1,取2mol四甲氧基硼锂和2mol的含LiO(SO2)(C6H4)(0C2H4)5O-结构的四羟基苯,加入反应器中(惰性气氛),加入3000g苯作溶剂,室温下搅拌4h;
步骤2,加热至50℃,搅拌反应6h,制得前驱体;
步骤3,加入1mol五异丁二醇单甲醚、1mol十丙二醇单甲醚、1mol甲氧基丙酸、1mol甲氧基五(2-三氟甲基丙酸),保持加热,继续搅拌反应8h;
步骤4,抽真空,直至溶剂和反应副产物甲醇全部除去,即制得聚合物P2;
步骤5,将5g聚合物P2和1gLiFSI,加热80℃混合均匀,倒在干净的平板玻璃上,冷却至室温,制得厚度为0.45mm的聚合物电解质膜SPE2。
将制备得到的聚合物电解质膜SPE1冲成φ16mm的圆片,组装成锂/SPE1/锂的扣式电池进行室温交流阻抗(EIS)和锂离子迁移数测试;组装成锂/SPE1/不锈钢的扣式电池进行室温循环伏安测试(CV)。其室温离子电导率为2.2*10-5S/cm,电化学窗口5V以上,室温锂离子迁移数为0.85。
实施例3
本实施例聚合物电解质制备方法如下:
步骤1,取1mol四甲氧基硼锂和1mol的含F(SO2)NLi(SO2)(C6H4)(0C2H4)10O-结构的四羟基苯,加入反应器中(惰性气氛),加入2000g二硫化碳作溶剂,室温下搅拌5h;
步骤2,加热至65℃,搅拌反应6h,制得前驱体;
步骤3,加入0.5mol五异丙醇甲醚、0.5mol十(三氟甲基乙醇酸)甲酯、0.5mol甲氧基异丙酸、0.5mol甲氧基-十-三氟甲基乙酸,保持加热,继续搅拌反应12h;
步骤4,抽真空,直至溶剂和反应副产物甲醇全部除去,即制得聚合物P3;
步骤5,将2g聚合物P3和0.5gLiOTf,加热60℃混合均匀,倒在干净的平板玻璃上,冷却至室温,制得厚度为0.4mm的聚合物电解质膜SPE3。
将制备得到的聚合物电解质膜SPE3冲成φ16mm的圆片,组装成锂/SPE3/锂的扣式电池进行室温交流阻抗(EIS)和锂离子迁移数测试;组装成锂/SPE3/不锈钢的扣式电池进行室温循环伏安测试(CV)。其室温离子电导率为1.8*10-5S/cm,电化学窗口5V以上,室温锂离子迁移数为0.91。
实施例4
本实施例聚合物结构如图1所示,其制备方法如下:
步骤1,取1mol四甲氧基硼锂和1mol的含(CF3)(SO2)NLi(SO2)(C6H4)(0C2H4)5O-结构的四羟基苯,加入反应器中(惰性气氛),加入1500g甲苯作溶剂,室温下搅拌5h;
步骤2,加热至110℃,搅拌反应7h,制得前驱体;
步骤3,加入0.2mol五丙二醇单甲醚、0.2mol十乙二醇单甲醚,保持加热,继续搅拌反应9h;
步骤4,抽真空,直至溶剂和反应副产物甲醇全部除去,即制得聚合物P4;
步骤5,将5g聚合物P4和1.4gLiTFSI,加热80℃混合均匀,倒在干净的平板玻璃上,冷却至室温,制得厚度为0.45mm的聚合物电解质膜SPE3。
将制备得到的聚合物电解质膜SPE3冲成φ16mm的圆片,组装成锂/SPE3/锂的扣式电池进行室温交流阻抗(EIS)和锂离子迁移数测试;组装成锂/SPE1/不锈钢的扣式电池进行室温循环伏安测试(CV)。其室温离子电导率为2.8*10-5S/cm,电化学窗口5V以上,室温锂离子迁移数为0.96。
对比例1
称取6g聚环氧乙烷(MW=600000)、2.2gLiTFSI,加入40ml乙腈,密封45℃搅拌12h,倒在干净的平板玻璃上,制得厚度为0.5mm的聚合物电解质膜SPEO。采用与实施例1相同的方法将聚合物电解质膜SPEO组装成扣电,测得其室温离子电导率为2.3*10-7S/cm,电化学窗口约3.85V,室温锂离子迁移数为0.21。
由上述本发明实施例1-4与对比例1数据对比可知,本发明合物电解质电化学窗口较宽,含有柔性链段和苯环刚性结构,既保证了电解质的可塑性,同时又增大了机械强度;柔性连段含有大量醚氧键,能够传导锂离子,而刚性结构中包含氟、三氟甲基、磺酰亚胺等电子离域性较强的基团,能够促进锂离子的解离,能提升离子电导率;同时,该聚合物电解质为聚阴离子型单离子导体,具有较高的锂离子迁移数。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
2.如权利要求1所述的聚合物固体电解质,其特征在于,所述锂盐为六氟磷酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、双(氟磺酰)亚胺锂、双(三氟甲基磺酰)亚胺锂、三氟甲磺酸锂、四氟硼酸锂、高氯酸锂、(氟磺酰)三氟甲基磺酰亚胺锂、四氯铝酸锂、六氟砷酸锂中的至少一种。
3.如权利要求1所述的聚合物固体电解质,其特征在于,所述聚合物中醚氧和锂盐的摩尔比为(1-100):1。
4.如权利要求3所述的聚合物固体电解质,其特征在于,所述聚合物中醚氧和锂盐的摩尔比为(10-20):1。
5.一种如权利要求1所述的聚合物固体电解质的制备方法,其特征在于,包括以下步骤:
步骤1,取四甲氧基硼锂和含R5结构的四羟基苯,加入反应器中,加入溶剂,室温下搅拌1-4h;其中,四甲氧基硼锂和含R5结构的四羟基苯的摩尔比为1:1;其中溶剂的用量为四甲氧基硼锂和含R5结构的四羟基苯总量的2-20倍;
步骤2,加热至40-100℃,搅拌反应1-10h,制得前驱体;
步骤3,加入R1、R2所对应的一元醇和R3、R4对应的一元羧酸或酯,保持加热,继续搅拌反应1-10h;其中,一元醇和四甲氧基硼锂的摩尔比为1-2:1000,一元羧酸和四甲氧基硼锂的摩尔比为1-2:1000;
步骤4,抽真空,直至溶剂和反应副产物全部除去,即制得聚合物;
步骤5,取质量比为(10-20):1的所述聚合物和所述锂盐加热40-120℃混合均匀,即制得所述聚合物电解质。
6.如权利要求5所述的聚合物固体电解质的制备方法,其特征在于,所述溶剂为去离子水、乙醚、甲醇、苯、甲苯、二甲苯、氯仿、二硫化碳、乙腈、丙酮、N,N-二甲基吡咯烷酮、N,N-二甲基甲酰胺中的一种或多种。
7.一种如权利要求1所述的聚合物电解质的应用,其特征在于,所述聚合物电解质与有机溶剂、无机填料及其他聚合物中的至少一种进行复合,得到复合电解质。
8.如权利要求7所述的聚合物电解质的应用,其特征在于,所述有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、γ-丁内酯、二氧五环、四氢呋喃、二甲基三幅乙酰胺、二甲基亚砜中的至少一种;所述无机填料氧化物固体电解质、硫化物固体电解质、氧化亚硅、二氧化硅、氧化钛、氧化锆、氧化铝、勃姆石中的至少一种。
9.如权利要求7所述的聚合物电解质的应用,其特征在于,所述其他聚合物为聚偏二氟乙烯、聚偏二氟乙烯-六氟丙烯共聚物、聚丙烯酸、聚丙烯腈、聚甲基丙烯碳酸甲酯、聚环氧乙烷、聚乙烯、聚丙烯、聚酰胺、聚酰亚胺、聚乙烯醇、聚乙烯缩丁醛中的至少一种。
10.如权利要求7所述的聚合物电解质的应用,其特征在于,所述聚合物电解质用于制备锂离子电池或金属锂电池。
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