WO2014101460A1 - 功能化氯化胆碱离子液体、其制备方法及其在电化学储能器件中的应用 - Google Patents
功能化氯化胆碱离子液体、其制备方法及其在电化学储能器件中的应用 Download PDFInfo
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- WO2014101460A1 WO2014101460A1 PCT/CN2013/082892 CN2013082892W WO2014101460A1 WO 2014101460 A1 WO2014101460 A1 WO 2014101460A1 CN 2013082892 W CN2013082892 W CN 2013082892W WO 2014101460 A1 WO2014101460 A1 WO 2014101460A1
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- WIPO (PCT)
- Prior art keywords
- ionic liquid
- choline chloride
- functionalized
- room temperature
- solvent
- Prior art date
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 55
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 title claims abstract description 38
- 235000019743 Choline chloride Nutrition 0.000 title claims abstract description 38
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 title claims abstract description 38
- 229960003178 choline chloride Drugs 0.000 title claims abstract description 38
- 238000012983 electrochemical energy storage Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 239000002001 electrolyte material Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 239000011829 room temperature ionic liquid solvent Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- -1 alkaline earth metal salts Chemical class 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000005349 anion exchange Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002000 Electrolyte additive Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 description 19
- MYNNBUAEFSCZDG-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide trimethyl(2-trimethylsilyloxyethyl)azanium Chemical compound C[N+](C)(C)CCO[Si](C)(C)C.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F MYNNBUAEFSCZDG-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 13
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 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 description 8
- 238000000034 method Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 150000003841 chloride salts Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XFXJXURAALDGSW-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;2-hydroxyethyl(trimethyl)azanium Chemical compound C[N+](C)(C)CCO.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XFXJXURAALDGSW-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- VHSLGFZDYCMVHY-UHFFFAOYSA-N boric acid;oxalyl difluoride Chemical compound OB(O)O.FC(=O)C(F)=O VHSLGFZDYCMVHY-UHFFFAOYSA-N 0.000 description 2
- LFOBOFBSSXPQGD-UHFFFAOYSA-N chloro-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)Cl LFOBOFBSSXPQGD-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910014421 LiNi1/3Mn1/3CO1/3 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229940075419 choline hydroxide Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940112042 peripherally acting choline derivative muscle relaxants Drugs 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- RBYFNZOIUUXJQD-UHFFFAOYSA-J tetralithium oxalate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RBYFNZOIUUXJQD-UHFFFAOYSA-J 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- JBVFFUNQEWRSCL-UHFFFAOYSA-M trimethyl(2-propoxyethyl)azanium;chloride Chemical compound [Cl-].CCCOCC[N+](C)(C)C JBVFFUNQEWRSCL-UHFFFAOYSA-M 0.000 description 1
- WUDMGEZUZOUASN-UHFFFAOYSA-N trimethyl(2-trimethylsilyloxyethyl)azanium Chemical compound C[N+](C)(C)CCO[Si](C)(C)C WUDMGEZUZOUASN-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
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- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
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- C—CHEMISTRY; METALLURGY
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- C07C255/00—Carboxylic acid nitriles
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- C07C255/16—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same carbon atom of an acyclic carbon skeleton
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
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- 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
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Abstract
本发明公开了式I所示的功能化氯化胆碱离子液体制备方法及其在电化学储能器件中的应用,作为电解质材料或添加剂应用于锂离子电池和超级电容器。所述离子液体电解质材料有较好的生物相容性、阻燃性,具有高的离子电导率、低粘度和宽电化学窗口。其中R1选自如下基团:(CH2=CH-(CH2)n)->CN(CH2)n-、或R2
3Si-,其中R2选自CH3-(CH2)m-,n选自1〜3的整数,m选自0〜2的整数;或其中一个R2为(CH3)3Si-O-。阴离子A选自如下基团:Cl-、Br-、I-、BF4-、NO3-、SO4
2-、CF3COO-、CF3SO3
-、(CF3SO2)2N-、PF6
-、BF2C2O4
-、或者B(C2O4)2-。
Description
功能化氯化胆碱离子液体、 其制备方法及其在电化学储能器件中的应用 技术领域
本发明涉及化学技术领域, 尤其涉及功能化的氯化胆碱室温离子液体材料, 其制备方法及其作为电解质材料或添加剂在电化学储能器件中的应用。
技术背景
目前,锂离子电池产业中所使用的电解质材料主要是环状碳酸酯和线型碳酸 酯类化合物的多元溶剂体系和 LiPF6锂盐, 电解质体系的工作模式在技术上仍然 存在安全性隐患,其主要原因是碳酸酯类有机电解质材料具有很高的挥发性和可 燃性。 在要求高安全性、 大容量和高倍率放电的混合动力和全电汽车应用领域, 安全性问题是制约这些材料应用的重要因素。因此, 国内外都在积极地研究开发 安全、 有效和环境友好的新一代有机电解质材料。
在室温或室温附近温度下呈液态的由离子构成的物质, 称为室温离子液体、 室温熔融盐、 有机离子液体等, 但倾向于简称离子液体。 由于其不易挥发, 不易 燃, 良好的热稳定性、 好的化学和电化学稳定性, 在绿色化学、 工业催化、 工业 溶剂等方面具有广泛的应用前景。因为离子液体的高安全、高电化学稳定等特性, 因此使用离子液体作为锂离子电池的电解液的研究在活跃地进行。
用于锂离子电池的离子液体电介质材料, 可以分为两种: 一种是离子液体的 锂盐溶体; 另一种是离子液体的锂盐熔体再加上相应的添加剂。第一代的离子液 体是以 A1C 为阴离子的有机熔盐,这种离子液体容易水解,与水反应放出 HC1, 所以对于第一代离子液体锂离子电池中的应用研究停留在此。第二代的离子液体 是以咪唑类阳离子为正离子和氟化的无机或者有机阴离子为负离子的有机室温 熔盐, 这种离子液体表现出不足的电化学还原稳定性, 因此在高能电池中不被认 为是有商业应用前景的。第三代离子液体使用非咪唑类阳离子和氟化的无机或有 机阴离子。 目前最适合于锂离子电池的离子液体是 N,N-二烷基哌啶 (专利 JP2006260952) 。 但是这些离子液体也致使锂离子电池的输出功率大为下降,因 为这些高电化学稳定性的离子液体有高的粘度,与传统碳酸酯类电解质相比这使 得锂离子传导速率大为下降 ( 0. Borodinet al. J. of Phydical Chemistry B, 2006, 110(34), pp. 16879-16886) 。 离子液体基电解质锂离子电池与传统碳酸酯基电解
质锂离子电池相比如今还是输出功率小, 充电容量也比较小。 Lee et al. (Electrochem. Comm. 8 (2006)460)报道过使用 N上带有酯基的咪唑离子液体作为 锂离子电池电解质提高了锂离子电导率和锂离子的扩散速率。但是这些咪唑离子 液体电化学稳定性不足。 R. West等在专利 US7679884B2和 US2009088583-A1 中,报道了硅基季膦和硅基季胺类离子液体, 这些离子液体显示出改善的电化学 稳定性, 但是仍有较高的粘度。
氯化胆碱在细胞发挥功能时起非常重要的作用,它的生物合成和分解调控细 胞的生命活动具有优秀的生物相容性, 并且可以生物降解。此外, 氯化胆碱作为 伺料添加剂等等, 实现了工业化生产, 是很便宜的原料。 另外, 氢氧化胆碱曾用 作 aldol縮合反应的碱性催化剂。 具有低熔点的胆碱衍生物是多种研究的题目, 一些胆碱的类似物已经合成出来 [Pemak, Chmistry-A Eurpean Journal, 2007, 13(24),pp. 6817-6827] [Me3NC2H4Y][Cl] (Y=OH, CI, OC(0)Me, OC(O)Ph)和 MC12 (M=Zn, Sn) 是室温附近导电的粘稠液体, 常用来做电沉积。 但是, 基于氯化 胆碱的离子液体还没有作为锂离子电池的电解液或者添加剂使用的。
发明内容:
本发明的目的是提供一种新型的功能化氯化胆碱室温离子液体。
本发明的另一个目的是提供上述功能化氯化胆碱室温离子液体在电化学储 能器件中的应用。
本发明是通过以下技术方案予以实现的:
式 I
其中 R1选自如下基团: (CH2=CH-(CH2)n) -、 CN(CH2)n -、 或 R2 3Si-, R2选自 CH3-(CH2)m-,n选自 1〜3的整数, m选自 0〜2的整数; 或其中一个 R2为 (CH3) 阴离子 A选自如下基团: CI-、 Br -、 I-、 BF4-、 NO3 S04 2-、 CF3COO CF3SO3 ( CF3SO2) 2N―、 PF6—、 BF2C204—、 或 B ( C2O4) 2。
式 I化合物制备方法有方法一和方法二。 举例说明如下。
方法一: 在冰浴冷却条件下, 氯化胆碱与等摩尔量氢氧化钠在乙腈溶剂中室 温反应 20分钟, 然后滴加 1.1倍摩尔量的 -X卤代烷烃回流反应 8小时, 或氯 化胆碱与等摩尔量有机硅试剂(如六甲基二硅氮烷、五甲基氯二硅氧烷和三甲基 氯硅烷) 回流反应 16小时。 反应后过滤除去固体, 旋转蒸发除去溶剂, 然后用 二氯甲烷和乙醚为溶剂重结晶得到 R1-和 R Si-功能化氯化胆碱离子液体。 此功 能化氯化胆碱离子液体与等摩尔量的碱金属或碱土金属盐 MA (阴离子 A为 BF4-、 N03-、 S04 2-、 CF3COO CF3SO3 ( CF3SO2 ) 2N -、 PF6-、 BF2C204-、或者 B ( C2O4 ) 2" ) 溶于水或其他溶剂进行阴离子交换, 搅拌反应 4-6小时后, 使用二氯甲烷溶 剂萃离子取交换后产物, 除去溶剂和干燥后得到目标离子液体。
方法一反应式如下所示:
CH Θ
© ?H2 L NaOH
HOCH2CH2-N-CH: R1-OCH2CH2-N-CH
2. R,X
Θ
CI
LiA
Θ
anion exchange a
R1 = CH2=CH(CH2)n;SiR2 3; CN(CH2)n
方法二: 在 R1为 R Si-的情况下, 室温将氯化胆碱和等摩尔量的碱金属或 碱土金属盐 MA (阴离子 A为 BF4-、 N03-、 SO42-、 CF3COO CF3SO3 ( CF3SO2) 2N -、 PF6-、 BF2C204-、 或者 B ( C2O4) 2" ) 溶于水或其他溶剂进行阴离子交换, 搅拌反应 4-6小时后, 使用二氯甲烷或者其他溶剂萃取, 除去溶剂后得到阴离子 交换后的氯化胆碱离子液体。在第二步反应中, 阴离子交换后的氯化胆碱离子液 体与相应的有机硅试剂(如六甲基二硅氮烷、五甲基氯二硅氧烷和三甲基氯硅烷) 回流反应 16小时, 抽真空除去残余低沸点物质后得到目标离子液体。
方法二反应式如下所示:
®
© CH2 CH:
LiA
HOCH2CH2-N-CH3 HOCHpCH -N-CH
anion exchange CH
CH3 3
Θ CI
Θ
R,X
OCHpCH -N-CH
Ri = SiR2 3
本发明的另一个目的是提供上述功能化的氯化胆碱离子液体作为电解质材 料或者添加剂在电化学储能器件中的应用。
上述室温离子液体电解质材料可用做季胺盐型离子液体电解质材料,作为电 解质材料或添加剂应用于锂离子电池。所述锂离子电池负极可选自石墨,钛酸锂, 纳米硅中的一种,正极可选自钴酸锂,磷酸铁锂, LiNi1/3Mn1/3Co1/302、 /LiNi0.6Mn0.602 和 LiMn02中的一种。
上述室温离子液体电解质材料可用做季胺盐型离 Θ A子液体电解质材料,作为电 解质材料或添加剂应用于电化学超级电容器。所述电化学超级电容器的电极选自 活性炭、 金属氧化物、 导电聚合物。
本发明的有益效果是: 跟现有技术相比,所述离子液体电解质材料有较好的 生物相容性, 具有阻燃性, 以及高离子电导率、 低粘度和宽电化学窗口。 Θ A 附图说明:
图 1是 2-烯丙氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐的线性伏安 扫描图;
图 2是以 0.8 M 双(三氟甲基磺酰基)亚胺锂的 2-烯丙氧基乙基三甲基铵 双(三氟甲基磺酰基)亚胺离子液体为电解质的钛酸锂锂金属电池的循环性能 (■ - 比容量, 库仑效率);
图 3是以 0.8 M 双(三氟甲基磺酰基)亚胺锂的 2-烯丙氧基乙基三甲基铵 双(三氟甲基磺酰基)亚胺离子液体添加 10%碳酸亚乙烯酯添加剂为电解质的石 墨半电池的循环性能 (■-放电比容量, 充电比容量);
图 4是以 0.8 M 双(三氟甲基磺酰基)亚胺锂的 2-烯丙氧基乙基三甲基铵 双(三氟甲基磺酰基)亚胺离子液体添加 10%碳酸亚乙烯酯添加剂为电解质的磷 酸铁锂锂金属电池的循环性能 (■ -比容量, 库仑效率);
图 5是 2-三甲基硅氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐的线性 伏安扫描图;
图 6是 2-三甲基硅氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐的电导 率随温度变化图;
图 7是 2-三甲基硅氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐超级电 容循环伏安性能;
图 8是 2-三甲基硅氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐添加 AN 超级电容循环伏安性能;
图 9是 2-三甲基硅氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐添加 90%AN超级电容充放电曲线;
图 10是 2-三甲基硅氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐添加 90%AN超级电容大电流充放电性能。
具体实施方式:
以下通过实施例对本发明做进一步说明, 但不构成对本发明保护范围的限 制。
实施例 1: 2-烯丙氧基乙基三甲基铵氯盐的合成
在冰浴冷却条件下, 0.5 mol 氯化胆碱和 0.5 mol 氢氧化钠在乙腈溶剂中室 温反应 20分钟,然后滴加 0.55 mol摩尔量的烯丙溴, 回流反应 8小时。 反应后过 滤除去固体, 旋转蒸发除去溶剂, 然后用二氯甲烷和乙醚为溶剂重结晶得到 2- 烯丙氧基乙基三甲基铵氯盐: NMR (CDC ): σ 3.47 (m, 9H, +N(CH3)3), 3.90, 3.94 (dd, 4H, OCH2CH20), 4.02 (m, 2H, CH2=CH-CH2-0), 5.23 (ddq, 2H, CH2=CH-CH2-0), 5.84 (ddt, 1H, CH2=CH-CH2-0); 13C NMR (CDCb): σ 54.61, 63.98, 65.68, 72.21, 118.43, 133.27.
实施例 2: 2-烯丙氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐的合成 0.4 mol 2-烯丙氧基乙基三甲基铵氯盐(实施例 1的产物)与等摩尔量双(三 氟甲基磺酰基)亚胺锂溶于水进行阴离子交换, 机械搅拌 4-6小时后, 使用二氯 甲烷溶剂萃取离子取交换后产物,除去溶剂和干燥后得目标离子液体 2-烯丙氧基 乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐: NMR CDCls): σ 3.19 (ηι,9Η, +N(CH3)3), 3.58, 3.86 (m, 4H, OCH2CH20), 4.05 (m, 2H, CH2=CH-CH2-0), 5.28 (ddq, 2H, CH2=CH-CH2-0), 5.85 (m, 1H, CH2=CH-CH2-0); 13C NMR (CDCb): σ
54.65, 63.50, 66.20, 72.31, 118.70, 132.97.
实施例 3: 胆碱双 (三氟甲基磺酰基) 亚胺盐的合成
室温下, 将 0.5 mol氯化胆碱和等摩尔量的双 (三氟甲基磺酰基) 亚胺锂溶 于水进行离子交换, 机械搅拌 4-6小时后使用二氯甲烷萃取, 除去溶剂后得到阴 离子交换后的胆碱双 (三氟甲基磺酰基) 亚胺盐: NMR (300MHz, CDCb): δ 3.16 (s, 9H, +N(CH3)3), 3.40 (s, 1H, OH), 3.45 (s, 2H, CH20), 4.03 (s, 2H, CH2N+); 13C NMR (300MHz, CDC ): 54.06, 56.21, 67.66, 119.75.
实施例 4: 2-三甲基硅氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐的合 成
在 0.4 mol胆碱双 (三氟甲基磺酰基) 亚胺盐 (实施例 3的产物) 中, 滴入
0.4 mol六甲基二硅氮烷回流反应 16小时, 抽真空除去残余低沸点物质后得到目 标离子液体 2-三甲基硅氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐: NMR (300MHz, CDC ): δ 0.16 (s, 9Η, Si(CH3)3), 3.22 (s, 9H, +N(CH3)3), 3.50 (s, 2H, CH20), 4.00 (s, 2H, CH2N+); 13C NMR (300MHz, CDC ): -1.04, 54.55, 56.81, 67.86, 119.87.
实施例 5: 2-烯丙氧基乙基三甲基铵双草酸硼酸盐的合成
2-烯丙氧基乙基三甲基铵双草酸硼酸盐是使用与实施例 2相似的方法合成 的。 0.4 mol 2-烯丙氧基乙基三甲基铵氯盐 (实施例 1的产物) 与等摩尔量双草 酸硼酸锂溶于水进行阴离子交换, 机械搅拌 4-6小时后, 使用二氯甲烷溶剂萃取 离子取交换后产物,除去溶剂和干燥后得目标离子液体 2-烯丙氧基乙基三甲基铵 双草酸硼酸盐: NMR (CDCb): σ 3.44 (m, 9H, +N(CH3)3), 3.89, 3.91 (m, 4H, OCH2CH2O), 4.04 (m, 2H, CH2=CH-CH2-0), 5.28 (ddq, 2H, CH2=CH-CH2-0), 5.87 (m, 1H, CH2=CH-CH2-0); 13C NMR (CDCb): σ 54.67, 63.63, 66.92, 72.37, 118.85, 132.01, 158.89。
实施例 6: 2-烯丙氧基乙基三甲基铵双氟草酸硼酸盐的合成
2-烯丙氧基乙基三甲基铵双氟草酸硼酸盐是使用与实施例 2相似的方法合成 的。 0.4 mol 2-烯丙氧基乙基三甲基铵氯盐 (实施例 1的产物) 与等摩尔量双氟 草酸硼酸锂溶于水进行阴离子交换, 机械搅拌 4-6小时后, 使用二氯甲烷溶剂萃 取离子取交换后产物,除去溶剂和干燥后得目标离子液体 2-烯丙氧基乙基三甲基
铵双氟草酸硼酸盐: ¾ NMR (CDC ): σ 3.38 (m, 9H, +N(CH3)3), 3.80, 3.89 (m, 4H, OCH2CH2O), 4.03 (m, 2H, CH2=CH-CH2-0), 5.27 (ddq, 2H, CH2=CH-CH2-0), 5.87 (m, 1H, CH2=CH-CH2-0); 13C NMR (CDCb): σ 54.64, 63.67, 66.72, 72.22, 118.67, 133.05, 160
实施例 腈丙氧基乙基三甲基铵氯盐的合成
2-腈丙氧基乙基三甲基铵氯盐是使用与实施例 1相似的方法合成的。在冰浴 冷却条件下, 0.5 mol 氯化胆碱和 0.5 mol氢氧化钠在乙腈溶剂中室温反应 20分 钟, 然后滴加 0.55 mol腈丙基溴回流反应 8小时, 旋转蒸发除去溶剂, 然后用甲 醇和乙醚为溶剂重结晶得到 2-腈丙氧基乙基三甲基铵氯盐: ^ NMR^CDCb): σ 3.40 (m, 9H, +N(CH3)3), 3.88, 3.94 (dd, 4H, OCH2CH2O), 3.68 (m, 2H, CNCH2-CH2-O), 2.72 (m, 2H, CN-CH7-CH7-O 电化学储能性能说明
实施例 8: 2-烯丙氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐性能 下面, 以 2-烯丙氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐(实施例 2 所得产物)为例,对本发明功能化氯化胆碱室温离子液体的电化学储能性能进行 说明。
2-烯丙氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐的电化学窗口测定使 用三电极玻璃电池体系, 以 Pt丝为工作电极, Li丝为对电极和另一 Li丝为参考 电极。 所得线性伏安扫描图如图 1示, 电化学窗口为 0.5-5.2V, 优于咪唑类离子 液体(通常 4V, A. Lewandowski, Journal of Power Sources 194 (2009) 601-609)。
2-烯丙氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐中参入 0.8 M双(三 氟甲基磺酰基)亚胺锂后得到没有添加剂电解液, 以此电解液、钛酸锂为正极的 锂金属电池的循环性能如图 2所示。 循环稳定, 容量保持在 145mAh/g不衰减。
2-烯丙氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐中参入 0.8 M双(三 氟甲基磺酰基) 亚胺锂和 10%碳酸亚乙烯酯后得到有添加剂的电解液, 以此电 解液、 石墨为正极的半电池的电池的循环性能如图 3 所示。
2-烯丙氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐中参入 0.8 M双(三 氟甲基磺酰基) 亚胺锂和 10%碳酸亚乙烯酯后得到有添加剂的电解液, 以此电
解液、 磷酸铁锂为正极的锂金属电池的电池的循环性能如图 4所示。
实施例 9: 2-三甲基硅氧基乙基三甲基铵双 (三氟甲基磺酰基) 亚胺盐性能 下面, 以 2-三甲基硅氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐(实施 例 4所得产物)为例,对本发明功能化氯化胆碱室温离子液体的电化学储能性能 进行说明。
2-三甲基硅氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐的电化学窗口测 定使用三电极玻璃电池体系, 以 Pt丝为工作电极, Li丝为对电极和另一 Li丝为 参考电极。其线性伏安扫描图如图 5所示, 电化学窗口为 0-5.3V。还原电位低于 咪唑类离子液体(咪唑类通常在 lV vs. Li/Li+),氧化电位也高于咪唑类离子液体 (通常 4 V vs. Li/Li+)。 并且由于还原电位在 0V, 2-三甲基硅氧基乙基三甲基铵 双(三氟甲基磺酰基)亚胺盐室温离子液体适用于锂金属电池和高压锂金属电池。
2-三甲基硅氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐的电导率测定使 用玻璃碳电极电池体系。 电导率随温度变化如图 6所示。
下面, 以 2-三甲基硅氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐(实施 例 4所得产物)为例,对本发明功能化氯化胆碱室温离子液体的电化学超级电容 器性能进行说明。
发明人研究了纯 2-三甲基硅氧基乙基三甲基铵双(三氟甲基磺酰基)亚胺盐 作为电解液, 活性炭电极组成的对称型超级电容器, 以 5 mv/s的扫描速度, 在不 同截止电压 (1-5 V)内的循环伏安性能 (图 7)。 该电解液在 1-4 V范围内, 循环伏安 曲线呈对称的矩形, 表明活性炭电极具有很好的可逆性, 显示出良好的双电层电 容特性。
图 8为低粘度 A 的添加对其循环伏安性能的影响, 随着 AN 添加量的增加 (20%〜90%) 循环伏安曲线呈现更好的矩形。 因此我们选择添加体积分数为 90% 的 AN/2-三甲基硅氧基乙三甲基铵双(三氟甲基磺酰基)亚胺盐作为电解液, 活性炭电极组成的对称型超级电容器, 来研究其电容器性能。
图 9为 90% 的 AN/2-三甲基硅氧基乙三甲基铵双(三氟甲基磺酰基)亚胺盐 作为电解液, 活性炭电极组成的对称型超级电容器, 在 0.2 A/g 电流密度下的恒 电流充放电曲线。 活性炭电极在 0〜3.5 V电压范围内放电曲线呈现线性变化, 没 有见到明显的析气现象和损坏。 其电压范围远高于商用四乙基四氟硼酸胺
(Et4NBF4)/PC电解液 (0〜2.7V)。
图 10为 90%的 AN/2-三甲基硅氧基乙三甲基铵双 (三氟甲基磺酰基) 亚胺 盐作为电解液, 活性炭电极组成的对称型超级电容器的倍率性能。当电流密度为 0.2 A-g 1 时, 活性炭电极的比电容为 90 F -1; 电流密度增大到 2A_g- 1 时, 比电 容仍能达到 70 F-g"1, 表现非常好的大电流充放电性能。
Claims
式 I
其中 R1选自如下基团: (CH2=CH-(CH2)n)-、 CN(CH2)n-、 或 R2 3Si -, R2选自 CH3-(CH2)m-,n选自 1〜3的整数, m选自 0〜2的整数; 或其中一个 R2为 (CH3)
2、 如权利要求 1所述的功能化氯化胆碱离子液体, 其特征在于其阴离子 A 选自如下基团: CI-、 Br -、 I-、 BF4-、 N03-、 SO42-、 CF3COO CF3SO3 (CF3S02)
2N -、 PF6-、 BF2C204-、 或 B (C2O4) 2。 Θ A
3、 权利要求 1所述的功能化氯化胆碱离子液体的制备方法, 其特征在于: 在冰浴冷却条件下, 氯化胆碱和等摩尔量氢氧化钠在乙腈溶剂中室温反应 20分 钟, 然后滴加 1.1倍摩尔量的卤代烷烃, 回流反应 8小时; 或氯化胆碱与等摩尔 量有机硅试剂回流反应 16小时; 反应后过滤除去固体, 旋转蒸发除去溶剂, 然 后用二氯甲烷和乙醚为溶剂重结晶得到功能化氯化胆碱离子液体,此功能化氯化 胆碱离子液体与等摩尔量的碱金属或碱土金属盐溶于水或其他溶剂进行阴离子 交换, 搅拌反应 4-6小时后, 使用二氯甲烷溶剂萃离子取交换后产物, 除去溶剂 和干燥后得到目标离子液体。
4、 权利要求 1所述的功能化氯化胆碱室温离子液体的制备方法, 其特征在 于: 室温下,将氯化胆碱和等摩尔量的碱金属或碱土金属盐溶于水或其他溶剂进 行阴离子交换, 搅拌反应 4-6小时后, 使用二氯甲烷或者其他溶剂萃取, 除去溶 剂后得到阴离子交换后的氯化胆碱离子液体;阴离子交换后的氯化胆碱离子液体 与有机硅试剂回流反应 16小时, 抽真空除去残余低沸点物质后得到目标离子液 体。
5、 权利要求 1所述的功能化氯化胆碱室温离子液体作为电解质材料或者添 加剂在电化学储能器件中的应用。
6、 如权利要求 5所述的功能化的氯化胆碱室温离子液体在电化学储能器件
中的应用,其特征在于所述功能化氯化胆碱室温离子液体用做季胺盐型离子液体 电解质材料, 作为电解质材料或添加剂应用于锂离子电池或超级电容器。
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