CN111574734A - 一种可自愈固态电解质薄膜及其制备方法和应用 - Google Patents
一种可自愈固态电解质薄膜及其制备方法和应用 Download PDFInfo
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- CN111574734A CN111574734A CN202010494821.0A CN202010494821A CN111574734A CN 111574734 A CN111574734 A CN 111574734A CN 202010494821 A CN202010494821 A CN 202010494821A CN 111574734 A CN111574734 A CN 111574734A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 32
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- 125000004386 diacrylate group Chemical group 0.000 claims description 24
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical group 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 125000005463 sulfonylimide group Chemical group 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 7
- AEXDMFVPDVVSQJ-UHFFFAOYSA-N trifluoro(trifluoromethylsulfonyl)methane Chemical group FC(F)(F)S(=O)(=O)C(F)(F)F AEXDMFVPDVVSQJ-UHFFFAOYSA-N 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 235000007686 potassium Nutrition 0.000 claims description 4
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- YSNLHLJYEBEKMC-UHFFFAOYSA-N P(O)(=O)(F)F.[Li] Chemical compound P(O)(=O)(F)F.[Li] YSNLHLJYEBEKMC-UHFFFAOYSA-N 0.000 claims description 2
- ZOGQGRQUKIZBQQ-UHFFFAOYSA-N [Li].B(O)(F)F.C(C(=O)O)(=O)O Chemical compound [Li].B(O)(F)F.C(C(=O)O)(=O)O ZOGQGRQUKIZBQQ-UHFFFAOYSA-N 0.000 claims description 2
- RTZKMGZSJBRJFI-UHFFFAOYSA-N boric acid;lithium Chemical compound [Li].OB(O)O RTZKMGZSJBRJFI-UHFFFAOYSA-N 0.000 claims description 2
- 230000037228 dieting effect Effects 0.000 claims description 2
- QGFUJXDXUWUFJG-UHFFFAOYSA-N lithium;perchloric acid Chemical compound [Li].OCl(=O)(=O)=O QGFUJXDXUWUFJG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 claims description 2
- ZIISGGOPQWHYDA-UHFFFAOYSA-N difluorooxyborinic acid Chemical compound B(O)(OF)OF ZIISGGOPQWHYDA-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 40
- 230000000379 polymerizing effect Effects 0.000 description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- 125000006309 butyl amino group Chemical group 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- DKUCZWFPWYNORJ-UHFFFAOYSA-M C(C(=O)O)(=O)[O-].B(OF)(OF)O.[Li+] Chemical compound C(C(=O)O)(=O)[O-].B(OF)(OF)O.[Li+] DKUCZWFPWYNORJ-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108010061711 Gliadin Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OKVJWADVFPXWQD-UHFFFAOYSA-N difluoroborinic acid Chemical compound OB(F)F OKVJWADVFPXWQD-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical group [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical group [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明是一种可自愈固态电解质薄膜,所述可自愈固态电解质薄膜包括如下原料:单体、交联剂、引发剂以及电解质盐,所述交联剂与所述单体的摩尔比为0.1%,所述引发剂与所述单体的摩尔比为1%,所述电解质盐在所有原料的混合溶液中的浓度为0.1mol/L‑0.9mol/L。该薄膜的制备方法,包括如下步骤:(1)量取单体,再分别加入交联剂,引发剂及电解质盐,搅拌使其充分溶解得到透明溶液;(2)将步骤1中的溶液置于片状模具中,在紫外光下照射使其中单体交联固化,即可得到可自愈固态电解质薄膜。本发明所述的高拉伸、可自愈的固态电解质薄膜制备性能良好,工艺简单,在柔性可拉伸电子器件领域具有广阔的应用前景。
Description
技术领域
本发明属于固态电解质制备技术领域,具体的说是涉及一种可自愈固态电解质薄膜及其制备方法和应用。
背景技术
近年来,诸如电子皮肤、智能织物、植入式医疗器械等柔性可穿戴电子器件受到日益广泛的关注,因此对可穿戴的柔性电子器件的需求也随之增高,可穿戴的柔性电子器件要求相关的器件具备优异的柔性和稳定性,但是,作为柔性电子器件中重要的组成部分,柔性、可拉伸、可自愈的电解质薄膜的制备依然面对很大的挑战。目前电解质薄膜中研究较多的以水凝胶电解质薄膜为主,水凝胶电解质具有良好的电导率,然而水凝胶电解质弹性模量较小,且其中水分易挥发,较易造成相关柔性电子器件的失效,与水凝胶电解质相比,固态电解质内部不含有液态组分,具有很好的环境稳定性。
固态电解质薄膜具有良好的机械性能、柔性以及很好的可组装性,其中聚氧化乙烯(PEO)应用较为广泛,然而,聚合物的共性问题是结晶程度较高,导致其电导率较低,且不具备可穿戴电子器件所需要的可拉伸性,因此,降低聚合物的结晶度,进而增加相关固态电解质薄膜的电导率和拉伸性成为制备具有优良性质的固态电解质的研究热点。一般的途径是在体系中加入增塑剂,或者采用与其他聚合物共聚等方法对固态电解质进行改性,但是以上制备方法成膜性较差,导致电化学性能不稳定。
作为一种可穿戴的器件,柔性电子器件的发展要求其中各单元具有一定的自愈性,自愈性的引入会提高相关器件使用的安全性和稳定性,然而以PEO为代表的固态电解质因为内部聚合物链段上并不包含相关基团,不能引入动态非共价键作用,从而不能有效的获得自愈功能。
发明内容
为了解决上述问题,本发明提供了一种一种可自愈固态电解质薄膜及其制备方法和应用,该可自愈固态电解质薄膜由单体聚合得到,其中所述单体为液态丙烯酸酯小分子,可作为溶剂溶解交联剂,引发剂及电解质盐,溶解及混合均匀后在紫外光照下聚合得到固态电解质薄膜。经由单体聚合得到的聚合物链上包含氨基甲酸酯基团,可在聚合物链间形成氢键,因为氢键为一动态可逆非共价键,所以聚合得到具有良好自愈性质的固态电解质薄膜。
为了达到上述目的,本发明是通过以下技术方案实现的:
本发明是一种可自愈固态电解质薄膜,所述可自愈固态电解质薄膜包括如下原料:单体、交联剂、引发剂以及电解质盐,所述交联剂与所述单体的摩尔比为0.1%,所述引发剂与所述单体的摩尔比为1%,所述电解质盐在所有原料的混合溶液中的浓度为0.1mol/L-0.9mol/L。
本发明的进一步改进在于:所述单体为丙烯酸酯,所述交联剂为聚二丙烯酸酯或聚乙二醇二丙烯酸酯,所述引发剂为1-羟基环己基苯基酮,所述电解质盐为锂盐、钠盐、钾盐或铵盐。
本发明的进一步改进在于:单体丙烯酸酯为液态,可作为溶剂溶解其余组分,液态丙烯酸酯类单体中包含氨基甲酸酯基团,氨基甲酸酯基团是一种可自愈基团,所述锂盐为双三氟甲基磺酰亚胺锂、三氟甲磺酰-全氟丁基磺酰亚胺锂、三氟甲磺酰-全氟丙基磺酰亚胺锂、双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、二草酸硼酸锂、草酸二氟硼酸锂、二氟磷酸锂、4,5-二氰基-2-三氟甲基咪哩锂、高氯酸锂或氯化锂,所述钠盐为双三氟甲磺酰亚胺钠、高氯酸钠、双氟磺酰亚胺钠、氯化钠、硝酸钠、氟硅酸钠或邻苯二甲酸钠,所述钾盐为双氟磺酰亚胺钾、氯化钾、硝酸钾或邻苯二甲酸氢钾,所述铵盐为四氟硼酸四乙基铵、氯化铵或硝酸铵。
本发明是一种可自愈固态电解质薄膜的制备方法,所述制备方法包括如下步骤:
(1)量取一定量的单体,再分别加入交联剂,引发剂及电解质盐,搅拌使其充分溶解得到透明溶液;
(2)将步骤1中配置好的溶液置于片状模具中,在紫外光下照射使其中单体交联固化,即可得到所述可自愈固态电解质薄膜。
本发明的进一步改进在于:所述步骤(1)中,所述交联剂与所述单体的摩尔比为0.1%,所述引发剂与所述单体的摩尔比为1%,所述电解质盐在所有原料的混合溶液中的浓度为0.1mol/L-0.9mol/L。
本发明的进一步改进在于:所述单体为丙烯酸酯,单体丙烯酸酯为液态,液态丙烯酸酯类单体中包含氨基甲酸酯基团,所述交联剂为聚二丙烯酸酯或聚乙二醇二丙烯酸酯,所述引发剂为1-羟基环己基苯基酮,所述电解质盐为锂盐、钠盐、钾盐或铵盐。
本发明的进一步改进在于:所述锂盐为双三氟甲基磺酰亚胺锂、三氟甲磺酰-全氟丁基磺酰亚胺锂、三氟甲磺酰-全氟丙基磺酰亚胺锂、双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、二草酸硼酸锂、草酸二氟硼酸锂、二氟磷酸锂、4,5-二氰基-2-三氟甲基咪哩锂、高氯酸锂或氯化锂,所述钠盐为双三氟甲磺酰亚胺钠、高氯酸钠、双氟磺酰亚胺钠、氯化钠、硝酸钠、氟硅酸钠或邻苯二甲酸钠,所述钾盐为双氟磺酰亚胺钾、氯化钾、硝酸钾或邻苯二甲酸氢钾,所述铵盐为四氟硼酸四乙基铵、氯化铵或硝酸铵。
本发明的进一步改进在于:所述步骤(2)中,在采用紫外光照射进行光固化时,所采用的紫外光波长为365 nm,照射功率为400 W,照射时间为1-60min。
一种可自愈固态电解质薄膜的应用,所述可自愈固态电解质薄膜用于柔性可拉伸传感器的电解质,所述柔性可拉伸传感器由可自愈固态电解质薄膜和连接在可自愈固态电解质薄膜两端的金属电极组成。
本发明的有益效果是:本发明所制备的固态电解质薄膜不仅具有良好的导电性和较高的拉伸性,而且表现出优异的可重复的自愈合性能,并且愈合后的固态电解质薄膜可保持和原有薄膜一致的力学性质和电化学行为;本发明所构建的柔性可拉伸传感器具有很好的柔性和可重复弯曲性;本发明所构建的柔性可拉伸传感器表现出了较好的敏感性和分辨不同种类外部刺激的能力。
本发明所述的高拉伸、可自愈的固态电解质薄膜制备性能良好,工艺简单,在柔性可拉伸电子器件领域具有广阔的应用前景。
附图说明
图1是本发明实施例1中固态电解质薄膜的应力-应变曲线。
图2是本发明实施例1中固态电解质薄膜的阻抗谱曲线。
图3是本发明实施例1中固态电解质薄膜在不同温度下重量变化曲线。
图4是本发明实施例1中固态电解质薄膜的自愈合照片。
图5是本发明实施例1-5中固态电解质薄膜的阻抗谱曲线。
图6是本发明实施例6中柔性可拉伸传感器的结构示意图。
图7是本发明实施例6中柔性可拉伸传感器在不同种类外部刺激下的阻抗谱曲线。
具体实施方式
以下将以图式揭露本发明的多个实施方式,为明确说明起见,许多实务上的细节将在以下叙述中一并说明。然而,应了解到,这些实务上的细节不应用以限制本发明。也就是说,在本发明的部分实施方式中,这些实务上的细节是非必要的。
本发明是一种可自愈固态电解质薄膜,该可自愈固态电解质薄膜包括如下原料:单体、交联剂、引发剂以及电解质盐,所述交联剂与所述单体的摩尔比为0.1%,所述引发剂与所述单体的摩尔比为1%,所述电解质盐在所有原料的混合溶液中的浓度为0.1mol/L-0.9mol/L,所述单体为丙烯酸酯,所述交联剂为聚二丙烯酸酯或聚乙二醇二丙烯酸酯,所述引发剂为1-羟基环己基苯基酮,所述电解质盐为锂盐、钠盐、钾盐或铵盐,单体丙烯酸酯为液态,可作为溶剂溶解其余组分,液态丙烯酸酯类单体中包含氨基甲酸酯基团,氨基甲酸酯基团是一种可自愈基团,所述锂盐为双三氟甲基磺酰亚胺锂、三氟甲磺酰-全氟丁基磺酰亚胺锂、三氟甲磺酰-全氟丙基磺酰亚胺锂、双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、二草酸硼酸锂、草酸二氟硼酸锂、二氟磷酸锂、4,5-二氰基-2-三氟甲基咪哩锂、高氯酸锂或氯化锂,所述钠盐为双三氟甲磺酰亚胺钠、高氯酸钠、双氟磺酰亚胺钠、氯化钠、硝酸钠、氟硅酸钠或邻苯二甲酸钠,所述钾盐为双氟磺酰亚胺钾、氯化钾、硝酸钾或邻苯二甲酸氢钾,所述铵盐为四氟硼酸四乙基铵、氯化铵或硝酸铵。
该可自愈固态电解质薄膜的制备方法包括如下步骤:
(1)量取2 mL的2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯,再分别加入0.0056克聚二丙烯酸酯或聚乙二醇二丙烯酸酯,0.02克1-羟基环己基苯基酮 及一定量的电解质盐双三氟甲烷磺酰亚胺锂,搅拌使其充分溶解得到透明溶液A;
(2)将步骤1中的溶液A注入到间隔为500μm~1500μm的玻璃模具中,紫外光照射条件下聚合1-60 min,得到可自愈固态电解质薄膜。
本发明的可自愈固态电解质薄膜用于柔性可拉伸传感器的电解质,所述柔性可拉伸传感器由可自愈固态电解质薄膜和连接在可自愈固态电解质薄膜两端的金属电极组成。
实施例1
本发明的可自愈固态电解质薄膜的制备方法包括如下步骤:
(1)量取2 mL的2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯,再分别加入0.0056克聚二丙烯酸酯或聚乙二醇二丙烯酸酯,0.02克1-羟基环己基苯基酮 及0.0574克的电解质盐双三氟甲烷磺酰亚胺锂,搅拌使其充分溶解得到透明溶液A;
(2)将步骤1中的溶液A注入到间隔为500μm~1500μm的玻璃模具中,紫外光照射条件下聚合1-60 min,得到可自愈固态电解质薄膜。
实施例2
本发明的可自愈固态电解质薄膜的制备方法包括如下步骤:
(1)量取2 mL的2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯,再分别加入0.0056克聚二丙烯酸酯或聚乙二醇二丙烯酸酯,0.02克1-羟基环己基苯基酮 及0.1723克的电解质盐双三氟甲烷磺酰亚胺锂,搅拌使其充分溶解得到透明溶液A;
(2)将步骤1中的溶液A注入到间隔为500μm~1500μm的玻璃模具中,紫外光照射条件下聚合1-60 min,得到可自愈固态电解质薄膜。
实施例3
本发明的可自愈固态电解质薄膜的制备方法包括如下步骤:
(1)量取2 mL的2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯,再分别加入0.0056克聚二丙烯酸酯或聚乙二醇二丙烯酸酯,0.02克1-羟基环己基苯基酮 及0.2871克的电解质盐双三氟甲烷磺酰亚胺锂,搅拌使其充分溶解得到透明溶液A;
(2)将步骤1中的溶液A注入到间隔为500μm~1500μm的玻璃模具中,紫外光照射条件下聚合1-60 min,得到可自愈固态电解质薄膜。
实施例4
本发明的可自愈固态电解质薄膜的制备方法包括如下步骤:
(1)量取2 mL的2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯,再分别加入0.0056克聚二丙烯酸酯或聚乙二醇二丙烯酸酯,0.02克1-羟基环己基苯基酮 及0.4019克的电解质盐双三氟甲烷磺酰亚胺锂,搅拌使其充分溶解得到透明溶液A;
(2)将步骤1中的溶液A注入到间隔为500μm~1500μm的玻璃模具中,紫外光照射条件下聚合1-60 min,得到可自愈固态电解质薄膜。
实施例5
本发明的可自愈固态电解质薄膜的制备方法包括如下步骤:
(1)量取2 mL的2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯,再分别加入0.0056克聚二丙烯酸酯或聚乙二醇二丙烯酸酯,0.02克1-羟基环己基苯基酮 及0.5168克的电解质盐双三氟甲烷磺酰亚胺锂,搅拌使其充分溶解得到透明溶液A;
(2)将步骤1中的溶液A注入到间隔为500μm~1500μm的玻璃模具中,紫外光照射条件下聚合1-60 min,得到可自愈固态电解质薄膜。
实施例6
本发明的可自愈固态电解质薄膜的制备方法包括如下步骤:
(1)量取2 mL的2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯,再分别加入0.0056克聚二丙烯酸酯或聚乙二醇二丙烯酸酯,0.02克1-羟基环己基苯基酮 及0.2871克的电解质盐双三氟甲烷磺酰亚胺锂,搅拌使其充分溶解得到透明溶液A;
(2)将步骤1中的溶液A注入到间隔为500μm~1500μm的玻璃模具中,紫外光照射条件下聚合1-60 min,得到可自愈固态电解质薄膜。
(3)在步骤2制备所得的可自愈固态电解质薄膜两端贴上导电铜胶带作为电极得到柔性可拉伸传感器。
本发明所制备的可自愈固态电解质薄膜具有良好的导电性和可拉伸性,同时还具有可自愈的性能,以其为电解质制备的柔性可拉伸传感器,不仅具有高拉伸能力,还具有区分不同种类外部刺激的能力,在柔性电子器件中具有广阔的应用前景。
以上所述仅为本发明的实施方式而已,并不用于限制本发明。对于本领域技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原理的内所作的任何修改、等同替换、改进等,均应包括在本发明的权利要求范围之内。
Claims (10)
1.一种可自愈固态电解质薄膜,其特征在于:所述可自愈固态电解质薄膜包括如下原料:单体、交联剂、引发剂以及电解质盐,所述交联剂与所述单体的摩尔比为0.1%,所述引发剂与所述单体的摩尔比为1%,所述电解质盐在所有原料的混合溶液中的浓度为0.1mol/L-0.9mol/L。
2.根据权利要求1所述一种可自愈固态电解质薄膜,其特征在于:所述单体为丙烯酸酯,所述交联剂为聚二丙烯酸酯或聚乙二醇二丙烯酸酯,所述引发剂为1-羟基环己基苯基酮,所述电解质盐为锂盐、钠盐、钾盐或铵盐。
3.根据权利要求2所述一种可自愈固态电解质薄膜,其特征在于:单体丙烯酸酯为液态,液态丙烯酸酯类单体中包含氨基甲酸酯基团,所述锂盐为双三氟甲基磺酰亚胺锂、三氟甲磺酰-全氟丁基磺酰亚胺锂、三氟甲磺酰-全氟丙基磺酰亚胺锂、双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、二草酸硼酸锂、草酸二氟硼酸锂、二氟磷酸锂、4,5-二氰基-2-三氟甲基咪哩锂、高氯酸锂或氯化锂,所述钠盐为双三氟甲磺酰亚胺钠、高氯酸钠、双氟磺酰亚胺钠、氯化钠、硝酸钠、氟硅酸钠或邻苯二甲酸钠,所述钾盐为双氟磺酰亚胺钾、氯化钾、硝酸钾或邻苯二甲酸氢钾,所述铵盐为四氟硼酸四乙基铵、氯化铵或硝酸铵。
4.一种可自愈固态电解质薄膜的制备方法,其特征在于:所述制备方法包括如下步骤:
(1)量取一定量的单体,再分别加入交联剂,引发剂及电解质盐,搅拌使其充分溶解得到透明溶液;
(2)将步骤1中配置好的溶液置于片状模具中,在紫外光下照射使其中单体交联固化,即可得到所述可自愈固态电解质薄膜。
5.根据权利要求4所述一种可自愈固态电解质薄膜的制备方法,其特征在于:所述步骤(1)中,所述交联剂与所述单体的摩尔比为0.1%,所述引发剂与所述单体的摩尔比为1%,所述电解质盐在所有原料的混合溶液中的浓度为0.1mol/L-0.9mol/L。
6.根据权利要求4所述一种可自愈固态电解质薄膜的制备方法,其特征在于:所述单体为丙烯酸酯,单体丙烯酸酯为液态,液态丙烯酸酯类单体中包含氨基甲酸酯基团,所述交联剂为聚二丙烯酸酯或聚乙二醇二丙烯酸酯,所述引发剂为1-羟基环己基苯基酮,所述电解质盐为锂盐、钠盐、钾盐或铵盐。
7.根据权利要求4所述一种可自愈固态电解质薄膜的制备方法,其特征在于:所述锂盐为双三氟甲基磺酰亚胺锂、三氟甲磺酰-全氟丁基磺酰亚胺锂、三氟甲磺酰-全氟丙基磺酰亚胺锂、双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、二草酸硼酸锂、草酸二氟硼酸锂、二氟磷酸锂、4,5-二氰基-2-三氟甲基咪哩锂、高氯酸锂或氯化锂,所述钠盐为双三氟甲磺酰亚胺钠、高氯酸钠、双氟磺酰亚胺钠、氯化钠、硝酸钠、氟硅酸钠或邻苯二甲酸钠,所述钾盐为双氟磺酰亚胺钾、氯化钾、硝酸钾或邻苯二甲酸氢钾,所述铵盐为四氟硼酸四乙基铵、氯化铵或硝酸铵。
8.根据权利要求4所述一种可自愈固态电解质薄膜的制备方法,其特征在于:所述步骤(2)中,在采用紫外光照射进行光固化时,所采用的紫外光波长为365 nm,照射功率为400W,照射时间为1-60min。
9.一种如权利要求1所述一种可自愈固态电解质薄膜的应用,其特征在于:
所述可自愈固态电解质薄膜用于柔性可拉伸传感器的电解质。
10.根据权利要求8所述一种可自愈固态电解质薄膜的应用,其特征在于:所述柔性可拉伸传感器由可自愈固态电解质薄膜和连接在可自愈固态电解质薄膜两端的金属电极组成。
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