CN117525598A - 难燃电解质及其制备方法以及锂离子电池 - Google Patents
难燃电解质及其制备方法以及锂离子电池 Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 70
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 76
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 48
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 40
- -1 lithium salt compounds Chemical class 0.000 claims abstract description 27
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 17
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003660 carbonate based solvent Substances 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims abstract description 9
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004210 ether based solvent Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002861 polymer material Substances 0.000 claims abstract description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 150000005678 chain carbonates Chemical class 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical group 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 125000005587 carbonate group Chemical group 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 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 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 description 8
- 150000003949 imides Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- JSHASCFKOSDFHY-UHFFFAOYSA-N 1-butylpyrrolidine Chemical compound CCCCN1CCCC1 JSHASCFKOSDFHY-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical group B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- 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
- H01M10/0566—Liquid materials
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- H—ELECTRICITY
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
一种难燃电解质,其包括特定溶剂、锂盐和氟化溶剂,所述特定溶剂为碳酸酯类溶剂、醚类溶剂、丁二腈(succinonitrile)、环丁砜(sulfolane)、四甘醇二甲醚(tetraglyme)、离子型液体(ionic liquids)或其组合;或者所述难燃电解质包括1‑正丁基‑1‑甲基吡咯烷二(三氟甲基磺酰)酰亚胺、锂盐和碳酸酯类溶剂。本发明进一步提供所述难燃电解质的制备方法及一种锂离子电池。所述锂离子电池包括正极、负极、复合固态电解质膜,及所述难燃电解质,所述复合固态电解质膜的材料包括锂盐化合物、高分子材料、固态电解质和塑化剂。
Description
技术领域
本发明涉及一种难燃电解质及其制备方法,及采用该难燃电解质的锂离子电池。
背景技术
电动汽车及储能系统等领域对锂离子电池的需求量大,但现有碳酸酯类电解质有燃烧的安全性问题。具有阻燃效果的添加剂可提升电解质的难燃特性,但容易造成电池性能的下降。故,人们希望性能优良的难燃电解质及利用该难燃电解质的电池能够在不降低电池性能的前提下,提升电池的安全性。
目前常见的具有阻燃效果的添加剂,如磷酸二甲酯(DMMP)、磷酸三乙酯(TEP)和磷酸三甲酯(TMP)等不易燃的磷酸盐化合物,在一定程度上保证了电解质的安全性,但由于作为电池电极的石墨表面的强催化活性,电池的稳定性差仍然系一个普遍的问题。
发明内容
有鉴于此,确有必要提供一种难燃电解质及其制备方法,以及采用该难燃电解质的锂离子电池,所述难燃电解质不影响锂离子电池的稳定性。
一种难燃电解质,其包括特定溶剂、锂盐和氟化溶剂,所述特定溶剂为碳酸酯类溶剂、醚类溶剂、丁二腈(succinonitrile)、环丁砜(sulfolane)、四甘醇二甲醚(tetraglyme)、离子型液体(ionic liquids)或其组合;或者所述难燃电解质包括1-正丁基-1-甲基吡咯烷二(三氟甲基磺酰)酰亚胺、锂盐和碳酸酯类溶剂。
进一步,所述碳酸酯类溶剂为环状碳酸酯类和/或链状碳酸酯类,
所述环状碳酸酯类为碳酸乙烯酯(Ethylene Carbonate,EC)、碳酸丙烯酯(Propylene Carbonate,PC)或其组合,所述链状碳酸酯类为碳酸二甲酯(dimethylcarbonate,DMC)、碳酸二乙酯(diethyl carbonate,DEC)、碳酸甲乙酯或其组合。
进一步,所述醚类溶剂为1,2-二甲氧基乙烷(1,2-dimethoxyethane,DME)、二乙二醇二甲基醚(Diglyme)、三乙二醇二甲基醚(triethylene glycol dimethyl ether,TREGDME)、四乙二醇二甲基醚(tetraethylene glycol dimethyl ether,TEGDME)或其组合。
进一步,所述锂盐的浓度为5mol/kg至7mol/kg,优选为5mol/kg至6mol/kg。
进一步,所述锂盐为双三氟甲磺酰基亚胺锂(lithium bis(trifluoromethanesulfonyl)imide,LiN(CF3SO2)2),简称LiTFSI)、双氟磺酰亚胺锂(LiO4NS2F2,LiFSI)、六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)或其组合。
进一步,所述氟化溶剂为氟代碳酸乙烯酯(fluoroethylene carbonate,FEC)。
进一步,所述特定溶剂包含碳酸酯类溶剂和醚类溶剂或由碳酸酯类溶剂和醚类溶剂组成。碳酸酯类溶剂和醚类溶剂摩尔比为10:1~1:10。
进一步,所述特定溶剂由碳酸乙烯酯和1,2-二甲氧基乙烷组成,EC和DME的摩尔比为10:1~1:10。
进一步,所述难燃电解质由碳酸乙烯酯和1,2-二甲氧基乙烷的混合液、双三氟甲磺酰基亚胺锂和氟代碳酸乙烯酯组成,其中,LiTFSI的浓度为5mol/kg至7mol/kg,优选为5mol/kg至6mol/kg。
一种锂离子电池,其包括正极、负极、复合固态电解质膜,及所述难燃电解质,所述复合固态电解质膜的材料包括锂盐化合物、高分子材料、固态电解质和塑化剂。
一种难燃电解质的制备方法,其包括以下步骤:
提供一特定溶剂,所述特定溶剂为碳酸酯类溶剂、醚类溶剂、丁二腈、环丁砜、四甘醇二甲醚、离子型液体或其组合;
向所述特定溶剂中加入锂盐;及
待锂盐溶解后,加入一氟化溶剂。
与现有技术相比,本发明采用特定溶剂,提高锂盐浓度至5mol/kg以上,并加入适量的添加剂,可以避免锂盐析出、电池性能下降,并确保电解质具有难燃特性及确保锂离子电池的稳定性。
附图说明
图1为本发明提供的锂离子电池的结构示意图。
图2为本发明提供的锂离子电池的充放电曲线图。
图3为传统锂离子电池的充放电曲线图。
图4为本发明提供的锂离子电池的充放电曲线图。
主要组件符号说明
锂离子电池 10
正极 12
负极 14
难燃电解液 16
复合固态电解质膜 18
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合附图及具体实施例对本发明提供的难燃电解质及其制备方法,以及采用该难燃电解质的锂离子电池作进一步的详细说明。
本发明提供一种难燃电解质,该难燃电解质包括特定溶剂、锂盐和氟化溶剂。优选的,所述氟化溶剂为氟代碳酸乙烯酯。所述难燃电解质中锂盐的浓度为5mol/kg至7mol/kg。优选的,所述难燃电解质中锂盐的浓度为5mol/kg至6mol/kg。所述氟化溶剂的质量比为1~20%,优选为10%。氟化溶剂可以避免锂盐析出及改善锂离子电池负极的稳定性。在一实施例中,所述氟化溶剂为FEC,所述难燃电解质由特定溶剂、锂盐和FEC组成,FEC的质量比为10%。
所述特定溶剂为碳酸酯类溶剂、醚类溶剂、丁二腈、环丁砜、四甘醇二甲醚、离子型液体或其组合。所述离子型液体可以为N-甲基,丁基吡咯烷双三氟甲磺酰亚胺盐(N-Butyl,methylpyrrolidinium bis(trifluoromethylsulfonyl)imide)、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐(1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide)、1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐(1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide)、N-甲基,丁基吡咯烷双氟磺酰亚胺盐(N-Butyl,methylpyrrolidinium bis(fluorosulfonyl)imide)、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐(1-butyl-3-methylimidazolium bis[fluorosulfonyl]imide)、1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐(1-ethyl-3-methylimidazolium bis[fluorosulfonyl]imide)等。
在一实施方式中,所述特定溶剂包含碳酸酯类溶剂和醚类溶剂。
在另一实施方式中,所述特定溶剂由碳酸酯类溶剂和醚类溶剂组成。
所述碳酸酯类溶剂可以为环状碳酸酯类和/或链状碳酸酯类。环状碳酸酯类为碳酸乙烯酯、碳酸丙烯酯或其组合。链状碳酸酯类为碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯或其组合。
所述醚类溶剂可以为1,2-二甲氧基乙烷、二乙二醇二甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚或其组合。
所述锂盐为双三氟甲磺酰基亚胺锂(lithiumbis(trifluoromethanesulfonyl)imide,LiN(CF3SO2)2),简称LiTFSI)、双氟磺酰亚胺锂(lithium bis(fluorosulfonyl)imide,LiO4NS2F2,LiFSI)、六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)或其组合。
在一实施方式中,所述特定溶剂由EC和DME组成,EC和DME的摩尔比为10:1~1:10,优选的,EC和DME的摩尔比为1:2。所述锂盐为LiTFSI,也即所述难燃电解质由EC和DME的混合液、LiTFSI和FEC组成,其中,锂盐(LiTFSI)的浓度为5mol/kg至6mol/kg。
本发明进一步提供所述难燃电解质的制备方法,其包括以下步骤:
S1,提供所述特定溶剂;
S2,向所述特定溶剂中加入锂盐,搅拌;及
S3,待锂盐完全溶解后,加入氟化溶剂,搅拌。
步骤S1中,在一实施方式中,所述特定溶剂由EC等碳酸酯类溶剂和DME等醚类溶剂组成。由于EC等碳酸酯类溶剂在温度低时为固态,故,需要确保步骤S1中的EC等碳酸酯类溶剂和DME等醚类溶剂完全混合得到所述特定溶剂,才可以进行后续的步骤。步骤S2和S3的顺序不限,也即,将特定溶剂、锂盐和氟化溶剂相互混合溶解在一起的顺序不限。
在一实施方式中,碳酸酯类溶剂和醚类溶剂均为有机溶剂。以一定体积比混合碳酸酯类溶剂和醚类溶剂这两个有机溶剂。其中,碳酸酯类有机溶剂常温下为固态,可事先加热至60℃以上约两小时后,将固态的碳酸酯类有机溶剂溶解。本实施例中,所述碳酸酯类有机溶剂为碳酸乙烯酯,所述醚类有机溶剂为1,2-二甲氧基乙烷,所述碳酸乙烯酯与所述1,2-二甲氧基乙烷的体积比为1:2。
步骤S2中,在一实施方式中,向所述特定溶剂中添加锂盐以增加大量的锂离子,锂离子与溶剂间具有作用力,避免溶剂分子被气化,从而提高了所述难燃电解质的难燃特性。本实施例中,所述锂盐为LiTFSI。
步骤S3中,在一实施例中,所述氟化溶剂为氟代碳酸乙烯酯(fluoroethylenecarbonate,FEC),添加所述氟化溶剂的作用系避免LiTFSI等锂盐的析出及改善硅碳等负极的稳定性,并且增强锂离子与溶剂间的作用力,避免溶剂分子被气化,从而使得难燃电解质不易燃。
以下为所述难燃电解质的制备方法的具体实施例。
在饱和水蒸汽气压低于2帕斯卡以下的环境,分别取EC和DME,以EC和DME的体积比为1:2混合EC和DME,搅拌均匀,得到特定溶剂,作为离子传导介质。将EC和DME放入定量瓶做标准体积定量并均匀搅拌,其中EC常温下常为固态,可事先加温至60℃以上约两小时后,将其溶解。
然后,秤取锂盐,将锂盐加入所述特定溶剂中,并持续搅拌至锂盐均匀溶解,锂盐的浓度为5.14mol/kg。
最后,待锂盐溶解后,加入适量的FEC,并搅拌,得到所述难燃电解质。表1为难燃电解质及对照组的对比。以明火接触表1中的电解质I至电解质XII 5秒后,确认电解质I至电解质XII系否会燃烧,测试结果如表1所示。
表1难燃电解质及对照组的对比
表1中,EC系碳酸乙烯酯,ILE-P系1-正丁基-1-甲基吡咯烷二(三氟甲基磺酰)酰亚胺(1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide),DME系1,2-二甲氧基乙烷,DEC系碳酸二乙酯,LiTFSI系双三氟甲磺酰基亚胺锂,LiDFOB系二氟草酸硼酸锂(lithium difluoro(oxalato)borate)。
由表1可以得知,溶剂为EC和DME(EC与DME的摩尔比为1:2)的混合液,锂盐浓度为5.14mol/kg时,电解质难燃。溶剂为EC、DME(EC与DME的摩尔比为1:2)与FEC的混合液,锂盐浓度为5.14mol/kg时,电解质难燃。溶剂为EC、DME(EC与DME的摩尔比为1:2)、FEC与LiDFOB的混合液,锂盐浓度为5.14mol/kg时,电解质难燃。
而且,由电解质I得知,溶剂为ILE-P与DEC的混合液(ILE-P与DEC的质量比为8:2),ILE-P与LiTFSI的摩尔比为8:2,LiTFSI的重量摩尔浓度为0.59mol/kg时,电解质难燃。可见,难燃电解质也可以包括1-正丁基-1-甲基吡咯烷二(三氟甲基磺酰)酰亚胺、锂盐和碳酸酯类溶剂。在一具体实施例中,难燃电解质由1-正丁基-1-甲基吡咯烷二(三氟甲基磺酰)酰亚胺、锂盐(比如LiTFSI)和碳酸酯类溶剂(比如DEC)组成。
请参见图1,本发明进一步提供一种锂离子电池10,所述锂离子电池10包括正极12、负极14、难燃电解液16和复合固态电解质膜18。
所述正极12的材料不限,可以为锂镍锰钴氧、锂镍锰氧等,所述负极14的材料不限,可以为石墨、硅碳及锂金属等。所述难燃电解液16为前面已经详细描述的难燃电解质。
所述复合固态电解质膜18的材料包括锂盐化合物、高分子材料、固态电解质和塑化剂。所述复合固态电解质膜18由锂盐化合物、高分子材料、固态电解质和塑化剂制备而成。所述锂盐化合物可以为氟化锂(LiF)、双氟磺酼亚胺锂(LiO4NS2F2,简称LiFSI)、双三氟甲烷磺酰亚胺锂(LiN(CF3SO2)2,简称LiTFSI)、双(全氟乙基磺酰亚胺)锂(Li(C2F5SO2)2N,简称LiBETI)、二草酸硼酸锂(LiB(C2O4)2),简称LiBOB)等或其组合。所述高分子材料可以为PVDF、PVDF-HFP、PVA、PLA、PEG、PMMA、PMA、PAA等或其组合。所述固态电解质可以为LLZO、LLZTO、LATP等或其组合。所述塑化剂可以为碳酸乙烯酯、丁二腈、环丁砜、四甘醇二甲醚等或其组合。应用于锂离子电池的常规锂盐化合物都满足本发明。
在一实施例中,使用PVDF、PMMA、锂盐化合物及固态电解质、塑化剂混和后涂布于一基材上,经烘烤后取下,形成所述复合固态电解质膜18。
在干燥环境中,自下至上将负极14、复合固态电解质膜18、正极12、复合固态电解质膜18、负极14按顺序形成多层电芯。然后在真空环境中,将所述难燃电解质注入所述多层电芯后,进行化成,得到所述锂离子电池10。以下对所述锂离子电池10进行电化学性质验证。
图2为所述锂离子电池10的充放电曲线图。由图2可以得知,使用难燃电解质后,放电容量大于200mAh/g(205mAh/g),第一圈不可逆小于12%,皆与目前材料水平相当,故采用所述难燃电解质的锂离子电池10具有良好的电池性能。
图3为传统锂离子电池的充放电曲线图,图4为所述锂离子电池10的充放电曲线图。图3的传统锂离子电池与图4的锂离子电池10相比,前者采用传统隔离膜和难燃电解质(采用表1中的电解质VII),后者采用所述复合固态电解质膜18和难燃电解质(也系采用表1中的电解质VII),其余的都相同。由图3和图4可以得知,复合固态电解质膜18的表现与传统隔离膜相当。图2、图3及图4都系使用难燃电解质的电池的充放电结果。图2为前3圈的充放电结果,图3及图4为化成后的充放电结果。由图3与图4可以得知,所述锂离子电池10中,采用所述难燃电解质和所述复合固态电解质膜18互相搭配,可以使所述锂离子电池10的充放电表现与采用传统隔离膜的锂离子电池相当,容量可达到200mAh/g。
所述难燃电解质及其制备方法,以及采用该难燃电解质的锂离子电池具有以下优点:第一、本发明采用特定溶剂,提高锂盐浓度至5mol/kg以上,并加入适量的添加剂,可以避免锂盐析出、电池性能下降,并确保电解质具有难燃特性;第二、本发明使用难燃电解质、复合固态电解质膜、正负极组成了具有高能量及高安全性的锂离子固态电池。
另外,本领域技术人员还可在本发明精神内做其他变化,当然,这些依据本发明精神所做的变化,都应包含在本发明所要求保护的范围之内。
Claims (10)
1.一种难燃电解质,其特征在于,其包括特定溶剂、锂盐和氟化溶剂,所述特定溶剂为碳酸酯类溶剂、醚类溶剂、丁二腈、环丁砜、四甘醇二甲醚、离子型液体或其组合;或者所述难燃电解质包括1-正丁基-1-甲基吡咯烷二(三氟甲基磺酰)酰亚胺、锂盐和碳酸酯类溶剂。
2.如权利要求1所述的难燃电解质,其特征在于,所述特定溶剂包含碳酸酯类溶剂和醚类溶剂或由碳酸酯类溶剂和醚类溶剂组成。
3.如权利要求1或2所述的难燃电解质,其特征在于,所述碳酸酯类溶剂为环状碳酸酯类和/或链状碳酸酯类,所述环状碳酸酯类为碳酸乙烯酯、碳酸丙烯酯或其组合,所述链状碳酸酯类为碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯或其组合。
4.如权利要求1或2所述的难燃电解质,其特征在于,所述醚类溶剂为1,2-二甲氧基乙烷、二乙二醇二甲基醚、三乙二醇二甲基醚、四乙二醇二甲基醚或其组合。
5.如权利要求1或2所述的难燃电解质,其特征在于,所述锂盐的浓度为5mol/kg至7mol/kg。
6.如权利要求5所述的难燃电解质,其特征在于,所述锂盐为双三氟甲磺酰基亚胺锂、二(三氟甲基磺酰)亚胺锂、双氟磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂或其组合。
7.如权利要求1所述的难燃电解质,其特征在于,所述氟化溶剂为氟代碳酸乙烯酯。
8.如权利要求1所述的难燃电解质,其特征在于,所述特定溶剂由碳酸乙烯酯和1,2-二甲氧基乙烷组成,碳酸乙烯酯和1,2-二甲氧基乙烷的摩尔比为10:1~1:10。
9.一种锂离子电池,其包括正极、负极,其特征在于,所述锂离子电池进一步包括复合固态电解质膜及如权利要求1至权利要求8中任一项所述的难燃电解质,所述复合固态电解质膜的材料包括锂盐化合物、高分子材料、固态电解质和塑化剂。
10.一种难燃电解质的制备方法,其包括以下步骤:
提供一特定溶剂,所述特定溶剂为碳酸酯类溶剂、醚类溶剂、丁二腈、环丁砜、四甘醇二甲醚、离子型液体或其组合;
向所述特定溶剂中加入锂盐;及
待锂盐溶解后,加入一氟化溶剂。
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