CN114621278A - 硼酸酯功能化有机硅氧烷化合物及其制备方法和应用 - Google Patents
硼酸酯功能化有机硅氧烷化合物及其制备方法和应用 Download PDFInfo
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- -1 organosiloxane compound Chemical class 0.000 title claims abstract description 65
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000126 substance Substances 0.000 claims abstract description 14
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims description 69
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 24
- 125000005336 allyloxy group Chemical group 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- 239000002000 Electrolyte additive Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- DPGSPRJLAZGUBQ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane Substances CC1(C)OB(C=C)OC1(C)C DPGSPRJLAZGUBQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical group C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- YTEISYFNYGDBRV-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)oxy-dimethylsilyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)O[Si](C)C YTEISYFNYGDBRV-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 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 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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- CBMCZKMIOZYAHS-UHFFFAOYSA-N prop-1-enylboronic acid Chemical compound CC=CB(O)O CBMCZKMIOZYAHS-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 32
- 238000005160 1H NMR spectroscopy Methods 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000004821 distillation Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 230000005311 nuclear magnetism Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 8
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 8
- FUHPIKMOEZGMAU-UHFFFAOYSA-N 1-ethoxy-n,n-dimethylethanamine Chemical compound CCOC(C)N(C)C FUHPIKMOEZGMAU-UHFFFAOYSA-N 0.000 description 7
- 229910012820 LiCoO Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 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 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- AHEHMEDQTGXXRH-UHFFFAOYSA-N prop-1-enoxyboronic acid Chemical group CC=COB(O)O AHEHMEDQTGXXRH-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
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- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
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Abstract
Description
技术领域:
本发明涉及电化学储能技术领域,具体涉及一种硼酸酯功能化有机硅氧烷化合物及其制备方法和作为锂二次电池电解液添加剂的应用。
背景技术:
锂离子电池因其工作电压高、比容量大、循环寿命长、自放电小、无记忆效应、无污染等特点,被广泛应用在手机、笔记本等便携式设备和混合动力汽车等领域。
随着国家对动力汽车的能量密度和功率密度提出更高的要求,具有高能量密度的正极材料正广泛受到关注,如三元材料、LiNi0.5Mn1.5O4、高压LiCoO2等。但这些材料本身还存在一些固有的缺点,如循环过程中容量衰减快、材料结构稳定性差、高压(高温)循环寿命短、高温储存性能差等。可通过寻求一种新的电解液体系匹配高能量密度正极材料来提高锂二次电池的综合性能。目前商业上普遍使用的电解液主要是由六氟磷酸锂(LiPF6)盐和溶剂碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)等混合溶剂组成,这类碳酸酯电解液极易发生自身氧化分解,副反应产生的HF会加速正极材料中过渡金属离子(Ni、Co、Mn)溶出,导致正极材料表面结构坍塌、电池容量衰减和循环性能变差。电解液添加剂因其具有“用量少,效果显著”的特点,在基本不改变电池体积及成本的基础上能明显改善电池的性能。在锂二次电池的电解液体系中加入功能添加剂,该类添加剂将优先电解液氧化分解,在正极材料表面形成一层稳定致密的界面保护膜,阻断正极材料表面与电解液的直接接触,有效抑制电解液的氧化分解,解决了电解液体系易与正极材料发生副反应而导致锂二次电池性能下降、容量衰减等问题,有效提高锂二次电池的循环寿命和放电容量。
先前有专利报道过硅烷化合物(CN 102074736 A)和硅烷硼酸酯化合物(CN105355968 A)作为锂二次电池电解液添加剂,但该类添加剂不能兼顾保护电解液和电极材料。因此,急需开发新的功能电解液添加剂来提高电池的循环寿命和应用范围,从而获得高能量密度电池。
发明内容:
本发明的目的是提供一种硼酸酯功能化有机硅氧烷化合物及其制备方法和作为锂二次电池电解液添加剂的应用。
本发明是通过以下技术方案予以实现的:
化学结构式如式1、2、3所示的硼酸酯功能化有机硅氧烷化合物:
其中R1、R2、R3、R4、R5、R6选自相同或者不同的C1–C10烷基、烷氧基,n1为C1–C3烷基,n2为不同链长的硅氧烷,A为(CH2)n3O[(CH2)mO]x(CH2)y,其中n3、m、x和y分别为0-5的整数。
上述硼酸酯功能化有机硅氧烷化合物的制备方法,该方法包括如下步骤:烷氧硅氢烷与双键有机胺化合物或者双键硼酸酯化合物通过在惰性气体保护下进行硅氢化反应,反应温度为45~130℃,反应时间为4–24h,双键有机胺化合物与烷氧硅氢烷的摩尔比为1:1.0~1.2,双键硼酸酯与烷氧硅氢烷的摩尔比为1:1.0~1.1,制备得到硼酸酯功能化有机硅氧烷化合物;所述的双键有机胺化合物为2–(烯丙氧基)–N,N–二甲基乙胺或者2–(烯丙氧基)乙氧基–N,N二甲基乙胺;双键硼酸酯化合物为乙烯基硼酸频哪醇酯或者丙烯基硼酸邻二叔醇酯;烷氧硅氢烷为1,1,3,3–四甲基二硅氧烷或者1,1,3,3,5,5–六甲基三硅氧烷;硅氢化反应催化剂选自氯铂酸或Karstedt’s催化剂,加入的量为双键取代的聚醚链有机胺化合物或者双键硼酸酯化合物的0.1~1mol。
具体合成路线包括如下三路线:
路线1
路线2
路线3
本发明还提供式1所示的硼酸酯功能化有机硅氧烷化合物在锂二次电池中的应用,所述的硼酸酯功能化有机硅氧烷化合物作为锂二次电池电解液添加剂。
所述的锂二次电池电解液包括锂盐\溶剂和作为电解液添加剂的本发明所述硼酸酯功能化有机硅氧烷化合物。所述的导电锂盐在电解液中的浓度为0.5–1.5mol/L,所述的电解液添加剂的使用量为锂盐和溶剂总质量的0.1%–5%。有机溶剂包括碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯,三者的质量比1:1:1。所述的导电锂盐选自六氟磷酸锂(LiPF6)、二草酸硼酸锂(LiBOB)、二氟草酸硼酸锂(LiODFB)、高氯酸锂(LiClO4)、双三氟甲磺酰亚胺锂(LiTFSI)、双氟磺酰亚胺锂(LiFSI)中的一种或两种以上。该锂二次电池正极材料可使用LiNixCoyMnzO2(x+y+z=1)体系、LiCoO2。
本发明的有益效果如下:本发明硼酸酯功能化有机硅氧烷化合物作为锂二次电池电解液添加剂能优先于碳酸酯电解液分解,在正极材料界面形成一层含杂元素的致密稳定的保护膜。该层保护膜能阻断正极材料表面与电解液的直接接触,有效抑制电解液的氧化分解,提高有机碳酸酯溶剂的稳定性,促进电解液与正、负极材料的兼容性,降低正负极材料的金属溶出;还能有效提高电池的高温循环寿命、放电容量和倍率性能,提高电池的高压应用范围。
附图说明:
图1为本发明实施例1化合物的核磁氢谱和碳谱图;
图2为本发明实施例2化合物的核磁氢谱和碳谱图;
图3为本发明实施例3化合物的核磁氢谱和碳谱图;
图4为本发明实施例4化合物的核磁氢谱和碳谱图;
图5为本发明实施例5化合物的核磁氢谱和碳谱图;
图6为本发明实施例6化合物的核磁氢谱和碳谱图;
图7为本发明实施例7化合物的核磁氢谱和碳谱图;
图8为本发明实施例8化合物的核磁氢谱和碳谱图;
图9为本发明实施例9化合物的核磁氢谱和碳谱图;
图10为本发明实施例10化合物的核磁氢谱和碳谱图;
图11为本发明实施例11化合物的核磁氢谱和碳谱图;
图12为本发明实施例12与对比例1电解液的线性扫描曲线;
图13为本发明实施例12与对比例1电解液的常温循环性能测试;
图14为本发明实施例12与对比例1电解液的Graphite/NCM811电池的常温循坏性能测试;
图15为本发明实施例12与对比例1电解液的Graphite/NCM811电池的高温循坏性能测试;
图16为本发明实施例12与对比例1电解液的Li/NCM811电池的倍率性能测试;
图17为本发明实施例12与对比例1电解液的Li/NCM811电池的阻抗测试;
图18为本发明实施例12与对比例1电解液的LiCoO2/Li电池的dQ/dV曲线;
图19为本发明实施例12与对比例1电解液的Graphite2/Li电池的dQ/dV曲线;
图20为本发明实施实施例12与对比例1电解液的LiCoO2/Graphite电池的常温循环测试;
图21为本发明实施实施例12与对比例1电解液的LiCoO2/Graphite电池的高温循环测试;
图22为本发明实施例12与对比例1电解液的LiCoO2/Graphite电池的高温倍率性能测试;
图23为本发明实施例12与对比例1电解液的LiCoO2/Graphite电池的阻抗测试。
图24为本发明实施例16与对比例1电解液的线性扫描曲线;
图25为本发明实施例17与对比例1电解液的线性扫描曲线;
图26为本发明实施例18与对比例1电解液的线性扫描曲线;
图27为本发明实施例4与对比例1电解液的LiCoO2/Li电池的dQ/dV曲线;
图28为本发明实施例17与对比例1电解液的LiCoO2/Li电池的dQ/dV曲线。
具体实施方式:
以下是对本发明的进一步说明,而不是对本发明的限制。
实施例1:二硅氧烷单取代的2–(烯丙氧基)–N,N–二甲基乙胺(TMSPEA)的合成
氩气气氛和室温条件下,往三口烧瓶中加入2–(烯丙氧基)–N,N–二甲基乙胺(62.46g,0.484mol)与0.4g氯铂酸搅拌,在搅拌状态下滴加1,1,3,3–四甲基二硅氧烷(66.20g,0.494mol)。待滴加完毕后,45℃反应24h。通过减压蒸馏可得到二硅氧烷单取代的2–(烯丙氧基)–N,N–二甲基乙胺(TMSPEA),b.p.:77℃/0.13mmHg。
TMSPEA化学结构式如下:
TMSPEA 1H NMR(400MHz,CDCl3)δ4.59–4.57(m,1H),3.41(t,J=5.8Hz,2H),3.29(t,J=7.0Hz,2H),2.39(t,J=5.8Hz,2H),2.16(s,6H),1.55–1.47(m,2H),0.44–0.40(m,2H),0.05–0.046(m,6H),–0.0(s,6H);
TMSPEA 13C NMR(100MHz,CDCl3):δ73.80,68.63,58.79,45.72,23.09,13.85,0.67,-0.26。核磁1H NMR和13C NMR谱图见附图1。
实施例2:硼酸酯和胺基功能化有机硅氧烷化合物(TMBDSA1)的合成
氩气气氛和室温条件下,在三口烧瓶中加入二硅氧烷单取代的2–(烯丙氧基)–N,N–二甲基乙胺(19.8g,75.2mmol)与0.06g氯铂酸,在搅拌状态下滴加乙烯基硼酸频哪醇酯(11.60g,75.2mmol)。待滴加完毕后,45℃反应5h。通过减压蒸馏可得到硼酸酯和胺基功能化有机硅氧烷化合物(TMBDSA1),b.p.:115℃/0.18mmHg。
TMBDSA1化学结构式如下:
TMBDSA11H NMR(400MHz,CDCl3):δ3.44(t,J=6.0Hz,2H),3.31(t,J=7.2Hz,2H),2.42(t,J=5.8Hz,2H),2.19(s,6H),1.57–1.49(m,2H),1.17–1.14(m,12H),0.98–0.92(m,3H),0.45–0.41(m,2H),0.28(q,J=7.2Hz,1H),0.01–0.00(m,6H),-0.02(s,6H);
TMBDSA1 13C NMR(100MHz,CDCl3):δ82.36,74.00,68.66,58.81,45.78,24.83,24.60,23.24,14.15,8.32,0.25,0.11,–0.28。核磁1H NMR和13C NMR谱图见附图2。
实施例3:二硅氧烷单取代的2–(烯丙氧基)乙氧基–N,N–二甲基乙胺(TMSPDEA)的合成
氩气气氛和室温条件下,在三口烧瓶中加入2–(烯丙氧基)乙氧基–N,N–二甲基乙胺(63.31g,0.366mol)与0.3g氯铂酸,在搅拌状态下滴加二硅氧烷(50g,0.373mol)。待滴加完毕后,45℃反应24h。通过减压蒸馏可得到二硅氧烷单取代的2–(烯丙氧基)乙氧基–N,N–二甲基乙胺(TMSPDEA),b.p.:108℃/0.23mmHg。
TMSPDEA化学结构式如下:
TMSPDEA 1H NMR(400MHz,CDCl3)δ4.68–4.63(m,1H),3.60–3.55(m,6H),3.40(t,J=7Hz,2H),2.49(t,J=5.8Hz,2H),2.24(s,6H),1.63–1.55(m,2H),0.52–0.47(m,2H),0.16–0.13(m,6H),0.06–0.05(m,6H);
TMSPDEA 13C NMR(150.9MHz,CDCl3)δ74.10,70.36,69.97,69.30,58.78,45.82,23.26,13.94,0.84,-0.10。核磁1H NMR和13C NMR谱图见附图3。
实施例4:硼酸酯和胺基功能化有机硅氧烷化合物(TMBDSA2)的合成
氩气气氛和室温条件下,在三口烧瓶中加入中间体二硅氧烷单取代的2–(烯丙氧基)乙氧基–N,N–二甲基乙胺(30g,97.6mmol)与0.08g氯铂酸,在搅拌状态下滴加乙烯基硼酸频哪醇酯化合物(15.05g,97.6mmol)。待滴加完毕后,45℃反应5h。通过减压蒸馏可得到硼酸酯和胺基功能化有机硅氧烷化合物(TMBDSA2),b.p.:165℃/0.14mmHg。
TMBDSA2化学结构式如下:
TMBDSA2 1H NMR(400MHz,CDCl3):δ3.60–3.56(m,6H),3.40(t,J=7.2Hz,2H),2.50(t,J=5.8Hz,2H),2.25(s,6H),1.65–1.55(m,2H),1.21(s,12H),1.01(d,J=8.0Hz,3H),0.51–0.47(m,2H),0.35(q,J=7.2Hz,1H),0.08–0.01(m,12H);
TMBDSA213C NMR(100MHz,CDCl3):δ82.53,74.27,70.39,69.98,69.32,58.81,45.86,24.96,24.72,23.37,14.21,8.45,0.40,0.20,-0.16。核磁1HNMR和13C NMR谱图见附图4。
实施例5:三硅氧烷单取代的2–(烯丙氧基)–N,N–二甲基乙胺(HMSPEA)的合成
氩气气氛和室温条件下,在三口烧瓶中加入2–(烯丙氧基)–N,N二甲基乙胺(6.0g,47mmol)与0.04g氯铂酸,在搅拌状态下滴加三硅氧烷(10g,48mmol)滴加。滴加完毕后,45℃反应24h。通过减压蒸馏可得到中间体三硅氧烷单取代的2–(烯丙氧基)–N,N–二甲基乙胺(HMSPEA),b.p.:80℃/0.24mmHg。
HMSPEA化学结构式如下:
HMSPEA 1H NMR(400MHz,CDCl3):δ4.68-4.67(m,1H),3.50(t,J=5.8Hz,2H),3.38(t,J=7.0Hz,2H),2.49(t,J=6.0Hz,2H),2.25(s,6H),1.62–1.58(m,2H),0.53–0.49(m,2H),0.17–0.16(m,6H),0.06-0.05(m,8H),0.02(s,4H);
HMSPEA 13C NMR(100MHz,CDCl3):δ74.05,68.77,58.92,45.88,23.29,14.10,0.93,0.67,0.05。核磁1HNMR和13C NMR谱图见附图5。
实施例6:硼酸酯和胺基功能化有机硅氧烷化合物(HMBTSA)的合成
氩气气氛和室温条件下,在三口烧瓶中加入中间体三硅氧烷单取代的2–(烯丙氧基)–N,N–二甲基乙胺(4.5g,13.4mmol)与0.02g氯铂酸,在搅拌状态下滴加乙烯基硼酸频哪醇酯(2.06g,13.4mmol)。滴加完毕后,45℃反应5h。通过减压蒸馏可得到硼酸酯和胺基功能化有机硅氧烷化合物(HMBTSA),b.p.:141℃/0.14mmHg。
HMBTSA化学结构式如下:
HMBTSA 1H NMR(400MHz,CDCl3):δ3.51(t,J=6.0Hz,2H),3.38(t,J=7.2Hz,2H),2.49(t,J=5.8Hz,2H),2.26(s,6H),1.61–1.59(m,2H),1.23–1.20(m,12H),1.04-1.02(d,J=7.2Hz,2H),0.72–0.37(m,4H),0.10–0.00(m,18H);
HMBTSA 13C NMR(100MHz,CDCl3):δ82.42,73.93,68.61,58.77,45.74,24.84,24.68,24.58,23.21,14.03,8.28,1.16,1.14,0.23,-0.02。核磁1HNMR和13C NMR谱图见附图6。
实施例7:三硅氧烷单取代的2–(烯丙氧基)乙氧基–N,N–二甲基乙胺(HMSPDEA)的合成
氩气气氛和室温条件下,在三口烧瓶中加入2–(烯丙氧基)乙氧基–N,N二甲基乙胺(8.14g,47mmol)与0.04g氯铂酸,在搅拌状态下滴加三硅氧烷(10g,48mmol)。滴加完毕后,45℃反应24h。通过减压蒸馏可得到三硅氧烷单取代的2–(烯丙氧基)乙氧基–N,N–二甲基乙胺(HMSPDEA),b.p.:85℃/0.24mmHg。
HMSPDEA化学结构式如下:
HMSPDEA 1H NMR(400MHz,CDCl3)δ4.69–4.68(m,1H),3.80–3.79(m,1H),3.59-3.56(m,6H),3.43-3.39(t,J=7.0Hz,1H),2.52-2.49(m,2H),2.25(s,6H),1.64–1.54(m,2H),0.53–0.49(m,2H),0.18–0.16(m,6H),0.10–0.02(m,12H);
HMSPDEA 13C NMR(100MHz,CDCl3)δ74.16,70.39,69.99,69.31,58.79,45.85,45.83,23.30,14.05,0.98,0.94,0.81,0.76,0.68,0.65,0.05。核磁1HNMR和13C NMR谱图见附图7。
实施例8:硼酸酯和胺基功能化有机硅氧烷化合物(HMBTSA2)的合成
氩气气氛和室温条件下,在三口烧瓶中加入中间体三硅氧烷单取代的2–(烯丙氧基)–N,N–二甲基乙胺(3.7g,9.7mmol)与0.01g氯铂酸,随后将乙烯基硼酸频哪醇酯(1.5g,9.7mmol)滴加。滴加完毕后,45℃反应5h。通过减压蒸馏可得到硼酸酯和胺基功能化有机硅氧烷化合物(HMBTSA2),b.p.:130℃/0.18mmHg。
HMBTSA2化学结构式如下:
HMBTSA2 1H NMR(400MHz,CDCl3):δ3.59–3.57(m,6H),3.40(t,J=7.2Hz,2H),2.52-2.49(m,2H),2.25(s,6H),1.64–1.55(m,2H),1.20–1.19(m,12H),1.03-1.02(dd,J=7.2Hz,3H),0.53–0.35(m,3H),0.11–0.04(m,18H);
HMBTSA2 13C NMR(100MHz,CDCl3):δ82.52,74.19,70.37,69.97,69.24,58.74,45.78,24.94,24.69,23.31,14.08,8.39,1.24,1.07,0.33,0.08。核磁1HNMR和13C NMR谱图见附图8。
实施例9:硼酸酯化有机硅氧烷化合物(TMBEDS)的合成
氩气气氛和室温条件下,在三口烧瓶中加入乙烯基硼酸频哪醇酯(45.0g,0.292mol)与0.2g氯铂酸,随后滴加五甲基二硅氧烷(19.57g,0.146mol)。滴加完毕后,45℃反应5h。通过减压蒸馏可得到硼酸酯功能化有机硅氧烷化合物(TMBEDS),b.p.:143℃/0.12mmHg。
TMBEDS化学结构式如下:
TMBEDS 1HNMR(400MHz,CDCl3):δ1.23–1.20(m,24H),1.04-1.02(m,5H),0.74-0.34(m,3H),0.09-0.02(m,12H);
TMBEDS 13C NMR(100MHz,CDCl3):δ82.84,82.49,24.96,24.79,24.71,10.83,8.46,0.50,0.49,0.41,-0.16,-0.25,-0.27。核磁1HNMR和13C NMR谱图见附图9。
实施例10:(PMBEDS)硼酸酯化有机硅氧烷化合物的合成
氩气气氛和室温条件下,在三口烧瓶中加入乙烯基硼酸频哪醇酯(12.0g,77.9mmol)与0.06g氯铂酸,随后滴加五甲基二硅氧烷(11.67g,78.6mmol)。滴加完毕后,45℃反应5h。通过减压蒸馏可得到硼酸酯功能化有机硅氧烷化合物(PMBEDS),b.p.:75℃/0.19mmHg。
PMBEDS化学结构式如下:
PMBEDS 1H NMR(400MHz,CDCl3):δ1.23–1.20(m,12H),1.02-1.00(d,J=8.0Hz,2H),0.74-0.35(m,2H),0.08-0.01(m,15H);
PMBEDS 13C NMR(100MHz,CDCl3):δ82.87,82.50,24.95,24.79,24.72,10.81,8.41,1.95,1.92,0.26,0.15,-0.22。核磁1HNMR和13C NMR谱图见附图10。
实施例11:硼酸酯化有机硅氧烷化合物(PMBPDS)的合成
氩气气氛和室温条件下,在三口烧瓶中加入丙烯基硼酸邻二叔醇酯(13.22g,78.6mmol)与0.06g氯铂酸,随后滴加五甲基二硅氧烷(11.67g,78.6mmol)。滴加完毕后,45℃反应5h。通过减压蒸馏可得到硼酸酯功能化有机硅氧烷化合物(PMBPDS),b.p.:89℃/0.17mmHg。
PMBPDS化学结构式如下:
PMBPDS 1H NMR(400MHz,CDCl3):δ1.45–1.41(m,2H),1.22(s,12H),0.81(t,J=7.6Hz,2H),0.56-0.51(m,2H),0.04-0.01(m,15H);
PMBPDS 13C NMR(100MHz,CDCl3):δ82.75,24.80,21.60,17.92,1.94,0.36。核磁1HNMR和13C NMR谱图见附图11。
实施例12:
所需的基础电解液LB301=1M LiPF6EC/DMC/EMC(1:1:1)来自上海枭源能源科技有限公司,电解液中加入0.2%质量分数的实施例2制备的TMBDSA1,搅拌均匀后备用。
对比例1
基础电解液LB301=1M LiPF6EC/DMC/EMC(1:1:1),在此基础电解液中不添加任何其他添加剂。
实施例13:电极制作
将正极材料、导电剂、粘结剂和溶剂以一定比例混合,接着将混合物直接涂覆在铝箔集流体上并干燥制备正极。类似地,将负极材料、导电剂、粘结剂和溶剂以一定比例混合,后将混合物直接涂覆在铜箔集流体上并干燥制备负极。
正极材料为LiNixCoyMnzO2(x+y+z=1)或者LiCoO2;负极材料为石墨、锂金属、硅负极。
乙炔黑为导电剂;粘结剂可选自偏二氟乙烯/六氟丙烯共聚物、偏二氟乙烯(PVDF);溶剂可选自N-甲基吡咯烷酮(NMP)、丙酮。
一般选自具备优异浸润电解液的隔膜,如,聚乙烯、聚丙烯或者两者混合的隔膜。
实施例14:电池组装
在手套箱中组装CR2025扣式电池,将实施例13制作的正极极片作为正电极,负极极片作为负电极,并将实施例12电解液作为电解液,按照负极壳、负极片、电解液、隔膜、电解液、正极片、正极壳的顺序组装。组装完毕后,搁置12h得到三元NCM811纽扣电池。
在手套箱中组装CR2025扣式电池,将上述制作的正极极片作为正电极,负极极片作为负电极,并将实施例12电解液作为电解液,按照负极壳、负极片、电解液、隔膜、电解液、正极片、正极壳的顺序组装。组装完毕后,搁置12h得到钴酸锂纽扣电池。
实施例15:
参考实施例12,不同之处在于用实施例4制备的TMBDSA2代替添加剂TMBDSA1,其余按照与实施例12相同的操作条件制备锂二次电池电解液和组装电池,以及进行电池的电化学性能测试。
实施例16:
参考实施例12,不同之处在于用实施例9制备的TMBEDS代替添加剂TMBDSA1,其余按照与实施例12相同的操作条件制备锂二次电池电解液和组装电池,以及进行电池的电化学性能测试。
实施例17:
参考实施例12,不同之处在于用实施例10制备的PMBEDS代替添加剂TMBDSA1,其余按照与实施例12相同的操作条件制备锂二次电池电解液和组装电池,以及进行电池的电化学性能测试。
实施例18:
参考实施例12,不同之处在于用实施例11制备的PMBPDS代替添加剂TMBDSA1,其余按照与实施例12相同的操作条件制备锂二次电池电解液和组装电池,以及进行电池的电化学性能测试。
图12为本发明实施例12与对比例1电解液的线性扫描测试曲线图,发现添加剂能够优先电解液溶剂有电流变化,说明硼酸酯和胺基功能化有机硅氧烷化合物能够优先电解液溶剂发生氧化分解,并在在正极表面形成稳定致密的保护膜。
如图13、14和15,利用NCM811和石墨分别做正、负极,组装成扣式电池(2025),然后在深圳新威充/放电测试,充放电电压为3-4.3V。以1C的恒定电流对实施例12电池充电,然后以恒流1C放电。发现实施例12的NCM811/石墨全电池首次放电比容量为190.2mAh·g-1(对比例1仅为189.7mAh·g-1),常温循环的循环性能有所提高,容量保持率由82%提高至92%。同样,高温循环性能也明显提高。
图16为本发明实施例12与对比例1电解液电池的倍率性能测试,实施例12电池在10C高倍率下表现出较高容量。
图17为本发明实施例12与对比例1电解液电池的阻抗测试,添加剂能明显降低正极材料表面界面膜的阻抗。
LiCoO2和石墨扣式电池(2025),分别在常温和高温条件下对电池进行充/放电测试,充放电电压范围为3-4.5V。以1C的恒定电流对实施例12和对比例1充放电。
图18和图19分别为本发明实施例12与对比例1电解液半电池的dQ/dV测试,都能表现添加剂具有成膜的特性。
图20和图21为本发明实施例12与对比例1电解液,对电池的1C充放电常温和高温循环性能。如图所示,实施例12电解液在LiCoO2材料体系上也表现出较好的循环性能。
图22为本发明实施例12与对比例1电解液电池的倍率性能测试,实施例12电解液在高温5C的倍率下表现出高容量。
图23为本发明实施例12与对比例1电解液电池的阻抗测试,添加剂明显降低电极界面膜的阻抗。
图24、图25和图26,分别为本发明实施例16与对比例1、实施例17与对比例1、实施例18与对比例1电解液的线性扫描测试,发现添加剂能够优先电解液溶剂有微弱电流变化,说明硼酸酯功能化有机硅氧烷化合物能够优先电解液溶剂发生氧化分解,并在在正极表面形成稳定致密的保护膜,提高电解液的稳定性。
图27和图28分别为本发明实施例4与对比例1、实施例17与对比例1的电解液半电池的dQ/dV测试,表现硼酸酯功能化有机硅氧烷化合物添加剂具有成膜的特性。
Claims (4)
2.权利要求1所述硼酸酯功能化有机硅氧烷化合物的制备方法,其特征在于,该方法包括如下步骤:烷氧硅氢烷与双键有机胺化合物或者双键硼酸酯化合物通过在惰性气体保护下进行硅氢化反应,反应温度为45~130℃,反应时间为4–24h,双键有机胺化合物与烷氧硅氢烷的摩尔比为1:1.0~1.2,双键硼酸酯与烷氧硅氢烷的摩尔比为1:1.0~1.1,制备得到硼酸酯功能化有机硅氧烷化合物;所述的双键有机胺化合物为2–(烯丙氧基)–N,N–二甲基乙胺或者2–(烯丙氧基)乙氧基–N,N二甲基乙胺;双键硼酸酯化合物为乙烯基硼酸频哪醇酯或者丙烯基硼酸邻二叔醇酯;烷氧硅氢烷为1,1,3,3–四甲基二硅氧烷或者1,1,3,3,5,5–六甲基三硅氧烷;硅氢化反应催化剂选自氯铂酸或Karstedt’s催化剂,加入的量为双键取代的聚醚链有机胺化合物或者双键硼酸酯化合物的0.1~1mol。
4.根据权利要求3所述的应用,其特征在于,所述的锂二次电池电解液包括锂盐\溶剂和作为电解液添加剂的硼酸酯功能化有机硅氧烷化合物;所述的锂盐在电解液中的浓度为0.5–1.5mol/L,所述的电解液添加剂的使用量为锂盐和溶剂总质量的0.1%–5%;有机溶剂包括碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯,三者的质量比1:1:1;所述的导电锂盐选自六氟磷酸锂、二草酸硼酸锂、二氟草酸硼酸锂、高氯酸锂、双三氟甲磺酰亚胺锂、双氟磺酰亚胺锂中的一种或两种以上;锂二次电池正极材料使用LiNixCoyMnzO2体系或LiCoO2,x+y+z=1。
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