CN104380504B - 二次电池用负极及包含其的二次电池 - Google Patents
二次电池用负极及包含其的二次电池 Download PDFInfo
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- CN104380504B CN104380504B CN201380030852.9A CN201380030852A CN104380504B CN 104380504 B CN104380504 B CN 104380504B CN 201380030852 A CN201380030852 A CN 201380030852A CN 104380504 B CN104380504 B CN 104380504B
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- 238000013461 design Methods 0.000 description 1
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- 229920003244 diene elastomer Polymers 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000006073 displacement reaction Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- QDHCHVWSKUMZDZ-UHFFFAOYSA-N ethyl dihydrogen phosphite Chemical compound CCOP(O)O QDHCHVWSKUMZDZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
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- 150000002461 imidazolidines Chemical class 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
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- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
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- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
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- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
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- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
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- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明公开了一种二次电池用负极及包含其的二次电池。所述负极具有涂布于集电器上的包含负极活性材料负极混合物,其中所述负极活性材料包含在其表面上具有交联聚合物涂层的锂钛氧化物(LTO)粒子,其中在其上形成有交联聚合物涂层的所述LTO粒子具有形成在其间的多孔结构,并且涂层的交联聚合物为磷酸酯基化合物。
Description
技术领域
本发明涉及一种二次电池用负极及包含其的二次电池,在所述二次电池用负极中包含负极活性材料的负极混合物涂布于集电器上,其中所述负极活性材料包含在其表面上具有交联聚合物涂层的锂钛氧化物(LTO)粒子,其中在其上形成有交联聚合物涂层的所述LTO粒子具有形成在其间的多孔结构,并且所述涂层的交联聚合物为磷酸酯基化合物。
背景技术
随着移动装置技术的持续发展和对此需求的持续增加,对作为能源的二次电池的需求急剧增加。在这些二次电池中,展示高能量密度和运行电势、具有长循环寿命及具有低自放电率的锂二次电池可商购获得并被广泛使用。
此外,随着近来对环境问题的关注不断增加,对于电动车辆(EV)、混合动力电动车辆(HEV)等的研究正在进行,所述电动车辆(EV)、混合动力电动车辆(HEV)等能够替代作为空气污染背后主要原因之一的使用化石燃料的车辆如汽油车、柴油车等。作为EV、HEV等的电源,主要使用镍-金属氢化物(Ni-MH)二次电池。然而,正在积极开展对于具有高能量密度、高放电电压和高输出稳定性的锂二次电池的研究,并且一些锂二次电池可商购获得。
锂二次电池具有电极组件被含锂盐的非水电解液浸渍的结构,其中所述电极组件包含:通过在正极集电器上涂布正极活性材料而制备的正极;通过在负极集电器上涂布负极活性材料而制备的负极;以及置于所述正极和所述负极之间的多孔隔膜。
考虑到活性材料的离子导电性,这种锂二次电池需要电极具有特定水平或更高级别的孔隙率。
然而,在制备含有电极活性材料的电极浆料的过程中出现电极孔隙率的过度减少,由此导致C倍率快速减少。
根据特定应用,二次电池需要特定水平或更高的C倍率,特别地,用于需要高功率的电动工具的锂二次电池或用于EV及HEV的二次电池需要更高的C倍率。
因此,迫切需要开发可以解决上述问题的技术。
发明内容
技术问题
因此,实施了本发明以解决上述问题及其它尚未解决的技术问题。
作为各种广泛深入研究和实验的结果,本发明人确认,当使用其表面被作为交联聚合物的磷酸酯基化合物涂布的锂钛氧化物作为负极活性材料时,可以实现期望的效果,由此完成了本发明。
技术方案
根据本发明的一个方面,提供二次电池用负极,其中包含负极活性材料的负极混合物涂布于集电器上,其中所述负极活性材料包含在其表面上具有交联聚合物涂层的锂钛氧化物(LTO)粒子,其中在其上形成有交联聚合物涂层的所述LTO粒子具有形成在其间的多孔结构,并且所述涂层的交联聚合物为磷酸酯基化合物。
根据本发明的负极使用表面涂布有磷酸酯基化合物的LTO作为负极活性材料,由此可以提高功率输出特性,并且由于被稳定的电极界面还可以提高使用寿命。
特别地,即使涂层形成在LTO粒子的表面上,LTO粒子也保持预定的多孔结构,由此可以增大负极活性材料层的比表面积,并且可以提高孔间的连通性,因此可以增加电解液的浸渍比,这导致充放电特性提高。
也就是,磷酸酯基化合物具有与自由基的高反应性,由此被认为通过聚合过程中的改善而提高负极活性材料的电化学稳定性。
特别地,LTO电极在充放电期间可加速电解质分解反应(Ti4+<---→Ti3+),并且盐阴离子可加速LTO的催化和电化学反应。在这些方面,认为磷酸酯基可通过与阴离子结合而结合至具有高稳定性和还原反应性的的Ti3+,从而减少液体电解质分解,并且还有助于抑制所形成的膜的结构分解。
此外,用作负极活性材料的LTO充当催化剂,由此可加速磷酸酯基化合物的交联聚合,因此可最大化上述效果。
在一个实施方案中,磷酸酯基化合物可以为选自由下式1表示的磷酸酯基丙烯酸酯、由下式2表示的焦磷酸酯基丙烯酸酯和磷酸酯基氨基甲酸酯丙烯酸酯中的至少一种材料。
在式1和2中,R1和R2各自独立地为氢、甲基或F,且n为1~20的整数。
具体地,在式1和/或式2中,R1可以为氢,且n可以为1。
负极还可包含能与磷酸酯基化合物聚合的多官能化合物。
当负极活性材料的涂层与能与磷酸酯基化合物聚合的多官能化合物一起形成时,可进一步提高电池的各种特性。
也就是,当通过磷酸酯基化合物的交联聚合和具有优异弹性的多官能化合物而形成负极活性材料的涂层时,各材料的电化学性质和机械性质可互补,所述磷酸酯基化合物通过能够令人满意地配合锂离子的结构而具有高亲合力。
在一个实施方案中,多官能化合物可以是选自(甲基)丙烯酸酯基化合物、不饱和碳酸基化合物、乙烯基化合物中的至少一种材料。
(甲基)丙烯酸酯基化合物是每个分子具有至少两个丙烯酸酯基的(甲基)丙烯酸酯基化合物,且(甲基)丙烯酸酯基化合物可以为由式3表示的单体或其低聚物。
在式3中,R3、R4和R5各自独立地为氢或取代或未取代的C1-C4烷基,且m为1~20的整数。
此外,(甲基)丙烯酸酯基化合物可以是选自以下材料中的至少一种材料:二乙二醇二丙烯酸酯(Di(EG)DA)、二乙二醇二甲基丙烯酸脂(Di(EG)DM)、乙二醇二甲基丙烯酸酯(EGDM)、二丙二醇二丙烯酸酯(Di(PG)DA)、二丙二醇二甲基丙烯酸酯(Di(PG)DM)、乙二醇二乙烯醚(EGDVE)、乙氧基化(6)三羟甲基丙烷三丙烯酸酯(ETMPTA)、二乙二醇二乙烯醚(Di(EG)DVE)、三乙二醇二甲基丙烯酸酯(Tri(EG)DM)、双季戊四醇五丙烯酸酯(DPentA)、三羟甲基丙烷三丙烯酸酯(TMPTA)、三羟甲基丙烷三甲基丙烯酸酯(TMPTM)、丙氧基化(3)三羟甲基丙烷三丙烯酸酯(PO(3)TMPTA)、丙氧基化(6)三羟甲基丙烷三丙烯酸酯(PO(6)TMPTA)、聚(乙二醇)二丙烯酸酯(PA1)和聚(乙二醇)二甲基丙烯酸酯,但实施方案不限于此。
多官能化合物还可以与磷酸酯基化合物形成各种类型的共聚物,例如无规共聚物、嵌段共聚物、接枝共聚物等。
基于100重量份的负极活性材料,磷酸酯基化合物的量可以为0.01~50重量份,特别地为1~30重量份。
磷酸酯基化合物的涂层的厚度可以为0.001μm~10μm,特别地为0.1μm~5μm。
负极的孔隙率可以为10~50%,特别地为30~40%。
本文中使用的术语“孔隙率”指的是多孔材料的中空部分对多孔材料总体积的比率,还被称为孔隙度或空隙率。
根据本发明的二次电池用负极可使用以下方法制造,其包括:将包含作为负极活性材料的LTO的负极浆料涂布在集电器上,并对经涂布的集电器进行干燥(步骤(A));通过用溶解有磷酸酯基化合物的溶液浸渍由步骤(A)制造的负极,在LTO粒子的表面上形成磷酸酯基化合物涂层(步骤(B));以及通过热固化、利用电子束或伽马射线的照射进行的光固化或在30℃~80℃温度下进行的稳定反应,使磷酸酯基化合物聚合(步骤(C))。
在步骤(B)中,基于溶剂的重量,磷酸酯基化合物的量可以为0.1重量%~30重量%。
当基于溶剂重量的磷酸酯基化合物的量小于0.1重量%时,则难以形成涂层。另一方面,当基于溶剂重量的磷酸酯基化合物的量大于30重量%时,则锂离子的传输速率会减少,因此电池性能会劣化。这同样适用于其中将多官能化合物添加至磷酸酯基化合物的情况。也就是,基于溶剂的重量,磷酸酯基化合物和多官能化合物的总量(重量)可以为0.1~30重量%,特别地为1~20重量%。
基于溶剂的重量,能与磷酸酯基化合物聚合的多官能化合物在步骤(B)的溶液中的含量可以为0.1重量%~10重量%,特别地为0.1重量%~0.5重量%。当多官能化合物的量太低时,其效果不够。另一方面,当多官能化合物的量太大时,与磷酸酯基化合物的聚合会难以进行。
溶解有磷酸酯基化合物的溶液可包含聚合引发剂、电解液(增塑剂)和锂盐。
聚合引发剂的实例包括但不限于偶氮类化合物如2,2-偶氮二(2-氰基丁烷)、2,2-偶氮二(甲基丁腈)、2,2’-偶氮异丁腈(AIBN)和偶氮双二甲基-戊腈(AMVN),过氧类化合物如过氧化二苯甲酰、过氧化乙酰、过氧化二月桂酰、二叔丁基过氧化物、枯基过氧化氢和过氧化氢及氢过氧化物。特别地,聚合引发剂可以为AIBN、2,2’-偶氮二(2,4-二甲基戊腈)(V65)、二-(4-叔丁基环己基)-过氧二碳酸酯(DBC)等。
聚合引发剂在40℃~80℃的温度下分解形成自由基,并且可通过自由基聚合而与单体反应。通常,自由基聚合通过如下来进行:临时形成高活性分子或活性位点的引发反应,将单体添加至活性链末端并由此在链末端再次形成活性位点的增长反应,活性位点转移至其他分子的链转移反应,以及活性链中心被破坏的终止反应。
电解液还充当增塑剂。例如,电解液可以为非质子有机溶剂如N-甲基-2-吡咯烷酮、碳酸亚丙酯(PC)、碳酸亚乙酯(EC)、碳酸亚丁酯(BC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、γ-丁内酯、1,2-二甲氧基乙烷、四氢呋喃、2-甲基四氢呋喃、二甲亚砜、1,3-二氧戊环、甲酰胺、二甲基甲酰胺、二氧戊环、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二氧戊环衍生物、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、碳酸亚丙酯衍生物、四氢呋喃衍生物、醚、丙酸甲酯和丙酸乙酯。电解液可以单独使用或以其至少两种的组合使用。
锂盐是易溶于非水电解液中并且因此分解成锂离子的材料。其实例包括LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂族羧酸锂、四苯基硼酸锂和酰亚胺。这些锂盐可单独使用或其至少两种的组合使用。
基于总固体量,锂盐的含量可以为0.01重量%~30重量%,特别地为0.1重量%~20重量%。
此外,为了提高充放电特性和阻燃性,例如,可以向电解液中添加吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正甘醇二甲醚、六磷酰三胺(hexaphosphoric triamide)、硝基苯衍生物、硫、醌亚胺染料、N-取代的唑烷酮、N,N-取代的咪唑烷、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇、三氯化铝等。在某些情况下,为了赋予不燃性,电解液还可包含含卤素的溶剂如四氯化碳、三氟乙烯等。此外,为了提高高温储存特性,非水电解液还可包含二氧化碳气体。
在另一个实施方案中,根据本发明的二次电池用负极可使用以下方法制造,其包括:将包含作为负极活性材料的LTO和磷酸酯基化合物的负极浆料涂布在集电器上,并对经涂布的集电器进行干燥(步骤(a));以及在步骤(a)制造的负极上通过实施热固化、用电子束或伽马射线的照射进行的光固化或在30℃~80℃温度下进行的稳定反应使磷酸酯基化合物聚合。
本发明还提供包含二次电池用负极的二次电池。所制造的二次电池具有如下结构,其中电解液被包含在电极组件中,所述电极组件包含正极、负极和置于正极和负极之间的隔膜。
正极例如可通过如下制得:将正极活性材料、导电材料和粘合剂的混合物涂布到集电器上,并对经涂布的正极集电器进行干燥和压制。如果需要,所述混合物还可包含填料。
正极集电器通常制造成3~500μm的厚度。正极集电器没有特别限制,只要其在制造的锂二次电池中不引起化学变化且具有高导电性即可。例如,正极集电器可以由如下材料制成:不锈钢,铝,镍,钛,烧结碳,用碳、镍、钛或银进行表面处理的铝或不锈钢等。正极集电器可以在其表面具有微小的不规则处,以提高正极活性材料和正极集电器之间的粘附力。另外,可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式中的任一种使用正极集电器。
正极活性材料的实例包括但不限于:层状化合物如锂钴氧化物(LiCoO2)和锂镍氧化物(LiNiO2)或者被一种以上过渡金属置换的化合物;由Li1+xMn2-xO4(其中0≤x≤0.33)表示的锂锰氧化物如LiMnO3、LiMn2O3和LiMnO2;锂铜氧化物(Li2CuO2);钒氧化物如LiV3O8、LiV3O4、V2O5和Cu2V2O7;由LiNi1-xMxO2(其中M=Co、Mn、Al、Cu、Fe、Mg、B或Ga且0.01≤x≤0.3)表示的Ni位点型锂镍氧化物;由LiMn2-xMxO2(M=Co、Ni、Fe、Cr、Zn或Ta,且0.01≤x≤0.1)或Li2Mn3MO8(M=Fe、Co、Ni、Cu或Zn)表示的锂锰复合氧化物;其中一部分Li原子被碱土金属离子置换的LiMn2O4;二硫化物化合物;和Fe2(MoO4)3。
基于包含正极活性材料的混合物的总重量,通常以1~50重量%的量添加导电材料。对于导电材料没有特别限制,只要其在制造的电池中不引起化学变化并具有导电性而即可。导电材料的实例包括石墨如天然石墨或人造石墨;炭黑类材料如炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑和热裂法炭黑;导电纤维如碳纤维和金属纤维;金属粉末如氟化碳粉末、铝粉和镍粉;导电晶须如氧化锌和钛酸钾;导电金属氧化物如二氧化钛;以及聚亚苯基衍生物。
粘合剂是有助于电极活性材料与导电材料之间的粘合及电极活性材料对电极集电器的粘合的成分。基于包含正极活性材料的混合物的总重量,通常以1~50重量%的量添加粘合剂。粘合剂的实例包括聚偏二氟乙烯、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯基吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、三元乙丙橡胶(EPDM)、磺化的EPDM、丁苯橡胶、氟橡胶和各种共聚物。
任选地使用填料作为用于抑制正极膨胀的成分。填料没有特别限制,只要其为在制造的电池中不引起化学变化的纤维材料即可。填料的实例包括烯烃类聚合物如聚乙烯和聚丙烯;以及纤维材料如玻璃纤维和碳纤维。
负极可以通过将负极活性材料涂布在负极集电器上,并对经涂布的负极集电器进行干燥而制造。在某些情况下,还可将上述成分涂布到负极集电器上。
负极集电器通常制造成3~500μm的厚度。对于负极集电器没有特别限制,只要其在制造的二次电池中不引起化学变化并具有导电性而即可。例如,负极集电器可以由如下材料制成:铜,不锈钢,铝,镍,钛,烧结碳,用碳、镍、钛或银进行表面处理的铜或不锈钢,以及铝-镉合金。与正极集电器类似,负极集电器也可以在其表面上具有微小的不规则处以提高负极集电器和负极活性材料之间的粘合力,且可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式使用。
负极活性材料可以为上述的LTO。
特别地,LTO可以是Li4Ti5O12、LiTi2O4或其混合物,且更特别地,可以是Li4Ti5O12。
此外,负极活性材料的实例包括碳如硬碳和石墨类碳;金属复合氧化物如LixFe2O3(0≤x≤1),LixWO2(0≤x≤1)、SnxMe1-xMe’yOz(Me:Mn,Fe,Pb或Ge;Me’:Al,B,P,Si,I、II和III族元素,或者卤素;0<x≤1;1≤y≤3;且1≤z≤8);锂金属;锂合金;硅基合金;锡基合金;金属氧化物如SnO、SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4和Bi2O5;导电聚合物如聚乙炔;和Li-Co-Ni基材料,且这些负极活性材料可以组合使用。
根据本发明的二次电池可以为锂二次电池,且其实例包括但不限于:锂金属二次电池、锂离子二次电池、锂聚合物二次电池和锂离子聚合物二次电池。可以以各种形式制造二次电池。例如,电极组件可以被制造成包括卷型、堆叠型、堆叠/折叠型等的各种形式,且二次电池可具有其中电极组件安置于电池壳中的结构,所述电池壳为例如圆柱体罐、长方体罐或包括金属层和树脂层的层压片。这种构造在本领域内是已知的,因此在此省略对其的详细描述。
二次电池可用作用于下面描述的小型电子装置和中型和大型装置的电源。
本发明还提供包含所述二次电池作为单元电池的电池模块和包含所述电池模块的电池组。
电池组可用作需要高温稳定性、长循环寿命和高倍率特性的中型和大型装置的电源
中型和大型装置的实例包括但不限于电动机驱动的电动工具;电动车辆(EV),包括混合电动车辆(HEV)和插点式混合电动车辆(PHEV);电动双轮车辆如电动自行车和电动踏板车、电动高尔夫球车及和电力储存用***。
附图说明
图1是显示根据实验例2在45℃的室内测定的循环特性的图。
具体实施方式
现在,将参考下面的实施例对本发明进行更详细的描述。提供这些实施例仅用于解释本发明而不应被解释为对本发明的范围和主旨的限制。
<实施例1>
负极的制造
以95:2.5:2.5的重量比将作为负极活性材料的Li1.33Ti1.67O4、作为导电材料的超导电乙炔炭黑(Denka black)和作为粘合剂的PVdF添加到NMP中,并在其中混合以制备负极混合物。随后,将所述负极混合物在具有20μm厚度的铜箔上涂布至200μm厚,并轧制和干燥,从而完成负极的制造。
将制造的负极在涂布溶液中浸渍30分钟,以在其上形成涂层,且用电子束照射得到的结构以获得其上具有由磷酸酯基化合物形成的涂层的负极,所述涂布溶液通过将由下式a表示的磷酸酯基丙烯酸酯作为磷酸酯基材料以基于溶剂重量为10重量%的量溶解于作为溶剂的DMC中而制得。
电池的制造
以95:2.5:2.5的重量比将作为正极活性材料的LiNi0.5Mn1.5O4、作为导电材料的超导电乙炔炭黑和作为粘合剂的PVdF添加到NMP中,并在其中混合以制备正极混合物,将正极混合物涂布至具有20μm厚度的铝箔上,并轧制和干燥,从而完成正极的制造。
随后,将聚乙烯膜(厚度:20μm)作为隔膜置于制造的负极和正极之间,且将含有溶于EC/EMC(=1/2(体积%))的1M LiPF6的液体电解质注入其中,从而完成袋形电池的制造。
<实施例2>
以与实施例1中相同的方式制造袋形电池,不同之处在于将式2(其中R1为H,且n为1)的焦磷酸酯基丙烯酸酯用作磷酸酯基材料。
<实施例3>
以与实施例1中相同的方式制造袋形电池,不同之处在于,还将作为多官能化合物的双季戊四醇五丙烯酸酯(DPentA)以基于溶剂的重量为0.2重量%的量添加至含有磷酸酯基材料的溶液中。
<实施例4>
以与实施例2中相同的方式制造袋形电池,不同之处在于,还将作为多官能化合物的DPentA以基于溶剂的重量为0.2重量%的量添加至含有磷酸酯基材料的溶液中。
<实施例5>
负极的制造
以95:2.5:2.5的重量比将作为负极活性材料的Li1.33Ti1.67O4、作为导电材料的超导电乙炔炭黑和作为粘合剂的PVdF添加到NMP中,并在其中混合以制备负极混合物。随后,将所述负极混合物在具有20μm厚度的铜箔上涂布至200μm厚,并轧制和干燥,从而完成负极的制造。
将制造的负极在涂布溶液中浸渍30分钟,以在其上形成涂层,且用电子束照射得到的结构,以获得其上具有由磷酸酯基化合物形成的涂层的负极,所述涂布溶液通过将由下式a表示的磷酸酯基丙烯酸酯作为磷酸酯基材料以基于溶剂重量为0.2重量%的量溶于作为溶剂的DMC中而制得。
电池的制造
以95:2.5:2.5的重量比将作为正极活性材料的LiNi0.5Mn1.5O4、作为导电材料的超导电乙炔炭黑和作为粘合剂的PVdF添加到NMP中,并在其中混合以制备正极混合物,将正极混合物涂布至具有20μm厚度的铝箔上,并轧制和干燥,从而完成正极的制造。
随后,将聚乙烯膜(厚度:20μm)作为隔膜置于制造的负极和正极之间,且将含有溶于EC/EMC(=1/2(体积%))的1M LiPF6的液体电解质注入其中,从而完成袋形电池的制造。
<实施例6>
以与实施例5相同的方式制造袋形电池,不同之处在于,还将作为多官能化合物的DPentA以基于溶剂的重量为0.2重量%的量添加至含有磷酸酯基材料的溶液中。
<比较例1>
以与实施例1中相同的方式制造袋形电池,不同之处在于,不向制造的负极中添加磷酸酯基丙烯酸酯。
<比较例2>
以与实施例1中相同的方式制造2016硬币电池,不同之处在于使用通过向溶剂中添加以基于溶剂的重量为40重量%的量的式a的化合物而制备的涂布溶液。
<实验例1>
在2.75V下形成根据实施例1~6和比较例1和2制造的电池(设计容量:10.2mAh),在2.75V~1.6V的电压下对各电池实施C-倍率充放电循环,并确认其放电容量。结果示于下表1中。
表1
放电容量(1C) | |
实施例1 | 8.7mAh |
实施例2 | 8.2mAh |
实施例3 | 8.6mAh |
实施例4 | 8.4mAh |
实施例5 | 9.3mAh |
实施例6 | 8.7mAh |
比较例1 | 9.2mAh |
比较例3 | 7.2mAh |
<实验例2>
在45℃的室内,测定实施例1和3及比较例1和2的电池在1.6V~2.75V的电压和5C下的充放电期间的5C/5C循环特性。测定结果示于图1中。
本领域技术人员可以以上述内容为基础,在本发明的范围内进行各种应用和变化。
工业应用性
从上述可清楚,根据本发明的二次电池用负极使用其表面用磷酸酯基化合物涂布的锂钛氧化物作为负极活性材料,因此可以因稳定的电极界面而展现优异的高温存储特性、高功率输出特性和优异的寿命特性。
Claims (21)
1.一种二次电池用负极,其包含:涂布于集电器上的包含负极活性材料的负极混合物,其中所述负极活性材料包含在其表面上具有交联聚合物涂层的锂钛氧化物(LTO)粒子,
其中在其上形成有交联聚合物涂层的所述LTO粒子具有形成在其间的多孔结构,并且所述涂层的交联聚合物为磷酸酯基化合物,
其中所述磷酸酯基化合物为选自由下式1表示的磷酸酯基丙烯酸酯、由下式2表示的焦磷酸酯基丙烯酸酯和磷酸酯基氨基甲酸酯丙烯酸酯中的至少一种材料,
其中R1和R2各自独立地为氢、甲基或F,且n为1~20的整数。
2.根据权利要求1的负极,还包含能与所述磷酸酯基化合物聚合的多官能化合物。
3.根据权利要求2的负极,其中所述多官能化合物是选自(甲基)丙烯酸酯基化合物、不饱和碳酸基化合物和乙烯基化合物中的至少一种材料。
4.根据权利要求3的负极,其中所述(甲基)丙烯酸酯基化合物是每个分子具有至少两个丙烯酸酯基的(甲基)丙烯酸酯基化合物。
5.根据权利要求4的负极,其中所述(甲基)丙烯酸酯基化合物是由式3表示的单体或其低聚物:
其中R3、R4和R5各自独立地为氢或取代或未取代的C1-C4烷基,且m为1~20的整数。
6.根据权利要求4的负极,其中所述(甲基)丙烯酸酯基化合物为选自以下材料中的至少一种材料:二乙二醇二丙烯酸酯(Di(EG)DA)、二乙二醇二甲基丙烯酸脂(Di(EG)DM)、乙二醇二甲基丙烯酸酯(EGDM)、二丙二醇二丙烯酸酯(Di(PG)DA)、二丙二醇二甲基丙烯酸酯(Di(PG)DM)、乙二醇二乙烯醚(EGDVE)、乙氧基化(6)三羟甲基丙烷三丙烯酸酯(ETMPTA)、二乙二醇二乙烯醚(Di(EG)DVE)、三乙二醇二甲基丙烯酸酯(Tri(EG)DM)、双季戊四醇五丙烯酸酯(DPentA)、三羟甲基丙烷三丙烯酸酯(TMPTA)、三羟甲基丙烷三甲基丙烯酸酯(TMPTM)、丙氧基化(3)三羟甲基丙烷三丙烯酸酯(PO(3)TMPTA)、丙氧基化(6)三羟甲基丙烷三丙烯酸酯(PO(6)TMPTA)、聚(乙二醇)二丙烯酸酯(PA1)和聚(乙二醇)二甲基丙烯酸酯。
7.根据权利要求1的负极,其中基于100重量份的负极活性材料,磷酸酯基化合物的量为0.01重量份~50重量份。
8.根据权利要求1的负极,其中由磷酸酯基化合物形成的交联聚合物涂层的厚度为0.001μm~10μm。
9.根据权利要求1的负极,所述负极具有10%~50%的孔隙率。
10.一种制造权利要求1的二次电池用负极的方法,所述方法包括:
将包含作为负极活性材料的锂钛氧化物(LTO)的负极浆料涂布在集电器上,并对经涂布的集电器进行干燥;
通过利用溶解有磷酸酯基化合物的溶液浸渍由上述步骤制造的负极,在LTO粒子的表面上形成磷酸酯基化合物涂层;以及
通过热固化、用电子束或伽马射线的照射进行的光固化或在30℃~80℃温度下进行的稳定反应,使磷酸酯基化合物聚合。
11.根据权利要求10的方法,其中基于溶剂的重量,所述磷酸酯基化合物的含量为0.1重量%~30重量%。
12.根据权利要求10的方法,其中所述溶液包含聚合引发剂、电解液和锂盐。
13.根据权利要求12的方法,其中基于固体的总重量,所述锂盐的含量为1重量%~30重量%。
14.根据权利要求10的方法,其中在所述形成步骤中使用的溶液中,基于溶剂的重量,能与磷酸酯基化合物聚合的多官能化合物的含量为0.1重量%~10重量%。
15.一种制造权利要求1的二次电池用负极的方法,所述方法包括:
将包含作为负极活性材料的锂钛氧化物(LTO)和磷酸酯基化合物的负极浆料涂布在集电器上,并对经涂布的集电器进行干燥;以及
在通过涂布制造的负极上通过实施热固化、利用电子束或伽马射线的照射进行的光固化或在30℃~80℃温度下进行的稳定反应,使磷酸酯基化合物聚合。
16.一种二次电池,其包含权利要求1~9任一项的二次电池用负极。
17.根据权利要求16的二次电池,其中所述二次电池是锂二次电池。
18.一种电池模块,其包含权利要求17的二次电池作为单元电池。
19.一种电池组,其包含权利要求18的电池模块。
20.一种装置,其包含权利要求19的电池组。
21.根据权利要求20的装置,其中所述装置为电动车辆、混合电动车辆、插电式混合电动车辆或用于储存电力的***。
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TWI481101B (zh) | 2015-04-11 |
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