CN115084650A - 储能器与机动车 - Google Patents
储能器与机动车 Download PDFInfo
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- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
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Abstract
本发明涉及一种尤其用于机动车(1)的储能器(4)。该储能器(4)具有:二次单电池(8),该二次单电池带有两个互补的电极(12)、将这些电极隔开的分隔器(16)、包围电极(12)和分隔器(16)的单电池壳体(10);以及电解质(14),单电池壳体(10)填充有该电解质。此外,在单电池壳体(10)内存在空心玻璃球(20),这些空心玻璃球填充有一定量的电解质(14)和/或添加物,并且这些空心玻璃球与容纳在单电池壳体(10)中的电解质(14)接触。
Description
技术领域
本发明涉及一种储能器,尤其用于机动车的储能器。本发明此外涉及一种具有这种储能器的机动车。
背景技术
用于机动车、尤其用于电动地运行的(也包括设计为插电式混合动力的)机动车的储能器,通常包括至少一个、但往往大量的(尤其电化学的)二次单电池(Sekundaerzelle),即可再充电电池单体。这些二次单电池通常多个地组合在一个电池模块中,并且多个电池模块组合成牵引电池以提高可调用的功率。尤其地,在此采用基于锂的二次单电池,尤其锂离子单电池(“Li-Ionen-Zellen”)。
然而,二次单电池-尤其由于副反应-经受老化过程,老化过程尤其会导致锂离子的“损失”。由于锂离子在电化学反应中在二次单电池内形成电荷载体,因此这种损失公知地会导致电荷传输减少,这又导致二次单电池的电容量和/或性能的-通常不希望的-降低。
发明内容
本发明的目的是实现储能器的延迟老化。
根据本发明,该目的通过一种尤其用于机动车的储能器来实现。此外根据本发明,该目的通过一种机动车来实现。本发明的有利的和部分本身创造性的实施方式和改进方案在以下描述中阐明。
根据本发明的储能器优选用于使用在机动车、尤其陆上有轮机动车中,或与其一起使用。在此,储能器具有(尤其至少)一个二次单电池,所述二次单电池具有(最少至少)两个彼此互补的电极(即尤其阳极和阴极)、将这些电极隔开(即尤其在空间上彼此分隔)的分隔器以及包裹着电极和分隔器的单电池壳体。此外,储能器具有电解质,该电解质优选地同样是二次单电池的一部分,并且单电池壳体填充有该电解质。此外,二次单电池具有位于单电池壳体内的空心玻璃球,这些空心玻璃球填充有一定量的电解质和/或添加物,并且这些空心玻璃球-尤其以其外面-与容纳在单电池壳体中的电解质接触。
电解质优选为液体,也称为电解质溶液或液体电解质。
单电池壳体可选地由比较刚性的金属板或由层压箔形成。后者尤其用于在二次单电池形成所谓的“软包电池”时的情况。
添加物优选地是用于电解质的添加物,该添加物例如用于提高其耐温性和/或抑制老化过程等。
玻璃球优选地形成用于额外量的电解质或添加物(可选地也用于多种添加物)的蓄存器,该蓄存器实现在二次单电池的运行期间时间延迟地提供相应的内容物。在此,这种时间延迟的提供优选地通过下述方式进行:破坏玻璃球的(外)壁,并且由此引起内容物(即电解质或添加物)排出到二次单电池的“游离”电解质中。由此例如可以通过添加额外的锂离子来使得已经老化的电解质“刷新”或“更新”。因此可以延长二次单电池的使用寿命和/或延迟其老化。
在优选的实施方案中,空心玻璃球的壁仅由玻璃形成。
在进一步优选的实施方案中,如此选择空心玻璃球的玻璃,使得其通过与电解质的化学反应而溶解,可选地完全溶解。这具有的优点是,这种化学反应基本上可以独立于二次单电池的运行状态和/或其负荷率地进行,并且因此可以比较容易地预先确定相应的空心玻璃球的内容物的释放时间点。此外,玻璃的溶解常常由副产物引发,这些副产物在二次单电池的运行中形成,并且(尤其除了消耗锂离子之外)同样导致电池老化、至少导致其性能降低。通过它们与玻璃的化学反应,这些副产物可以有利地被“捕获”(例如结合或转化),并且因此可以减缓和/或延迟电池老化。
在二次单电池的运行中常常出现的副产物例如是水和氢氟酸(HF),它们尤其由电解质的锂盐(或可能还有几种不同的锂盐,如果存在的话)形成。后者尤其当电解质中存在痕量水时就是这种情况。备选地亦或附加地,电解质的降解产物也可以与六氟磷酸盐(HF6)反应,并在这种情况下释放氢氟酸。众所周知,氢氟酸在这种情况下会侵蚀和溶解玻璃。
除了至少一种有机溶剂之外,电解质还具有至少一种锂盐(也叫:“锂-导电盐”)。作为这种锂盐,例如至少采用LiAsF6、LiClO4、LiSbF6、LiPtCl6、Li(CF3)SO3(LiTf)、LiC(SO2CF3)3、基于磷酸盐的锂盐–例如LiPF6、LiPF3(CF3)3(LiFAP)和LiPF4(C2O4)(LiTFOB)、基于硼酸盐的锂盐–例如LiBF4、LiB(C2O4)2(LiBOB)、LiBF2(C2O4)(LiDFOB)、LiB(C2O4)(C3O4)(LiMOB)、Li(C2F5BF3)(LiFAB)和Li2B12Fi2(LiDFB)、L-和/或磺酰亚胺锂盐–例如LiN(SO2CF3)2(LiTFSI)和LiN(SO2C2F5)2(LiBETI)。特别优选的锂-导电盐是LiPF6(六氟磷酸锂)或其混合物。作为溶剂,例如采用碳酸亚乙酯、碳酸亚丙酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、乙腈、戊二腈、己二腈、庚二腈、γ-丁内酯、γ-戊内酯、二甲氧基乙烷、1,3-二恶烷、乙酸甲酯和/或其混合物。
作为添加物,例如可以采用三(2,2,2-三氟乙基)亚磷酸酯(TTFP)、1-甲基-2-吡咯烷酮、氟化氨基甲酸酯和/或六甲基磷酰胺。
在一种适宜的实施方案中,空心玻璃球的玻璃例如是硅酸盐玻璃、铝硅酸盐玻璃、磷硅酸盐玻璃、磷酸盐玻璃、硼酸盐玻璃和/或硼硅酸盐玻璃。
在一种有利的实施方案中,空心玻璃球的壁如此设计,使得壁不会通过前述化学反应而完全溶解,而是仅部分溶解。由此相应空心玻璃球的内容物可以在某个时间点排出,但在壁的可溶组分溶解后,球结构至少部分得以保持。这种例如骨骼形式的、在初始状态下穿过可溶性组分的“剩余结构”,那么可以有利地继续形成某种空间承载结构,并且例如防止二次单电池的具有空心玻璃球的元件的结构坍塌(后者尤其是在比较大的空心玻璃球的情况下)。对此,例如由硼硅酸盐玻璃构成的玻璃空心球的实施方案是适宜的。在这种情况下,由于与电解质(或前述副产物)的反应,硅酸盐部分会随着时间的推移而溶解,但由硼形成的结构仍以骨骼的形式“挺立”。可选地,空心玻璃球的这种部分溶解(以及由此剩余结构的保留)也可以通过不同玻璃或不同掺杂玻璃的组合来实现。例如,用硼或锗掺杂引起在电解质中的不同溶解度,从而可以设置具有一种掺杂的内球和具有另一种掺杂的包围该内球的外球。
在另一种适宜的实施方案中,空心玻璃球的溶解时长通过选择空心玻璃球的壁的壁厚来预设。换言之,直到空心玻璃球的壁并且因此尤其空心玻璃球本身已经溶解的时长,即因此内容物的释放时间点(或时间段),通过合适地选择壁厚来预设。玻璃的反应性也受到化学预应力(或成为预张力,即Vorspannung)的影响,从而在可选的(附加的或备选的)实施方案中,溶解速度由相应的化学预应力预设。为了化学预应力,借助盐浴在玻璃中执行离子交换(小离子相对大离子或者反过来)。
在可选的变型方案中,在此采用具有不同壁厚和/或不同尺寸(即尤其不同直径)的空心玻璃球。由此空心玻璃球内含物的释放可以有利地在比较长的时间段上延伸。在此众所周知地,并非每个空心玻璃球都需要与其他空心玻璃球不同,而是可以采用空心玻璃球的混合物,其覆盖预设范围的不同尺寸。
在适宜的变型方案中,壁厚在1纳米和30微米之间的范围内,尤其在5纳米和5微米之间。空心玻璃球的直径优选在10纳米和1毫米之间的范围内,尤其在50纳米和500微米之间,优选在0.1和100微米之间。
在优选的实施方案中,空心玻璃球容纳在二次单电池的前述分隔器和/或至少一个非活动结构元件的涂层中。在此有利地,通常本来就需要的分隔器涂层可以被扩展额外的用途-即作为用于空心玻璃球的载体材料。这鉴于经济地制造也是有利的,因为不需要额外的涂层过程。对于空心玻璃球如前所述地被设计成使得保持剩余结构(即不化学溶解)的情况,在该实施方案中,也可以避免或至少减少分隔器涂层的厚度损失,从而使相应电极与分隔器之间的接触不丧失。
尤其地,这种非活动结构元件是单电池壳体的壁(例如即前述板件或“袋膜”)和/或电极的电流导出部的(尤其未涂覆的)区段。这又具有如下优点,即,可以避免在某些情况下发生的对活动结构元件(尤其电极或分隔器)的特性的影响。对于使该或每个电流导出部设有包含空心玻璃球的涂层的情况,该或相应的电流导出部的接触区域为了随后的电流接触适宜地应保持没有涂层或至少可导电。例如,为此在涂层时使用掩模(或称为掩盖部,即Maske),该掩模导致相应的接触区域不被涂覆。
原则上,空心玻璃球也可以布置在电极的涂层中。然而在此,在电极制造期间、尤其在通常执行的压延过程期间,空心玻璃球的机械破坏的风险比较高。
此外在本发明的范围内还可以设想的是,将空心玻璃球例如嵌入到电极材料或其他结构元件本身中。然而,这里存在如下风险,即,在空心玻璃球溶解后,剩余的空位导致机械不稳定和/或电活动减少。
此外,空心玻璃球还可以-作为前述实施方案的补充或备选-布置在二次单电池的本来就存在的空腔中,只要它们与电解质流体连接。这样的空腔例如是该或相应的电极的本来就存在的孔,所述孔大多数具有在20至30体积百分比范围内的孔隙率。这种孔在此具有尤其0.1至15微米的范围内的尺寸(直径),并且因此至少部分地处于空心玻璃球的前述直径的范围内,从而空心玻璃球-至少其具有对应直径范围的部分-也可以被引入到这些孔中。
根据本发明的机动车尤其形成先前提到的机动车,并且在此包括前述储能器。因此,在适宜的实施方案中,机动车具有与储能器相同的前述特征。此外,对于机动车也出现与储能器相同的优点。
在此以及在下文中,连词“和/或”尤其应这样来理解为,即,借助该连词关联的各特征既可以共同地又可以彼此备选地构造。
附图说明
下面依据附图更详细地阐述本发明的实施例。其中:
图1示出了电动运行的具有储能器的机动车的示意图;和
图2以示意性的局部剖视图示出了机动车的储能器的二次单电池。
在所有图中,彼此相应的部分始终设有相同的附图标记。
具体实施方式
在图1中示意性地示出了机动车1。该机动车1是陆上有轮车辆,具体为乘用车。机动车1电动驱动并且为此具有电动机2以及牵引电池4。牵引电池4又具有多个电池模块6,在此具体为四个,这些电池模块又具有多个二次单电池8(见图2)。因此,牵引电池4是机动车1的储能器。
每个二次单电池8都具有单电池壳体(简称:壳体10),在单电池壳体中多个成对的电极12布置在也简称为“电解质”的电解质溶液14内。在当前实施例中,仅示出了一对电极12。二次单电池8此外具有分隔器16,该分隔器布置在两个电极12之间并且在空间上将它们彼此分隔开。在每个电极12处此外连结有接触金属箍18(也称为“电流导出部”),该接触金属箍以介质密封的方式从壳体10引出。
为了延缓二次单电池8由于锂离子的消耗而老化,每个二次单电池8具有用于时间延迟地释放电解质的蓄存器。蓄存器由大量的空心玻璃球20形成,这些空心玻璃球在其内腔中包围一定量的电解质溶液14。空心玻璃球20如此地布置在二次单电池8中,使得空心玻璃球20持续地与容纳在壳体10中的“游离”电解质溶液14接触。由此空心玻璃球20的玻璃被电解质溶液14分解,直到空心玻璃球20的壁(即它们的玻璃壳)瓦解并且内容物由此被释放。
在所示的实施例中,空心玻璃球20嵌入到在壳体10内侧的未示出的涂层中,然而以这样的方式,使得提供与电解质溶液14的接触。
在备选的或可选的附加实施例中-在图2中用虚线示出-空心玻璃球20嵌入到分隔器16和/或接触金属箍18的相应涂层中(为了清楚起见,仅针对分离器16的一侧和一个接触金属箍18示出)。
为了能够预设空心玻璃球20的内容物释放的时间点和因此其溶解时长,空心玻璃球20的壁厚选择为相应地厚(更大的壁厚值)或薄。为了使释放的时间段设计得尽可能长,使用具有不同壁厚值的空心玻璃球20。为了阐明,图2中的空心玻璃球20用不同的尺寸示出。
本发明的主题不限于前述实施例。更确切地说,本领域技术人员可以从以上描述中推导出本发明的其他实施方式。尤其本发明的依据不同实施例描述的各个特征及其设计变型方案也可以以其他方式相互组合。
附图标记清单:
1机动车
2电动机
4牵引电池
6电池模块
8二次单电池
10壳体
12电极
14电解质溶液
16分隔器
18接触金属箍
20空心玻璃球。
Claims (10)
1.一种尤其用于机动车(1)的储能器(4),具有:
二次单电池(8),所述二次单电池带有两个互补的电极(12)、将这些电极隔开的分隔器(16)、包裹所述电极(12)和所述分隔器(16)的单电池壳体(10);以及电解质(14),所述单电池壳体(10)填充有所述电解质,
其特征在于,
在所述单电池壳体(10)内存在空心玻璃球(20),所述空心玻璃球填充有一定量的电解质(14)和/或添加物,并且所述空心玻璃球与容纳在所述单电池壳体(10)中的电解质(14)接触。
2.根据权利要求1所述的储能器(4),
其中,所述空心玻璃球(20)的壁仅由玻璃形成。
3.根据权利要求1或2所述的储能器(4),
其中,如此选择所述空心玻璃球(20)的玻璃,使得所述玻璃通过与所述电解质的化学反应而溶解,尤其其中,作为玻璃采用硅酸盐玻璃、铝硅酸盐玻璃、磷硅酸盐玻璃、磷酸盐玻璃、硼酸盐玻璃和/或硼硅酸盐玻璃。
4.根据权利要求3所述的储能器(4),
其中,所述空心玻璃球(20)的壁如此设计,使得所述壁通过所述化学反应仅部分溶解,并且在初始状态下穿过所述空心玻璃球(20)的可溶性组分的剩余结构在所述可溶性组分溶解后得以保留。
5.根据权利要求3或4所述的储能器(4),
其中,所述空心玻璃球(20)的溶解时长通过选择所述壁的壁厚来预设。
6.根据权利要求5所述的储能器(4),
其中,采用具有不同壁厚和/或不同直径的空心玻璃球(20)。
7.根据权利要求5或6所述的储能器(4),
其中,所述空心玻璃球(20)具有在1纳米至30微米的范围内、尤其在5纳米和5微米之间的壁厚。
8.根据权利要求1至7中任一项所述的储能器(4),
其中,所述空心玻璃球(20)容纳在所述二次单电池(8)的分隔器(16)和/或至少一个非活动结构元件(10)的涂层中。
9.根据权利要求8所述的储能器(4),
其中,所述非活动结构元件是所述单电池壳体(10)的壁和/或是所述电极(12)的电流导出部(18)的区段。
10.一种机动车(1),具有根据权利要求1至9中任一项所述的储能器(4)。
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