CN112042032A - 用于运行锂离子电池的方法、锂离子电池和机动车 - Google Patents
用于运行锂离子电池的方法、锂离子电池和机动车 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 26
- -1 imidazolium compound Chemical class 0.000 claims abstract description 20
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910010941 LiFSI Inorganic materials 0.000 claims abstract description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910013188 LiBOB Inorganic materials 0.000 claims abstract description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims abstract description 6
- 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 claims abstract description 6
- 239000000654 additive Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 3
- YQFWGCSKGJMGHE-UHFFFAOYSA-N 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1 YQFWGCSKGJMGHE-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000004693 imidazolium salts Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- DNYFRZWSAXJSSI-UHFFFAOYSA-N trifluoro(sulfosulfonyl)methane Chemical compound OS(=O)(=O)S(=O)(=O)C(F)(F)F DNYFRZWSAXJSSI-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种用于运行锂离子电池(1)的方法,锂离子电池包括至少一个锂离子电池单元和加热装置(2),该加热装置(2)构造用于在5℃至90℃的温度范围内运行锂离子电池(1),该锂离子电池单元具有阳极(4)、阴极(5)、分隔件(6)、集电器(7)和电解质(3),所述方法包括在5℃至90℃的温度范围内运行锂离子电池(1)的步骤,并且所述电解质(3)包含:LiBOB作为导电盐和选自PC和EC的至少一种作为溶剂或LiFSI和/或LiDFOB作为导电盐和至少一种乙二醇醚和/或DMC作为溶剂或LiFSI和/或LiTFSI和/或LiDFOB和/或LiTDI作为导电盐和至少一种选自咪唑鎓化合物、吡咯烷鎓化合物和哌啶鎓化合物的化合物作为溶剂。
Description
技术领域
本发明涉及一种用于运行锂离子电池的方法、锂离子电池和机动车,其具有高使用安全性和长使用寿命。
背景技术
迄今为止,锂离子电池设计用于在-40℃至+60℃的温度范围内运行。为了避免低温下的功率损失,例如由DE 102012210146 A1已知借助加热装置将电池单元芯加热到适合的温度。由于要求锂离子电池即使在低温下也能正常工作,所以需要使用低沸点溶剂,但低沸点溶剂在高温下(例如基于较高的压力产生和形成***性空气溶剂混合物的趋势等)又不利于电池的整体安全性。这需要使用冷却***。总之,这种锂离子电池的构造非常复杂并且在安全性和因此锂离子电池的寿命方面存在风险。
发明内容
鉴于上述现有技术,本发明的任务在于,提出一种用于运行锂离子电池的方法以及一种锂离子电池和包括这种锂离子电池的机动车,它们的突出之处在于,在结构设计简单的同时用户安全性高并且锂离子电池的使用寿命长。
所述任务通过独立权利要求的特征来解决。
因此,所述任务通过一种用于运行锂离子电池的方法来解决,该锂离子电池尤其是构造为锂离子蓄电池并且包括至少一个锂离子电池单元、通常是多个堆叠的锂离子电池单元以及加热装置。每个锂离子电池单元还包括阳极、阴极、分隔件、集电器和电解质。加热装置在此构造用于在5℃至90℃的温度范围内运行锂离子电池。
因此,根据本发明,尤其是通过使用加热装置使锂离子电池仅在5℃至90℃并且尤其是10℃至80℃的温度范围内运行。换句话说,这意味着,通过使用根据本发明的方法,锂离子电池仅在正温度范围内运行并且也仅为此而设计。由此带来许多优点:例如可使用一般不能在低温下使用的导电盐。这些导电盐通常的突出之处在于更高的稳定性,这反映在锂离子电池的持续良好的功率输出中。还可使用安全性优化的、使用寿命优化的、电压水平优化的并且成本优化的溶剂。
因此,电解质包含LiBOB(双草酸硼酸锂)作为导电盐和至少一种选自PC(碳酸亚丙酯)、EC(碳酸亚乙酯)及其混合物的溶剂。这种电解质不含倾向于形成HF的LiPF6。因此提高了用户安全性。该溶剂具有高沸点,这大大提高了锂离子电池运行的安全性。另外,这种电解质与石墨非常良好地相容,石墨主要存在于电池的电极中、尤其是在阳极侧,从而延长了锂离子电池的使用寿命。LiBOB的突出之处还在于高的热稳定性,这也有利于锂离子电池的使用寿命。
作为替代方案,电解质包含LiFSI(双(氟磺酰基)亚氨酸锂)和/或LiDFOB(二氟草酸硼酸锂)作为导电盐和至少一种乙二醇醚和/或DMC(碳酸二甲酯)作为溶剂。也可使用多种乙二醇醚。还可与DMC组合使用。这种电解质也不含倾向于形成HF的LiPF6,由此提高了锂离子电池的用户安全性。另外,所使用的导电盐非常稳定。乙二醇醚和DMC通常具有高沸点,因而从这个角度也改善了锂离子电池的使用寿命和安全性。
作为另一替代方案,电解质包含LiFSI(双(氟磺酰基)亚氨酸锂)和/或LiTFSI(双(三氟甲烷)磺酸亚磺酸锂)和/或LiDFOB(二氟硼酸锂)和/或LiTDI(4,5-二氰基锂-2-(三氟甲基)锂)咪唑作为导电盐和至少一种选自咪唑鎓化合物、吡咯烷鎓化合物和哌啶鎓化合物的化合物作为溶剂。这意味着,一种或多种咪唑鎓化合物、一种或多种吡咯烷鎓化合物或一种或多种咪唑鎓化合物或这些化合物的任意组合均可用作溶剂。上述溶剂的突出之处是蒸汽压低、在约200℃的温度下不易燃且具有高燃点。因此,通过使用这种电解液可显著提高用户安全性和锂离子电池的使用寿命。这种电解液也不含倾向于形成HF的LiPF6,由此进一步提高了锂离子电池的用户安全性。另外,所述导电盐的突出之处在于高的热稳定性,这也有利于锂离子电池的热稳定性。
因此,根据本发明的方法允许锂离子电池能够在高的功率密度和电压水平下运行并且具有高的用户安全性、良好的热稳定性和因此电池的非常好的使用寿命。此外,通过将锂离子电池设计成在5℃至90℃的温度范围内运行而无需冷却,这大大简化了方法。此外,这使锂离子电池的材料和设计具有更多的设计可能性。
从属权利要求的内容是本发明的有利扩展方案和实施方式。
根据一种有利的扩展方案规定,如果电解质包含LiFSI和/或LiDFOB作为导电盐和至少一种乙二醇醚和/或DMC作为溶剂,则导电盐的总浓度大于3M至10M、优选4M至7M。这在非常好的长期稳定性下提高了锂离子电池的功率密度。
基于在热负荷下的非常好的稳定性和高可用性,乙二醇醚优选选自:1,1-二甲氧基乙烷、1,2-二甲氧基乙烷、双(2-甲氧基乙基)醚及其混合物。
为了进一步提高温度稳定性,所述咪唑鎓化合物、吡咯烷鎓化合物和哌啶鎓化合物具有氟化阴离子。
特别有利的是,基于低蒸汽压、高燃点和低易燃性,吡咯烷鎓化合物是1-丙基-1-甲基吡咯烷鎓双(氟磺酰基)酰亚胺。
此外,通过有利的扩展方案可进一步提高用户安全性,根据该扩展方案,电解质不含氟化导电盐、尤其是不含LiPF6。
为了提高长期稳定性,有利的是,在锂离子电池投入运行之前,电解质还包含至少一种防腐蚀添加剂、尤其是至少一种含氟的防腐蚀添加剂。本领域技术人员可从市售的防腐蚀添加剂中选择适合的防腐蚀添加剂。作为用于铝的防腐蚀添加剂,尤其是可少量使用LiPF6,即相对于电解质总质量其质量百分比最大为3%。当锂离子电池投入运行时,LiPF6完全被消耗以便在含铝表面、如壳体或集电器上形成防腐蚀层并且因此不再是电解质的组成部分。
为了进一步简化方法的实施,加热装置是电池单元内部加热装置。这意味着,加热装置直接设置在电池单元内部、例如设置在所谓的卷芯(jelly roll)或电极堆垛之间,从而显著简化了热量的高效供应。作为替代方案,加热装置也可设置在电池单元壳体外部,在此与电池单元内部加热类似,加热能量来自于电池单元本身。加热装置例如可构造成加热垫的形式。
本发明的另一方面涉及一种锂离子电池,其尤其是构造为锂离子蓄电池并且包括至少一个锂离子电池单元和加热装置、尤其是电池单元内部加热装置的形式,所述加热装置构造用于在5℃至90℃的温度范围内运行锂离子电池,所述锂离子电池单元具有阳极、阴极、分隔件、集电器和电解质,并且所述电解质LiBOB作为导电盐和选自PC和EC的至少一种作为溶剂或LiFSI和/或LiDFOB作为导电盐和至少一种乙二醇醚和/或DMC作为溶剂或LiFSI和/或LiTFSI和/或LiDFOB和/或LiTDI作为导电盐和至少一种选自咪唑鎓化合物、吡咯烷鎓化合物和哌啶鎓化合物的化合物作为溶剂。根据本发明的锂离子电池尤其是通过使用加热装置在5℃至90℃、尤其是10℃至80℃的温度范围内运行并且突出之处在于基于根据本发明设计的电解质与加热装置组合而在高功率密度的同时具有高用户安全性、长使用寿命、设计和材料方面的高设计自由度。
关于优点、有益效果和解释,补充参考关于根据本发明的用于运行锂离子电池的方法的说明。此外应指出,根据本发明的方法适合于借助根据本发明的锂离子电池来应用,或者根据本发明的锂离子电池适合于实施根据本发明的方法。因此,优点、有益效果和扩展方案相互适用。
作为本发明的另一方面,还描述了一种机动车,其包括如上所述的锂离子电池。该机动车的突出之处在于持续高功率和高使用安全性。基于所设置的加热装置而无需冷却锂离子电池,因此也无需设置可能会影响机动车紧凑性的冷却回路。
附图说明
本发明的其它细节、特征和优点从下述说明和附图中得出。附图如下:
图1示出根据本发明一种实施方式的锂离子电池的示意性剖面图。
具体实施方式
附图中仅示出本发明的重要特征。为清楚起见,所有其它特征都被省略。
具体而言,图1示出锂离子电池1,其尤其是构造为锂离子蓄电池并且其包括一个锂离子电池单元和加热装置2。加热装置2构造成电池单元内部加热装置的形式。在此不言而喻,锂离子电池可包括多个尤其是堆叠的锂离子电池单元。
锂离子电池单元包括阳极4、阴极5、分隔件6、集电器7和电解质3。阳极4和阴极5如通常那样构造并且通常包括碳载体材料。电解质3可存在于阳极4、阴极5和分隔件6中并且也可能存在于集电器7中并且包含LiBOB作为导电盐和至少一种选自PC和EC的溶剂,在此也可使用PC和EC的混合物。作为替代方案,电解质3可包含LiFSI和/或LiDFOB作为导电盐和至少一种乙二醇醚和/或DMC作为溶剂或者LiFSI和/或LiTFSI和/或LiDFOB和/或LiTDI作为导电盐和至少一种选自咪唑鎓化合物、吡咯烷鎓化合物和哌啶鎓化合物的化合物作为溶剂。根据本发明的锂离子电池1通常设置在壳体中并且尤其是通过使用加热装置2在5℃至90℃、尤其是10℃至80℃的温度范围内运行。
基于锂离子电池1和专门设计的电解质3的符合规定的使用,可在高功率密度的同时实现高用户安全性、长使用寿命以及设计和材料方面的高设计自由度。锂离子电池1基于在非常高功率密度下的紧凑结构、非常好的热稳定性、高用户安全性以及长使用寿命而特别适合用于机动车。
附图标记列表
1 锂离子电池
2 加热装置
3 电解质
4 阳极
5 阴极
6 分隔件
7 集电器
Claims (10)
1.用于运行锂离子电池(1)的方法,所述锂离子电池包括至少一个锂离子电池单元和加热装置(2),该加热装置(2)构造用于,在5℃至90℃的温度范围内运行锂离子电池(1),该锂离子电池单元具有阳极(4)、阴极(5)、分隔件(6)、集电器(7)和电解质(3),所述方法包括在5℃至90℃的温度范围内运行锂离子电池(1)的步骤,并且所述电解质(3)包含:
a)LiBOB作为导电盐和选自PC和EC的至少一种作为溶剂,或
b)LiFSI和/或LiDFOB作为导电盐和至少一种乙二醇醚和/或DMC作为溶剂,或
c)LiFSI和/或LiTFSI和/或LiDFOB和/或LiTDI作为导电盐和至少一种选自咪唑鎓化合物、吡咯烷鎓化合物和哌啶鎓化合物的化合物作为溶剂。
2.根据权利要求1所述的方法,其中,如果电解质(3)包含LiFSI和/或LiDFOB作为导电盐和至少一种乙二醇醚和/或DMC作为溶剂,则导电盐的总浓度大于3M至10M、优选4M至7M。
3.根据权利要求1或2所述的方法,其中,所述乙二醇醚选自:1,1-二甲氧基乙烷、1,2-二甲氧基乙烷、双(2-甲氧基乙基)醚及其混合物。
4.根据权利要求1所述的方法,其中,所述咪唑鎓化合物、吡咯烷鎓化合物和哌啶鎓化合物具有氟化阴离子。
5.根据权利要求1或4所述的方法,其中,所述吡咯烷鎓化合物是1-丙基-1-甲基吡咯烷鎓双(氟磺酰基)酰亚胺。
6.根据前述权利要求中任一项所述的方法,其中,所述电解质(3)不含氟化导电盐。
7.根据前述权利要求中任一项所述的方法,其中,在锂离子电池(1)投入运行之前,所述电解质(3)还包括至少一种含氟的防腐蚀添加剂。
8.根据前述权利要求中任一项所述的方法,其中,所述加热装置(2)是电池单元内部加热装置。
9.锂离子电池,包括至少一个锂离子电池单元(1)和加热装置(2),所述加热装置(2)构造用于在5℃至90℃的温度范围内运行锂离子电池(1),所述锂离子电池单元具有阳极(4)、阴极(5)、分隔件(6)、集电器(7)和电解质(3),并且所述电解质(3)包含:
a)LiBOB作为导电盐和选自PC和EC的至少一种作为溶剂,或
b)LiFSI和/或LiDFOB作为导电盐和至少一种乙二醇醚和/或DMC作为溶剂,或
c)LiFSI和/或LiTFSI和/或LiDFOB和/或LiTDI作为导电盐和至少一种选自咪唑鎓化合物、吡咯烷鎓化合物和哌啶鎓化合物的化合物作为溶剂。
10.机动车,包括根据权利要求9所述的锂离子电池(1)。
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