CN111033820A - 非水电解质二次电池用正极及非水电解质二次电池 - Google Patents
非水电解质二次电池用正极及非水电解质二次电池 Download PDFInfo
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- CN111033820A CN111033820A CN201980003807.1A CN201980003807A CN111033820A CN 111033820 A CN111033820 A CN 111033820A CN 201980003807 A CN201980003807 A CN 201980003807A CN 111033820 A CN111033820 A CN 111033820A
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Abstract
作为实施方式的一例的正极,具备:正极集电体;形成于正极集电体的至少一面侧的正极复合材料层;和,夹设于正极集电体与正极复合材料层之间的中间层。中间层由热导率不足50W/mK的绝缘性的无机颗粒、热导率为50W/mK以上的高热导颗粒、热塑性树脂、和聚偏二氟乙烯构成。无机颗粒的含量相对于中间层的质量为50质量%以上。
Description
技术领域
本公开涉及非水电解质二次电池用正极及非水电解质二次电池。
背景技术
以往,已知有在集电体与复合材料层之间形成有包含无机颗粒的中间层的非水电解质二次电池用正极。例如,专利文献1中公开了一种正极,其具备厚度为1~5μm且包含无机颗粒及导电材料的中间层,所述无机颗粒的氧化能力比作为正极活性物质的锂金属复合氧化物低。专利文献1中记载了其可以维持良好的集电性,并且可以抑制正极活性物质和铝集电体的氧化还原反应导致的放热。
现有技术文献
专利文献
专利文献1:日本特开2016-127000号公报
发明内容
然而,锂离子电池等非水电解质二次电池中,抑制内部短路等异常发生时的放热为重要课题。对于专利文献1的技术而言,也期待其发挥上述效果,但内部短路等异常发生时的放热抑制仍有改良的余地。
作为本公开的一方式的非水电解质二次电池用正极的特征在于,其具备:正极集电体;形成于前述正极集电体的至少一面侧的正极复合材料层;和,夹设于前述正极集电体与前述正极复合材料层之间的中间层,前述中间层由热导率不足50W/mK的绝缘性的无机颗粒、热导率为50W/mK以上的高热导颗粒、热塑性树脂和聚偏二氟乙烯构成,前述无机颗粒的含量相对于前述中间层的质量为50质量%以上。
作为本公开的一方式的非水电解质二次电池的特征在于,具备:上述正极;负极;和,非水电解质。
通过作为本公开的一方式的非水电解质二次电池用正极,可以抑制电池的异常发生时的放热。
附图说明
图1为作为实施方式的一例的非水电解质二次电池的剖视图。
图2为作为实施方式的一例的非水电解质二次电池用正极的剖视图。
具体实施方式
作为本公开的一方式的非水电解质二次电池用正极如上所述其具备:具有热导率不足50W/mK的绝缘性的无机颗粒、热导率为50W/mK以上的高热导颗粒、热塑性树脂和聚偏二氟乙烯的中间层。绝缘性的无机颗粒和聚偏二氟乙烯确保中间层的强度,另外还确保中间层对复合材料层及集电体的密合性。进而,通过使用热导率为50W/mK以上的高热导颗粒、及在内部短路等异常发生时会熔融而密合于高热导颗粒的表面以使颗粒间连接的热塑性树脂,可以使短路部位处产生的热迅速扩散,从而可以抑制短路面积的扩大导致的放热。
本发明人等发现:通过使用高热导颗粒和热塑性树脂来改善中间层的热传导性、并提高中间层的热传导性,由此可以抑制内部短路等异常发生时的电池温度的上升。可以认为通过高热导颗粒和热塑性树脂的协同作用,中间层的热传导性得到大幅改善。
以下,对实施方式的一例进行详细地说明。以下例示出将卷绕型的电极体14收纳在圆筒形的电池壳体而成的圆筒形电池,但电极体并不限定于卷绕型,也可以为由多个正极和多个负极隔着分隔件交替层叠而成的层叠型。另外,电池壳体并不限定于圆筒形,也可以为方形(方形电池)、硬币形(硬币形电池)等金属制壳体、由树脂薄膜构成的树脂制壳体(层压电池)等。需要说明的是,本说明书中,数值(A)~数值(B)的记载若无特别说明则表示数值(A)以上且数值(B)以下。
图1为作为实施方式的一例的非水电解质二次电池10的剖视图。如图1所例示,非水电解质二次电池10具备电极体14、非水电解质(未图示)、收纳电极体14及非水电解质的电池壳体15。电极体14具备正极11、负极12和分隔件13,且具有由正极11和负极12隔着分隔件13卷绕而成的卷绕结构。电池壳体15由有底圆筒形状的外装罐16、和封堵外装罐16的开口部的封口体17构成。
非水电解质二次电池10具备分别配置于电极体14上下的绝缘板18、19。图1示出的例中,安装于正极11的正极引线20通过绝缘板18的贯通孔延伸至封口体17侧,安装于负极12的负极引线21通过绝缘板19的外侧延伸至外装罐16的底部侧。正极引线20通过焊接等与作为封口体17的底板的局部开口的金属板23的下表面连接,作为与局部开口的金属板23电连接的封口体17的顶板的盖27成为正极端子。负极引线21通过焊接等与外装罐16的底部内表面连接,外装罐16成为负极端子。
外装罐16例如为有底圆筒形状的金属制容器。外装罐16和封口体17之间设置有垫片28,从而确保电池内部的密闭性。外装罐16中,形成有例如侧面部的一部分向内侧突出的用于支撑封口体17的突出部22。突出部22优选沿着外装罐16的圆周方向形成环状,并通过其上表面支撑封口体17。
封口体17从电极体14侧起具有依次层叠有局部开口的金属板23、下阀体24、绝缘构件25、上阀体26及盖27的结构。构成封口体17的各构件例如具有圆板形状或环形状,除了绝缘构件25外的各构件彼此电连接。下阀体24与上阀体26在各中央部彼此连接,各周缘部之间夹设有绝缘构件25。通过异常放热而电池的内压上升时,下阀体24以将上阀体26向盖27侧顶起的方式变形并断裂、下阀体24与上阀体26之间的电流通路被切断。进而内压上升时,上阀体26断裂,从而气体由盖27的开口部被排出。
[正极]
图2为示出作为实施方式的一例的正极11的一部分的剖视图。如图2所示,正极11具备:正极集电体30、形成于正极集电体30的至少一面侧的正极复合材料层31、和夹设于正极集电体30与正极复合材料层31之间的中间层32。正极集电体30可以使用铝等在正极11的电位范围内稳定的金属的箔、表层配置有该金属的薄膜等。正极集电体30的一例为厚度10~20μm的铝或铝合金的金属箔。
正极复合材料层31包含正极活性物质、导电材料及粘结材料,优选隔着中间层32形成于正极集电体30的两面。正极11可以通过以下方法制作:在形成有中间层32的正极集电体30上涂布包含正极活性物质、导电材料和粘结材料等的正极复合材料浆料,使涂膜干燥后,进行压延,从而在集电体的两面形成正极复合材料层31。正极复合材料层31的厚度例如在正极集电体30的单侧为30~100μm。
作为正极活性物质,可以例示出含有Co、Mn、Ni、Al等金属元素的锂金属复合氧化物。构成锂金属复合氧化物的金属元素例如为选自Mg、Al、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Y、Zr、Sn、Sb、W、Pb及Bi中的至少1种。其中,优选包含选自Co、Ni、Mn及Al中的至少1种。作为优选的锂金属复合氧化物的一例,可举出含有Co、Ni及Mn的锂金属复合氧化物,含有Co、Ni及Al的锂金属复合氧化物。
作为导电材料,可以例示出炭黑、乙炔黑、科琴黑、石墨、碳纳米管、碳纳米纤维、石墨烯等碳材料。作为粘结剂,可以例示出聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVdF)等含氟树脂、聚丙烯腈(PAN)、聚酰亚胺、丙烯酸类树脂、聚烯烃等。另外,也可以将这些树脂和羧甲基纤维素(CMC)或其盐、聚环氧乙烷(PEO)等组合使用。
正极复合材料层31中的导电材料的含量例如相对于正极活性物质100质量份为0.5~15质量份,优选为1~10质量份。若导电材料的含量在该范围内,变得容易确保正极复合材料层31的良好的导电性。另外,正极复合材料层31中粘结材料的含量例如相对于正极活性物质100质量份为0.1~10质量份,优选为0.5~5质量份。若粘结材料的含量在该范围内,变得容易确保活性物质颗粒之间、活性物质颗粒与导电材料颗粒、及活性物质颗粒与正极集电体30的良好的粘结性。
正极11如上所述,具备形成于正极集电体30与正极复合材料层31之间的中间层32。正极复合材料层31形成于正极集电体30的两侧,因此中间层32也形成于正极集电体30的两面。中间层32为热传导性比正极复合材料层31高的层,并具有内部短路产生时使短路部位处产生的热迅速扩散、抑制短路面积的扩大导致的电池温度的上升的功能。中间层32由热导率不足50W/mK的绝缘性的无机颗粒35、热导率为50W/mK以上的高热导颗粒36、热塑性树脂37和聚偏二氟乙烯(PVdF)构成。无机颗粒35的含量相对于中间层32的质量为50质量%以上。
中间层32包含的PVdF发挥作为粘结材料的功能。PVdF的含量相对于中间层32的质量优选为0.1~10质量%,更优选为1~5质量%。若PVdF的含量在该范围内,变得容易确保各颗粒之间、各颗粒与正极集电体30、及各颗粒与正极复合材料层31的良好的粘结性。需要说明的是,热塑性树脂37在电池的通常使用时,也可以与PVdF一同发挥作为粘结材料的功能。
无机颗粒35为包含无机化合物的绝缘性的颗粒,并改善中间层32的强度。无机颗粒35例如比高热导颗粒36硬,也可以通过正极11的压延工序埋入至正极集电体30。无机颗粒35通过埋入至正极集电体30而改善中间层32的剥离强度。无机颗粒35不存在时,难以确保中间层32的强度,无法实现中间层32的功能。
作为无机颗粒35的一例,可举出氧化锰、氧化硅(二氧化硅)、氧化钛(二氧化钛)、氧化铝(三氧化二铝)等无机氧化物的颗粒。其中,优选选自氧化钛、及氧化铝中的至少1种,特别优选氧化铝。无机颗粒35的平均粒径并没有特别限定,优选为0.1~2μm。本说明书中,若无特别说明,则平均粒径是指,通过激光衍射法测定的体积平均粒径,粒径分布中的体积积算值为50%的中值粒径(50%粒径)。平均粒径使用激光衍射散射式粒度分布测定装置而测定。
无机颗粒35的含量相对于中间层32的质量至少为50质量%,优选为55~85质量%,更优选为60~80质量%。若无机颗粒35的含量在该范围内,变得容易确保中间层32的强度。
高热导颗粒36为热导率为50W/mK以上的颗粒,并改善中间层32的热传导性。高热导颗粒36的热导率优选为100W/mK以上,更优选为200W/mK以上。高热导颗粒36的热导率通过激光闪光法测定。通过使用高热导颗粒36,中间层32的热传导性得到改善,可以使内部短路产生时的短路部位处产生的热迅速扩散。
高热导颗粒36为金属颗粒及无机化合物颗粒(陶瓷颗粒)均可。作为高热导颗粒36的一例,可举出选自含有Al的金属颗粒、含有Au的金属颗粒、含有W的金属颗粒、氮化铝颗粒、氮化硼颗粒、氮化硅颗粒、及碳化硅颗粒中的至少1种。其中优选金属颗粒,特别优选含有Al的金属颗粒,例如铝颗粒、铝合金颗粒。高热导颗粒36的平均粒径并没有特别限定,优选比无机颗粒35的平均粒径大,为1~5μm。
高热导颗粒36的含量相对于中间层32的质量例如为3~40质量%,优选为5~35质量%,更优选为10~30质量%。若高热导颗粒36的含量在该范围内,可以使内部短路产生时于短路部位处产生的热迅速扩散,变得容易抑制电池温度的上升。高热导颗粒36优选以相对于无机颗粒35的质量为0.1~0.5倍的质量被包含于中间层32。另外,高热导颗粒36优选以相对于热塑性树脂37的质量为0.5~5倍的质量被包含于中间层32。
热塑性树脂37因内部短路时产生的热而发生熔融并与高热导颗粒36的表面密合以使颗粒间连接,从而改善中间层32的热传导性。热塑性树脂37例如将高热导颗粒36连接而形成传热通路。另外,基于热塑性树脂37由固体变化为液体时的潜热,内部短路产生时的放热也被抑制。热塑性树脂37的融点并没有特别限定,优选为110~200℃,更优选为120~150℃。
热塑性树脂37是在电池的通常使用时为固体、且在内部短路等异常发生时会熔融的树脂。作为热塑性树脂37的一例,可举出选自聚烯烃、聚碳酸酯、聚酰胺酰亚胺、聚苯乙烯、聚氨酯、及丙烯酸类树脂中的至少1种。聚烯烃例如为聚乙烯、乙烯与α烯烃的共聚物、聚丙烯等。这些之中优选聚烯烃,特别优选聚乙烯或乙烯与α烯烃的共聚物。
热塑性树脂37的含量相对于中间层32的质量例如为1~30质量%,优选为3~25质量%,更优选为5~20质量%。若热塑性树脂37的含量在该范围内,可以确保中间层32的强度、高热导颗粒36的适当的充填量,并且内部短路产生时可以高效地连接高热导颗粒36,从而变得易于抑制电池温度的上升。热塑性树脂37优选以相对于高热导颗粒36的质量为0.2~2倍的质量被包含于中间层32。
中间层32的厚度并没有特别限定,优选比正极集电体30及正极复合材料层31的厚度小。中间层32的厚度的一例为1~10μm,优选为1~5μm。中间层32在正极集电体30的表面上例如以0.1g/m2~20g/m2的表面密度形成。中间层32可以通过以下方法形成:于正极集电体30上涂布包含无机颗粒35、高热导颗粒36、热塑性树脂37及PVdF的浆料,并使涂膜干燥。
[负极]
负极12具备负极集电体、和形成于该集电体上的负极复合材料层。负极集电体可以使用铜等在负极12的电位范围内稳定的金属的箔、表层配置有该金属的薄膜等。负极复合材料层优选包含负极活性物质及粘结材料、且形成于负极集电体的两面。负极12可以通过以下方法制作:于负极集电体上涂布包含负极活性物质、粘结材料等的负极复合材料浆料,并使涂膜干燥后,进行压延,从而在负极集电体的两面形成负极复合材料层。
作为负极活性物质,只要能够可逆地吸储、释放锂离子就不特别限定,例如可以使用天然石墨、人造石墨等碳材料,Si、Sn等与Li合金化的金属,或包含Si、Sn等的金属化合物等。作为该金属化合物的例子,可举出SiOx(0.5≤x≤1.6)所示的硅化合物、Li2ySiO(2+y)(0<y<2)所示的硅化合物等。另外,负极复合材料层也可以包含锂钛复合氧化物作为负极活性物质。使用锂钛复合氧化物时,优选在负极复合材料层中添加炭黑等导电材料。
负极复合材料层包含的粘结材料可以使用PTFE、PVdF等含氟树脂、PAN、聚酰亚胺、丙烯酸类树脂、聚烯烃、苯乙烯-丁二烯橡胶(SBR)等。另外,负极复合材料层也可以含有CMC或其盐、聚丙烯酸(PAA)或其盐、聚乙烯醇(PVA)等。粘结材料的含量例如相对于负极活性物质100质量份为0.1~10质量份,优选为0.5~5质量份。
[分隔件]
分隔件13可以使用具有离子透过性及绝缘性的多孔性片。作为多孔性片的具体例,可举出微多孔薄膜、织布、无纺布等。作为分隔件的材质,优选聚乙烯、聚丙烯等聚烯烃、纤维素等。分隔件13可以为单层结构,也可以具有层叠结构。另外,分隔件13的表面也可以形成芳族聚酰胺系树脂等耐热性高的树脂层。
在分隔件13与正极11及负极12的至少一者的界面上,也可以形成包含无机物的填料的填料层。作为无机物的填料,可举出例如含有Ti、Al、Si、Mg等金属的氧化物、磷酸化合物等。可以将含有该填料的浆料涂布于正极11、负极12或分隔件13的表面而形成填料层。
[非水电解质]
非水电解质包含非水溶剂、和溶解于非水溶剂的电解质盐。非水溶剂可以使用例如酯类、醚类、乙腈等腈类、二甲基甲酰胺等酰胺类、及这些2种以上的混合溶剂等。非水溶剂也可以含有这些溶剂的氢的至少一部分被氟等卤素原子取代的卤素取代体。作为卤素取代体,可举出氟碳酸亚乙酯(FEC)等氟化环状碳酸酯、氟化链状碳酸酯、氟丙酸甲酯(FMP)等氟化链状羧酸酯等。
作为上述酯类的例子,可举出碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯等环状碳酸酯、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸甲基丙酯、碳酸乙基丙酯、碳酸甲基异丙酯等链状碳酸酯、γ-丁内酯(GBL)、γ-戊内酯(GVL)等环状羧酸酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯(MP)、丙酸乙酯等链状羧酸酯等。
作为环状醚类的例子,可举出1,3-二氧戊环、4-甲基-1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、环氧丙烷、1,2-环氧丁烷、1,3-二噁烷、1,4-二噁烷、1,3,5-三噁烷、呋喃、2-甲基呋喃、1,8-肉桂醇、冠醚等。作为链状醚类的例子,可举出1,2-二甲氧基乙烷、二乙醚、二丙醚、二异丙醚、二丁醚、二己醚、乙基乙烯醚、丁基乙烯醚、甲基苯醚、乙基苯醚、丁基苯醚、戊基苯醚、甲氧基甲苯、苄基乙醚、二苯醚、二苄醚、邻二甲氧基苯、1,2-二乙氧基乙烷、1,2-二丁氧基乙烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丁醚、1,1-二甲氧基甲烷、1,1-二乙氧基乙烷、三乙二醇二甲醚、四乙二醇二甲醚等。
电解质盐优选锂盐。作为锂盐的例子,可举出LiBF4、LiClO4、LiPF6、LiAsF6、LiSbF6、LiAlCl4、LiSCN、LiCF3SO3、LiCF3CO2、Li(P(C2O4)F4)、LiPF6-x(CnF2n+1)x(1<x<6,n为1或2)、LiB10Cl10、LiCl、LiBr、LiI、氯硼烷锂、低级脂肪族羧酸锂、Li2B4O7、Li(B(C2O4)F2)等硼酸盐类、LiN(SO2CF3)2、LiN(C1F2l+1SO2)(CmF2m+1SO2){l,m为0以上的整数}等酰亚胺盐类等。锂盐这些可以单独使用1种,也可以混合使用多种。这些之中从离子传导性、电化学的稳定性等观点来看,优选使用LiPF6。锂盐的浓度例如每1L非水溶剂中为0.8~1.8摩尔。
实施例
以下,通过实施例进一步说明本公开,但本公开并不限定于这些实施例。
<实施例1>
[正极的制作]
将80质量份的氧化铝(Al2O3)颗粒(热导率36W/mK)、10质量份的铝颗粒(热导率236W/mK)、7质量份的聚乙烯、和3质量份的PVdF混合,适量添加N-甲基-2-吡咯烷酮(NMP)从而制备浆料。接着,通过将该浆料涂布于由厚度15μm的铝箔形成的正极集电体的两面并使其干燥,从而形成厚度2μm的中间层。
将97质量份作为正极活性物质的LiNi0.5Co0.2Mn0.3O2所示的锂金属复合氧化物、2质量份的乙炔黑(AB)、和1质量份的PVdF混合,适量添加NMP,从而制备正极复合材料浆料。接着,将该正极复合材料浆料涂布于形成有中间层的正极集电体的两面并使其干燥。将其切成规定的电极尺寸,使用辊进行压延,从而制作在正极集电体的两面依次形成有中间层及正极复合材料层的正极。
[负极的制作]
将98.7质量份的石墨粉末、0.7质量份的羧甲基纤维素钠(CMC-Na)、0.6质量份的苯乙烯-丁二烯橡胶(SBR)的分散剂混合,适量添加水,从而制备负极复合材料浆料。接着,将该负极复合材料浆料涂布于由铜箔形成的负极集电体的两面并使其干燥。将其切成规定的电极尺寸,使用辊进行压延,从而制作在负极集电体的两面形成有负极复合材料层的负极。
[非水电解质的制备]
将碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、和碳酸二甲酯(DMC)以3:3:4的体积比混合。在该混合溶剂中,使LiPF6以浓度成为1.2mol/L的方式溶解而制备非水电解质。
[电池的制作]
分别给上述正极安装铝引线、给上述负极安装镍引线,通过隔着聚乙烯制的分隔件交替层叠而制作层叠型电极体。将该电极体收纳于由铝层压片构成的电池外壳体内,注入上述非水电解质后,密封外壳体,从而制作非水电解质二次电池。
[短路试验]
将制作好的电池以0.3C进行恒定电流充电至充电终止电压为4.3V,并以4.3V进行恒定电压充电至电流值为0.05C。在25℃的环境下,于充电的电池的侧面中央部刺穿圆钉,圆钉完全贯通电池时停止圆钉的刺穿,并测定焦耳放热量。
<实施例2,3及比较例1~3>
中间层的形成中,除了将构成材料的配混比变更为表1示出的以外,与实施例1同样地制作电池,并进行短路试验。
[表1]
如表1所示,实施例的电池与比较例的电池相比,在短路试验中放热量均为较低的值。即,实施例的电池与比较例的电池相比,内部短路产生时的放热被大幅地抑制。中间层不存在三氧化二铝时(比较例1),不存在铝时(比较例2)、及不存在聚乙烯时(比较例3),未见放热量的抑制效果。可以认为:中间层不存在三氧化二铝时,短路时中间层剥离,放热量变大。
附图标记说明
10 非水电解质二次电池
11 正极
12 负极
13 分隔件
14 电极体
15 电池壳体
16 外装罐
17 封口体
18、19 绝缘板
20 正极引线
21 负极引线
22 突出部
23 局部开口的金属板
24 下阀体
25 绝缘构件
26 上阀体
27 盖
28 垫片
30 正极集电体
31 正极复合材料层
32 中间层
35 无机颗粒
36 高热导颗粒
37 热塑性树脂
Claims (8)
1.一种非水电解质二次电池用正极,其具备:
正极集电体;
形成于所述正极集电体的至少一面侧的正极复合材料层;和
夹设于所述正极集电体和所述正极复合材料层之间的中间层,
所述中间层由热导率不足50W/mK的绝缘性的无机颗粒、热导率为50W/mK以上的高热导颗粒、热塑性树脂、和聚偏二氟乙烯构成;
所述无机颗粒的含量相对于所述中间层的质量为50质量%以上。
2.根据权利要求1所述的非水电解质二次电池用正极,其中,所述高热导颗粒为选自含有Al的金属颗粒、含有Au的金属颗粒、含有W的金属颗粒、氮化铝颗粒、氮化硼颗粒、氮化硅颗粒、及碳化硅颗粒中的至少1种。
3.根据权利要求1或2所述的非水电解质二次电池用正极,其中,所述热塑性树脂为选自聚烯烃、聚碳酸酯、聚酰胺酰亚胺、聚苯乙烯、聚氨酯、及丙烯酸类树脂中的至少1种。
4.根据权利要求1~3中任一项所述的非水电解质二次电池用正极,其中,所述无机颗粒为选自氧化钛、及氧化铝中的至少1种。
5.根据权利要求1~4中任一项所述的非水电解质二次电池用正极,其中,所述高热导颗粒的含量相对于所述中间层的质量为5~35质量%。
6.根据权利要求1~5中任一项所述的非水电解质二次电池用正极,其中,所述热塑性树脂的含量相对于所述中间层的质量为3~25质量%。
7.根据权利要求1~6中任一项所述的非水电解质二次电池用正极,其中,以相对于所述热塑性树脂的质量为0.5~5倍的质量包含所述高热导颗粒。
8.一种非水电解质二次电池,其具备:
权利要求1~7中任一项所述的正极;
负极;和,
非水电解质。
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JPWO2019146413A1 (ja) | 2021-01-14 |
WO2019146413A1 (ja) | 2019-08-01 |
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EP3745501B1 (en) | 2024-05-01 |
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US20200365908A1 (en) | 2020-11-19 |
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