CN112563461A - 一种负极极片及锂金属电池 - Google Patents

一种负极极片及锂金属电池 Download PDF

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CN112563461A
CN112563461A CN201910850600.XA CN201910850600A CN112563461A CN 112563461 A CN112563461 A CN 112563461A CN 201910850600 A CN201910850600 A CN 201910850600A CN 112563461 A CN112563461 A CN 112563461A
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negative electrode
lithium metal
protective film
lithium
fluorine
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CN112563461B (zh
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李谦
程萌
刘成勇
胡波兵
付佳玮
黄圣源
郭永胜
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP20862029.4A priority patent/EP3890069B1/en
Priority to PCT/CN2020/106470 priority patent/WO2021047330A1/zh
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Abstract

本发明提供一种负极极片及锂金属电池。所述负极极片包括负极集流体以及设于负极集流体至少一个表面上的锂金属负极，在锂金属负极远离负极集流体的表面上设有聚合物保护膜，所述聚合物保护膜包含柠檬酸共聚物，所述柠檬酸共聚物的数均分子量Mn为10,000～1,000,000。本发明可在负极极片中的锂金属负极的表面形成高抗拉强度、高穿刺强度、高延展率、高固液能力的聚合物保护膜，将本发明的负极极片用于锂金属二次电池中，可有效减缓甚至抑制锂枝晶的生长，降低电解液与锂金属的副反应消耗，提高锂金属二次电池的首次充放电库仑效率，显著改善锂金属二次电池的循环稳定性和安全性。

Description

一种负极极片及锂金属电池
技术领域
本发明涉及电池领域，尤其涉及一种负极极片及锂金属电池。
背景技术
金属锂以其极高的理论比容量：3860mAh g-1、最低的还原电势：-3.04V vs.标准氢电极、以及低密度：0.534g cm-3等优点，成为下一代高比能二次电池负极材料的最佳选择。然而，锂离子在负极表面的不规则沉积引发的不可控锂枝晶的生长，造成了锂金属电池使用过程中的安全问题，进而制约了锂金属电池的广泛应用。
目前，锂金属电池领域的诸多研究集中于向电解液中加入功能添加剂，如碳酸亚乙烯酯、氟代碳酸乙烯酯、2-甲基呋喃以及一些碱金属阳离子等。利用上述添加剂与金属锂发生吸附、分解、聚合等作用而形成可增强金属锂表面SEI膜的新保护膜、改善锂二次电池的循环性能。但上述现有技术存在的问题是，这些原位形成的保护膜机械强度较弱且覆盖金属锂不完全，不能完全阻止在锂沉积/溶出过程中由于锂金属形貌变化而引起的SEI膜剧烈、持续重组；锂枝晶的生成及随即引发的诸多问题并未得到实质性的解决。
发明内容
鉴于背景技术中存在的问题，本发明的目的在于提供一种负极极片及锂金属电池，以提高锂金属电池使用过程中的安全性。
为了达到上述目的，本发明的第一方面提供了一种负极极片，包括负极集流体以及设于负极集流体至少一个表面上的锂金属负极，在所述锂金属负极远离所述负极集流体的表面上设有聚合物保护膜，所述聚合物保护膜包含柠檬酸共聚物，所述柠檬酸共聚物的数均分子量Mn为10,000～1,000,000。
本发明的第二方面提供了一种锂金属电池，包括正极极片、负极极片、间隔于正极极片和负极极片之间的隔离膜、电解液，所述负极极片为本发明第一方面所提供的负极极片。
相对于现有技术，本发明至少包括如下所述的有益效果：
本发明所提供的负极极片中，在锂金属负极的表面有数均分子量Mn为10,000～1,000,000的柠檬酸共聚物。柠檬酸共聚物结构中含有大量可以和锂金属反应的羧基和羟基，因而可在负极极片的表面形成具有高抗拉强度、高穿刺强度、高延展率、高固液能力的聚合物保护膜。当将本发明所提供的负极极片用于锂金属二次电池中时，可有效减缓甚至抑制锂枝晶的生长，降低电解液与锂金属的副反应消耗，提高锂金属二次电池的首次充放电库仑效率，显著改善锂金属二次电池的循环稳定性和安全性。
附图说明
图1为对比例2中的聚合物膜在1,000倍放大下的扫描电镜图；
图2为对比例2中的聚合物膜在10,000倍放大下的扫描电镜图；
图3为实施例2中的聚合物膜在500倍放大下的扫描电镜图；
图4为实施例2中的聚合物膜在10,000倍放大下的扫描电镜图；
图5为对比例1和实施例2的锂金属电池的循环性能对比图。
具体实施方式
下面详细说明根据本发明的负极极片和锂金属电池。
本发明第一方面的负极极片，包括负极集流体以及设于负极集流体至少一个表面上的锂金属负极，在所述锂金属负极远离所述负极集流体的表面上设有聚合物保护膜，所述聚合物保护膜包含柠檬酸共聚物，所述柠檬酸共聚物的数均分子量Mn为10,000～1,000,000。
本发明的负极极片中，在锂金属负极的表面设有聚合物保护膜，所述聚合物保护膜包含数均分子量Mn为10,000～1,000,000的柠檬酸共聚物，柠檬酸共聚物结构中含有大量可以和锂金属反应的羧基和羟基，可形成具有高抗拉强度、高穿刺强度、高延展率、高固液能力的聚合物保护膜。当将本发明的负极极片用于锂金属二次电池中时，能够有效减缓甚至抑制锂枝晶的生长，降低电解液与锂金属的副反应消耗，提高锂金属二次电池的首次充放电库仑效率，显著改善锂金属二次电池的循环稳定性能和安全性能。
所述柠檬酸共聚物包含式(I)所示的PLA-co-CA和/或式(II)所示的PEG-co-CA反应活性嵌段聚合物：
Figure BDA0002196772760000031
其中，m取自10～5000，n取自10～5000。
优选地，m取自400～600，n取自1000～2000，Mn为80,000～350,000。
优选地，本发明的负极极片中，所述聚合物保护膜还包括含氟锂盐、含氟成膜剂及无机填料；所述含氟锂盐选自双三氟甲基磺酰亚胺锂(LiTFSI)、双氟甲基磺酰亚胺锂(LiFSI)、二草酸硼酸锂(LiBOB)、二氟草酸硼酸锂(LiDFOB)中的一种或几种，这些锂盐有助于在锂金属表面原位形成LiF，一定程度上抑制锂枝晶生长；所述含氟成膜剂选自聚偏氟乙烯(PVDF)、聚偏氟乙烯-六氟丙烯(PVDF-HFP)或聚四氟乙烯(PTFE)中的一种或几种，这些含氟成膜剂同样可以在锂金属表面原位生成LiF；所述无机填料选自Al2O3、TiO2或SiO2中的一种或几种，这些惰性填料的引入，可以更显著提升聚合物保护膜的化学稳定性和机械强度。
优选地，所述无机填料粒径为10nm～1000nm，优选50nm～500nm。该尺寸范围内的无机纳米粒子的引入，能够更有效地提升聚合物保护膜的机械强度。
优选地，所述聚合物保护膜中的反应活性嵌段聚合物、含氟成膜剂、无机填料、含氟锂盐的质量份配比依次为25份～60份、30份～80份、1份～10份、1份～10份。进一步优选地，所述聚合物保护膜中的反应活性嵌段聚合物、含氟成膜剂、无机填料、含氟锂盐的质量份配比依次为30份～40份、50份～70份、3份～8份、3份～8份。
优选地，在本发明的负极极片中，聚合物保护膜的厚度为5um～30um，优选15um～20um。在本发明所提供的上述范围内，保护膜的厚度和抑制锂枝晶生长能力呈正相关，但过厚的保护膜会增加电池极化，影响电池能量效率。
另外，聚合物保护膜的抗拉强度为0.5MPa～3.0MPa，优选2.0MPa～3.0MPa；聚合物保护膜的穿刺强度为0.5MPa～2.0MPa，优选0.9MPa～2.0MPa；聚合物保护膜的延展率为100％～500％，优选250％～500％。抗拉强度、穿刺强度和延展率可通过调整配方中活性嵌段聚合物、含氟成膜剂及无机填料的比例进行调节，但较高的抗拉强度和穿刺强度能够更为有效地抑制锂枝晶的生长；较高的延展率则保证了锂金属电池在充放电过程中的膨胀不至于导致保护膜破损。
优选地，所述聚合物保护膜的固液能力为50％～200％，优选100％～200％。
在本发明的负极极片中，所述负极集流体通常是汇集电流的结构或零件，所述负极集流体可以是本领域各种适用于作为电化学储能装置负极集流体的材料，例如，所述负极集流体可以是包括但不限于金属箔，更具体可以是包括但不限于铜箔。
在本发明的负极极片中，所述锂金属负极可以设置在负极集流体的其中一个表面上，也可以设置在负极集流体的两个表面上。
本领域技术人员可以选择常规的方法制备本发明的负极极片，对于锂金属负极表面上所设置的聚合物保护膜，则可以采用干法挤压或湿法涂布的方法进行制膜。下面是对本发明的负极极片制备过程的举例说明。
本发明的负极极片的制备工艺一(其中，采用干法挤压进行制膜)：
(1)选用10μm～50μm的锂带和6μm～12μm的铜箔，在20MPa～50MPa的压力下过辊后裁片，得到锂金属负极极片；
(2)加热使聚合物保护层各组分熔融混匀后，将其挤压涂覆至锂金属负极极片表面。
本发明的负极极片的制备工艺二(其中，采用湿法涂布进行制膜)：
(1)选用10μm～50μm的锂带和6μm～12μm的铜箔，在20MPa～50MPa的压力下过辊后裁片，得到锂金属负极极片；
(2)选用三乙基磷酸酯作为溶剂，加热至70℃，将聚合物保护层搅拌分散均匀后，将其涂布至锂金属负极表面，随后室温下真空干燥4小时。
本发明第二方面的锂金属电池包括正极极片、负极极片、间隔于正极极片和负极极片之间的隔离膜、电解液，其中，所述负极极片即为本发明第一方面的负极极片。
优选地，在本发明的锂金属电池中，所述电解液优选包含氟代碳酸乙烯酯、线性碳酸乙烯酯和含氟锂盐。其中，所述氟代碳酸乙烯酯在电解液中的质量百分含量为20％～50％；所述含氟锂盐为双三氟甲基磺酰亚胺锂(LiTFSI)、双氟甲基磺酰亚胺锂(LiFSI)、二草酸硼酸锂(LiBOB)和二氟草酸硼酸锂(LiDFOB)中的一种或两种以上混合物。
本发明的锂金属电池中，采用上述电解液配合使用，其中氟代碳酸乙烯酯和含氟锂盐可以和锂金属负极形成较为稳定的固液界面，从而在一定程度上减缓锂金属对电解液的消耗；聚合物保护层对氟代碳酸乙烯酯的固液能力较好，可以进一步降低其消耗；线性碳酸乙烯酯粘度较低，离子电导率较高，可提高电池的倍率性能。
此外，本发明的锂金属电池中的正极极片和隔离膜则可以采用本领域内常规的正极极片和隔离膜。例如：
在本发明的锂金属电池中，正极极片可以包括正极集流体以及设置在正极集流体至少一个表面上的正极活性物质层。正极极片中，所述正极活性物质层可设置在正极集流体的其中一个表面上也可以设置在正极集流体的两个表面上。本领域技术人员可选择合适的方法制备所述正极极片，例如，可以包括如下步骤：将正极活性材料、粘结剂、导电剂混合形成浆料后，涂布于正极集流体上。
其中，所述正极活性物质的具体种类没有特别的限制，只要能满足接受、脱出锂离子即可。所述正极活性物质既可为层状结构材料，使锂离子在二维空间扩散，也可为尖晶石结构，使锂离子在三维空间扩散。优选地，所述正极活性物质可选自锂过渡金属氧化物、锂过渡金属氧化物添加其它过渡金属或非过渡金属或非金属得到的化合物中的一种或几种。具体地，所述正极活性物质可优选选自锂钴氧化物、锂镍氧化物、锂锰氧化物、锂镍锰氧化物、锂镍钴锰氧化物、锂镍钴铝氧化物、橄榄石结构的含锂磷酸盐中的一种或几种。
其中，所述橄榄石结构的含锂磷酸盐的通式可为LiFe1-x-yMnxM’yPO4，0≤x≤1，0≤y<1，0≤x+y≤1，M’选自除Fe、Mn外的其它过渡金属元素或非过渡金属元素中的一种或几种，M’优选选自Cr、Mg、Ti、Al、Zn、W、Nb、Zr中一种或几种。优选地，橄榄石结构的含锂磷酸盐选自磷酸铁锂、磷酸锰锂、磷酸锰铁锂中的一种或几种。
所述锂过渡金属氧化物选自LiCoO2、LiMnO2、LiNiO2、LiMn2O4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2、LiNixMn2-xO4中的一种或几种，其中0＜x＜1、0＜y＜1、0＜x+y＜1；优选地，所述锂过渡金属氧化物选自LiCoO2、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Mn0.05O2、LiNi0.8Co0.15Al0.05O2、LiNi0.5Mn1.5O4、LiMn2O4中的一种或几种。
正极极片中，所述正极活性物质层还可包括导电剂以及粘结剂，其中导电剂以及粘结剂的种类和含量不受具体的限制，可根据实际需求进行选择。所述粘结剂通常包括含氟聚烯烃类粘结剂，相对于所述含氟聚烯烃类粘结剂来说，水通常是良溶剂，即所述含氟聚烯烃类粘结剂通常在水中具有良好的溶解性，例如，所述含氟聚烯烃类粘结剂可以是包括但不限于聚偏氟乙烯(PVDF)、偏氟乙烯共聚物或它们的改性(例如，羧酸、丙烯酸、丙烯腈等改性)衍生物等。在所述正极材料层中，粘结剂的质量百分比含量可以是由于粘结剂本身的导电性较差，因此粘结剂的用量不能过高。优选地，正极活性物质层中粘结剂的质量百分含量小于等于2wt％，以获得较低的极片阻抗。所述正极极片的导电剂可以是本领域各种适用于锂离子(二次)电池的导电剂，例如，可以是包括但不限于乙炔黑、导电炭黑、碳纤维(VGCF)、碳纳米管(CNT)、科琴黑等中的一种或多种的组合。所述导电剂的重量可以占正极材料层总质量的1wt％～10wt％。更优选地，正极极片中导电剂与正极活性物质的重量比大于等于1.5:95.5。
正极极片中，所述正极集流体的种类也不受具体的限制，可根据实际需求进行选择。所述正极集流体通常可以为层体，所述正极集流体通常是可以汇集电流的结构或零件，所述正极集流体可以是本领域各种适用于作为电化学储能装置正极集流体的材料，例如，所述正极集流体可以是包括但不限于金属箔，更具体可以是包括但不限于镍箔、铝箔。
在本发明的锂金属电池中，隔离膜可以是本领域各种适用于电化学储能装置隔离膜的材料，例如，可以是包括但不限于聚乙烯、聚丙烯、聚偏氟乙烯、芳纶、聚对苯二甲酸乙二醇酯、聚四氟乙烯、聚丙烯腈、聚酰亚胺，聚酰胺、聚酯和天然纤维中的一种或多种的组合。
制备本发明的锂金属电池的方法对于本领域技术人员来说应该是已知的，例如，所述正极极片、隔离膜和负极极片各自都可以是层体，从而可以裁剪成目标尺寸后依次叠放，还可以卷绕至目标尺寸，以用于形成电芯，并可以进一步与电解液结合以形成锂金属电池。
另外，本发明还提出了评估本发明的锂金属电池中所增设的聚合物保护膜性能的参数，即保护膜的固液系数(Electrolyte Holding coefficient,EH)，其测试方法如下：称量无保护膜锂金属负极的质量，记为m0，有保护膜锂金属负极的质量，记为m1；将有保护膜锂金属负极浸入电解液中8h，使其吸满电解液后取出，擦去表面沾附的电解液，称量质量，记为m2，((m1-m0)/(m2-m0)-1)即为传统的保液系数(electrolyte intake coefficient)。随后将其放入25℃恒温箱静置，每隔24h称量其质量，直至其质量变化小于等于1％，记录其最终质量m3，固液系数EH＝((m3-m0)/(m1-m0)-1)。传统的保液系数主要体现的保护膜的孔隙等物理结构对电解液的储存，而固液系数能够反映保护膜化学结构对电解液的吸附能力，更能够真实的反映保护膜在长循环锂二次电池中对电解液的储存，因而比保液系数在长循环锂二次电池中更有参考价值。
下面结合具体实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
按照上文中的制备方法制备实施例1～8的锂金属电池。所述锂金属电池包括正极极片、负极极片、间隔于正极极片和负极极片之间的隔离膜、电解液。其中，负极极片包括负极集流体(铜箔)以及设置在负极集流体一个表面上的锂金属负极，在锂金属负极远离负极集流体的表面上设置有聚合物保护膜。正极极片为镍钴锰三元锂材料(NCM811)。电解液包含氟代碳酸乙烯酯、线性碳酸乙烯酯和含氟锂盐；其中，氟代碳酸乙烯酯(FEC)在电解液中的质量百分含量为35％；锂盐选用双三氟甲基磺酰亚胺锂(LiTFSI)，浓度为1mol/L。
此外，按照相同的步骤制备对比例1、2的锂金属电池，其与实施例1-8的锂金属电池的区别在于，对比例1的锂金属电池中不设聚合物保护膜、对比例2的锂金属电池中的聚合物膜内仅包含了含氟成膜剂和含氟锂盐。
下表1示出了实施例1～8、对比例1～2中的聚合物膜的具体参数：
表1实施例、对比例的聚合物膜具体参数
Figure BDA0002196772760000081
Figure BDA0002196772760000091
对实施例1～8和对比例2中的聚合物保护膜进行如下表征和检测：
通过扫描电子显微镜(SEM,SU8010,Hitachi,Japan)表征了对实施例1～8和对比例2中的聚合物保护膜的微观形态。图1、2是对比例2中的聚合物膜在1,000倍放大下和10,000倍放大下的扫描电镜图(SEM图)；图3、4是实施例2中的聚合物膜在500倍放大下和10,000倍放大下的扫描电镜图(SEM图)。
通过电化学阻抗谱测量实施例1～8以及对比例2的聚合物膜的固液系数(Electrolyte Holding coefficient,EH)和传统的保液系数(electrolyte intakecoefficient)。
通过如下仪器及方法检测实施例1～8、对比例2中的聚合物膜的力学膜性能。通过三丰VL-50-B台式测力测厚仪测试保护膜的厚度。通过三思纵横UTM6104系列电子万能试验机测试保护膜的针刺强度、拉伸强度和延伸率，针刺强度测试参数：速度(50mm/min)、试样厚度(0.015mm)，拉伸强度、延伸率测试参数：间距(50mm)、速度(500mm/min)、试样厚度(0.015mm)。
下表2和3分别示出了实施例1～8和对比例2中的聚合物保护膜的力学膜性能、形貌及电性能：
表2实施例、对比例的聚合物膜的力学膜性能
Figure BDA0002196772760000101
表3实施例、对比例的聚合物膜的形貌及电性能
Figure BDA0002196772760000102
通过如下方法对实施例1～8和对比例1、2的锂金属电池进行电池循环性能的检测：将锂金属电池以0.5C(60mA)的恒定电流充电至4.3V，后以4.3V恒压充电至电流降到0.05C(6mA)，再以0.5C(60mA)的恒定电流放电至3.0V，得首周放电比容量(Cd1)；如此反复充放电至第n周，得锂二次电池循环n周后的放电比容量记为Cdn。容量保持率＝循环n周后的放电比容量(Cdn)/首周放电比容量(Cd1)，当容量保持率降低至80％时，即认为电池循环寿命终止。
图5为对比例1和实施例2的锂金属电池的循环性能对比图。
下表4示出了实施例1～8和对比例1～2中的锂金属电池的循环性能：
表4实施例、对比例的锂金属电池的循环性能
Figure BDA0002196772760000111
从表4可以看出：实施例1～8的锂金属电池由于聚合物保护膜的作用，其循环寿命明显高于对比例中的锂金属电池。
此外，拆开实施例1～8及对比例1、2的各锂金属二次电池，使用光学显微镜观察金属锂负极片表面，实施例1～8的锂金属电池的金属锂负极片的表面形成的界面膜较薄且致密，而对比例1、2的锂金属电池的金属锂负极片表面覆盖较厚的、蓬松的黑褐色沉积物，且沉积物中含有大量的锂枝晶。这是由于实施例的金属锂负极片表面设有聚合物保护膜后，该聚合物保护膜具有较高的机械强度，抑制了锂枝晶的生长；此外，聚合物保护膜也有很好的固液能力，从而降低了电解液的过度消耗，提高了电池的循环寿命；聚合物保护膜结构中有羧基、羟基可以和锂金属缓慢反应，生成-COOLi、-OLi，从而抑制了锂金属与电解液的副反应，进一步降低了电解液的消耗；同时，这种温和、缓慢的反应有助于在金属锂负极片表面形成性能良好的SEI膜，进一步抑制金属锂负极片和电解液的过度反应，提高了锂二次电池的安全性能和循环性能。
根据上述说明书的揭示和教导，本领域技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。

Claims (10)

1.一种负极极片，包括负极集流体以及设置于所述负极集流体至少一个表面上的锂金属负极，其特征在于，
所述锂金属负极远离所述负极集流体的表面上设有聚合物保护膜，所述聚合物保护膜包含柠檬酸共聚物，所述柠檬酸共聚物的数均分子量Mn为10,000～1,000,000。
2.根据权利要求1所述的负极极片，其特征在于：所述柠檬酸共聚物包含式(I)和/或式(II)所示的反应活性嵌段聚合物：
Figure FDA0002196772750000011
其中，
m取自10～5000，n取自10～5000。
3.根据权利要求2所述的负极极片，其特征在于，所述反应活性嵌段聚合物满足：m取自400～600，n取自1000～2000，数均分子量Mn为80,000～350,000。
4.根据权利要求1所述的负极极片，其特征在于，所述聚合物保护膜还包括含氟锂盐、含氟成膜剂及无机填料，所述含氟锂盐选自双三氟甲基磺酰亚胺锂、双氟甲基磺酰亚胺锂、二草酸硼酸锂、二氟草酸硼酸锂中的一种或几种；所述含氟成膜剂选自聚偏氟乙烯、聚偏氟乙烯-六氟丙烯或聚四氟乙烯中的一种或几种；所述无机填料选自Al2O3、TiO2或SiO2中的一种或几种。
5.根据权利要求4所述的负极极片，其特征在于，所述无机填料粒径为10nm～1000nm，优选50nm～500nm。
6.根据权利要求4所述的负极极片，其特征在于，
所述聚合物保护膜中的反应活性嵌段聚合物、含氟成膜剂、无机填料、含氟锂盐的质量份配比依次为25份～60份、30份～80份、1份～10份、1份～10份；
优选地，所述聚合物保护膜中的反应活性嵌段聚合物、含氟成膜剂、无机填料、含氟锂盐的质量份配比依次为30份～40份、50份～70份、3份～8份、3份～8份。
7.根据权利要求1所述的负极极片，其特征在于，所述聚合物保护膜的厚度为5um～30um，优选15um～20um。
8.根据权利要求7所述的负极极片，其特征在于，所述聚合物保护膜的抗拉强度为0.5MPa～3.0MPa，优选2.0MPa～3.0MPa；所述聚合物保护膜的穿刺强度为0.5MPa～2.0MPa，优选0.9MPa～2.0MPa；所述聚合物保护膜的延展率为100％～500％，优选250％～500％。
9.根据权利要求8所述的负极极片，其特征在于，所述聚合物保护膜的固液能力为50％～200％，优选100％～200％。
10.一种锂金属电池，包括正极极片、负极极片、间隔于正极极片和负极极片之间的隔离膜、电解液，其特征在于，所述负极极片为权利要求1至9中任一项所述的负极极片。
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