CN112909225A - 具有碳化硅添加剂的阴极活性材料 - Google Patents
具有碳化硅添加剂的阴极活性材料 Download PDFInfo
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 42
- 239000006182 cathode active material Substances 0.000 title abstract description 12
- 239000000654 additive Substances 0.000 title abstract description 10
- 230000000996 additive effect Effects 0.000 title description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 67
- 239000010406 cathode material Substances 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 lithium transition metal Chemical class 0.000 claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 239000007769 metal material Substances 0.000 claims abstract description 13
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 12
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims abstract description 7
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- 239000000463 material Substances 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
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- 239000011029 spinel Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
本公开涉及具有碳化硅添加剂的阴极活性材料。本公开涉及锂电池阴极材料，其包含基于锂过渡金属的材料和结晶碳化硅，该基于锂过渡金属的材料选自锂过渡金属氧化物和锂过渡金属磷酸盐，该结晶碳化硅驻留在该基于锂过渡金属的材料的晶界处，从而形成沿该晶界的导电通道，该晶体碳化硅小于该阴极材料的10重量％。
Description
技术领域
本公开涉及用于锂电池的阴极活性材料，该阴极活性材料包括碳化硅添加剂。
背景技术
锂电池在充电和放电操作期间分别采用阴极活性材料来释放和存储阳离子。此类阴极活性材料可包括过渡金属氧化物和磷酸盐，它们通常用于与电解质交换锂阳离子。然而，作为阴极活性材料的具有优异性能的过渡金属氧化物和磷酸盐越来越多地达到它们的性能极限。增加阴极厚度是能够开发出具有改善的能量密度的锂电池的最有效的方法之一。已发现厚阴极增加了电池单元极化并且未充分利用活性材料。前者受电子导电性影响，而后者受活性材料中锂离子扩散影响。因此，仍然有必要开发满足厚阴极(对于固体电解质为5um-50um)和超厚阴极(对于液体电解质为大于150um)的同时实现高能量密度和高倍率能力的要求的阴极材料。
发明内容
本文公开了用于锂电池的阴极材料的具体实施，该阴极材料包括基于锂过渡金属的颗粒和碳化硅颗粒，该基于锂过渡金属的颗粒选自锂过渡金属氧化物和锂过渡金属磷酸盐，该碳化硅颗粒驻留在基于锂过渡金属的颗粒的晶界处，从而形成沿该晶界的导电通路。
该碳化硅颗粒可各自具有小于100nm的最长尺寸。
该碳化硅颗粒可小于阴极材料的10重量％。
该碳化硅颗粒可小于阴极材料的1重量％。
该碳化硅颗粒可具有1至25的纵横比。
该碳化硅颗粒可为纳米纤维颗粒。
该碳化硅的纳米纤维粒子可具有介于5和25之间包括端值在内的纵横比。
本文所公开的阴极材料可具有0-50％的孔内体积。
本文还公开了包含本文所公开的阴极材料的锂电池。该锂电池可为具有一个或多个锂金属电池单元的锂金属电池。该锂电池可为具有一个或多个锂离子电池单元的锂离子电池。
附图说明
在阅读本公开时通过结合附图对以下具体实施方式得以最佳理解。应当强调的是，根据惯例，附图的各种特征部不是成比例的。相反，为了清楚起见，各种特征部的尺寸可被任意扩大或缩小。
图1A为高分辨率TEM图像，示出了LCO的块体晶粒和包含位于该块体晶粒之间的碳化硅的结晶晶界。
图1B为图1A的一部分的放大图像。
图1C为图1A的另一部分的放大图像。
图2A为热处理后的LCO阴极材料的高分辨率SEM图像。
图2B为如本文所公开的LCO和0.5重量％的SiC在热处理后的高分辨率SEM图像。
图3A为使用LCO阴极材料的锂电池单元的放电曲线。
图3B为使用LCO和1.0重量％的SiC作为阴极材料的锂电池单元的放电曲线。
图4为根据实施方案的锂电池单元的平面图。
图5为用于图4的锂电池单元的层的侧视图的示意图。
图6A为根据实施方案的固态电池单元的透视图。
图6B为图6A的固态电池单元的分解图。
具体实施方式
纯态的电化学活性阴极材料(例如，可商购获得的LiCoO2)可能不提供足够高的锂离子扩散和电子导电性。纯阴极和复合阴极两者的改进的阴极性能部分地需要阴极内部的高的有效扩散系数。在单元放电时，阴极内部的质量和电荷传输允许尽可能多的电化学活性物质(离子和电子)在尽可能短的时间内插入到阴极中，并进入到最远离阴极-电解质交界部的阴极位置中。快速的离子晶界传导可有效地向和从负责容量和能量存储的电化学反应的位置提供离子，该离子位于晶粒块体内部。本文所公开的用于锂电池的阴极材料通过提供碳化硅添加剂来改善阴极内的离子和电子扩散，该碳化硅添加剂提供围绕在阴极活性材料的块体晶粒周围和该块体晶粒之间的路径。
活性阴极材料的小晶粒尺寸有利于缩短锂离子和电子在锂化/脱锂化过程中的迁移路径，并因此改善电化学性能。本文所公开的锂电池阴极材料包括碳化硅添加剂，该碳化硅添加剂抑制晶粒生长并提供非常致密的阴极微结构。
本文所公开的锂电池阴极材料包含基于锂过渡金属的材料和结晶碳化硅，该基于锂过渡金属的材料选自锂过渡金属氧化物和锂过渡金属磷酸盐，该结晶碳化硅驻留在该基于锂过渡金属的材料的晶界处，从而形成沿该晶界的导电通路。
该基于锂过渡金属的材料可为嵌入锂离子化合物，诸如具有通式LiMO2和LiMxOy的锂过渡金属氧化物，以及具有通式LiMPO4的锂过渡金属磷酸盐，其中M为一种或多种过渡金属阳离子。作为非限制性示例，该基于锂过渡金属的材料可包括：层型材料，诸如LiCoO2、LiNi1/3Mn1/3Co1/3O2和LiNi0.8Co0.15Al0.05O2；橄榄石型材料，诸如LiFePO4；尖晶石型材料，诸如LiMn2O4；以及其他类似的材料。
该结晶碳化硅驻留在该基于锂过渡金属的材料的晶界处，从而形成沿该晶界的导电通路。这可在图1A至图1C中看到，其使用LiCoO2(LCO)作为该基于锂过渡金属的材料并且包含0.5重量％的碳化硅，该材料在800℃退火。图1A是示出沿块体LCO 12之间的晶界的晶体碳化硅10的高分辨率TEM图像。该碳化硅驻留在晶界处并且以纳米级围绕晶粒。图1B和图1C是图1A的在图中用箭头指示的部分的放大图像。碳化硅导电通路的块体颗粒之间的宽度为约20nm或更小、10nm或更小，并且可以为5nm或更小。
将碳化硅与基于锂过渡金属的材料或它们的前体混合并处理以形成阴极膜。该碳化硅即使在高温热处理之后也不会分解并结合到活性材料中，如图1A至图1C所证实。在阴极材料退火之后，该晶体碳化硅位于该基于锂过渡金属的材料的块体晶粒之间，从而围绕该基于锂过渡金属的材料的晶粒并提供穿过阴极材料的导电通路。
该碳化硅促进阴极材料的压实而不导致显著的晶粒生长，这通常在高温压实期间发生。已经发现的是，低至700℃的热处理可产生非常致密的微结构。图2A和图2B分别为不含碳化硅的LCO和含有0.5重量％碳化硅的LCO的高分辨率SEM图像。图2A中的纯LCO在850℃退火，而具有碳化硅的LCO在800℃退火。具有SiC添加剂的LCO的密度大于理论密度的95％，而不具有添加剂的LCO小于理论密度的90％，并且具有SiC添加剂的LCO晶粒为500nm或更小，而不具有SiC添加剂的LCO晶粒大于2000nm。
所公开的阴极材料中的该碳化硅颗粒可为具有小于100nm的最长尺寸的任何颗粒形状。该碳化硅颗粒可为球形或细丝状或纤维形，具有1至25的纵横比(L/D)。在一些实施方案中，该碳化硅颗粒为具有介于5和25之间包括端值在内的纵横比的纳米纤维。
碳化硅不是电化学活性的，因此用量应足以提供围绕块体活性材料的纳米级导电通路。该碳化硅可小于阴极材料的10重量％。在一些实施方案中，该碳化硅可小于阴极材料的1重量％。
使用本文所公开的阴极材料的锂电池实现了更好的倍率性能和改善的扩散特性。图3A是用10μm厚的LCO晶片形成的电池单元的放电曲线，而图3B是用10μm厚的LCO晶片和1重量％的SiC形成的电池单元的放电曲线。通过干喷将LCO和SiC的混合物沉积在固体电解质或基底上。然后将刚沉积的膜在高温下退火。然后阴极膜在0.2C(循环1和2)、0.5C(循环3)、1C(循环4)和2C(循环5)下贴靠金属锂进行循环。图3B中所示的在不同放电速率下较平坦的放电曲线和最小的电压降表明使用本文所公开的阴极材料的单元中增强的电子和离子导电性。
本文所公开的阴极材料可与具有全部固体组分的全固态电池一起使用。本文所公开的阴极材料还可用于具有含液体或固体电解质的非金属锂阳极的锂离子电池以及含液体、固体或凝胶电解质的锂金属电池。
可根据以下方法制备锂电池。作为非限制性示例，可使用本文所公开的阴极材料来制备阴极。其上形成有阴极活性层的阴极集流体可通过使用干喷涂和沉积诸如PVD和CVD(作为非限制性示例)将阴极活性材料组合物直接涂布在阴极集流体上来制备，该阴极集流体可为例如铝片或铝箔。还可将阴极活性层浇铸在单独的载体上以形成膜，然后可通过将该膜与载体分离并且将分离的膜层压在阴极集流体上来制备阴极。
可用阳极活性材料和任选的粘结剂和/或溶剂制备阳极。该粘结剂可为任何合适的粘结剂，例如以下中的一种或多种：偏二氟乙烯/六氟丙烯共聚物、聚偏二氟乙烯、聚丙烯腈、聚(甲基丙烯酸甲酯)、聚四氟乙烯(PTFE)和丁苯橡胶基聚合物。该溶剂可为任何合适的溶剂，例如以下中的一种或多种：N-甲基吡咯烷酮(NMP)、丙酮和水。
示例性阳极活性材料包括：元素材料，诸如锂；合金，其包括Si、Sn、Al、Ge、Pb、Bi和Sb的合金或其他锂化合物；以及嵌入主体材料，诸如碳基材料。该碳基材料可包括结晶碳和无定形碳中的一种或多种。该结晶碳可包括一种或多种石墨，诸如，例如，无定形、板状、片状、球形或纤维状石墨，其中该石墨可为天然石墨或人造石墨。无定形碳可包括以下中的一种或多种：软碳(例如，低温焙烧碳)、硬碳、中间相沥青碳化物和焙烧焦炭。例如，可通过溅射或蒸镀金属阳极以在阳极集流体上形成阳极活性材料组合物来制备阳极，该阳极集流体可为例如铜片或铜箔。也可通过如下方式制备阳极：将阳极活性材料组合物浇铸在单独的载体上以形成膜，然后将该膜与该单独的载体分离，并将分离的膜层压到阳极集流体上。
可将如果使用的分隔件插在阴极和阳极之间。该分隔件不被特别限制，并且可使用任何分隔件。可使用对电解质具有高保湿能力和/或对电解质离子转移具有低阻力的分隔件。该分隔件可包括例如以下中的一种或多种：玻璃纤维、聚酯、特氟隆、聚乙烯、聚丙烯和聚四氟乙烯(PTFE)。该分隔件可为非织造织物或织造织物类型。该电解质不被特别限制，并且该电解质可为液体电解质、凝胶和/或固体。例如，液体电解质可为溶液的形式，其中锂盐溶解于有机溶剂中。凝胶电解质可为凝胶的形式，其中上述液体电解质浸渍到由离子导电聚合物构成的基质聚合物中。
图4例示了根据实施方案的锂电池单元100的平面图；该锂电池单元100包括叠堆102，该叠堆包含多个层，该多个层包括阴极、分隔件、电解质和阳极。这些层可以平面构型保持平坦或可被卷绕成卷绕构型(例如，“果冻卷”)，但其他构型也是可能的。通过沿折叠线112折叠柔性片材来形成柔性袋状部。例如，柔性片材可由具有聚合物膜(诸如聚丙烯)的铝制成。在折叠柔性片材之后，例如可以通过沿侧面密封部110和沿平台密封部108施加热来密封柔性片材。叠堆102还包括耦合到阴极和阳极的一组导电引片106。该导电引片106可延伸穿过袋状部中的密封部以为电池单元100提供端子。然后，导电引片106可用于将电池单元100与一个或多个其他电池单元电耦合以形成电池组。锂电池可组合在呈任何构型的电池组中。例如，电池组可以串联、并联或串并联构型耦合电池单元来形成。
图5为用于图1的锂电池单元100的层的侧视图的示意图。该层可包括阴极集流体202、阴极活性涂层204、间隔件206、阳极活性涂层208和阳极集流体210。阴极集流体202和阴极活性涂层204可形成锂电池单元的阴极，并且阳极集流体210和阳极活性涂层208可形成锂电池单元的阳极。
图6A为固态锂电池300的示例的透视图，并且图6B为固态锂电池300的层的分解图。固态锂电池300具有阳极集流体302、阳极304、固体电解质306、阴极308、阴极集流体310和任选的基底312。这些层可作为薄层按顺序沉积在基底312上。这些层用封装材料314封装。另选地，阴极308和/或阴极集流体310可具有足够的机械强度以支撑这些层，使得不需要衬底312。阴极308为本文所公开的阴极材料。阳极材料可为锂金属或可为上文所列的其他材料。作为非限制性示例，该固体电解质可为含硫化合物(例如，硫银锗矿、LGPS、LPS等)、石榴石结构氧化物(例如，具有各种掺杂剂的LLZO)、NASICON型磷酸盐玻璃陶瓷(LAGP)、氮氧化物(例如，锂磷氮氧化物或LIPON)、以及聚合物(PEO)。
除非另有定义，否则本文所用的所有技术和科学术语的含义与本公开所属领域的普通技术人员通常理解的含义相同。描述了优选的方法、技术、设备和材料，但与所述方法、技术、设备或材料类似或等同的任何方法、技术、设备或材料均可用于本公开的实践或测试中。本文所述的结构还应当理解为是指此类结构的功能等同物。
需要说明的是，如本文和所附权利要求中所使用，单数形式“一”，“一个”以及“该”包括复数引用，除非上下文明确地另有规定。因此，例如，提及“一个要素”是指一个或多个要素，并且包括本领域技术人员已知的其等同物。
虽然已结合某些实施方案描述了本公开，但应当理解，本公开并不限于所公开的实施方案，相反，其旨在涵盖所附权利要求范围内所包括的各种修改形式和等同布置，所述范围将被赋予最广泛的解释，以便涵盖法律允许的所有此类修改形式和等同结构。
Claims (17)
1.一种用于锂电池的阴极材料，包括：
基于锂过渡金属的颗粒，所述基于锂过渡金属的颗粒选自锂过渡金属氧化物和锂过渡金属磷酸盐；和
碳化硅，所述碳化硅驻留在所述基于锂过渡金属的颗粒的晶界处，从而形成沿所述晶界的导电通路。
2.根据权利要求1所述的阴极材料，其中碳化硅颗粒各自具有小于100nm的最长尺寸。
3.根据权利要求1所述的阴极材料，其中所述碳化硅小于所述阴极材料的10重量％。
4.根据权利要求1所述的阴极材料，其中所述碳化硅小于所述阴极材料的1重量％。
5.根据权利要求1所述的阴极材料，其中碳化硅颗粒具有1至25的纵横比。
6.根据权利要求1所述的阴极材料，其中所述碳化硅为纳米纤维颗粒。
7.根据权利要求6所述的阴极材料，其中所述纳米纤维颗粒具有介于5和25之间包括端值在内的纵横比。
8.根据权利要求1所述的阴极材料，所述阴极材料在高温热处理之后具有大于LiCoO2的理论密度的95％的密度和小于500nm的晶粒。
9.一种锂金属电池单元，包括：
包含根据权利要求1所述的阴极材料的阴极；
包含锂化合物的阳极；和
电解质。
10.根据权利要求9所述的锂金属电池单元，其中所述单元为全固态单元。
11.一种锂离子电池单元，包括：
包含根据权利要求1所述的阴极材料的阴极；
阳极，所述阳极包含以下中的一种或多种：能够与锂形成合金的金属和准金属、它们的合金、或它们的氧化物、以及碳材料；和
液体电解质、凝胶电解质和聚合物电解质中的一种或多种。
12.一种锂电池阴极材料，包括：
基于锂过渡金属的材料，所述基于锂过渡金属的材料选自锂过渡金属氧化物和锂过渡金属磷酸盐；和
结晶碳化硅，所述结晶碳化硅驻留在所述基于锂过渡金属的材料的晶界处，从而形成沿所述晶界的导电通路，所述结晶碳化硅小于所述阴极材料的10重量％。
13.根据权利要求12所述的锂电池阴极材料，其中所述结晶碳化硅为所述阴极材料的1重量％或更少。
14.根据权利要求12所述的锂电池阴极材料，其中所述结晶碳化硅为纳米纤维形式。
15.根据权利要求12所述的锂电池阴极材料，其中所述结晶碳化硅材料具有小于100nm的最长尺寸。
16.根据权利要求12所述的锂电池阴极材料，其中所述结晶碳化硅材料具有1至25的纵横比。
17.根据权利要求12所述的锂电池阴极材料，所述锂电池阴极材料在高温热处理之后具有大于LiCoO2的理论密度的95％的密度和小于500nm的晶粒。
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- 2020-09-30 CN CN202011058698.4A patent/CN112909225A/zh active Pending
- 2020-10-06 WO PCT/US2020/054382 patent/WO2021112952A1/en active Application Filing
- 2020-10-06 DE DE112020005931.6T patent/DE112020005931T5/de active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010123423A (ja) * | 2008-11-20 | 2010-06-03 | Sumitomo Electric Ind Ltd | 非水電解質電池用正極および非水電解質電池 |
| US20120326079A1 (en) * | 2011-06-24 | 2012-12-27 | Gue-Sung Kim | Composite cathode active material, cathode and lithium battery including the composite cathode active material, and method of preparing the composite cathode active material |
| KR20140067789A (ko) * | 2012-11-27 | 2014-06-05 | 주식회사 티씨케이 | 이차전지의 음극재료 제조방법 |
| CN108550832A (zh) * | 2018-05-15 | 2018-09-18 | 肇庆益晟商贸有限公司 | 一种掺杂稀土元素的锂电池正极材料及其制备方法 |
| CN109494361A (zh) * | 2018-10-29 | 2019-03-19 | 安徽五行动力新能源有限公司 | 一种锂电池正极材料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US11271210B2 (en) | 2022-03-08 |
| DE112020005931T5 (de) | 2022-10-06 |
| WO2021112952A1 (en) | 2021-06-10 |
| US20210175506A1 (en) | 2021-06-10 |
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