CN111508727B - 一种金属网能量存储电极的制备方法 - Google Patents

一种金属网能量存储电极的制备方法 Download PDF

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CN111508727B
CN111508727B CN202010154547.2A CN202010154547A CN111508727B CN 111508727 B CN111508727 B CN 111508727B CN 202010154547 A CN202010154547 A CN 202010154547A CN 111508727 B CN111508727 B CN 111508727B
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陈图强
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Abstract

本发明公开了一种包括锂离子电池和超级电容器在内的能量存储装置。这种装置由特定阴极和阳极组成，其中电极材料层，聚合物电解质和封装材料在金属网状集电器上以一定的模式沉积。将该阴极和阳极电极以一定方式排列并层压，形成柔性储能装置。该装置的复合结构和有关材料涂层在金属网上的特定模式，给予该能量存储装置柔性和可折叠性。

Description

一种金属网能量存储电极的制备方法
技术领域
本发明涉及能量存储装置领域，主要包括锂离子电池和超级电容器。更具体地，本发明涉及柔性电子设备所需的柔性锂离子电池和超级电容器。
背景技术
柔性电子技术的发展需要与其柔性和可弯曲性相匹配的柔性能量存储装置。锂离子电池因其高能量密度、层状电池结构以及可能极少的液体含量，成为开发柔性能量存储装置的优先选择。超级电容器，具有高功率密度和与锂离子电池类似的单元结构，成为柔性能量存储装置的备选之一。
制备柔性储能装置的一种可行的方法是开发相应的柔性电极。人们在这一领域已经做了大量的工作，包括开发锂离子电池或超级电容器的柔性电极和聚合物电解质。开发柔性电极的一般思路是将具有合适的纳米结构的活性电极材料，嵌入柔性基材或与该柔性基材复合，而该基材具有或不具有电化学活性。例如，碳纳米管(CNT)，石墨烯，碳纤维和碳纤维布已被用作制造柔性锂离子阳极和阴极以及柔性超级电容器电极。这些柔性电极的确提高了设备的柔性，但有很大的局限性。这些层状柔性电极通常被堆叠折叠形成装置。由于结合力不足，电极层之间无法避免在反复弯曲或折叠过程中产生层离。虽然一些新的制备方法，包括层压，真空渗透，涂覆，缠绕或印刷，已尝试用于制造柔性锂离子电池或超级电容器的，形成各种形状结构的柔性储能装置，但它们似乎都不适合大规模生产。
近年来，为改善锂离子电池和超级电容器的工作性能，金属网被用作集电器来代替金属箔。Shi等人在一篇文献(Nano Energy，2014，6，82-91)中报道了一种柔性超级电容器，该超级电容器通过将碳材料沉积在不锈钢(SS)网格上，然后用这样的一对网状电极夹住一个被有机电解质溶液润湿的隔膜而得。不幸的是，由于电极和隔膜之间缺乏足够的结合力，反复弯曲可能使层状电极产生层离，而导致超级电容器故障。Chen在美国专利(US9,905,370)中公开了一种3-D锂离子电池和超级电容器，其中将超细金属网(UMM)用作集电器，电极材料薄膜和固态电解质薄膜依次沉积在超细金属网丝的表面上，形成基于UMM的电极。以固体电解质为粘合剂，将这些UMM阳极和阴极交替堆叠和层压，从而形成基于UMM的3-D能量存储设备，以实现更佳的电化学和机械性能特性。金属丝网基材与沉积在金属丝上的电极材料和聚合物电解质材料，通过层压形成一种微米复合结构，为3-D锂离子电池和超级电容器提供一定程度的柔韧性，但这种结构不足以保证实质性的可弯折性。
与常规基于金属箔为集电器的电极相比，这些金属网电极，由于较高的网孔孔隙度而允许承载更多的电极材料，使电池有更高的能量和功率密度。另外，具有孔结构和高表面积的网状基材，使电极材料层与金属基底层的结合力更强。美国专利(US 9,905,370)中公开的一种基于金属网格的能量存储装置，它的新颖结构可以显着改善装置柔性，因为这种能量存储装置是金属纤维增强的，并具有连续聚合物电解质相的复合材料。这样的结构可以提高物体的柔韧性并降低由弯折带来的电极分层的风险。然而，必须认识到，聚合物电解质一般不具有用于结构应用的机械强度，来承受柔性装置的反复弯曲或折叠。因此，这种金属网柔性能量存储装置需要进一步引入新的柔性结构特征。由于金属网的开放结构，如果引入柔性树脂封装材料作为金属网储能装置连续的、分布均匀的基体，则可以显着改善储能装置的柔性和可折叠性。
发明内容
本发明的目的是赋予金属网能量存储装置柔性和可折叠性。
本发明包括：1)应用金属网作为电极基体集电器，2)以一定的图案形式在金属网线上依次沉积电极材料和电解质涂层，来制备金属网阳极和阴极，以及3)用聚合物电解质和聚合物封装装材料作为粘合剂，通过层压图案对齐的阳极和阴极组件，并使柔性封装材料渗透到组件的开孔结构中，形成主要包括锂离子电池和超级电容器的柔性能量存储装置。
因此，本发明的一个目的就是要求保护一种柔性、可折叠的能量存储装置。这种装置的制备包括按顺序和以一定的图案在金属网线上沉积电极材料、电解质和柔性封装材料，形成阴极和阳极，然后将图案对齐的阴极和阳极进行层压，获得柔性能量存储装置。本发明的另一个目的是进一步公开具有用于折叠和弯曲能力特征的柔性能量存储装置。该装置至少有一个柔性封装材料和金属网组成的主要线性带，给予被保护的柔性能量存储装置沿该主带所形成的轴折叠和弯曲的能力。该柔性装置有两组由柔性封装材料和金属网组成的副直线带，同组的直线带相互平行；作为优选，两组平行带以90°相交，从而形成多个柔性正方形，以增加装置的整体柔性。
附图说明
本发明的原理可参考具体实施列，并结合附图来理解。其中：
图1是一金属网状电极集电器的平面图。
图2是一对金属网状电极的平面图。
图3是金属网柔性电源装置的平面侧视图。
图4是金属网柔性电源装置相邻的金属网线电极的截面侧视图，说明金属网线，电极材料层、电解质层、以及封装装材料层的详细结构关系。
具体实施方式
如图1所示,金属网10被用作能量存储装置的集电器和具有结构强度的基材，传导电流并给予器械结构上的柔性。所有合适的金属都可以用于制备金属网10，包括铝，铜，镍，锑，铬，铁或硅等。网丝直径和网孔可以在10至100微米的范围内。
如图2所示，一对网状电极，阴极12A和阳极12B，其组成包括：网状基材10(其中阴极10A和阳极10B)，电极涂层14A和14B，电解质涂层16A和16B，以及主封装带20A和20B，和二级封装带22A和22B。电极(阴极或阳极)材料层14直接涂覆在金属网丝上，而电解质16随后涂覆在电极层上。封装带20和22直接嵌入没有电极和电解质涂层的金属网格中。至少有一个较宽的主封装带20，直接嵌入无电极和电解质涂层的金属网孔中，该主封装带使装置可以沿着带的轴线折叠。有两组相交的次(二)级封装带22，组成许多正方形或其他四边形的柔性单元，以提高装置的柔性。组内的封装带之间相互平行。值得注意的是，网状电极的边缘可以是填充在金属网中的封装材料20，或者先不填充，而最后用封装材料填充并封闭由阳极和阴极组成的装置。
如图3所示，基于金属网的能量存储装置30，包括金属网阴极12A和阳极12B，通过对齐、层压并封在封装材料20中。层压是通过聚合物电解质层和封装材料层各自自身内聚粘合以及它们相互间的粘合来实现的。同样，可以先以电解质作为粘合剂层压电极对，然后将柔性聚合物包装材料渗透到排列整齐的孔结构中来实现装置柔性。主(一级)封装带由可柔性可折叠金属网带嵌入在柔性高分子封装材料基体中形成。多组二级封装带同样由金属网带和柔性高分子封装材料组成(其结构未在图3中显示)提供了额外的柔性。值得注意的是，电解质或封装装材料的内聚粘合消除了阳极和阴极之间的界面，这使该装置成为一个完整的复合材料体。
图4是相邻的金属网线电极的截面侧视图，显示了柔性装置30的两对相邻的阳极和阴极的金属网线的结构特征，该金属线10A和10B涂有圆柱形电极涂层(14A和14B)和电解质涂层16，并被埋藏在封装材料20中。该结构的阴极和阳极的网线完全对齐并粘结在一起，但是本发明并不排除正负网状电极组件的其他排列方式。另外，电极和电解质涂层的厚度可以足够小而不完全堵塞网孔，从而允许后续封装材料的填充。
与先前公开的3D金属网能量存储装置(Chen，US 9,905,370)相似，电极涂层在金属网线表面的附着力比在金属箔表面更强。这是因为网线上的涂层具有封闭的结构，并且金属网的表面积比平面金属箔更大。同样，随后的电解质涂层更牢固地粘结在圆柱形电极涂层上。对于柔性电极来讲，这是一个非常好的属性，因为这种封闭结构的涂层和它的强附着力，将极大阻碍由于反复弯曲或折叠而导致的层间分离。聚合物电解质层自身的内聚，使电极之间高效粘合结成一体，从而形成具有金属线(纤维)增强的聚合物复合材料结构的柔性装置。但是，必须认识到，聚合物电解质并非旨在用于结构性应用；它们一般不具备能承受柔性设备反复弯曲或折叠的机械强度。因此，本发明的柔性能量存储装置引入了新的柔性特征。
与先前公开的3D金属网能量存储装置(Chen，US 9,905,370)相比，本发明公开了新的旨在增加能量储存装置柔性和可折叠性的特征。这些特征包括：1)一个具有柔性的聚合物封装材料，作为复合材料基体，将阳极/阴极组件埋藏在其中；2)在装置中间的一级折叠封装带，由聚合物封装材料与埋藏在其中的金属网带组成；3)分布在整个装置中的两组二级折叠封装带，同样由聚合物封装材料与埋藏在其中的金属网带组成，以及4)未被电极和电解质材料完全覆盖的网孔，允许柔性聚合物封装材料渗透以增强柔性和强度。
应当指出，这些特征的引入在提高柔韧性的同时，减少了活性电极材料的载荷，从而降低了器件的能量和功率密度。因此，对于特定的应用，本发明不必包括全部四个特征。此外，由于网孔的尺寸很小，通常在几十微米的范围内，因此在涂覆电极和电解质涂层之后可能难以使孔保持开放。在这种情况下，为保证装置足够的柔性，二级柔性聚合物封带的存在变得至关重要。
作为储能装置，锂离子电池通常使用金属氧化物作为阴极，碳材料作为阳极。本发明允许使用任何合适的锂离子电池正极材料，包括LiCoO2，LiNiO2，LiMn2O4，LiFePO4或LiNixCoyMnz，涂覆在金属网状集电器上网线上。
可以将这种粉末形式的材料与导电添加剂，聚合物粘合剂与溶剂混合形成浆液，将该浆液涂敷到网线的表面上。活性材料、导电添加剂和聚合物粘合剂的相对比例可变，范围包括：50wt％至90wt％的活性材料、0wt％至15wt％的导电添加剂，余量为聚合物粘合剂。阴极材料还可以通过其他方法，包括溶液化学，气相、或电化学的方法沉积在网线的表面上。网线表面上的阴极涂层不必完全覆盖网孔，阴极涂层的厚度范围可在2微米至200微米。
本发明允许使用任何合适的锂离子阳极材料，包括石墨，Si或LiTiO。这种粉末形式的材料可以和导电添加剂、聚合物粘合剂、溶剂混合形成浆液，并将该浆液涂敷到网线的表面上。活性材料、导电添加剂和聚合物粘合剂的相对比例可变；范围包括：50wt％至90wt％的活性材料、0wt％至15wt％的导电添加剂，余量为聚合物粘合剂。阳极材料还可以通过其他方法，包括溶液化学，气相、或电化学的方法沉积在网线的表面上。网线表面上的阴极涂层不必完全覆盖网孔，阴极涂层的厚度范围在2微米至200微米。
本发明允许将聚合物或凝胶聚合物电解质沉积在锂离子阴极或阳极电极涂层上。任何合适的聚合物电解质均可用于本发明。可以用多种方式沉积聚合物电解质，包括流延，浸涂，旋涂，喷涂或其他涂覆技术。聚合物电解质涂层的厚度可在2微米至200微米的范围内变化。
超级电容器，也称为电化学双电层电容器，作为能量存储装置，使用高表面积碳作为电极材料，包括活性炭，碳纳米管，以及石墨烯等。赝电容金属氧化物，诸如RuO2，NiO和IrO2等，也可用作电极材料。这种粉末形式的材料可以和导电添加剂、聚合物粘合剂、溶剂混合形成浆液，并将该浆液涂敷到网线的表面上。“活性材料”和聚合物粘合剂的相对比例可变；范围包括：50wt％至95wt％的活性材料，余量为聚合物粘合剂。超级电容器电极材料还可以通过其他包括溶液化学，气相、或电化学的方法沉积在网线的表面上。网线表面上的阴极涂层不必完全覆盖网孔，并且涂层的厚度范围在2微米至200微米。
本发明允许将聚合物或凝胶聚合物电解质沉积在超级电容器电极涂层上。任何合适的聚合物电解质均可用于本发明。可以用多种方式沉积聚合物电解质，包括流延，浸涂，旋涂，喷涂或其他涂覆技术。聚合物电解质涂层的厚度可在2微米至200微米的范围内变化。
柔性聚合物封装材料可以用于封装或者渗透已层压好的阳极/阴极组件。本发明允许使用任何合适的柔性聚合物材料来封闭该装置，这些包括聚硅氧烷，聚氨酯，聚酯(PET)，聚酰亚胺(PI)，聚萘二甲酸乙二醇酯(PEN)，聚醚酰亚胺(PEI)和含氟聚合物或共聚物。柔性聚合物包装层的厚度范围可以在2微米至2毫米内。值得说明的是，封装材料可以渗入至主折叠带，二级弯曲带，未被堵塞的网孔和金属网状未涂覆的边缘的所有多孔结构中，从而将金属网阳极和阴极组件紧紧地粘合在一起，并使其成为一个完整的复合材料体。

Claims (11)

1.一种柔性能量存储装置，包括：a)至少一个阴极，b)至少一个阳极，和c)一对用于封装所述阴极和阳极的柔性聚合物封装层；其中所述阴极包括：金属网状集电器，沉积在金属网线上的阴极材料层，和沉积在阴极材料层上的固体电解质层；所述阳极包括：金属网集电器，沉积在金属网线上的阳极材料层，和沉积在阳极材料层上的固体电解质层；所述阴极和阳极上的固体电解质层相互粘合；所述聚合物封装层与所述固体电解质层相互粘合；所述封装层通过所述阴极和阳极的开孔结构相互粘合。
2.根据权利要求1所述的柔性能量存储装置，其中所述开孔结构包括没有被电极和电解质材料完全填充的网孔的空隙。
3.根据权利要求 1 所述的柔性能量存储装置，其中所述开孔结构包括至少一个裸露金属网的主要线性条带，其带宽范围为 10 微米至 10 毫米。
4.根据权利要求 1 所述的柔性能量存储装置，其中所述开孔结构包括两组相交的裸露金属网次级线性平行条带，其条带范围为 5 微米至 5毫米，相邻条带之间的距离范围为5 微米至 10 毫米。
5.根据权利要求1所述的柔性能量存储装置，其中所述金属网集电器，由 Al，Cu，Ni，Sb，Cr，Fe 和 Si 材料组成，其线径范围为 10 微米至 1000 微米，网孔径尺寸范围为 10微米至 2000 微米。
6.如权利要求1所述的柔性能量存储装置，其特征在于，所述阴极材料层包括：锂离子阴极活性材料，导电添加剂和聚合物粘合剂，其中所述活性材料包括选自由S，LiCoO2，LiNiO2，LiMn2O4，LiFePO4和LiNixCoyMnz组成的材料；所述导电添加剂包括选自由石墨和炭黑组成的材料；所述聚合物粘合剂包括选自由PVDF，EPDM，CMC，PTFE和SBR组成的材料；其中所述阴极材料层的厚度范围为2微米至200微米。
7.如权利要求1所述的柔性能量存储装置，其特征在于，所述阳极材料层包括：锂离子阳极活性材料，导电添加剂和聚合物粘合剂；其中所述活性材料包括选自由LiTiO ，石墨，和硅组成的材料；所述导电添加剂包括选自由石墨和炭黑组成的材料；所述聚合物粘合剂包括选自由PVDF，EPDM，CMC，PTFE和SBR组成的材料；其中所述阴极材料层的厚度范围为2微米至200微米。
8.根据权利要求1所述的柔性能量存储装置，其中所述阴极和阳极材料层包括：超级电容器材料，导电添加剂和聚合物粘合剂；其中所述超级电容器材料包括选自活性炭，石墨烯，和碳纳米管组成的材料；其中所述导电添加剂包括选自石墨和炭黑组成的材料；所述聚合物粘合剂包含选自由PVDF，EPDM，CMC，PTFE和SBR组成的材料；以及所述导电添加剂包括选自由石墨和炭黑组成的材料；其中所述阴极材料层的厚度范围为2微米至200微米。
9.根据权利要求1所述的柔性能量存储装置，其中所述固体电解质层包含聚合物电解质材料，并且所述电解质层的厚度范围为2微米至200微米。
10.根据权利要求1所述的柔性能量存储装置，其中所述柔性聚合物封装层包含选自由聚硅氧烷，聚氨酯，聚酯，聚酰亚胺(PI)，聚醚酰亚胺(PEI)和含氟聚合物或共聚物组成的材料，其中所述柔性聚合物封装层的厚度为2微米至2毫米。
11.根据权利要求1所述的柔性能量存储装置，其中所述柔性聚合物封装层包含选自由聚硅氧烷，聚氨酯，聚对苯二甲酸乙二酯(PET)，聚酰亚胺(PI)，聚萘二甲酸乙二醇酯(PEN)，聚醚酰亚胺(PEI)和含氟聚合物或共聚物组成的材料，其中所述柔性聚合物封装层的厚度为2微米至2毫米。
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