CN114243212A - 一种基于重离子径迹膜的锂金属/锂离子电池功能化隔膜及其制备方法 - Google Patents
一种基于重离子径迹膜的锂金属/锂离子电池功能化隔膜及其制备方法 Download PDFInfo
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- 150000002500 ions Chemical class 0.000 title claims abstract description 78
- 229910052744 lithium Inorganic materials 0.000 title abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 38
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
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- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
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- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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Abstract
本发明公开了一种基于重离子径迹膜的锂金属/锂离子电池功能化隔膜及其制备方法。所述基于重离子径迹膜的功能化隔膜包括基膜和功能化层,基膜为重离子径迹膜,功能化层为沉积于基膜的表面和孔道壁面上的陶瓷层,重离子径迹膜的材质为聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酰亚胺、聚醚酰亚胺或聚丙烯;陶瓷层的材质为三氧化二铝、二氧化硅、氮化硅、碳化硅或氧化锆。本发明功能化隔膜采用有机聚合物材质作为基膜,因此厚度很薄,因此具有较低的内阻,从而具有较高的锂离子电导率;且具有聚合物材质拥有的柔性特质,可以随意发生卷绕、折叠而不变形,因此比无机类的隔膜更具有实际应用的价值。
Description
技术领域
本发明涉及一种基于重离子径迹膜的锂金属/锂离子电池功能化隔膜及其制备方法,属于锂金属/锂离子电池以及聚合物薄膜技术领域。
背景技术
能源对人类社会具有重要的意义,随着化石能源的消耗和随之而来的环境污染、气候变暖等问题,追求清洁和可再生能源成为人类发展的重要主题。自从1991年索尼公司发布第一款商用锂离子电池以来,锂离子电池成为各种电化学储能装置的关键研究对象之一,并已广泛应用于便携式电子设备、新能源汽车和智能电网等储能领域。然而,现有技术的锂离子电池的电极材料(特别是负极材料—石墨)的能量密度几乎达到其物理极限,远远不足以满足电动汽车和智能电网等先进储能系统的快速发展对电极材料的能量密度提出的更高要求。在所有的负极材料中,锂金属具有较高的理论比容量(3860mAh g-1,是商业化应用石墨负极的十倍)和最低的氧化还原电势(相对于标准氢电极为-3.04V),一直被认为是锂基电池的负极材料中的“圣杯”,并且是具有高能量密度的正极材料(例如硫和氧)的锂硫电池、锂空电池等高能储能系统最有前途的负极材料之一。
然而,锂金属负极的实际应用面临着巨大的挑战,主要是在锂金属重复电镀和剥离过程中,锂离子将形成异质且不稳定的沉积层,导致不可控的锂枝晶的生长,从而致使电池性能的下降,甚至会刺穿隔膜导致电池内部短路,严重时引发安全问题。为了寻求抑制锂枝晶生长的方法,近年来提出了几种模型来阐述锂枝晶的生长机理,其中电荷诱导模型得到了广泛的认可,该模型认为锂金属表面成核部位的突起具有比其他部位更高的电场,这将吸引更多的Li+,从而促进尖端锂枝晶的生长(图1)。并且高曲率的突起为不均匀的锂沉积提供了更大的表面积,进一步促进了锂枝晶的生长。从上述机理出发,在锂金属表面上实现均匀的Li+沉积对于抑制锂枝晶的生长具有重要意义(图2)。隔膜作为电池结构中的关键组件,不仅是防止两个电极直接接触的物理屏障,而且是调控锂离子在电解液中传输性能的有力工具。利用隔膜实现Li+在锂金属表面的均匀分布从而抑制锂枝晶的生长是一种简单有效、且易于大规模应用的方案。
目前商用的锂离子电池隔膜是经由干法(熔融拉伸法)或者湿法(热致相分离)拉伸后具有微孔结构的聚烯烃隔膜,由于这类隔膜具有电化学性能稳定、力学性能优异、生产成本低廉等优势,从而得到了广泛的应用。但受限于拉伸工艺自身,很难生产出孔径均一的隔膜,且孔径偏大,因此很难对Li+的空间分布进行有效调控。一些研究者们采用无机多孔膜,例如阳极氧化铝(AAO)多孔膜,作为电池隔膜,这类隔膜的孔径均一,但孔径偏大、厚度较厚、质脆易碎,不易于大面积推广。另一些研究者们基于传统聚烯烃隔膜或者阳极氧化铝隔膜,在其表面进行无机或者有机多孔材料的涂覆,例如快离子导体(LLZTO)、金属有机骨架(MOF)、氧化石墨烯(GO)、介孔二氧化硅(MSTF)等,这些涂覆层作为离子再分配器,拥有更小的孔径和更好的孔径均一性,从而能够实现Li+在空间的均匀分布。但额外增加的涂覆工艺增加了隔膜的生产成本,且涂覆后的隔膜厚度变厚,导致电池内阻的增加,且涂覆层与基膜的界面结合经常不稳固,涂覆层在长期的电池循环过程中会逐渐发生脱落,影响电池的电化学性能。因此,要实现锂离子在空间上的均匀分布,一个具有厚度较薄的、孔径较小的且孔径均一性优异的有机聚合物薄膜是必须的。
发明内容
本发明的目的是提供一种基于重离子径迹膜的锂金属/锂离子电池功能化隔膜,能够将隔膜孔径及其均一性与隔膜厚度、内阻、力学性能以及生产成本等方面统一兼顾,能够保障隔膜在液态电解液环境下长期的电化学稳定性;功能化层使隔膜拥有较强的电解液亲液性,有助于提升锂金属/锂离子电池的电化学性能;能够实现锂离子在锂金属表面的均匀分布,从而实现抑制锂枝晶生长的效果。
本发明所提供的基于重离子径迹膜的功能化隔膜,包括基膜和功能化层;
所述基膜为重离子径迹膜;
所述功能化层为沉积于所述基膜的表面和孔道壁面上的陶瓷层。
所述重离子径迹膜的材质为聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺(PI)、聚醚酰亚胺(PEI)或聚丙烯(PP);
所述陶瓷层的材质为三氧化二铝(Al2O3)、二氧化硅(SiO2)、氮化硅(Si3N4)、碳化硅(SiC)或氧化锆(ZrO2)。
所述功能化隔膜上孔道为定向排列的直通孔道;
所述功能化隔膜上孔道的孔径为6~96nm,如40±5nm、46±5nm或50±5nm;
所述功能化隔膜上孔密度为1×1010~1×1011/cm2,如1~2×1010/cm2、1×1010/cm或2×1010/cm2。
所述重离子径迹膜孔道的孔径为10~100nm,如55±5nm、50±5nm或45±5nm,孔密度与所述功能化隔膜上孔密度一致;
所述重离子径迹膜的厚度为6~30μm;
所述陶瓷层的厚度为2~5nm,如2~3nm。
本发明功能化隔膜中设置功能化层,能够保障隔膜在电解液中的电化学稳定性;增强隔膜在电解液中的亲液性能,促进锂离子在纳米孔道里的输运。
本发明进一步提供了所述功能化隔膜的制备方法,包括如下步骤:
S1、采用重离子垂直辐照聚合物薄膜,得到辐照后的重离子径迹膜;
S2、将所述辐照后的离子径迹膜进行化学刻蚀,得到多孔的重离子径迹膜;
S3、在步骤S2得到的所述重离子径迹膜上沉积所述功能化层,即得到所述功能化隔膜。
上述的制备方法中,步骤S1中,所述重离子可为氙离子、铋离子或钽离子;
所述重离子的离子能量为0.1~100MeV/u,如氙离子为19.5MeV/u,钽离子为12.5MeV/u,铋离子为9.8MeV/u;
所述垂直辐照的密度为1×109~1×1011ions/cm2。
上述的制备方法中,步骤S2中,所述化学刻蚀采用的刻蚀液为下述1)-5)中任一种:
1)所述聚合物薄膜为聚对苯二甲酸乙二醇酯膜或聚萘二甲酸乙二醇酯膜,所述刻蚀液为氢氧化钠溶液,摩尔浓度为1~10mol/L;
2)所述聚合物薄膜为聚酰亚胺膜或聚醚酰亚胺膜,所述刻蚀液为次氯酸钠溶液,其中有效氯的质量百分比含量为5~15%;
3)所述聚合物薄膜为聚丙烯膜,所述刻蚀液为铬酸溶液,摩尔浓度为5~15mol/L。
上述的制备方法中,步骤S2中,所述化学刻蚀的温度为30~80℃,时间为2~120min。
上述的制备方法中,步骤S3中,采用原子层沉积的方式沉积所述功能化层;
采用设有三个气体喷射部的原子层沉积装置沉积所述功能化层;
以沉积Al2O3为例,说明三体气体喷射部的作用:
在原子层沉积Al2O3时,第一气体喷射部向真空腔内喷射三甲基铝(TMA),第二气体喷射部向真空腔内喷射水蒸气(H2O),第三气体喷射部向真空腔内喷射惰性气体氮气(N2),TMA和H2O在所述基膜重离子径迹膜表面和孔道壁部位形成Al2O3沉积层。
本发明提供的基于重离子径迹膜的功能化隔膜能够应用于液态电解质锂金属/锂离子电池中。
特别注意的是,如若本发明提供的功能化隔膜应用于其他类型的储能电池中,也在本发明的保护范围之内。
本发明基于重离子径迹膜的功能化隔膜,采用具有孔径较小、孔径均一的重离子径迹膜作为基膜,该重离子径迹膜具有直通的孔道,不存在盲孔,不存在曲折孔,从而保证该膜具有较低的内阻,从而拥有较高的离子电导率;再利用ALD技术,在薄膜表面和孔道壁形成一层较薄的钝化层,该钝化层能够保障薄膜在液态电解质中的长期的电化学稳定性,从而能够保证锂金属/锂离子电池的长期循环;另外该钝化层能够增强薄膜在电解液中的亲液性,从而促进锂离子在纳米孔道里的快速输运,增强锂金属/锂离子电池的电化学性能。本发明利用多孔隔膜实现了Li+在锂金属表面的均匀分布,从而抑制了锂枝晶的生长,可使液态锂金属/锂离子电池具有优异的电化学性能和安全性能,并且制造工艺简单,可以大面积推广,从而为锂金属/锂离子电池的实际应用提供了一种优选方案。
本发明基于重离子径迹膜的功能化隔膜采用有机聚合物材质作为基膜,因此厚度很薄(6~30μm),优于目前商业化应用的聚烯烃隔膜(25μm)和基于聚烯烃隔膜的修饰(>30μm),以及传统无机隔膜(55μm)和基于传统无机隔膜的修饰(>60μm)的膜厚,因此具有较低的内阻,从而具有较高的锂离子电导率;且具有聚合物材质拥有的柔性特质,可以随意发生卷绕、折叠而不变形,因此比无机类的隔膜更具有实际应用的价值。在基膜表面和孔道壁沉积的钝化层,隔绝了电解液和基膜的直接接触,起到了保护基膜的作用;另外沉积的钝化层具有亲液的特性,这能够增强锂离子在孔道里的输运。
附图说明
图1为不均匀的锂离子流导致锂枝晶的生长示意图。
图2为均匀的锂离子流实现无枝晶的锂沉积示意图。
图3为本发明制备的功能化隔膜的剖面示意图。
图4为本发明制备的功能化隔膜的正面示意图。
图5为本发明实施例1制备的PEI重离子径迹膜的正面SEM图。
图6为本发明实施例1制备的PEI重离子径迹膜的截面SEM图。
图7为商业隔膜Celgard 2400的正面SEM图。
图8为本发明对比例1制备的PEI重离子径迹膜的SEM-EDS图。
图9为本发明实施例1制备的基于PEI重离子径迹膜的功能化隔膜的SEM-EDS图。
图10为商业隔膜Celgard 2400、本发明对比例1和本发明实施例1制备的隔膜的接触角测试结果。
图11为本发明实施例1制备的基于PEI重离子径迹膜的功能化隔膜的锂离子电池的循环性能。
图12为本发明实施例1的基于PEI重离子径迹膜的功能化隔膜的锂离子电池的首次充放电曲线。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
本发明采用孔径小、均一性好、膜厚薄的重离子径迹膜作为基膜,在其表面和孔道表面沉积一层保护层,制备得到功能化的锂金属/锂离子电池隔膜,其中,功能化层的作用是:1)保障隔膜在电解液中的电化学稳定性;2)促进锂离子在纳米孔道里的输运。利用本发明公开的电池隔膜,可以实现锂离子在锂金属表面的均匀分布,保证锂金属/锂离子电池长期循环的稳定性。
图3和图4分别为本发明提供的基于重离子径迹膜的功能化隔膜的剖面示意图和正面示意图。
实施例1、
1)利用重离子加速器提供的高能重离子束流,为重离子氙(该重离子能量为19.5MeV/u),垂直辐照12μm的PEI薄膜,辐照密度为2×1010ions/cm2。
2)将重离子辐照的PEI膜在60℃的水浴温度下进行化学蚀刻,蚀刻液为有效氯含量为12%的NaClO溶液,pH值用硼酸调节至10.0,并在整个蚀刻过程中维持溶液的pH值恒定,蚀刻时间为5h,得到直径为55±5nm的竖直纳米孔的PEI重离子径迹膜,孔密度为2×1010/cm2。
3)将制备好的PEI基膜进行Al2O3钝化层的沉积,沉积温度为150℃,沉积时间为1min,最终获得沉积厚度为3nm的Al2O3,从而得到用于锂金属电池的基于重离子径迹膜的功能化隔膜,孔道的孔径为50±5nm。
本实施例制备的PEI重离子径迹膜的正面SEM图如图5所示,可以看出,本发明方法制备的PEI重离子径迹膜的孔径较小,孔径均一,孔密度高,从横截面SEM(图6)可以看出,该膜具有竖直分布的直通孔道,而从商业隔膜的正面SEM图(图7)可以看出商业隔膜的孔径偏大且孔径不均一。
功能化层的存在能够保障隔膜的电化学稳定性,并且可以增加隔膜的亲液性,从而有助于锂离子在孔道内的快速输运。
实施例2、
1)利用重离子加速器提供的高能重离子束流,为重离子Bi(该重离子能量为9.8MeV/u),垂直辐照12μm的PEN薄膜,辐照密度为1×1010ions/cm2。
2)将重离子辐照的PEN在40℃的水浴温度下进行化学蚀刻,蚀刻液为摩尔浓度为3mol/L的NaOH水溶液,蚀刻时间为100min,得到直径为50±5nm的竖直纳米孔的PEN重离子径迹膜,孔密度为1×1010/cm2。
3)将制备好的PEN基膜进行SiO2钝化层的沉积,沉积温度为100℃,沉积时间为50s,最终获得沉积厚度为2nm的SiO2,从而得到本发明用于锂金属电池的基于重离子径迹膜的功能化隔膜,功能化隔膜的孔道的孔径为46±5nm。
实施例3、
1)利用重离子加速器提供的高能重离子束流,为重离子钽(该重离子能量为12.5MeV/u),垂直辐照8μm的PI薄膜,辐照密度为2×1010ions/cm2。
2)将重离子辐照的PI在40℃的水浴温度下进行化学蚀刻,蚀刻液为有效氯含量为12%的NaClO水溶液,pH值用硼酸调节至9.5,并在整个蚀刻过程中维持溶液的pH值恒定,蚀刻时间为60min,得到直径为45±5nm的竖直纳米孔的PI重离子径迹膜,孔密度为2×1010/cm2。
3)将制备好的PI基膜进行Al2O3钝化层的沉积,沉积温度为150℃,沉积时间为1min,最终获得沉积厚度为3nm的Al2O3,从而得到本发明用于锂金属电池的基于重离子径迹膜的功能化隔膜,功能化隔膜的孔道的孔径为40±5nm。
对比例1、
1)利用重离子加速器提供的高能重离子束流,为重离子氙(该重离子能量为19.5MeV/u),垂直辐照12um的PEI薄膜,辐照密度为2×1010ions/cm2。
2)将重离子辐照的PEI膜在60℃的水浴温度下进行化学蚀刻,蚀刻液为有效氯含量为12%的NaClO溶液,pH值用硼酸调节至10.0,并在整个蚀刻过程中维持溶液的PH值恒定,蚀刻时间为5h,得到直径为60±5nm的竖直纳米孔的PEI重离子径迹膜,孔密度为2×1010/cm2。
对对比例1和实施例1制备的隔膜进行元素分析,实验结果如图8和图9所示,实验发现对比例1制备的隔膜表面无Al元素分布,而实施例1制备的隔膜表面分布着均匀、致密的Al元素,这说明成功地在对比例1所制的隔膜表面进行了Al2O3的原子层沉积。
对对比例1和实施例1制备的隔膜以及商业隔膜Celgard2400进行接触角测试,实验结果如图10所示。实验发现商业隔膜Celgard 2400的接触角为116°,对比例1制备的隔膜的接触角为68°,实施例1制备的隔膜的接触角为55°。实施例1制备的隔膜较对比例1制备的隔膜及商业隔膜Celgard 2400拥有更小的接触角,表明其拥有更好的亲液性。
将实施例1制备的隔膜组装成磷酸铁锂—锂扣式电池,在1C充放电条件下测试电池的循环性能,如图11所示,电池能够实现长期稳定循环,循环100圈时其容量保持率达95.5%。
首次充放电曲线如图12所示,首次充电比容量达137.2mAh/g,放电比容量达124.9mAh/g,库仑效率达91.1%,表现出良好的电池性能。
本发明方法制备得到的基于重离子径迹膜的功能化隔膜,功能化层能够保障隔膜在电解液环境中的电化学稳定性,并拥有较高的电解液亲液性。该隔膜可以实现锂离子在锂金属表面的均匀分布,使锂金属/锂离子电池具有优异的安全性能和电池性能。
Claims (10)
1.一种基于重离子径迹膜的功能化隔膜,包括基膜和功能化层;
所述基膜为重离子径迹膜;
所述功能化层为沉积于所述基膜的表面和孔道壁面上的陶瓷层。
2.根据权利要求1所述的功能化隔膜,其特征在于:所述重离子径迹膜的材质为聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酰亚胺、聚醚酰亚胺或聚丙烯;
所述陶瓷层的材质为三氧化二铝、二氧化硅、氮化硅、碳化硅或氧化锆。
3.根据权利要求1或2所述的功能化隔膜,其特征在于:所述功能化隔膜上孔道为定向排列的直通孔道;
所述功能化隔膜上孔道的孔径为6~96nm;
所述功能化隔膜上孔密度为1×1010~1×1011/cm2。
4.根据权利要求1-3中任一项所述的功能化隔膜,其特征在于:所述重离子径迹膜孔道的孔径为10~100nm;
所述重离子径迹膜的厚度为6~30μm;
所述陶瓷层的厚度为2~5nm。
5.权利要求1-4中任一项所述功能化隔膜的制备方法,包括如下步骤:
S1、采用重离子垂直辐照聚合物薄膜,得到辐照后的重离子径迹膜;
S2、将所述辐照后的离子径迹膜进行化学刻蚀,得到多孔的重离子径迹膜;
S3、在步骤S2得到的所述重离子径迹膜上沉积所述功能化层,即得到所述功能化隔膜。
6.根据权利要求5所述的制备方法,其特征在于:步骤S1中,所述重离子为氙离子、铋离子或钽离子;
所述重离子的离子能量为0.1~100MeV/u;
所述垂直辐照的密度为1×1010~1×1011ions/cm2。
7.根据权利要求5或6所述的制备方法,其特征在于:步骤S2中,所述化学刻蚀采用的刻蚀液为下述1)-5)中任一种:
1)所述聚合物薄膜为聚对苯二甲酸乙二醇酯膜或聚萘二甲酸乙二醇酯膜,所述刻蚀液为氢氧化钠溶液,摩尔浓度为1~10mol/L;
2)所述聚合物薄膜为聚酰亚胺膜或聚醚酰亚胺膜,所述刻蚀液为次氯酸钠溶液,其中有效氯的质量百分比含量为5~15%,溶液的pH为8.0~12.0;
3)所述聚合物薄膜为聚丙烯膜,所述刻蚀液为铬酸溶液,摩尔浓度为5~15mol/L。
8.根据权利要求5-7中任一项所述的制备方法,其特征在于:步骤S2中,所述化学刻蚀的温度为30~80℃,时间为2~120min。
9.根据权利要求5-8中任一项所述的制备方法,其特征在于:步骤S3中,采用原子层沉积的方式沉积所述功能化层。
10.根据权利要求9所述的制备方法,其特征在于:采用设有三个气体喷射部的原子层沉积装置沉积所述功能化层。
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