WO2019210595A1 - 一种有效抑制锂金属电池枝晶不可控生长的锂片、其制备方法及用途 - Google Patents

一种有效抑制锂金属电池枝晶不可控生长的锂片、其制备方法及用途 Download PDF

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WO2019210595A1
WO2019210595A1 PCT/CN2018/098088 CN2018098088W WO2019210595A1 WO 2019210595 A1 WO2019210595 A1 WO 2019210595A1 CN 2018098088 W CN2018098088 W CN 2018098088W WO 2019210595 A1 WO2019210595 A1 WO 2019210595A1
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lithium sheet
lithium
pattern
micro
nano
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French (fr)
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程鑫
卢周广
李志强
张腾飞
黄兴隆
张雨
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Southern University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to the field of battery technology, for example, to a lithium sheet which effectively inhibits the uncontrolled growth of dendrites of a lithium metal battery, a preparation method thereof and use thereof.
  • lithium metal is a very promising high energy density anode material in lithium batteries because of its theoretical capacity of up to 3860 mA ⁇ h/g and a very low redox potential (relative to standard hydrogen electrodes).
  • -3.04V redox potential
  • lithium metal plays a key role in meeting the demand for high energy density batteries for electric vehicles and advanced electronic equipment for new and growing applications.
  • the formation of lithium dendrites with low coulombic efficiency hinders the practical application of lithium metal anodes for rechargeable lithium batteries.
  • the generation of lithium dendrites and the dead lithium it produces may cause safety problems such as thermal runaway or even burning, or explosion.
  • the biomimetic method can be improved by using a 3D collector to bond the polymer electrolyte.
  • the uncontrollable lithium dendrite problem is an urgent problem to be solved in the development of rechargeable lithium batteries based on lithium metal anodes.
  • the present disclosure provides a lithium sheet which is effective for inhibiting uncontrolled growth of dendrites of a lithium metal battery, a preparation method thereof and use thereof.
  • the use of a lithium plate of a specific structure as a negative electrode can effectively suppress the uncontrolled growth of dendrites of a lithium metal battery.
  • the present disclosure provides a lithium sheet which is a lithium sheet having a pit structure and/or a groove structure, the pit structure and/or the groove structure being a micro/nano structure pattern.
  • micro/nano structure as used in the present disclosure means that the structure is on a two-dimensional plane perpendicular to the depth of the pit and/or the groove, and the dimension of at least one dimension is on the order of micrometers or nanometers, the micrometer level or nanometer.
  • the level may be, for example, 50 nm to 900 ⁇ m, for example, 50 nm, 60 nm, 80 nm, 100 nm, 150 nm, 200 nm, 300 nm, 350 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m. 70 ⁇ m, 150 ⁇ m, 200 ⁇ m, 300 ⁇ m, 400 ⁇ m, 500 ⁇ m, 600 ⁇ m, 700 ⁇ m, 800 ⁇ m or 900 ⁇ m, and the like.
  • the "at least one dimension" may be one dimension of a two-dimensional plane or two dimensions of a two-dimensional plane.
  • micro/nano structure pattern refers to a pattern formed by a plurality of micro/nano structures in a two-dimensional plane perpendicular to the depth of the pits and/or grooves, the plurality of which may be, for example, two per square centimeter.
  • 10 3 to 10 8 in the dimensional plane, for example, 10 3 , 3 ⁇ 10 3 , 5 ⁇ 10 3 , 8 ⁇ 10 3 , 10 4 , 2 ⁇ 10 4 , 5 ⁇ 10 4 , 7.5 ⁇ 10 4 , 10 5 , 1.5 ⁇ 10 5 , 3 ⁇ 10 5 , 6.5 ⁇ 10 5 , 8 ⁇ 10 5 , 10 6 , 2 ⁇ 10 6 , 4 ⁇ 10 6 , 6 ⁇ 10 6 , 8 ⁇ 10 6 , 10 7 , 2.5 ⁇ 10 7 , 3.5 ⁇ 10 7 , 6.5 ⁇ 10 7 , 8.5 ⁇ 10 7 or 10 8 , etc.
  • the present disclosure can better achieve the effect of suppressing the growth of lithium dendrites by forming a lithium sheet into a micro/nano structure pattern.
  • the "pit and/or groove” as used in the present disclosure means that it may be a pit structure, a groove structure, or a combination of a pit structure and a groove structure.
  • the dimples and/or grooves of the present disclosure may be of a regular shape or an irregular shape, and the grooves may be straight grooves or curved grooves, and the dimples may be square in horizontal section.
  • a pit (referred to as a square pit), a circular pit having a horizontal cross section (referred to as a circular pit) or a pit having an elliptical horizontal cross section (abbreviated as an elliptical pit).
  • the micro-nano structure pattern is a regular periodic pattern.
  • it may be a periodic pattern formed by a single micro-nano structure pit, each pit is regularly arranged and has a certain pitch; or may be a periodic pattern formed by a single micro-nano structure groove, and each groove rule Arranged and have a certain spacing; it may also be a regular pattern formed by a combination of micro-nano structure pits and micro-nano structure grooves.
  • the lithium sheet has a thickness of 0.5 mm to 1 mm, such as 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.85 mm, 0.9 mm, or 1 mm.
  • the pits and/or grooves have a depth of 50 nm to 100 ⁇ m, such as 50 nm, 75 nm, 80 nm, 100 nm, 115 nm, 130 nm, 160 nm, 200 nm, 235 nm, 270 nm, 300 nm, 350 nm, 400 nm, 450 nm.
  • the pits and/or grooves have a depth of from 5 ⁇ m to 15 ⁇ m, and in this range, the space in which the pits and/or recesses accommodate lithium is suitable.
  • the depth of the pits and/or grooves is 1/10 to 1 times the minimum line width, for example, 1/10, 1/9, 1/8, 1/7.5, 1/7, 1/6, 1/5, 1/4, 1/3, 1/2 or 1 etc. Within this range, pit and/or groove structures are less difficult to manufacture, and lithium is more easily deposited in a tightly packed form. .
  • the "minimum line width" as used in the present disclosure refers to the minimum distance between two points passing through the center of the plane on the plane perpendicular to the depth of the pits and/or grooves.
  • the minimum line width refers to the distance in the width direction of the strip; for a rectangular pit, the minimum line width refers to the distance of the wide side; for a square pit, the minimum line width refers to The distance of the side length; for an elliptical pit, the minimum line width refers to the distance of the short side of the ellipse.
  • lithium is preferentially deposited on the pits and/or grooves of the uneven surface, which is specifically a micro-nano structure pattern, which provides space for the growth of lithium dendrites, thereby effectively suppressing lithium.
  • the growth of lithium dendrites in metal batteries avoids the phenomenon of piercing the battery separator and improves the performance of the lithium battery.
  • the present disclosure provides the use of the lithium sheet described as a negative electrode.
  • the present disclosure provides a method for preparing a lithium sheet, which comprises: performing a roll-to-roll embossing or a board-to-plate embossing on a lithium sheet using a metal template.
  • the present disclosure embosses a roll-to-roll embossing or a board-to-plate embossing, and transfers the micro-nano structure of the metal stencil to the negative-electrode lithium sheet, thereby forming a negative-electrode lithium sheet having a micro-nano structure, which can effectively suppress lithium metal.
  • the growth of lithium dendrites in the battery and the phenomenon of piercing the battery separator improve the performance of the lithium battery.
  • the method includes:
  • the hardness of the metal template is greater than the hardness of the lithium sheet
  • the metal template is a pattern having a convex structure, and the lithium sheet is embossed to form a pit structure and/or a groove structure on the surface of the lithium sheet;
  • the micro-nano structure pattern is a regular periodic pattern.
  • the metal template in step (1) is a nickel template.
  • the preparation method of the nickel template is:
  • the nickel seed layer of step (B) has a thickness of 50 nm to 100 nm, such as 50 nm, 60 nm, 70 nm, 80 nm, 85 nm, 90 nm or 100 nm.
  • the silicon wafer of step (A) is a cleaned silicon wafer.
  • the method of coating as described in step (A) is spin coating.
  • the method of forming the nickel seed layer in the step (B) is magnetron sputtering or electron beam evaporation.
  • the method includes transferring the micro-nano structure of the nickel template onto the negative lithium sheet by plate-to-plate imprinting. More specifically, it includes:
  • a photoresist is spin-coated on a clean silicon wafer, and a pattern on the mask is used to form a micro-nano pattern;
  • a layer of 50 nm to 100 nm of nickel is plated by magnetron sputtering or electron beam evaporation as a seed layer, followed by thickening by electroplating, and finally demolded to form a nickel template;
  • the prepared nickel template was patterned by nano-embossing on the lithium sheet in a water-free and oxygen-free environment to obtain a lithium sheet having a micro-nano pattern.
  • the present disclosure provides a lithium metal battery comprising the lithium sheet as a negative electrode.
  • the present disclosure provides a lithium metal battery, the negative electrode of which is a negative electrode as described above, and the lithium metal battery further includes a positive electrode, a separator, an electrolyte, and a battery can.
  • the embodiment of the present disclosure has a structure of pits and/or grooves by forming a lithium sheet into a specific uneven surface, and the pits and/or grooves are micro-nano structure patterns.
  • the micro-nano structure pattern can effectively control the free growth of dendrites of lithium metal batteries.
  • the present disclosure adopts a nanoimprint technology, in particular, a roll-to-roll nanoimprinted lithium metal battery negative electrode, which can realize large-scale industrial mass production, and has a stable pattern, a large specific surface area, and a pattern that is not easily defective.
  • micro-nano processing technology adopted in an embodiment of the present disclosure is mature and stable, and can realize precise control of the graphic size, and can be produced from nanometer to micrometer-level patterns.
  • FIG. 1 is a process flow diagram of preparing a lithium sheet having a micro/nano structure by a plate-to-plate imprinting process according to an embodiment of the present disclosure
  • FIG. 2 is a schematic view of the finished product of a lithium sheet having a micro/nano structure prepared by a plate-to-plate imprinting process according to an embodiment of the present disclosure
  • FIG. 3 is a simplified schematic diagram of a roll-to-roll imprint process according to an embodiment of the present disclosure
  • FIG. 5a and 5b are SEM images of lithium deposited on a negative electrode lithium sheet having a micro/nano structure according to an embodiment of the present disclosure, wherein FIG. 5b is an enlarged view of a broken-line frame region in FIG. 5a.
  • the embodiment provides a method for preparing a lithium sheet having a micro/nano structure, comprising: transferring the micro-nano structure of the nickel template onto the negative lithium sheet by plate-to-plate imprinting.
  • a method of preparing a lithium sheet having a micro/nano structure includes:
  • a photoresist is spin-coated on a clean silicon wafer, and a pattern on the mask is used to form a micro-nano pattern;
  • a layer of 100 nm nickel seed is plated by magnetron sputtering or electron beam evaporation, followed by thickening by electroplating, and finally demolded to form a nickel template;
  • the prepared nickel template was patterned by nano-embossing on the lithium sheet in a water-free and oxygen-free environment to obtain a lithium sheet having a micro-nano pattern.
  • FIG. 1 is a process flow diagram of preparing a lithium sheet having a micro/nano structure by a plate-to-plate imprint process according to an embodiment of the present disclosure.
  • FIG. 2 is a schematic view of the finished product of a lithium sheet having a micro/nano structure prepared by a plate-to-plate imprinting process according to an embodiment of the present disclosure.
  • Example 2 The other methods and conditions were the same as in Example 1 except that the thickness of the nickel seed layer was 50 nm.
  • Example 2 The other methods and conditions were the same as in Example 1 except that the thickness of the nickel seed layer was 75 nm.
  • the embodiment provides a method for preparing a lithium sheet having a micro/nano structure, comprising: transferring a micro-nano structure of a nickel template onto a negative lithium sheet by roll-to-roll embossing.
  • a method of preparing a lithium sheet having a micro/nano structure includes:
  • a photoresist is spin-coated on a clean silicon wafer, and a pattern on the mask is used to form a micro-nano pattern;
  • a layer of 100 nm nickel seed is plated by magnetron sputtering or electron beam evaporation, followed by thickening by electroplating, and finally demolded to form a nickel template;
  • the prepared nickel template was patterned by roll-to-roll nanoimprint on a lithium sheet in an anhydrous and oxygen-free environment to obtain a lithium sheet having a micro/nano pattern.
  • FIG. 3 is a simplified schematic diagram of a roll-to-roll imprint process according to an embodiment of the present disclosure.
  • FIG. 4 is an SEM image of a lithium sheet having a micro/nano structure according to an embodiment of the present disclosure. It can be seen from the figure that the lithium sheet after the micro-nano processing has a uniformly distributed square groove pattern, and the square groove is formed. The sides of the square are approximately 5 ⁇ m long and have a depth of approximately 50 nm with a certain spacing between the grooves.
  • FIG. 5a and 5b are SEM images of lithium deposited on a negative electrode lithium sheet having a micro/nano structure according to an embodiment of the present disclosure, wherein FIG. 5b is an enlarged view of a broken-line frame region in FIG. 5a. It can be seen from Fig. 5a and Fig. 5b that lithium is preferentially deposited on the bottom of the square pattern and the groove wall, and is attached in a small particle shape, and does not produce any dendritic lithium.
  • the micro-nano processing pattern is not large due to the battery cycle.
  • the change of lithium metal is almost deposited in the pattern groove after each battery cycle, indicating that the lithium sheet after micro-nano processing can effectively suppress the problem that lithium dendrites break through the SEI film due to excessive local current density.
  • the application of lithium metal batteries offers a possibility.

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Abstract

本公开提供了一种有效抑制锂金属电池枝晶不可控生长的锂片、其制备方法及用途。该锂片具有凹坑结构和/或凹槽结构，所述凹坑结构和/或凹槽结构为微纳结构图形，通过采用该特定结构的锂片作为负极可以有效抑制锂金属电池枝晶不可控生长，避免了刺穿电池隔膜的现象，提高了锂电池的性能。

Description

一种有效抑制锂金属电池枝晶不可控生长的锂片、其制备方法及用途 技术领域
本公开涉及电池技术领域，例如涉及一种有效抑制锂金属电池枝晶不可控生长的锂片、其制备方法及用途。
背景技术
相关技术中，提高锂离子电池能量密度是商业化锂电池行业长期发展的一个重要追求方向，然而，由于商业化的石墨负极它的理论容量只有372mA·h/g，限制了电池的应用，还有许多负极材料如硅、锡、过度金属氧化物等都可以用于取代目前商业化的石墨负极。
除了上述这些材料外，锂金属是基于锂电池中一个非常有前途的高能量密度负极材料，因为它的理论容量高达3860mA·h/g，而且有一个很低的氧化还原电位(相对标准氢电极为-3.04V)，因此，锂金属在满足针对日益增长新型应用的电动汽车和先进的电子设备对高能量密度电池的需求中起着关键作用。然而，锂金属电池在充放电循环过程中，锂枝晶的形成伴随着低的库伦效率阻碍了锂金属负极用于可充放电锂电池的实际应用。尤其是，锂枝晶的产生和它产生的死锂可能会导致出现诸如热失控甚至燃烧、或爆炸等安全问题。
相关技术中，通过在锂金属上面涂一层LiF，或者在电解液中加聚硫化物、LiNO 3、Cs +、离子液体等，使用3D收集器结合高分子电解液，生物仿生的方法可以改善锂金属表面的SEI(solid electrolyte interphase)膜等。
以上技术，对不可控锂枝晶生长的改善程度是很有限的，它们不能大规模的应用于高通量的工业化生产。
总之，不可控的锂枝晶问题是发展基于锂金属负极的可充电锂电池急需解决的问题。
发明内容
本公开提供一种有效抑制锂金属电池枝晶不可控生长的锂片、其制备方法及用途。通过采用特定结构的锂片作为负极能够有效抑制锂金属电池枝晶不可控生长。
本公开在一实施例中提供一种锂片，所述锂片为具有凹坑结构和/或凹槽结 构的锂片，所述凹坑结构和/或凹槽结构为微纳结构图形。
本公开所述“微纳结构”指：该结构在与凹坑和/或凹槽的深度垂直方向所在二维平面上，至少一个维度的尺寸为微米级别或纳米级别，所述微米级别或纳米级别例如可以是50nm～900μm，例如50nm、60nm、80nm、100nm、150nm、200nm、300nm、350nm、400nm、500nm、600nm、700nm、800nm、900nm、1μm、10μm、20μm、30μm、40μm、50μm、60μm、70μm、150μm、200μm、300μm、400μm、500μm、600μm、700μm、800μm或900μm等。所述“至少一个维度”可以是二维平面的一个维度，也可以是二维平面的两个维度。
本公开所述“微纳结构图形”指：多个微纳结构在与凹坑和/或凹槽的深度垂直方向所在二维平面内形成的图形，所述多个例如可以是每平方厘米二维平面内有10 3～10 8个，例如10 3个、3×10 3个、5×10 3个、8×10 3个、10 4个、2×10 4个、5×10 4个、7.5×10 4个、10 5个、1.5×10 5个、3×10 5个、6.5×10 5个、8×10 5个、10 6个、2×10 6个、4×10 6个、6×10 6个、8×10 6个、10 7个、2.5×10 7个、3.5×10 7个、6.5×10 7个、8.5×10 7个或10 8个等。
本公开通过使锂片形成微纳结构图形，可以更好地达到抑制锂枝晶生长的效果。
本公开所述“凹坑和/或凹槽”指：可以是凹坑结构，也可以是凹槽结构，还可以是凹坑结构和凹槽结构的组合。
本公开的凹坑和/或凹槽可以是规则的形状，也可以是不规则的形状，所述凹槽可以是直槽也可以是弯曲状的槽，所述凹坑可以是水平截面为方形的凹坑(简称方形凹坑)、水平截面为圆形的凹坑(简称为圆形凹坑)或水平截面为椭圆形的凹坑(简称为椭圆形凹坑)等。
在一实施例中，所述微纳结构图形为规则的周期性图形。举例说明，可以是单独的微纳结构凹坑形成的周期性图形，各个凹坑规则排列，且具有一定的间距；也可以是单独的微纳结构凹槽形成的周期性图形，各凹槽规则排列，且具有一定的间距；还可以是微纳结构凹坑和微纳结构凹槽共同组合形成的规则性图形。
在一实施例中，所述锂片的厚度为0.5mm～1mm，例如0.5mm、0.6mm、0.7mm、0.8mm、0.85mm、0.9mm或1mm等。
在一实施例中，所述凹坑和/或凹槽的深度为50nm～100μm，例如50nm、 75nm、80nm、100nm、115nm、130nm、160nm、200nm、235nm、270nm、300nm、350nm、400nm、450nm、500nm、550nm、600nm、650nm、700nm、750nm、800nm、850nm、900nm、1μm、2μm、3μm、4μm、5μm、6μm、6.5μm、7μm、8μm、10μm、15μm、20μm、35μm、50μm、60μm、70μm、80μm、90μm或100μm等。
在一实施例中，所述凹坑和/或凹槽的深度为5μm～15μm，在此范围内，凹坑和/或凹槽容纳锂的空间比较适宜。
在一实施例中，所述凹坑和/或凹槽的深度为最小线宽的1/10～1倍，例如1/10、1/9、1/8、1/7.5、1/7、1/6、1/5、1/4、1/3、1/2或1等，在此范围内，凹坑和/或凹槽结构制造难度更低，锂更容易以紧密堆积的形式沉积。
本公开所述“最小线宽”指：与凹坑和/或凹槽的深度垂直方向所在平面上，穿过平面中心的两点的最小距离。例如，对于一个长条形的凹槽，最小线宽指长条的宽度方向的距离；对于一个长方形的凹坑，最小线宽指宽边的距离；对于一个正方形的凹坑，最小线宽指边长的距离；对于一个椭圆形的凹坑，最小线宽指椭圆短边的距离。
在电池充放电过程中，锂优先沉积在不平整表面的凹坑和/或凹槽处，其具体是一种微纳结构图形，这为锂枝晶的生长提供了空间，从而有效抑制了锂金属电池中锂枝晶的生长、避免了刺穿电池隔膜的现象，提高了锂电池的性能。
本公开在一实施例中提供一种所述的锂片的用途，所述锂片用作负极。
本公开在一实施例中提供一种所述的锂片的制备方法，所述方法包括：采用金属模板对锂片进行卷对卷压印或板对板压印。
本公开在一实施例中通过卷对卷压印或板对板压印，将金属模板的微纳结构转移到负极锂片上，从而可以形成具有微纳结构的负极锂片，能够有效抑制锂金属电池中锂枝晶的生长以及刺穿电池隔膜的现象，提高了锂电池的性能。
在一示例性实施例中，所述方法包括：
(1)制备金属模板；
所述金属模板的硬度大于锂片的硬度；
所述金属模板为具有凸起结构的图形，且压印锂片后使锂片表面形成凹坑结构和/或凹槽结构；
(2)在无水无氧环境中，通过卷对卷压印或板对板压印对锂片进行图形化， 使锂片具有凹坑结构和/或凹槽结构，所述凹坑结构和/或凹槽结构为微纳结构图形。
在一实施例中，所述微纳结构图形为规则的周期性图形。
在一实施例中，步骤(1)所述金属模板为镍模板。
在一实施例中，所述镍模板的制备方法为：
(A)在硅片上涂覆光刻胶，利用掩膜板上的图形进行曝光，最后显影出微纳图案；
(B)去除光刻胶，然后形成一层50nm～100nm的镍种子层；
(C)电镀增厚，脱模得到镍模板。
在一实施例中，步骤(B)所述镍种子层的厚度为50nm～100nm，例如50nm、60nm、70nm、80nm、85nm、90nm或100nm等。
在一实施例中，步骤(A)所述硅片为清洗干净的硅片。
在一实施例中，步骤(A)所述涂覆的方法为旋涂。
在一实施例中，步骤(B)所述形成镍种子层的方法为磁控溅射或电子束蒸镀。
在一示例性实施例中，所述方法包括：通过板对板压印，将镍模板的微纳结构转移到负极锂片上。更具体地，包括：
首先在洁净的硅片上旋涂光刻胶，利用掩膜板上的图形形成，从而制作出微纳图案；
ICP干法刻蚀，去除光刻胶；
然后用磁控溅射或电子束蒸镀镀上一层50nm～100nm的镍作种子层，接着用电镀的方法增厚，最后脱模制成镍模板；
将制作好的镍模板在无水无氧的环境中通过板对板纳米压印在锂片上进行图形化，从而得到具有微纳图案的锂片。
在一示例性实施例中，仅将板对板纳米压印替换为卷对卷纳米压印，其他方法与前述示例性实施例的技术方案相同，卷对卷纳米压印简易示意图参见图3。
本公开在一实施例中提供一种锂金属电池，所述锂金属电池包含所述的锂片作为负极。
本公开在一实施例中提供了一种锂金属电池，所述锂金属电池的负极为前 述的负极，所述锂金属电池还包括正极、隔膜、电解液和电池壳等部件。
与相关技术相比，本公开实施例通过将锂片制成特定的不平整表面，具有凹坑和/或凹槽等结构，所述凹坑和/或凹槽为微纳结构图形，这种微纳结构图形可以有效控制锂金属电池枝晶的自由生长问题。
本公开在一实施例中采用纳米压印技术，特别是卷对卷纳米压印锂金属电池负极，可以实现大规模工业化量产，而且图形稳定规则，图形比表面积大，图形不易产生缺陷。
本公开在一实施例中采用的微纳加工技术，工艺成熟稳定，可实现图形尺寸的精确控制，从纳米级到微米级别的图案均可制作。
附图说明
附图用来提供对本公开技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本公开的技术方案，并不构成对本公开技术方案的限制。
图1是本公开一实施例提供的采用板对板压印工艺制备具有微纳结构的锂片的工艺流程图；
图2是本公开一实施例提供的采用板对板压印工艺制备的具有微纳结构的锂片的成品效果图；
图3是本公开一实施例提供的采用卷对卷压印工艺的简易示意图；
图4是本公开一实施例提供的具有微纳结构的锂片的SEM图像；
图5a和图5b是本公开一实施例提供的具有微纳结构的负极锂片沉积锂之后的SEM图像，其中，图5b为图5a中虚线框区域的放大图。
具体实施例
实施例1
本实施例提供一种具有微纳结构的锂片的制备方法，包括：通过板对板压印，将镍模板的微纳结构转移到负极锂片上。
在一个实施例中，制备具有微纳结构的锂片的方法包括：
首先在洁净的硅片上旋涂光刻胶，利用掩膜板上的图形形成，从而制作出微纳图案；
ICP干法刻蚀，去除光刻胶；
然后用磁控溅射或电子束蒸镀镀上一层100nm的镍种子层，接着用电镀的 方法增厚，最后脱模制成镍模板；
将制作好的镍模板在无水无氧的环境中通过板对板纳米压印在锂片上进行图形化，从而得到具有微纳图案的锂片。
图1是本公开一实施例提供的采用板对板压印工艺制备具有微纳结构的锂片的工艺流程图。
图2是本公开一实施例提供的采用板对板压印工艺制备的具有微纳结构的锂片的成品效果图。
实施例2
除镍种子层的厚度为50nm外，其他方法和条件与实施例1相同。
实施例3
除镍种子层的厚度为75nm外，其他方法和条件与实施例1相同。
实施例4
本实施例提供一种具有微纳结构的锂片的制备方法，包括：通过卷对卷压印，将镍模板的微纳结构转移到负极锂片上。
在一个实施例中，制备具有微纳结构的锂片的方法包括：
首先在洁净的硅片上旋涂光刻胶，利用掩膜板上的图形形成，从而制作出微纳图案；
ICP干法刻蚀，去除光刻胶；
然后用磁控溅射或电子束蒸镀镀上一层100nm的镍种子层，接着用电镀的方法增厚，最后脱模制成镍模板；
将制作好的镍模板在无水无氧的环境中通过卷对卷纳米压印在锂片上进行图形化，从而得到具有微纳图案的锂片。
图3是本公开一实施例提供的采用卷对卷压印工艺的简易示意图。
图4是本公开一实施例提供的具有微纳结构的锂片的SEM图像，由图可以看出，经过微纳加工后的锂片出现了呈均匀分布的方形凹槽图案，方形凹槽的方形边长大约5μm，深度大约50nm，并且凹槽之间有一定的间距。
图5a和图5b是本公开一实施例提供的具有微纳结构的负极锂片沉积锂之后的SEM图像，其中，图5b为图5a中虚线框区域的放大图。由图5a和图5b可以看出，锂优先沉积在方形图案底部和槽壁，而且呈小颗粒状附着，并没有产生任何枝晶状锂，微纳加工图案并没有因为电池循环后而产生大的变化，每 次电池循环后锂金属几乎都沉积在图案槽里面，说明微纳加工后的锂片可以有效地抑制由于局部电流密度过大引起的锂枝晶冲破SEI膜的问题，为新一代锂金属电池的应用提供了一种可能。
申请人声明，本公开通过上述实施例来说明本申请的详细方法，但本公开并不局限于上述详细方法，即不意味着本公开必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本公开的任何改进，对本公开产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本公开的保护范围和公开范围之内。

Claims (16)

  1. 一种锂片，所述锂片为具有凹坑结构和/或凹槽结构的锂片，所述凹坑结构和/或凹槽结构为微纳结构图形。
  2. 根据权利要求1所述的锂片，其中，所述微纳结构图形为规则的周期性图形。
  3. 根据权利要求1或2所述的锂片，所述锂片的厚度为0.5mm～1mm。
  4. 根据权利要求1-3任一项所述的锂片，其中，所述凹坑和/或凹槽的深度为50nm～100μm。
  5. 根据权利要求4所述的锂片，其中，所述凹坑和/或凹槽的深度为5μm～15μm。
  6. 根据权利要求1-5任一项所述的锂片，其中，所述凹坑和/或凹槽的深度为最小线宽的1/10～1倍。
  7. 如权利要求1-6任一项所述的锂片的用途，所述锂片用作负极。
  8. 如权利要求1-6任一项所述的锂片的制备方法，所述方法包括：采用金属模板对锂片进行卷对卷压印或板对板压印，使锂片具有凹坑结构和/或凹槽结构，所述凹坑结构和/或凹槽结构为微纳结构图形。
  9. 根据权利要求8所述的方法，其中，所述压印为纳米压印。
  10. 根据权利要求8所述的方法，所述方法包括：
    (1)制备金属模板；
    所述金属模板的硬度大于锂片的硬度；
    所述金属模板为具有凸起结构的图形，且压印锂片后使锂片形成凹坑结构和/或凹槽结构；
    (2)在无水无氧环境中，通过卷对卷压印或板对板压印对锂片进行图形化，使锂片具有凹坑结构和/或凹槽结构，所述凹坑结构和/或凹槽结构为微纳结构图形。
  11. 根据权利要求8-10任一项所述的方法，其中，所述微纳结构图形为规则的周期性图形。
  12. 根据权利要求8-11任一项所述的方法，其中，步骤(1)所述金属模板为镍模板。
  13. 根据权利要求12所述的方法，其中，所述镍模板的制备方法为：
    (A)在硅片上涂覆光刻胶，利用掩膜板上的图形进行曝光，最后显影出微 纳图案；
    (B)去除光刻胶，然后形成一层50nm～100nm的镍种子层；
    (C)电镀增厚，脱模得到镍模板。
  14. 根据权利要求13所述的方法，其中，步骤(A)所述涂覆的方法为旋涂。
  15. 根据权利要求13所述的方法，其中，步骤(B)所述形成镍种子层的方法为磁控溅射或电子束蒸镀。
  16. 一种锂金属电池，所述锂金属电池包含权利要求1-6任一项所述的锂片作为负极。
PCT/CN2018/098088 2018-05-02 2018-08-01 一种有效抑制锂金属电池枝晶不可控生长的锂片、其制备方法及用途 Ceased WO2019210595A1 (zh)

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