CN118315594B - Current collector of novel lithium metal anode material, and preparation method and application thereof - Google Patents
Current collector of novel lithium metal anode material, and preparation method and application thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000010405 anode material Substances 0.000 title 1
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 52
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007773 negative electrode material Substances 0.000 claims abstract description 52
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 56
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011889 copper foil Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 238000007599 discharging Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 229910017941 Ag—Li Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 2
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 2
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 2
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011532 electronic conductor Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
本发明公开了一种新型锂金属负极材料的集流体及其制备方法和应用，涉及电池材料技术领域，解决锂金属作为负极材料容易形成锂枝晶，以及体积变化大影响电池寿命和安全的技术问题；本发明包括银纳米颗粒、硫化锂、三聚氰胺和导电炭黑，所述银纳米颗粒、硫化锂纳米颗、三聚氰胺和导电炭黑的质量比为（5~7）:（1~2）:（1~2）:1；本发明提供的新型锂金属负极材料的集流体能够有效抑制锂枝晶的生长，缓解充放电过程内部产生的应力，提高电池的寿命和安全，同时保障锂金属负极材料的电化学动力学性能。
The present invention discloses a novel current collector of lithium metal negative electrode material and a preparation method and application thereof, which relates to the technical field of battery materials and solves the technical problems that lithium metal as negative electrode material is easy to form lithium dendrites and the large volume change affects the battery life and safety. The present invention comprises silver nanoparticles, lithium sulfide, melamine and conductive carbon black, and the mass ratio of the silver nanoparticles, lithium sulfide nanoparticles, melamine and conductive carbon black is (5-7): (1-2): (1-2): 1. The novel current collector of lithium metal negative electrode material provided by the present invention can effectively inhibit the growth of lithium dendrites, relieve the stress generated inside the charge and discharge process, improve the battery life and safety, and at the same time ensure the electrochemical kinetic performance of the lithium metal negative electrode material.
Description
技术领域Technical Field
本发明涉及电池材料技术领域，具体涉及一种新型锂金属负极材料的集流体及其制备方法和应用。The present invention relates to the technical field of battery materials, and in particular to a current collector of a novel lithium metal negative electrode material and a preparation method and application thereof.
背景技术Background Art
传统锂离子电池采用石墨作为负极材料，而石墨负极理论比容量和能量密度低，严重限制了其进一步的应用。锂金属因为其具有极高的理论比容量(3860mAh/g)，最低的氧化还原电势(-3.04V相对于标准氢电极)和低的密度(0.534g/cm3)等优点。因此，采用锂金属作负极材料能够大幅度提高锂离子电池的能量密度。Traditional lithium-ion batteries use graphite as the negative electrode material, but the theoretical specific capacity and energy density of graphite negative electrodes are low, which seriously limits its further application. Lithium metal has the advantages of extremely high theoretical specific capacity (3860mAh/g), the lowest redox potential (-3.04V relative to standard hydrogen electrode) and low density (0.534g/ cm3 ). Therefore, using lithium metal as the negative electrode material can greatly improve the energy density of lithium-ion batteries.
但是，锂金属负极材料在使用过程中也存在着一些问题，一方面，锂金属在充放电过程中锂离子的电化学行为不受控制，容易形成锂枝晶，导致循环寿命下降，随着枝晶的生长，甚至会刺破隔膜，导致短路，发生安全问题，另一方面，锂金属负极在充放电过程中会产生较大的体积变化，导致电池在充放电过程中内部形成压力，从而影响了电池的寿命和安全。However, there are also some problems with lithium metal negative electrode materials during use. On the one hand, the electrochemical behavior of lithium ions during the charging and discharging process of lithium metal is uncontrolled, and lithium dendrites are easily formed, resulting in a decrease in cycle life. As the dendrites grow, they may even puncture the diaphragm, causing a short circuit and safety problems. On the other hand, the lithium metal negative electrode will produce a large volume change during the charging and discharging process, causing pressure to form inside the battery during the charging and discharging process, thereby affecting the battery life and safety.
发明内容Summary of the invention
本发明是为了解决锂金属作为负极材料容易形成锂枝晶，以及体积变化大影响电池寿命和安全的技术问题，目的在于提供一种新型锂金属负极材料的集流体及其制备方法和应用，能够有效抑制锂枝晶的生长，缓解充放电过程内部产生的应力，提高电池的寿命和安全，同时保障锂金属负极材料的电化学动力学性能。The present invention aims to solve the technical problems that lithium metal as a negative electrode material is prone to form lithium dendrites and that the large volume change affects the battery life and safety. The present invention aims to provide a new type of current collector for lithium metal negative electrode material and its preparation method and application, which can effectively inhibit the growth of lithium dendrites, relieve the stress generated inside the charging and discharging process, improve the battery life and safety, and at the same time ensure the electrochemical kinetic performance of the lithium metal negative electrode material.
本发明通过下述技术方案实现：The present invention is achieved through the following technical solutions:
本发明的第一个目的是提供一种新型锂金属负极材料的集流体，包括银纳米颗粒、硫化锂、三聚氰胺和导电炭黑，所述银纳米颗粒、硫化锂纳米颗、三聚氰胺和导电炭黑的质量比为（5~7）:（1~2）:（1~2）:1。The first object of the present invention is to provide a new type of lithium metal negative electrode material current collector, comprising silver nanoparticles, lithium sulfide, melamine and conductive carbon black, wherein the mass ratio of the silver nanoparticles, lithium sulfide nanoparticles, melamine and conductive carbon black is (5~7):(1~2):(1~2):1.
本发明中银纳米颗粒具有较大的表面能，且与锂金属的晶格匹配度高，可以诱导锂离子在银纳米颗粒表面进行电化学沉淀，从而控制锂离子的电化学行为，抑制锂枝晶的生长；硫化锂具有较高的锂离子传导率，可以为锂离子的扩散和迁移提供通道；导电炭黑是电子导体，可以为电子传输提供通道；三聚氰胺具有较高的弹性，一方面可以更好的适应锂金属负极材料在充放电过程中的体积变化，缓解充放电过程内部产生的应力，提高电池的寿命和安全，另一方面三聚氰胺的弹性可以确保硫化锂、导电炭黑与银纳米颗粒在充放电过程中始终保持稳定接触，提高了锂金属负极材料的电化学动力学性能。The silver nanoparticles in the present invention have large surface energy and high lattice matching with lithium metal, and can induce lithium ions to electrochemically precipitate on the surface of the silver nanoparticles, thereby controlling the electrochemical behavior of lithium ions and inhibiting the growth of lithium dendrites; lithium sulfide has high lithium ion conductivity and can provide channels for the diffusion and migration of lithium ions; conductive carbon black is an electronic conductor and can provide channels for electronic transmission; melamine has high elasticity, which can better adapt to the volume change of lithium metal negative electrode materials during the charging and discharging process, relieve the stress generated inside the charging and discharging process, and improve the life and safety of the battery; on the other hand, the elasticity of melamine can ensure that lithium sulfide, conductive carbon black and silver nanoparticles always maintain stable contact during the charging and discharging process, thereby improving the electrochemical kinetic performance of the lithium metal negative electrode material.
作为本发明进一步的技术方案，所述银纳米颗粒、硫化锂、三聚氰胺和导电炭黑的质量比为6:2:1:1。As a further technical solution of the present invention, the mass ratio of the silver nanoparticles, lithium sulfide, melamine and conductive carbon black is 6:2:1:1.
作为本发明进一步的技术方案，所述硫化锂、三聚氰胺和导电炭黑采用纳米颗粒。As a further technical solution of the present invention, the lithium sulfide, melamine and conductive carbon black are nanoparticles.
本发明的第二个目的是提供一种新型锂金属负极材料的集流体的制备方法，包括以下步骤：The second object of the present invention is to provide a method for preparing a current collector of a novel lithium metal negative electrode material, comprising the following steps:
（1）将三聚氰胺溶于有机溶剂中，得到含有三聚氰胺的有机溶液；(1) dissolving melamine in an organic solvent to obtain an organic solution containing melamine;
（2）将银纳米颗粒、硫化锂和导电炭黑按照质量比进行混合，然后搅拌或者研磨，形成均匀的混合物；(2) mixing silver nanoparticles, lithium sulfide and conductive carbon black according to a mass ratio, and then stirring or grinding to form a uniform mixture;
（3）将步骤（2）得到均匀的混合物加入到步骤（1）得到的含有三聚氰胺的有机溶液中，然后搅拌或者研磨均匀，得到均匀的浆料；(3) adding the uniform mixture obtained in step (2) to the organic solution containing melamine obtained in step (1), and then stirring or grinding the mixture to obtain a uniform slurry;
（4）将步骤（3）得到的浆料均匀的涂抹到基底上，干燥处理，在基底形成一层薄膜，即得到新型锂金属负极材料的集流体。(4) The slurry obtained in step (3) is evenly applied to a substrate and dried to form a thin film on the substrate, thereby obtaining a current collector of a novel lithium metal negative electrode material.
作为本发明进一步的技术方案，所述步骤（1）中三聚氰胺的溶解条件为：在70~90℃的温度下，将三聚氰胺溶于吡啶溶液中。As a further technical solution of the present invention, the dissolution conditions of melamine in step (1) are: dissolving melamine in a pyridine solution at a temperature of 70-90°C.
作为本发明进一步的技术方案，所述三聚氰胺在吡啶溶液中的浓度为1mg/mL。As a further technical solution of the present invention, the concentration of melamine in the pyridine solution is 1 mg/mL.
作为本发明进一步的技术方案，所述银纳米颗粒、硫化锂、三聚氰胺和导电炭黑的质量比为（5~7）:（1~2）:（1~2）:1。As a further technical solution of the present invention, the mass ratio of the silver nanoparticles, lithium sulfide, melamine and conductive carbon black is (5-7):(1-2):(1-2):1.
作为本发明进一步的技术方案，步骤（4）中，干燥过程为：先在70~90℃的温度下，干燥20~28个小时，再在真空中，在70~90℃的温度下，干燥10~15小时。As a further technical solution of the present invention, in step (4), the drying process is: first drying at a temperature of 70-90° C. for 20-28 hours, and then drying in a vacuum at a temperature of 70-90° C. for 10-15 hours.
作为本发明进一步的技术方案，所述基底为铜箔。As a further technical solution of the present invention, the substrate is copper foil.
本发明第三个目的是提供一种新型锂金属负极材料的集流体在锂金属固态电池和锂金属液态电池中的应用。The third object of the present invention is to provide a new type of lithium metal negative electrode material current collector for use in lithium metal solid-state batteries and lithium metal liquid batteries.
本发明与现有技术相比，具有如下的优点和有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
本发明中银纳米颗粒具有较大的表面能，且与锂金属的晶格匹配度高，可以诱导锂离子在银纳米颗粒表面进行电化学沉淀，从而控制锂离子的电化学行为，抑制锂枝晶的生长；硫化锂具有较高的锂离子传导率，可以为锂离子的扩散和迁移提供通道；导电炭黑是电子导体，可以为电子传输提供通道；三聚氰胺具有较高的弹性，一方面可以更好的适应锂金属负极材料在充放电过程中的体积变化，缓解充放电过程内部产生的应力，提高电池的寿命和安全，另一方面三聚氰胺的弹性可以确保硫化锂、导电炭黑与银纳米颗粒在充放电过程中始终保持稳定接触，提高了锂金属负极材料的电化学动力学性能。The silver nanoparticles in the present invention have large surface energy and high lattice matching with lithium metal, and can induce lithium ions to electrochemically precipitate on the surface of the silver nanoparticles, thereby controlling the electrochemical behavior of lithium ions and inhibiting the growth of lithium dendrites; lithium sulfide has high lithium ion conductivity and can provide channels for the diffusion and migration of lithium ions; conductive carbon black is an electronic conductor and can provide channels for electronic transmission; melamine has high elasticity, which can better adapt to the volume change of lithium metal negative electrode materials during the charging and discharging process, relieve the stress generated inside the charging and discharging process, and improve the life and safety of the battery; on the other hand, the elasticity of melamine can ensure that lithium sulfide, conductive carbon black and silver nanoparticles always maintain stable contact during the charging and discharging process, thereby improving the electrochemical kinetic performance of the lithium metal negative electrode material.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
为了更清楚地说明本发明示例性实施方式的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。在附图中：In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without creative work. In the drawings:
图1是实施例1银纳米颗粒、硫化锂、三聚氰胺和导电炭黑组成的负极材料的集流体（简称Ag-Li2S-C-PM）在循环10次后的表面图；FIG1 is a surface image of the current collector of the negative electrode material composed of silver nanoparticles, lithium sulfide, melamine and conductive carbon black (referred to as Ag-Li 2 SC-PM) in Example 1 after 10 cycles;
图2是对比例未加银纳米颗粒的硫化锂、导电炭黑和三聚氰胺组成的负极材料的集流体（简称Li2S-C-PM）在循环10次后的表面图；FIG2 is a surface image of a current collector of a negative electrode material composed of lithium sulfide, conductive carbon black and melamine without silver nanoparticles added in a comparative example (referred to as Li 2 SC-PM) after 10 cycles;
图3是实施例1银纳米颗粒、硫化锂、三聚氰胺和导电炭黑组成的负极材料的集流体（Ag-Li2S-C-PM）在5mA cm-2的电流密度下和5mAh cm-2的面容量下的库伦效率图；3 is a coulombic efficiency diagram of the current collector (Ag-Li 2 SC-PM) of the negative electrode material composed of silver nanoparticles, lithium sulfide, melamine and conductive carbon black in Example 1 at a current density of 5 mA cm -2 and an area capacity of 5 mAh cm -2 ;
图4是对比例未加银纳米颗粒的硫化锂、三聚氰胺和导电炭黑组成的负极材料的集流体（Li2S-C-PM）在5mA cm-2的电流密度下和5mAh cm-2的面容量下的库伦效率图。FIG4 is a coulombic efficiency diagram of the current collector (Li 2 SC-PM) of the negative electrode material composed of lithium sulfide, melamine and conductive carbon black without adding silver nanoparticles in the comparative example at a current density of 5 mA cm -2 and an area capacity of 5 mAh cm -2 .
具体实施方式DETAILED DESCRIPTION
为使本发明的目的、技术方案和优点更加清楚明白，下面结合实施例和附图，对本发明作进一步的详细说明，本发明的示意性实施方式及其说明仅用于解释本发明，并不作为对本发明的限定。In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments and drawings. The exemplary implementation modes of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention.
在以下描述中，为了提供对本发明的透彻理解阐述了大量特定细节。然而，对于本领域普通技术人员显而易见的是：不必采用这些特定细节来实行本发明。在其他实施例中，为了避免混淆本发明，未具体描述公知的结构、电路、材料或方法。In the following description, a large number of specific details are set forth in order to provide a thorough understanding of the present invention. However, it is apparent to one of ordinary skill in the art that these specific details are not necessarily employed to practice the present invention. In other embodiments, in order to avoid obscuring the present invention, well-known structures, circuits, materials, or methods are not specifically described.
在整个说明书中，对“一个实施例”、“实施例”、“一个示例”或“示例”的提及意味着：结合该实施例或示例描述的特定特征、结构或特性被包含在本发明至少一个实施例中。因此，在整个说明书的各个地方出现的短语“一个实施例”、“实施例”、“一个示例”或“示例”不一定都指同一实施例或示例。此外，可以以任何适当的组合和、或子组合将特定的特征、结构或特性组合在一个或多个实施例或示例中。Throughout the specification, references to "one embodiment," "an embodiment," "an example," or "an example" mean that a particular feature, structure, or characteristic described in conjunction with the embodiment or example is included in at least one embodiment of the present invention. Therefore, the phrases "one embodiment," "an embodiment," "an example," or "an example" appearing in various places throughout the specification do not necessarily all refer to the same embodiment or example. Furthermore, particular features, structures, or characteristics may be combined in one or more embodiments or examples in any appropriate combinations and/or subcombinations.
现有技术中，锂金属负极材料在使用过程中存在着一些问题以下问题：一方面，锂金属在充放电过程中锂离子的电化学行为不受控制，容易形成锂枝晶，导致循环寿命下降，随着枝晶的生长，甚至会刺破隔膜，导致短路，发生安全问题，另一方面，锂金属负极在充放电过程中会产生较大的体积变化，导致电池在充放电过程中内部形成压力，从而影响了电池的寿命和安全。基于锂金属负极材料的以上缺陷，本发明现提出了一种新型锂金属负极材料的集流体及其制备方法和应用来解决这些问题。In the prior art, there are some problems with lithium metal negative electrode materials during use. The following problems exist: On the one hand, the electrochemical behavior of lithium ions in the process of charging and discharging lithium metal is uncontrolled, and lithium dendrites are easily formed, resulting in a decrease in cycle life. As the dendrites grow, they may even puncture the diaphragm, causing a short circuit and safety problems. On the other hand, the lithium metal negative electrode will produce a large volume change during the charging and discharging process, causing pressure to form inside the battery during the charging and discharging process, thereby affecting the life and safety of the battery. Based on the above defects of lithium metal negative electrode materials, the present invention now proposes a new type of lithium metal negative electrode material current collector and its preparation method and application to solve these problems.
下面为本发明的具体实施例。The following are specific embodiments of the present invention.
实施例1Example 1
本实施例提供一种新型锂金属负极材料的集流体的制备方法，包括以下制备步骤：This embodiment provides a method for preparing a current collector of a novel lithium metal negative electrode material, comprising the following preparation steps:
（1）将100mg三聚氰胺纳米颗粒在80℃下，溶于100mL吡啶溶液中，得到三聚氰胺浓度为1mg/mL的吡啶溶液；(1) dissolving 100 mg of melamine nanoparticles in 100 mL of pyridine solution at 80° C. to obtain a pyridine solution with a melamine concentration of 1 mg/mL;
（2）将600mg银纳米颗粒、200mg硫化锂纳米颗粒和100mg导电炭黑进行混合，然后搅拌或者研磨若干时间，形成均匀的混合物；(2) 600 mg of silver nanoparticles, 200 mg of lithium sulfide nanoparticles and 100 mg of conductive carbon black are mixed, and then stirred or ground for a certain period of time to form a uniform mixture;
（3）将步骤（2）得到均匀的混合物加入到步骤（1）得到的三聚氰胺浓度为1mg/mL的吡啶溶液中，然后搅拌或者研磨1h，得到均匀的浆料；(3) adding the uniform mixture obtained in step (2) to the pyridine solution with a melamine concentration of 1 mg/mL obtained in step (1), and then stirring or grinding for 1 hour to obtain a uniform slurry;
（4）将步骤（3）得到的浆料均匀的涂抹到铜箔上，然后在80℃下干燥24h，使吡啶溶液挥发，然后在真空下在80℃条件下再干燥12h，在铜箔上得到一层均匀的薄膜；(4) The slurry obtained in step (3) is evenly applied to the copper foil, and then dried at 80° C. for 24 hours to volatilize the pyridine solution, and then dried at 80° C. under vacuum for another 12 hours to obtain a uniform thin film on the copper foil;
（5）将步骤（4）得到的薄膜裁剪成极片形状，得到一种新型锂金属负极材料的集流体。(5) Cutting the film obtained in step (4) into an electrode shape to obtain a new type of current collector of lithium metal negative electrode material.
实施例2Example 2
本实施例提供一种新型锂金属负极材料的集流体的制备方法，包括以下制备步骤：This embodiment provides a method for preparing a current collector of a novel lithium metal negative electrode material, comprising the following preparation steps:
（1）将200mg三聚氰胺纳米颗粒在80℃下，溶于200mL吡啶溶液中，得到三聚氰胺浓度为1mg/mL的吡啶溶液；(1) dissolving 200 mg of melamine nanoparticles in 200 mL of pyridine solution at 80° C. to obtain a pyridine solution with a melamine concentration of 1 mg/mL;
（2）将600mg银纳米颗粒、200mg硫化锂纳米颗粒和100mg导电炭黑纳米颗粒进行混合，然后搅拌或者研磨若干时间，形成均匀的混合物；(2) mixing 600 mg of silver nanoparticles, 200 mg of lithium sulfide nanoparticles and 100 mg of conductive carbon black nanoparticles, and then stirring or grinding for a certain period of time to form a uniform mixture;
（3）将步骤（2）得到均匀的混合物加入到步骤（1）得到的三聚氰胺浓度为1mg/mL的吡啶溶液中，然后搅拌或者研磨1h，得到均匀的浆料；(3) adding the uniform mixture obtained in step (2) to the pyridine solution with a melamine concentration of 1 mg/mL obtained in step (1), and then stirring or grinding for 1 hour to obtain a uniform slurry;
（4）将步骤（3）得到的浆料均匀的涂抹到铜箔上，然后在80℃下干燥24h，使吡啶溶液挥发，然后在真空下在80℃条件下再干燥12h，在铜箔上得到一层均匀的薄膜；(4) The slurry obtained in step (3) is evenly applied to the copper foil, and then dried at 80° C. for 24 hours to volatilize the pyridine solution, and then dried at 80° C. under vacuum for another 12 hours to obtain a uniform thin film on the copper foil;
（5）将步骤（4）得到的薄膜裁剪成极片形状，得到一种新型锂金属负极材料的集流体。(5) Cutting the film obtained in step (4) into an electrode shape to obtain a new type of current collector of lithium metal negative electrode material.
实施例3Example 3
本实施例提供一种新型锂金属负极材料的集流体的制备方法，包括以下制备步骤：This embodiment provides a method for preparing a current collector of a novel lithium metal negative electrode material, comprising the following preparation steps:
（1）将100mg三聚氰胺纳米颗粒在80℃下，溶于100mL吡啶溶液中，得到三聚氰胺浓度为1mg/mL的吡啶溶液；(1) dissolving 100 mg of melamine nanoparticles in 100 mL of pyridine solution at 80° C. to obtain a pyridine solution with a melamine concentration of 1 mg/mL;
（2）将700mg银纳米颗粒、200mg硫化锂纳米颗粒和100mg导电炭黑纳米颗粒进行混合，然后搅拌或者研磨若干时间，形成均匀的混合物；(2) 700 mg of silver nanoparticles, 200 mg of lithium sulfide nanoparticles and 100 mg of conductive carbon black nanoparticles are mixed, and then stirred or ground for a certain period of time to form a uniform mixture;
（3）将步骤（2）得到均匀的混合物加入到步骤（1）得到的三聚氰胺浓度为1mg/mL的吡啶溶液中，然后搅拌或者研磨1h，得到均匀的浆料；(3) adding the uniform mixture obtained in step (2) to the pyridine solution with a melamine concentration of 1 mg/mL obtained in step (1), and then stirring or grinding for 1 hour to obtain a uniform slurry;
（4）将步骤（3）得到的浆料均匀的涂抹到铜箔上，然后在80℃下干燥24h，使吡啶溶液挥发，然后在真空下在80℃条件下再干燥12h，在铜箔上得到一层均匀的薄膜；(4) The slurry obtained in step (3) is evenly applied to the copper foil, and then dried at 80° C. for 24 hours to volatilize the pyridine solution, and then dried at 80° C. under vacuum for another 12 hours to obtain a uniform thin film on the copper foil;
（5）将步骤（4）得到的薄膜裁剪成极片形状，得到一种新型锂金属负极材料的集流体。(5) Cutting the film obtained in step (4) into an electrode shape to obtain a new type of current collector of lithium metal negative electrode material.
实施例4Example 4
本实施例提供一种新型锂金属负极材料的集流体的制备方法，包括以下制备步骤：This embodiment provides a method for preparing a current collector of a novel lithium metal negative electrode material, comprising the following preparation steps:
（1）将100mg三聚氰胺纳米颗粒在80℃下，溶于100mL吡啶溶液中，得到三聚氰胺浓度为1mg/mL的吡啶溶液；(1) dissolving 100 mg of melamine nanoparticles in 100 mL of pyridine solution at 80° C. to obtain a pyridine solution with a melamine concentration of 1 mg/mL;
（2）将700mg银纳米颗粒、100mg硫化锂纳米颗粒和100mg导电炭黑纳米颗粒进行混合，然后搅拌或者研磨若干时间，形成均匀的混合物；(2) mixing 700 mg of silver nanoparticles, 100 mg of lithium sulfide nanoparticles and 100 mg of conductive carbon black nanoparticles, and then stirring or grinding for a certain period of time to form a uniform mixture;
（3）将步骤（2）得到均匀的混合物加入到步骤（1）得到的三聚氰胺浓度为1mg/mL的吡啶溶液中，然后搅拌或者研磨1h，得到均匀的浆料；(3) adding the uniform mixture obtained in step (2) to the pyridine solution with a melamine concentration of 1 mg/mL obtained in step (1), and then stirring or grinding for 1 hour to obtain a uniform slurry;
（4）将步骤（3）得到的浆料均匀的涂抹到铜箔上，然后在90℃下干燥20h，使吡啶溶液挥发，然后在真空下在90℃条件下再干燥10h，在铜箔上得到一层均匀的薄膜；(4) The slurry obtained in step (3) is evenly applied to the copper foil, and then dried at 90° C. for 20 h to volatilize the pyridine solution, and then dried at 90° C. for another 10 h under vacuum to obtain a uniform thin film on the copper foil;
（5）将步骤（4）得到的薄膜裁剪成极片形状，得到一种新型锂金属负极材料的集流体。(5) Cutting the film obtained in step (4) into an electrode shape to obtain a new type of current collector of lithium metal negative electrode material.
实施例5Example 5
本实施例提供一种新型锂金属负极材料的集流体的制备方法，包括以下制备步骤：This embodiment provides a method for preparing a current collector of a novel lithium metal negative electrode material, comprising the following preparation steps:
（1）将100mg三聚氰胺纳米颗粒在80℃下，溶于100mL吡啶溶液中，得到三聚氰胺浓度为1mg/mL的吡啶溶液；(1) dissolving 100 mg of melamine nanoparticles in 100 mL of pyridine solution at 80° C. to obtain a pyridine solution with a melamine concentration of 1 mg/mL;
（2）将500mg银纳米颗粒、100mg硫化锂纳米颗粒和100mg导电炭黑纳米颗粒进行混合，然后搅拌或者研磨若干时间，形成均匀的混合物；(2) 500 mg of silver nanoparticles, 100 mg of lithium sulfide nanoparticles and 100 mg of conductive carbon black nanoparticles are mixed, and then stirred or ground for a certain period of time to form a uniform mixture;
（3）将步骤（2）得到均匀的混合物加入到步骤（1）得到的三聚氰胺浓度为1mg/mL的吡啶溶液中，然后搅拌或者研磨1h，得到均匀的浆料；(3) adding the uniform mixture obtained in step (2) to the pyridine solution with a melamine concentration of 1 mg/mL obtained in step (1), and then stirring or grinding for 1 hour to obtain a uniform slurry;
（4）将步骤（3）得到的浆料均匀的涂抹到铜箔上，然后在70℃下干燥28h，使吡啶溶液挥发，然后在真空下在70℃条件下再干燥15h，在铜箔上得到一层均匀的薄膜；(4) The slurry obtained in step (3) is evenly applied to the copper foil, and then dried at 70° C. for 28 hours to volatilize the pyridine solution, and then dried at 70° C. under vacuum for another 15 hours to obtain a uniform thin film on the copper foil;
（5）将步骤（4）得到的薄膜裁剪成极片形状，得到一种新型锂金属负极材料的集流体。(5) Cutting the film obtained in step (4) into an electrode shape to obtain a new type of current collector of lithium metal negative electrode material.
实施例6Example 6
本实施例提供一种新型锂金属负极材料的集流体的制备方法，包括以下制备步骤：This embodiment provides a method for preparing a current collector of a novel lithium metal negative electrode material, comprising the following preparation steps:
（1）将200mg三聚氰胺纳米颗粒在80℃下，溶于200mL吡啶溶液中，得到三聚氰胺浓度为1mg/mL的吡啶溶液；(1) dissolving 200 mg of melamine nanoparticles in 200 mL of pyridine solution at 80° C. to obtain a pyridine solution with a melamine concentration of 1 mg/mL;
（2）将500mg银纳米颗粒、200mg硫化锂纳米颗粒和100mg导电炭黑纳米颗粒进行混合，然后搅拌或者研磨若干时间，形成均匀的混合物；(2) 500 mg of silver nanoparticles, 200 mg of lithium sulfide nanoparticles and 100 mg of conductive carbon black nanoparticles are mixed, and then stirred or ground for a certain period of time to form a uniform mixture;
（3）将步骤（2）得到均匀的混合物加入到步骤（1）得到的三聚氰胺浓度为1mg/mL的吡啶溶液中，然后搅拌或者研磨1h，得到均匀的浆料；(3) adding the uniform mixture obtained in step (2) to the pyridine solution with a melamine concentration of 1 mg/mL obtained in step (1), and then stirring or grinding for 1 hour to obtain a uniform slurry;
（4）将步骤（3）得到的浆料均匀的涂抹到铜箔上，然后在70℃下干燥28h，使吡啶溶液挥发，然后在真空下在70℃条件下再干燥15h，在铜箔上得到一层均匀的薄膜；(4) The slurry obtained in step (3) is evenly applied to the copper foil, and then dried at 70° C. for 28 hours to volatilize the pyridine solution, and then dried at 70° C. under vacuum for another 15 hours to obtain a uniform thin film on the copper foil;
（5）将步骤（4）得到的薄膜裁剪成极片形状，得到一种新型锂金属负极材料的集流体。(5) Cutting the film obtained in step (4) into an electrode shape to obtain a new type of current collector of lithium metal negative electrode material.
对比例Comparative Example
本对比例与实施例1的区别在于，步骤（2）中未加入银纳米颗粒，其余与实施例1相同。The difference between this comparative example and Example 1 is that no silver nanoparticles are added in step (2), and the rest is the same as Example 1.
以下为实施例1和对比例的相关性能测试数据。The following are the relevant performance test data of Example 1 and the comparative example.
图1是实施例1银纳米颗粒、硫化锂、三聚氰胺和导电炭黑组成的负极材料的集流体（简称Ag-Li2S-C-PM）在循环10次后的表面图。FIG1 is a surface diagram of the current collector of the negative electrode material composed of silver nanoparticles, lithium sulfide, melamine and conductive carbon black (Ag-Li 2 SC-PM for short) in Example 1 after 10 cycles.
图2是对比例未加银纳米颗粒的硫化锂、导电炭黑和三聚氰胺组成的负极材料的集流体（简称Li2S-C-PM）在循环10次后的表面图。FIG. 2 is a surface image of a current collector of a negative electrode material composed of lithium sulfide, conductive carbon black and melamine without adding silver nanoparticles (referred to as Li 2 SC-PM) after 10 cycles.
从图1和图2的对比可以看到，在相同循环次数后，未加银纳米颗粒的负极材料的集流体表面枝晶现象明显，而本发明的负极材料的集流体表面没有明显的枝晶现象，这是因为本发明中银纳米颗粒具有较大的表面能，且与锂金属的晶格匹配度高，可以诱导锂离子在银纳米颗粒表面进行电化学沉淀，从而控制锂离子的电化学行为，抑制锂枝晶的生长。From the comparison of Figures 1 and 2, it can be seen that after the same number of cycles, the current collector surface of the negative electrode material without silver nanoparticles has obvious dendrite phenomenon, while the current collector surface of the negative electrode material of the present invention has no obvious dendrite phenomenon. This is because the silver nanoparticles in the present invention have a large surface energy and a high lattice matching degree with lithium metal, which can induce lithium ions to electrochemically precipitate on the surface of the silver nanoparticles, thereby controlling the electrochemical behavior of lithium ions and inhibiting the growth of lithium dendrites.
图3是实施例1银纳米颗粒、硫化锂、三聚氰胺和导电炭黑组成的负极材料的集流体（Ag-Li2S-C-PM）在5mA cm-2的电流密度下和5mAh cm-2的面容量下的库伦效率图。3 is a graph of the coulombic efficiency of the current collector (Ag-Li 2 SC-PM) of the negative electrode material composed of silver nanoparticles, lithium sulfide, melamine and conductive carbon black in Example 1 at a current density of 5 mA cm -2 and an area capacity of 5 mAh cm -2 .
图4是对比例未加银纳米颗粒的硫化锂、三聚氰胺和导电炭黑组成的负极材料的集流体（Li2S-C-PM）在5mA cm-2的电流密度下和5mAh cm-2的面容量下的库伦效率图。FIG4 is a coulombic efficiency diagram of the current collector (Li 2 SC-PM) of the negative electrode material composed of lithium sulfide, melamine and conductive carbon black without adding silver nanoparticles in the comparative example at a current density of 5 mA cm -2 and an area capacity of 5 mAh cm -2 .
从图3和图4的对比可以看到：From the comparison of Figure 3 and Figure 4, we can see that:
对比例未加银纳米颗粒，一开始5个循环因为SEI膜形成的消耗锂导致库伦效率较低，后面库伦效率可以稳定在97%左右，140个循环后，库伦效率急剧下降，这主要是因为没有纳米银颗粒诱导锂离子沉淀，从而形成锂枝晶，在循环过程中产生“死锂”，造成低库伦效率。而本发明对比例1加入银纳米颗粒，除了一开始形成SEI膜导致库伦效率低外，后面库伦效率一直稳定在98%左右，一直到305个循环后，库伦效率才出现下降，库伦效率明显好于对比例。The comparative example does not add silver nanoparticles. In the first 5 cycles, the coulombic efficiency is low because of the consumption of lithium by the formation of the SEI film. The coulombic efficiency can be stabilized at about 97% later. After 140 cycles, the coulombic efficiency drops sharply. This is mainly because there are no nanosilver particles to induce lithium ion precipitation, thereby forming lithium dendrites, and generating "dead lithium" during the cycle, resulting in low coulombic efficiency. In the comparative example 1 of the present invention, silver nanoparticles are added. Except for the formation of the SEI film at the beginning, which leads to low coulombic efficiency, the coulombic efficiency is stabilized at about 98% later. It is not until 305 cycles that the coulombic efficiency drops. The coulombic efficiency is significantly better than that of the comparative example.
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
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| CN110190243A (en) * | 2019-05-29 | 2019-08-30 | 华中科技大学 | Preparation and application of a lithium metal negative electrode with a composite film |
| CN118039922A (en) * | 2024-03-29 | 2024-05-14 | 江苏远航锦锂新能源科技有限公司 | Preparation method of negative electrode current collector of non-negative electrode lithium metal battery |
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