CN117175035A - A lithium metal anode bipolar artificial SEI film and its preparation method and application - Google Patents

A lithium metal anode bipolar artificial SEI film and its preparation method and application Download PDF

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CN117175035A
CN117175035A CN202311366444.2A CN202311366444A CN117175035A CN 117175035 A CN117175035 A CN 117175035A CN 202311366444 A CN202311366444 A CN 202311366444A CN 117175035 A CN117175035 A CN 117175035A
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lithium
sei film
artificial sei
lithium metal
carbonate
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陈人杰
邓成龙
陈楠
李丽
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Beijing Institute of Technology BIT
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Abstract

The artificial SEI film has high ion conductivity and high ion migration number, and contains bipolar functional groups, so that desolvation of lithium ions is promoted, and solvent-induced lithium negative electrode corrosion is reduced; but also can adsorb anions to improve the migration efficiency of lithium ions. The artificial SEI film can reduce concentration polarization of lithium ions, realize uniform deposition of lithium metal ions and inhibit generation of lithium metal dendrites. The artificial SEI film is a self-supporting film formed by mixing a polar polymer, a carbonic ester solvent, lithium salt, a polymer prepolymer and a photoinitiator and then in-situ curing. The artificial SEI film prepared by the method can effectively protect a lithium metal anode; the method has the advantages of simple preparation process, easy obtainment of raw materials by using conventional equipment, safety and no pollution, and is suitable for large-scale batch production. When the artificial SEI film is used for a lithium metal battery, the artificial SEI film can be matched with a high-voltage positive electrode material, and has good cycle performance.

Description

一种锂金属负极双极性人工SEI膜及其制备方法和应用A lithium metal anode bipolar artificial SEI film and its preparation method and application

技术领域Technical field

本发明涉及一种锂金属负极双极性人工SEI膜及其制备方法和应用,该人工SEI膜用于保护锂金属电池中的锂金属负极材料,属于金属锂电池的技术领域。The invention relates to a lithium metal negative electrode bipolar artificial SEI film and its preparation method and application. The artificial SEI film is used to protect lithium metal negative electrode materials in lithium metal batteries, and belongs to the technical field of metal lithium batteries.

背景技术Background technique

金属锂具有超高的理论比容量(3860mAhg-1)和极低的氧化还原电位(-3.040V vs.标准氢电极),是高能量密度金属锂电池(>500Wh Kg-1)负极的最佳材料。然而,由于金属锂与商用碳酸酯类电解质高反应活性,形成不均匀有机/无机固体电解质界面层(SEI膜)。调控金属锂负极界面是抑制金属锂负极失效的有效策略,包括电解质修饰和人工SEI膜构建。其中,电解质修饰主要有以下三种方式:高浓度电解质调控锂表面SEI膜的成分,利用添加剂调控锂离子均匀沉积以及促进金属锂表面稳定SEI膜的形成。然而,电池循环过程中电解质添加剂、锂盐等逐渐被消耗,导致后续生成的SEI膜组分和表面结构不均,继而引发锂的不均匀沉积和锂枝晶的产生。因此,探索结构均一、强韧性好和离子传导高且表面电子绝缘的高效人工SEI膜具有重要意义。Metal lithium has ultra-high theoretical specific capacity (3860mAhg -1 ) and extremely low redox potential (-3.040V vs. standard hydrogen electrode), making it the best negative electrode for high-energy-density lithium metal batteries (>500Wh Kg -1 ). Material. However, due to the high reactivity of metallic lithium with commercial carbonate electrolytes, an uneven organic/inorganic solid electrolyte interface layer (SEI film) is formed. Controlling the interface of metallic lithium anode is an effective strategy to inhibit the failure of metallic lithium anode, including electrolyte modification and artificial SEI film construction. Among them, there are three main methods of electrolyte modification: high-concentration electrolytes regulate the composition of the SEI film on the lithium surface, use additives to regulate the uniform deposition of lithium ions, and promote the formation of a stable SEI film on the surface of metallic lithium. However, during the battery cycle, electrolyte additives, lithium salts, etc. are gradually consumed, resulting in uneven composition and surface structure of the subsequently generated SEI film, which in turn triggers uneven deposition of lithium and the generation of lithium dendrites. Therefore, it is of great significance to explore efficient artificial SEI films with uniform structure, good strength and toughness, high ion conductivity and surface electronic insulation.

目前,采用人工SEI膜的方法可有效避免不可控锂枝晶生长并调控锂离子均匀扩散。华中科技大学黄云辉课题组报道了阳离子聚合物人工SEI膜,具有高离子迁移数,可有效提高锂锂对电池在碳酸盐电解质体系中稳定循环(1mA cm-2,700h),但该人工SEI膜的低离子电导率和不可避免的溶剂腐蚀限制了其进一步应用。(Adv.Mater.2021,33,2007428)中科院物理所李泓课题组报道了一种光固化聚合物人工SEI膜隔绝电解质与金属锂直接接触,避免的溶剂腐蚀锂负极,不有效保护了金属锂负极,并锂锂对称电池在碳酸盐电解质体系中稳定循环700h(0.5mA cm-2,1mA h cm-2)。(Nano Energy 95(2022)106983)但该人工SEI膜的低离子电导率和离子迁移数,使得电池在高倍率下循环稳定较差,依然限制了其进一步应用。清华大学张强和北京理工大学黄佳琦课题组报道了一种有机-无机复合人工SEI膜,该膜是由LLZTO无机颗粒与锂化的全氟磺酸树脂制备而成的一种高离子迁移数人工SEI膜(tLi+=0.82)。将该复合保护层直接涂覆在金属锂电极表面,可有效抑制锂枝晶的形成,但是低的室温离子电导率(3.0×10-5S cm-1)显著降低了其在室温下锂金属电池中的应用。(Adv.Mater.2019,1808392)因此,,亟待提供一种能广泛应用于锂二次电池的锂金属负极人工SEI膜材料,兼具高离子电导率和高离子迁移数,能够隔绝溶剂并稳定锂离子的剥离/沉积过程,抑制锂金属枝晶的生长,从而提高锂金属电池的安全性能以及循环性能。Currently, the method of using artificial SEI films can effectively avoid uncontrollable lithium dendrite growth and regulate the uniform diffusion of lithium ions. Huang Yunhui's research group at Huazhong University of Science and Technology reported a cationic polymer artificial SEI membrane, which has a high ion migration number and can effectively improve the stable cycling of lithium-ion batteries in carbonate electrolyte systems (1mA cm -2 , 700h). However, this artificial SEI The membrane's low ionic conductivity and inevitable solvent corrosion limit its further applications. (Adv.Mater.2021, 33, 2007428) Li Hong’s research group at the Institute of Physics, Chinese Academy of Sciences reported that a photocurable polymer artificial SEI film isolates the electrolyte from direct contact with metallic lithium, avoiding solvent corrosion of the lithium anode and ineffective protection of metallic lithium. Negative electrode, and lithium-lithium symmetrical battery can cycle stably for 700h in carbonate electrolyte system (0.5mA cm -2 ,1mA h cm -2 ). (Nano Energy 95(2022)106983) However, the low ion conductivity and ion migration number of the artificial SEI membrane make the battery have poor cycle stability at high rates, which still limits its further application. The research groups of Zhang Qiang of Tsinghua University and Huang Jiaqi of Beijing Institute of Technology reported an organic-inorganic composite artificial SEI membrane, which is a high ion migration number artificial SEI prepared from LLZTO inorganic particles and lithiated perfluorosulfonic acid resin. film (t Li+ =0.82). The composite protective layer is directly coated on the surface of the metallic lithium electrode, which can effectively inhibit the formation of lithium dendrites. However, the low room temperature ionic conductivity (3.0×10 -5 S cm -1 ) significantly reduces its lithium metal performance at room temperature. Applications in batteries. (Adv.Mater.2019,1808392) Therefore, it is urgent to provide a lithium metal anode artificial SEI film material that can be widely used in lithium secondary batteries, has both high ionic conductivity and high ion migration number, can isolate solvents and is stable The stripping/deposition process of lithium ions inhibits the growth of lithium metal dendrites, thereby improving the safety performance and cycle performance of lithium metal batteries.

发明内容Contents of the invention

鉴于此,本发明提供一种锂金属负极双极性人工SEI膜,其兼具高离子电导率和高离子迁移数,并提供制备该人工SEI膜的方法及其一种锂金属电池制备方法。所述方法过程简单,原料易得且安全无污染,适合大规模批量生产。In view of this, the present invention provides a lithium metal anode bipolar artificial SEI film that has both high ion conductivity and high ion migration number, and provides a method for preparing the artificial SEI film and a method for preparing a lithium metal battery. The method has a simple process, easy-to-obtain raw materials, is safe and pollution-free, and is suitable for large-scale batch production.

本发明的目的之二在于提供一种锂金属负极双极性人工SEI膜的制备方法;所述方法制备过程简单,原料易得且安全无污染,适合大规模批量生产。The second object of the present invention is to provide a method for preparing a lithium metal negative electrode bipolar artificial SEI film; the method has a simple preparation process, easily available raw materials, is safe and pollution-free, and is suitable for large-scale mass production.

本发明的目的之三在于提供一种金属锂电池,所述金属锂电池的人工SEI膜为本发明所述的一种锂金属负极双极性人工SEI膜。The third object of the present invention is to provide a metal lithium battery. The artificial SEI film of the metal lithium battery is a lithium metal negative electrode bipolar artificial SEI film according to the present invention.

为实现本发明的目的,提供以下技术方案。In order to achieve the purpose of the present invention, the following technical solutions are provided.

一种锂金属负极双极性人工SEI膜,所述人工SEI膜由碳酸酯、极性聚合物、聚合物预聚体、光引发剂和盐,经避光混匀后,直接涂抹与锂金属表面,在保护气氛下紫外光直接固化制备得到;所述保护气为惰性气体或氮气。A lithium metal negative electrode bipolar artificial SEI film. The artificial SEI film is composed of carbonate, polar polymer, polymer prepolymer, photoinitiator and salt. After being mixed evenly in the dark, it is directly applied with lithium metal. The surface is prepared by direct UV curing under a protective atmosphere; the protective gas is an inert gas or nitrogen.

所述碳酸酯为碳酸乙烯酯、氟代碳酸乙烯酯、三氟代碳酸丙烯酯、二氟代碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸二丙酯、碳酸二苯酯碳、碳酸丁烯酯、碳酸二丁酯,四丁醇二碳酸酯,碳酸甘油酯醇二氟乙酸酯,碳酸甘油酯醇基三氟乙酸酯,碳酸甘油醇酯基乙磺酸酯中的一种以上。The carbonate is ethylene carbonate, fluoroethylene carbonate, trifluoropropylene carbonate, difluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dicarbonate Propyl ester, diphenyl carbonate, butylene carbonate, dibutyl carbonate, tetrabutanol dicarbonate, glyceryl carbonate alcohol difluoroacetate, glyceryl carbonate alcohol trifluoroacetate, glyceryl carbonate alcohol One or more of the ester ethanesulfonate esters.

所述极性聚合物为聚丙烯腈、聚乙烯醇,聚N-氰基甲基丙烯酰胺和聚乙烯醇-β-氰乙基醚中的一种以上。The polar polymer is at least one of polyacrylonitrile, polyvinyl alcohol, poly-N-cyanomethacrylamide and polyvinyl alcohol-β-cyanoethyl ether.

所述锂盐为高氯酸锂、双三氟磺酰亚胺锂、双(氟磺酰)胺锂、六氟磷酸锂、六氟砷酸锂、双草酸硼酸锂、二草酸硼酸锂、四氟硼酸锂、磷酸锂、二氟磷酸锂中的一种以上。The lithium salt is lithium perchlorate, lithium bistrifluorosulfonimide, lithium bis(fluorosulfonyl)amine, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bisoxaloborate, lithium dioxaloborate, and lithium tetrafluoroborate , lithium phosphate, and lithium difluorophosphate.

所述聚合物预聚体为聚乙二醇二丙烯酸酯、丙烯酸丁酯、聚乙二醇甲醚甲基丙烯酸酯、乙氧基化三羟基甲基丙烷三丙烯酸酯、三羟甲基丙烯三缩水甘油醚,N、N-二甲基双丙烯酰胺,N-氰基甲基丙烯酰胺中的一种以上。优选所述聚合物预聚体的数均分子量为100~1000。The polymer prepolymers are polyethylene glycol diacrylate, butyl acrylate, polyethylene glycol methyl ether methacrylate, ethoxylated trihydroxymethylpropane triacrylate, and trimethylolpropylene triacrylate. Glycidyl ether, one or more of N, N-dimethylbisacrylamide and N-cyanomethacrylamide. Preferably, the polymer prepolymer has a number average molecular weight of 100 to 1,000.

所述光引发剂为2-羟基-2-甲基苯丙酮、2,2-二甲氧基-2-苯基苯乙酮、过氧化二苯甲酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮和双(2,4,6-三甲基苯甲酰基)-苯基氧化膦中的一种以上。其中,2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮已有商品,例如汽巴特殊化学品公司生产的Irgacure 2529;双(2,4,6-三甲基苯甲酰基)-苯基氧化膦已有商品,例如汽巴特殊化学品公司生产的Irgacure 819。The photoinitiator is 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-2-phenylacetophenone, benzophenone peroxide, 2-hydroxy-2-methyl- One or more of 1-[4-(2-hydroxyethoxy)phenyl]-1-propanone and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Among them, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone is already commercially available, such as Irgacure 2529 produced by Ciba Specialty Chemicals; Bis(2 ,4,6-Trimethylbenzoyl)-phenylphosphine oxide is already commercially available, such as Irgacure 819 produced by Ciba Specialty Chemicals.

优选极性聚合物、碳酸酯溶剂,锂盐、聚合物预聚体、和光引发剂的质量比为1~10:20~75:1~15:5~25:0.01~0.5。Preferably, the mass ratio of polar polymer, carbonate solvent, lithium salt, polymer prepolymer, and photoinitiator is 1 to 10: 20 to 75: 1 to 15: 5 to 25: 0.01 to 0.5.

一种本发明所述的锂金属负极双极性人工SEI膜的制备方法,所述方法步骤如下:A method for preparing a lithium metal negative electrode bipolar artificial SEI film according to the present invention. The steps of the method are as follows:

(1)在20~55℃的温度范围内以及在干燥的惰性气氛中,按照质量百分比计,将人工SEI膜预聚合溶剂为极性聚合物为1~10wt%、碳酸酯溶剂为20~75wt%、锂盐为1~15wt%、聚合物预聚体为5~25wt%和光引发剂为0.01~0.5wt%混合均匀后;(2)在保护气体保护下,近无水无氧环境中,将步骤(1)制得的混合物用刮刀直接涂布在锂金属负极表面;混合物涂布厚度为0.1μm~10μm;经紫外灯照射固化,得到本发明所述的一种锂金属负极双极性人工SEI膜。(1) In the temperature range of 20 to 55°C and in a dry inert atmosphere, the artificial SEI membrane prepolymerization solvent is 1 to 10 wt% of the polar polymer and 20 to 75 wt of the carbonate solvent in terms of mass percentage. %, lithium salt 1~15wt%, polymer prepolymer 5~25wt% and photoinitiator 0.01~0.5wt% after mixing evenly; (2) Under protective gas protection, in a nearly anhydrous and oxygen-free environment, The mixture prepared in step (1) is directly coated on the surface of the lithium metal negative electrode with a scraper; the coating thickness of the mixture is 0.1 μm to 10 μm; it is cured by ultraviolet light irradiation to obtain a lithium metal negative electrode bipolar electrode according to the present invention. Artificial SEI membrane.

其中,所述保护气为惰性气体或氮气,纯度大于等于99%。Wherein, the protective gas is an inert gas or nitrogen, and the purity is greater than or equal to 99%.

优选混合物涂布厚度为0.1μm~10μm。The preferred coating thickness of the mixture is 0.1 μm to 10 μm.

优选紫外灯的波长为365nm~400nm。The preferred wavelength of the ultraviolet lamp is 365 nm to 400 nm.

优选紫外灯照射1min~5min固化。It is preferred to irradiate the UV lamp for 1 to 5 minutes for curing.

有益效果beneficial effects

1.本发明提供了一种锂金属负极双极性人工SEI膜,所述电解质中采用极性聚合物作为组分,通过碳酸酯溶剂和锂盐,增强离子电导率;通过极性氰基(-C≡N)官能团与阴离子间离子-偶极相互作用,以及通过醇羟基官能团与碳酸酯溶剂分子间氢键相互作用,促进锂离子脱溶剂化,提高锂离子迁移能力,隔绝了游离碳酸酯分子与锂负极接触。聚合物预聚体和光引发剂的引入,通过官能团与锂金属间的相互作用,参与并促进在锂金属表面形成聚合物衍生SEI膜有机层,使得人工SEI膜紧密附着在锂金属负极表面,可以形成稳定的锂金属负极-人工SEI膜界面。1. The present invention provides a lithium metal negative electrode bipolar artificial SEI film. The electrolyte uses polar polymers as components, and enhances ion conductivity through carbonate solvents and lithium salts; through polar cyano groups ( -C≡N) functional group and the anion ion-dipole interaction, as well as the hydrogen bonding interaction between the alcoholic hydroxyl functional group and the carbonate solvent molecule, promote the desolvation of lithium ions, improve the lithium ion migration ability, and isolate the free carbonate Molecules come into contact with the lithium negative electrode. The introduction of polymer prepolymers and photoinitiators participates in and promotes the formation of a polymer-derived SEI film organic layer on the surface of lithium metal through the interaction between functional groups and lithium metal, making the artificial SEI film tightly adhere to the surface of the lithium metal anode, which can Form a stable lithium metal anode-artificial SEI film interface.

2.本发明提供了一种锂金属负极双极性人工SEI膜,所述双极性人工SEI膜兼具高离子电导率和高离子迁移数,有效地阻止游离碳酸酯溶剂的腐蚀,能够稳定金属锂的剥离/沉积的过程,抑制锂离子浓差极化引起锂枝晶的生长,而且在恒电流极化过程中展现出较低的过电势和长期的循环稳定性,能明显提高金属锂电池的电化学性能和安全性。2. The present invention provides a lithium metal negative electrode bipolar artificial SEI film. The bipolar artificial SEI film has both high ion conductivity and high ion migration number, effectively prevents corrosion of free carbonate solvents, and can stabilize The process of stripping/deposition of metallic lithium inhibits the growth of lithium dendrites caused by lithium ion concentration polarization, and exhibits lower overpotential and long-term cycle stability during galvanostatic polarization, which can significantly improve metallic lithium. Battery electrochemical performance and safety.

3.本发明提供了一种锂金属负极双极性人工SEI膜的制备方法,所述方法的制备过程简单,所使用的都是常规设备,原材料易得,且安全无污染,不需要使用有机溶剂如N,N-二甲基甲酰胺(DMF),乙腈等,适合大规模批量生产。3. The present invention provides a method for preparing a lithium metal negative electrode bipolar artificial SEI film. The preparation process of the method is simple, all conventional equipment is used, the raw materials are easily available, and it is safe and pollution-free, and does not require the use of organic materials. Solvents such as N,N-dimethylformamide (DMF), acetonitrile, etc. are suitable for large-scale batch production.

附图说明Description of drawings

图1为实施例1中制备的一种锂金属负极双极性人工SEI膜的扫描电镜图。Figure 1 is a scanning electron microscope image of a lithium metal negative electrode bipolar artificial SEI film prepared in Example 1.

图2为实施例1中制备的一种锂金属负极双极性人工SEI膜的离子迁移数图。Figure 2 is an ion migration number diagram of a lithium metal anode bipolar artificial SEI film prepared in Example 1.

图3为采用实施例1中制备的一种锂金属负极双极性人工SEI膜的锂锂对称电池在Figure 3 shows a lithium-lithium symmetrical battery using a lithium metal negative electrode bipolar artificial SEI film prepared in Example 1.

5mA/cm 2电流密度的恒电流电镀/剥离图。Galvanostatic plating/stripping diagram at 5mA/ cm2 current density.

具体实施方式Detailed ways

下面结合具体实施例对本发明进行详细说明,应当说明的是,以下各实施例是为了方便于技术人员理解本发明,并不在于限制本发明的保护范围,本领域普通技术人员,在不脱离本发明的基本构思的前提下,作出的改进,应当属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. It should be noted that the following embodiments are for the convenience of skilled persons in understanding the present invention and are not intended to limit the scope of protection of the present invention. Those of ordinary skill in the art will not deviate from the present invention. Improvements made based on the basic concept of the invention shall fall within the protection scope of the invention.

以下实施例中:In the following examples:

所述氩气均为纯度大于等于99%的氩气。The argon gas is all argon gas with a purity of greater than or equal to 99%.

对以下实施例中制备的一种极性聚合物网络凝胶电解质进行检测如下:A polar polymer network gel electrolyte prepared in the following examples was tested as follows:

(1)采用扫描电镜观测所述双极性人工SEI膜的形貌。(1) Use a scanning electron microscope to observe the morphology of the bipolar artificial SEI film.

测试仪器:日立S4800Test instrument: Hitachi S4800

(2)采用采用交流阻抗-稳态电流联用的测试所述电解质的双极性人工SEI膜的离子迁移数将测试体系组装成双极性人工SEI膜@锂金属│电解质│双极性人工SEI膜@锂金属对称电池,在CHI660E电化学工作站上采用线性伏安法测试,阻抗测试频率范围为0.1Hz~105Hz;i-t测试极化电压10mV。(2) Use AC impedance-steady-state current coupling to test the ion migration number of the bipolar artificial SEI membrane of the electrolyte to assemble the test system into a bipolar artificial SEI membrane@lithium metal│electrolyte│bipolar artificial The SEI film@lithium metal symmetrical battery was tested using linear voltammetry on the CHI660E electrochemical workstation. The impedance test frequency range was 0.1Hz~10 5 Hz; the IT test polarization voltage was 10mV.

测试仪器:CHI660E电化学工作站,上海辰华Testing instrument: CHI660E electrochemical workstation, Shanghai Chenhua

(3)电化学性能测试(3)Electrochemical performance test

锂对称电池的组装:在充满纯度大于等于99%氩气的手套箱中,将双极性人工SEI膜@锂金属、隔膜、电解质和双极性人工SEI膜@锂金属依次放入型号为2025的纽扣电池壳中,然后用压片机将两片电池壳压实扣紧,得到锂锂对称电池;组装好的锂电池在30℃下静置48h后,进行电化学性能测试。Assembly of lithium symmetrical battery: In a glove box filled with argon gas with a purity greater than or equal to 99%, put the bipolar artificial SEI film@lithium metal, separator, electrolyte and bipolar artificial SEI film@lithium metal in sequence with the model number 2025 into a button battery shell, and then use a tablet press to compact and fasten the two battery shells to obtain a symmetrical lithium-lithium battery; after the assembled lithium battery was left to stand at 30°C for 48 hours, the electrochemical performance test was performed.

采用LAND电池测试系统进行金属锂和钠的沉积/剥离测试,测试恒电流密度为5mA/cm 2,沉积面容量为1mAh/cm 2。The LAND battery test system was used to conduct the deposition/stripping test of metallic lithium and sodium. The test constant current density was 5mA/cm2 and the deposition surface capacity was 1mAh/cm2.

测试仪器:LAND电池测试系统,型号CT2001A,武汉金诺电子有限公司。Testing instrument: LAND battery test system, model CT2001A, Wuhan Jinnuo Electronics Co., Ltd.

实施例1:Example 1:

本实施例所提供的一种锂负极双极性人工SEI膜,包括5wt%聚乙烯醇-β-氰乙基醚、55wt%碳酸乙烯酯、15wt%双三氟磺酰亚胺锂、25wt%聚乙二醇二丙烯酸酯(Mn=400)和0.02wt%2-羟基-2-甲基苯丙酮。The lithium negative electrode bipolar artificial SEI film provided in this embodiment includes 5wt% polyvinyl alcohol-β-cyanoethyl ether, 55wt% ethylene carbonate, 15wt% lithium bistrifluorosulfonyl imide, 25wt% Polyethylene glycol diacrylate (Mn=400) and 0.02 wt% 2-hydroxy-2-methylpropiophenone.

制备方法如下:在充满氩气的手套箱中,其中,H2O小于0.1ppm;O2小于0.1ppm,在55℃的温度下,在55wt%碳酸乙烯酯中依次加入15wt%双三氟磺酰亚胺锂、5wt%聚乙烯醇-β-氰乙基醚、25wt%聚乙二醇二丙烯酸酯(Mn=400)和0.02wt%2-羟基-2-甲基苯丙酮,并在加入的过程中充分搅拌使其混合均匀,用刮刀将其直接涂布在锂金属负极表面;涂布厚度为5.0μm,紫外灯的波长为365nm~400nm,照射5min光固化即得到所述双极性人工SEI膜。The preparation method is as follows: in a glove box filled with argon, in which H 2 O is less than 0.1ppm; O 2 is less than 0.1ppm, at a temperature of 55°C, 15wt% bistrifluorosulfonate is sequentially added to 55wt% ethylene carbonate. Lithium imide, 5wt% polyvinyl alcohol-β-cyanoethyl ether, 25wt% polyethylene glycol diacrylate (Mn=400) and 0.02wt% 2-hydroxy-2-methylpropiophenone, and then added Stir thoroughly during the process to mix evenly, and use a scraper to apply it directly on the surface of the lithium metal anode; the coating thickness is 5.0 μm, the wavelength of the ultraviolet lamp is 365nm ~ 400nm, and the bipolarity is obtained by irradiation for 5 minutes and light curing. Artificial SEI membrane.

对本实施例中制备的一种极性聚合物网络凝胶电解质进行检测如下:A polar polymer network gel electrolyte prepared in this example was tested as follows:

(1)采用扫描电镜观测所述锂负极双极性人工SEI膜的形貌(1) Observe the morphology of the lithium anode bipolar artificial SEI film using a scanning electron microscope

所述锂负极双极性人工SEI膜的厚度为3.7μmThe thickness of the lithium negative bipolar artificial SEI film is 3.7 μm

(2)采用采用交流阻抗-稳态电流联用的测试所述锂负极双极性人工SEI膜的离子迁移数测量结果:所述锂负极双极性人工SEI膜的离子迁移数为0.86,如图2所示。(2) Measurement results of the ion migration number of the lithium anode bipolar artificial SEI film using AC impedance-steady-state current coupling: the ion migration number of the lithium anode bipolar artificial SEI film is 0.86, such as As shown in Figure 2.

(3)电化学性能测试(3)Electrochemical performance test

测试结果:锂锂对称电池在10mA/cm2电流密度和2mAh/cm2面容量时,稳定循环300h且无短路发生,如图3所示。Test results: When the lithium-lithium symmetrical battery has a current density of 10mA/ cm2 and a surface capacity of 2mAh/ cm2 , it can cycle stably for 300h without short circuit, as shown in Figure 3.

实施例2:Example 2:

本实施例所提供的一种锂负极双极性人工SEI膜,包括7wt%的聚乙烯醇-β-氰乙基醚和聚乙烯醇复合物、60wt%氟代碳酸乙烯酯、10wt%二草酸硼酸锂、23wt%聚乙二醇二丙烯酸酯(Mn=400)和0.02wt%的光引发剂。The lithium negative electrode bipolar artificial SEI film provided in this embodiment includes 7wt% polyvinyl alcohol-β-cyanoethyl ether and polyvinyl alcohol complex, 60wt% fluoroethylene carbonate, and 10wt% dioxalic acid Lithium borate, 23wt% polyethylene glycol diacrylate (Mn=400) and 0.02wt% photoinitiator.

制备方法如下:在充满氩气的手套箱中,其中,H2O小于0.1ppm;O2小于0.1ppm,在55℃的温度下,在60wt%氟代碳酸乙烯酯中依次加入10wt%的二草酸硼酸锂、7wt%的聚乙烯醇-β-氰乙基醚和聚乙烯醇复合物、23wt%聚乙二醇二丙烯酸酯(Mn=500)和0.02wt%的光引发剂,并在加入的过程中充分搅拌使其混合均匀,用刮刀将其直接涂布在锂金属负极表面;混合物涂布厚度为3.0μm,紫外灯的波长为365nm~400nm,照射5min~15min光固化即得到所述锂金属电池的人工SEI膜。The preparation method is as follows: in a glove box filled with argon, in which H 2 O is less than 0.1ppm; O 2 is less than 0.1ppm, at a temperature of 55°C, 10wt% dihydrogen is added in sequence to 60wt% fluoroethylene carbonate. Lithium oxalate borate, 7wt% polyvinyl alcohol-β-cyanoethyl ether and polyvinyl alcohol complex, 23wt% polyethylene glycol diacrylate (Mn=500) and 0.02wt% photoinitiator, and then added Stir thoroughly during the process to mix evenly, and use a scraper to apply it directly on the surface of the lithium metal anode; the coating thickness of the mixture is 3.0 μm, the wavelength of the ultraviolet lamp is 365nm ~ 400nm, and the irradiation is 5min ~ 15min for light curing to obtain the above Artificial SEI film for lithium metal batteries.

对本实施例中制备的一种极性聚合物网络凝胶电解质进行检测如下:A polar polymer network gel electrolyte prepared in this example was tested as follows:

(1)采用扫描电镜观测所述锂负极双极性人工SEI膜的形貌(1) Observe the morphology of the lithium anode bipolar artificial SEI film using a scanning electron microscope

所述锂负极双极性人工SEI膜的厚度为1.8μmThe thickness of the lithium negative bipolar artificial SEI film is 1.8 μm

(2)采用采用交流阻抗-稳态电流联用的测试所述锂负极双极性人工SEI膜的离子迁移数测量结果:所述锂负极双极性人工SEI膜的离子迁移数为0.89。(2) Measurement results of the ion migration number of the lithium anode bipolar artificial SEI film using AC impedance-steady-state current coupling: the ion migration number of the lithium anode bipolar artificial SEI film is 0.89.

(3)电化学性能测试(3)Electrochemical performance test

测试结果:锂锂对称电池在10mA/cm2电流密度和2mAh/cm2面容量时,稳定循环500h且无短路发生。Test results: At a current density of 10mA/ cm2 and a surface capacity of 2mAh/ cm2 , the lithium-lithium symmetrical battery can cycle stably for 500h without short circuit.

实施例3:Example 3:

本实施例所提供的一种锂负极双极性人工SEI膜,包括1wt%聚丙烯腈和聚乙烯醇复合物、75wt%碳酸甲乙酯、5wt%六氟磷酸锂、19wt%聚乙二醇二丙烯酸酯和0.02wt%2,2-二甲氧基-2-苯基苯乙酮。The lithium negative electrode bipolar artificial SEI film provided in this embodiment includes 1wt% polyacrylonitrile and polyvinyl alcohol complex, 75wt% ethyl methyl carbonate, 5wt% lithium hexafluorophosphate, and 19wt% polyethylene glycol diacrylate. and 0.02 wt% 2,2-dimethoxy-2-phenylacetophenone.

制备方法如下:在充满氩气的手套箱中,其中,H2O小于0.1ppm;O2小于0.1ppm,在55℃的温度下,在75wt%碳酸酯溶剂中依次加入5wt%六氟磷酸锂、1wt%聚丙烯腈和聚乙烯醇复合物、19wt%聚乙二醇二丙烯酸酯和0.02wt%2,2-二甲氧基-2-苯基苯乙酮,并在加入的过程中充分搅拌使其混合均匀,用刮刀直接涂布在锂金属负极表面;混合物涂布厚度为7.0μm,紫外灯的波长为365nm~400nm,照射5min~15min光固化即得到所述锂金属电池的人工SEI膜。The preparation method is as follows: in a glove box filled with argon, in which H 2 O is less than 0.1 ppm; O 2 is less than 0.1 ppm, at a temperature of 55° C., add 5 wt % lithium hexafluorophosphate and 1 wt % lithium hexafluorophosphate in sequence to 75 wt % carbonate solvent. Polyacrylonitrile and polyvinyl alcohol compound, 19wt% polyethylene glycol diacrylate and 0.02wt% 2,2-dimethoxy-2-phenylacetophenone, and stir thoroughly during the addition process. Mix evenly and apply it directly on the surface of the lithium metal negative electrode with a spatula; the coating thickness of the mixture is 7.0 μm, the wavelength of the ultraviolet lamp is 365nm to 400nm, and the artificial SEI film of the lithium metal battery is obtained by irradiation for 5min to 15min for light curing.

对本实施例中制备的一种极性聚合物网络凝胶电解质进行检测如下:A polar polymer network gel electrolyte prepared in this example was tested as follows:

(1)采用扫描电镜观测所述锂负极双极性人工SEI膜的形貌(1) Observe the morphology of the lithium anode bipolar artificial SEI film using a scanning electron microscope

所述锂负极双极性人工SEI膜的厚度为5.1μmThe thickness of the lithium negative bipolar artificial SEI film is 5.1 μm

(2)采用采用交流阻抗-稳态电流联用的测试所述锂负极双极性人工SEI膜的离子迁移数测量结果:所述锂负极双极性人工SEI膜的离子迁移数为0.66。(2) Measurement results of the ion migration number of the lithium anode bipolar artificial SEI film using AC impedance-steady-state current coupling: the ion migration number of the lithium anode bipolar artificial SEI film is 0.66.

(3)电化学性能测试(3)Electrochemical performance test

测试结果:锂锂对称电池在10mA/cm2电流密度和2mAh/cm2面容量时,稳定循环300h且无短路发生。Test results: When the lithium-lithium symmetrical battery has a current density of 10mA/ cm2 and a surface capacity of 2mAh/ cm2 , it can cycle stably for 300h without short circuit.

实施例4:Example 4:

本实施例所提供的一种锂负极双极性人工SEI膜,包括5wt%聚乙烯醇-β-氰乙基醚、70wt%氟代碳酸乙烯酯为、15wt%双三氟磺酰亚胺锂、10wt%的聚合物预聚体和0.02wt%的光引发剂。The lithium negative electrode bipolar artificial SEI film provided in this embodiment includes 5wt% polyvinyl alcohol-β-cyanoethyl ether, 70wt% fluoroethylene carbonate, and 15wt% lithium bistrifluorosulfonimide , 10wt% polymer prepolymer and 0.02wt% photoinitiator.

制备方法如下:在充满氩气的手套箱中,其中,H2O小于0.1ppm;O2小于0.1ppm,在50℃的温度下,在70wt%的氟代碳酸乙烯酯中依次加入15wt%二氟磷酸锂、5wt%的极性聚合物、10wt%的聚合物预聚体和0.02%的光引发剂,并在加入的过程中充分搅拌使其混合均匀,用刮刀直接涂布在锂金属负极表面;混合物涂布厚度为10μm,紫外灯的波长为365nm~400nm,照射5min~15min光固化即得到所述锂金属电池的人工SEI膜。The preparation method is as follows: in a glove box filled with argon, in which H 2 O is less than 0.1ppm; O 2 is less than 0.1ppm, at a temperature of 50°C, 15wt% dihydrogen is added in sequence to 70wt% fluoroethylene carbonate. Lithium fluorophosphate, 5wt% polar polymer, 10wt% polymer prepolymer and 0.02% photoinitiator, stir thoroughly during the addition process to mix evenly, and apply directly to the lithium metal anode with a spatula. Surface; the coating thickness of the mixture is 10 μm, the wavelength of the ultraviolet lamp is 365 nm to 400 nm, and the artificial SEI film of the lithium metal battery is obtained by irradiation for 5 min to 15 min of light curing.

对本实施例中制备的一种极性聚合物网络凝胶电解质进行检测如下:A polar polymer network gel electrolyte prepared in this example was tested as follows:

(1)采用扫描电镜观测所述锂负极双极性人工SEI膜的形貌(1) Observe the morphology of the lithium anode bipolar artificial SEI film using a scanning electron microscope

所述锂负极双极性人工SEI膜的厚度为8.3μmThe thickness of the lithium negative bipolar artificial SEI film is 8.3 μm

(2)采用采用交流阻抗-稳态电流联用的测试所述锂负极双极性人工SEI膜的离子迁移数测量结果:所述锂负极双极性人工SEI膜的离子迁移数为0.78。(2) Measurement results of the ion migration number of the lithium anode bipolar artificial SEI film using AC impedance-steady-state current coupling: the ion migration number of the lithium anode bipolar artificial SEI film is 0.78.

(3)电化学性能测试(3)Electrochemical performance test

测试结果:锂锂对称电池在10mA/cm2电流密度和2mAh/cm2面容量时,稳定循环360h且无短路发生。Test results: When the lithium-lithium symmetrical battery has a current density of 10mA/ cm2 and a surface capacity of 2mAh/ cm2 , it can cycle stably for 360h without short circuit.

实施例5:Example 5:

本实施例所提供的一种锂负极双极性人工SEI膜,包括10wt%聚N-氰基甲基丙烯酰胺和聚乙烯醇复合物、55wt%碳酸乙烯酯、10wt%双(氟磺酰)胺锂、25wt%聚合物预聚体和0.02wt%的光引发剂(2-羟基-2-甲基苯丙酮)。The lithium negative electrode bipolar artificial SEI film provided in this embodiment includes 10wt% poly-N-cyanomethacrylamide and polyvinyl alcohol complex, 55wt% ethylene carbonate, and 10wt% bis(fluorosulfonyl) Lithium amine, 25 wt% polymer prepolymer and 0.02 wt% photoinitiator (2-hydroxy-2-methylpropiophenone).

制备方法如下:在充满氩气的手套箱中,其中,H2O小于0.1ppm;O2小于0.1ppm,在50℃的温度下,在55wt%碳酸乙烯酯中依次加入10wt%双(氟磺酰)胺锂、10wt%聚N-氰基甲基丙烯酰胺和聚乙烯醇复合物、25wt%的聚合物预聚体和0.05wt%的2-羟基-2-甲基苯丙酮,并在加入的过程中充分搅拌使其混合均匀,用刮刀直接涂布在锂金属负极表面;混合物涂布厚度为1μm,紫外灯的波长为365nm~400nm,照射5min~15min光固化即得到所述锂金属电池的人工SEI膜。The preparation method is as follows: in a glove box filled with argon, in which H 2 O is less than 0.1ppm; O 2 is less than 0.1ppm, at a temperature of 50°C, 10wt% bis(fluorosulfonate) is sequentially added to 55wt% ethylene carbonate. Lithium amide, 10wt% poly-N-cyanomethacrylamide and polyvinyl alcohol complex, 25wt% polymer prepolymer and 0.05wt% 2-hydroxy-2-methylpropiophenone, and after adding Stir thoroughly during the process to mix evenly, and apply it directly on the surface of the lithium metal negative electrode with a scraper; the coating thickness of the mixture is 1 μm, the wavelength of the ultraviolet lamp is 365nm~400nm, and the lithium metal battery is obtained by irradiation for 5min~15min for light curing. Artificial SEI membrane.

对本实施例中制备的一种极性聚合物网络凝胶电解质进行检测如下:A polar polymer network gel electrolyte prepared in this example was tested as follows:

(1)采用扫描电镜观测所述锂负极双极性人工SEI膜的形貌(1) Observe the morphology of the lithium anode bipolar artificial SEI film using a scanning electron microscope

所述锂负极双极性人工SEI膜的厚度为0.3μmThe thickness of the lithium negative bipolar artificial SEI film is 0.3 μm

(2)采用采用交流阻抗-稳态电流联用的测试所述锂负极双极性人工SEI膜的离子迁移数测量结果:所述锂负极双极性人工SEI膜的离子迁移数为0.83。(2) Measurement results of the ion migration number of the lithium anode bipolar artificial SEI film using AC impedance-steady-state current coupling: the ion migration number of the lithium anode bipolar artificial SEI film is 0.83.

(3)电化学性能测试(3)Electrochemical performance test

测试结果:锂锂对称电池在10mA/cm2电流密度和2mAh/cm2面容量时,稳定循环300h且无短路发生。Test results: When the lithium-lithium symmetrical battery has a current density of 10mA/ cm2 and a surface capacity of 2mAh/ cm2 , it can cycle stably for 300h without short circuit.

Claims (9)

1. A lithium metal negative electrode bipolar artificial SEI film and a preparation method and application thereof are characterized in that the artificial SEI film comprises the following components: 1 to 10 weight percent of polar polymer, 20 to 75 weight percent of carbonate solvent, 1 to 15 weight percent of lithium (sodium/potassium) salt, 5 to 25 weight percent of polymer prepolymer and 0.01 to 0.5 weight percent of photoinitiator.
2. The lithium metal anode bipolar artificial SEI film according to claim 1, wherein at least one of the polar polymers: polyacrylonitrile, polyvinyl alcohol, poly-N-cyanomethacrylamide and polyvinyl alcohol- β -cyanoethyl ether.
3. The lithium metal anode bipolar artificial SEI film according to claim 1, wherein the carbonate solvent comprises at least one of: ethylene carbonate, fluoroethylene carbonate, propylene trifluorocarbonate, difluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dipropyl carbonate, diphenyl carbonate carbon, butylene carbonate, dibutyl carbonate, tetrabutol dicarbonate, glycerol carbonate alcohol difluoroacetate, glycerol carbonate alcohol trifluoroacetate, glycerol carbonate alcohol ethanesulfonate.
4. The lithium metal negative electrode bipolar artificial SEI film according to claim 1, wherein the lithium salt comprises at least one of: lithium perchlorate, lithium bis (fluorosulfonyl) amide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis (oxalato) borate, lithium dioxaoxalato borate, lithium tetrafluoroborate, lithium phosphate, and lithium difluorophosphate.
5. The lithium metal anode bipolar artificial SEI film according to claim 1, wherein the polymer pre-polymer comprises at least one of: polyethylene glycol diacrylate, butyl acrylate, polyethylene glycol methyl ether methacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triglycidyl ether, N, N-dimethyl bisacrylamide, N-cyanomethacrylamide.
6. The lithium metal negative electrode bipolar artificial SEI film according to claim 1, wherein the photoinitiator comprises at least one of: 2-hydroxy-2-methylpropionyl ketone, 2-dimethoxy-2-phenylacetophenone, benzophenone peroxide, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide.
7. A preparation method of a bipolar artificial SEI film for a lithium metal negative electrode is characterized by comprising the steps of uniformly mixing 1-10wt% of polar polymer, 20-75wt% of carbonate solvent, 1-15wt% of lithium salt, 5-25wt% of polymer prepolymer and 0.01-0.5wt% of photoinitiator in a dry inert atmosphere (or nitrogen) at a temperature range of 20-50 ℃.
8. The method for preparing the bipolar artificial SEI film for the lithium metal negative electrode, according to claim 7, is characterized in that: directly coating the surface of the lithium metal negative electrode by using a scraper; the thickness of the mixture coating is 0.1-10 mu m; the wavelength of the ultraviolet lamp is 365 nm-400 nm, and the artificial SEI film of the lithium metal battery is obtained after irradiation for 1 min-5 min for photo-curing.
9. A lithium metal battery, characterized in that the lithium metal battery comprises a lithium metal negative electrode, an artificial SEI bipolar artificial SEI film, an electrolyte, a separator and a positive electrode, wherein the artificial SEI film is the lithium metal negative electrode bipolar artificial SEI film according to any one of claims 1 to 6.
CN202311366444.2A 2023-10-20 2023-10-20 A lithium metal anode bipolar artificial SEI film and its preparation method and application Pending CN117175035A (en)

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