WO2018171245A1 - 一种锂金属电池的锂负极表面处理方法 - Google Patents

一种锂金属电池的锂负极表面处理方法 Download PDF

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WO2018171245A1
WO2018171245A1 PCT/CN2017/113592 CN2017113592W WO2018171245A1 WO 2018171245 A1 WO2018171245 A1 WO 2018171245A1 CN 2017113592 W CN2017113592 W CN 2017113592W WO 2018171245 A1 WO2018171245 A1 WO 2018171245A1
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lithium
negative electrode
carbonate
metal
electrolyte solution
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张强
闫崇
程新兵
黄佳琦
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清华大学
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • 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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  • the invention relates to a metal lithium negative electrode surface treatment method for a lithium metal battery, and belongs to the technical field of lithium metal batteries.
  • the commercial graphite material used as the negative pole of the battery has determined from the intrinsic characteristics that it can not meet the long range of new energy vehicles (400Wh kg -1 ). Scientific researchers have refocused their attention on the field of lithium metal batteries with lithium metal as the negative electrode. Metal lithium is used as a negative electrode with natural advantages, such as the most negative electrode potential (-3.040V) and extremely high theoretical capacity (3850mAh g -1 ), which determine the lithium metal battery in high voltage, high energy density batteries. There is great potential.
  • the metal lithium battery Since the metal lithium battery was proposed in the 1970s, it has faced several unresolved problems: for example, the production of metal lithium dendrites, some of which will leave the conductive skeleton and form a "dead lithium" that can no longer be used. The coulombic efficiency is reduced and the lithium source is lost; in addition, the large amount of lithium dendrites may cause the battery to be safely pierced by the diaphragm. The scientific research to solve the problem of lithium dendrite has never stopped. At present, the strategy to solve the problem of lithium metal is concentrated in the following aspects: reducing the local current of lithium ion deintercalation by constructing a support material (graphene) with a high specific surface structure.
  • a support material graphene
  • Density (patent number: CN105845891A); control of lithium ion deposition sites by self-limiting method (Small, 2014, 10, 4257); slowing down lithium ion deposition rate by adsorption of highly polar substances (Adv. Mater) .2016, 28, 2888); Controlling the uniform deposition of lithium ions by electrolyte additives (Patent No.: CN105870502A) Inducing directional selective deposition of lithium ions by reducing the overpotential of lithium metal deposition (Nature Energy, 2016, 1, 16010) A solid electrolyte membrane is formed on the surface of metallic lithium to prevent direct contact of the lithium surface with the electrolyte and to inhibit the generation of lithium dendrites (Adv. Mater. 2016, 28, 1853).
  • the object of the present invention is to provide a lithium negative electrode surface treatment method for a lithium metal battery, which can effectively inhibit the generation of lithium dendrites and reduce the lithium source by forming a stable solid electrolyte protective layer in situ on the surface of the metal lithium negative electrode.
  • the loss in turn, increases the life of the lithium negative electrode of the lithium metal battery during long battery life.
  • a lithium negative electrode surface treatment method for a lithium metal battery characterized in that the method comprises the following steps:
  • the additive is lithium carbonate, lithium nitrate, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroborate, lithium hexafluoroarsenate, potassium fluoride, silver fluoride, copper fluoride, sodium fluoride, vinylene carbonate.
  • an ester and a fluoroethylene carbonate is one or more of an ester and a fluoroethylene carbonate.
  • the organic solvent is ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran, sulfolane, 1,3-dioxolane, tetraethylene glycol One or more of methyl ether and dimethyl sulfoxide.
  • the thickness of the solid electrolyte protective film on the surface of the lithium sheet obtained by dropping the electrolyte solution of the present invention is preferably from 2 nm to 200 ⁇ m.
  • the invention has the following advantages and outstanding effects: the invention has simple operation method and is convenient for large-scale production and quantitative control; when the treated lithium sheet is used as a negative electrode of a lithium metal battery, the length of the whole battery can be improved. Endurance life, inhibit the production of metal lithium dendrites, isolate large areas of electrolyte and metal lithium, reduce the loss of lithium source, so that the Coulomb efficiency can be stabilized at 85 ⁇ 99.9%, and can be applied to both ester and ether electrolysis The liquid system promotes the industrialization process of lithium metal batteries.
  • the invention provides a method for treating a surface of a metal lithium negative electrode of a lithium metal battery, wherein the surface of the metal lithium negative electrode forms a solid electrolyte protective layer in situ, and the solid electrolyte protective layer is prepared by a chemical reaction method.
  • the precursor electrolyte solution for preparing the solid electrolyte layer contains a certain mass fraction of a salt additive and an organic solvent.
  • the salt additives are lithium carbonate, lithium nitrate, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroborate, lithium hexafluoroarsenate, potassium fluoride, silver fluoride, copper fluoride, sodium fluoride, and fluoroethylene carbonate.
  • the organic solvent is ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran, sulfolane, 1,3-dioxolane, tetraethylene glycol dimethyl ether, dimethyl One or more of sulfoxides.
  • the amount of the electrolyte solution dropped on the surface of the metallic lithium is 5 ⁇ L/cm -2 to 1000 ⁇ L/cm -2 , and the thickness of the solid electrolyte protective film on the surface of the lithium sheet obtained by the chemical reaction method is 2 nm to 200 ⁇ m.
  • Example 1 Preparing a solution of 1% lithium carbonate and 0.5% sodium fluoride in ethylene carbonate solution, taking 40 ⁇ L of the electrolyte solution evenly on the surface of a circular lithium sheet having a diameter of 16 mm, until the solvent is natural After the evaporation was completed, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 2 nm.
  • the prepared lithium metal sheet is used as a negative electrode to match the sulfur positive electrode for the whole battery. After testing, the coulombic efficiency of the lithium-sulfur battery can reach 99.0%, and the cycle life can reach 1000 cycles.
  • Example 2 Formulation of propylene carbonate dissolved in a mass fraction of 0.01% lithium nitrate and a mass fraction of 1% potassium fluoride To the solution, 10 ⁇ L of the electrolyte solution was uniformly dropped on the surface of a circular lithium sheet having a diameter of 16 mm, and after the solvent was completely evaporated, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 20 ⁇ m.
  • the prepared lithium metal sheet is used as a negative electrode and a lithium iron phosphate positive electrode for matching the whole battery. After testing, the coulombic efficiency of the lithium-sulfur battery can reach 99.6%, and the cycle life can reach 2000 cycles.
  • Example 3 A dimethyl carbonate solution having a mass fraction of 10.0% lithium perchlorate and a mass fraction of 3.0% silver fluoride was prepared, and 1000 ⁇ L of the electrolyte solution was uniformly dropped on the surface of a circular lithium sheet having a diameter of 16 mm. After the solvent was naturally evaporated completely, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 200 ⁇ m. The prepared lithium metal sheet was used as a negative electrode to match the nickel-cobalt-manganese ternary positive electrode to the whole battery. After testing, it was found that the lithium-sulfur battery can achieve a coulombic efficiency of 97.0% and a cycle life of 1000 cycles.
  • Example 4 Preparing a diethyl carbonate solution with a mass fraction of 20.0% lithium hexafluorophosphate and a mass fraction of 5.0% copper fluoride, and taking 2000 ⁇ L of the electrolyte solution uniformly on the surface of a circular lithium sheet having a diameter of 16 mm until the solvent is natural. After the evaporation was completed, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 100 ⁇ m. The prepared lithium metal sheet was used as a negative electrode to match the sulfur positive electrode for the whole battery. After testing, it was found that the lithium-sulfur battery can achieve a coulombic efficiency of 99.9% and a cycle life of 2000 cycles.
  • Example 5 Preparing a solution of 5.0% hexafluoroborate and a mass fraction of 0.01% sodium fluoride in ethyl carbonate, 50 ⁇ L of the electrolyte solution was uniformly dropped on the surface of a circular lithium sheet having a diameter of 16 mm. After the solvent was completely evaporated, a lithium sheet containing a solid electrolyte protective layer was obtained, and the thickness of the protective layer was 200 nm. The prepared lithium metal sheet was used as a negative electrode to match the nickel-cobalt-aluminum positive electrode to the whole battery. After testing, it was found that the lithium-sulfur battery can achieve a coulombic efficiency of 95.0% and a cycle life of 800 cycles.
  • Example 6 Preparing a tetrahydrofuran solution with a mass fraction of 0.5% lithium hexafluoroarsenate and a mass fraction of 0.05% potassium fluoride, and uniformly taking 100 ⁇ L of the electrolyte solution on the surface of a circular lithium sheet having a diameter of 16 mm until the solvent After the natural evaporation was completed, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 500 nm.
  • the prepared lithium metal sheet is used as a negative electrode and a lithium iron phosphate positive electrode for matching the whole battery. It has been found that the lithium-sulfur battery can achieve a coulombic efficiency of 90.0% and a cycle life of 600 cycles.
  • Example 7 A sulfolane solution having a mass fraction of 10.0% lithium carbonate and a mass fraction of 5.0% silver fluoride was prepared, and 60 ⁇ L of the electrolyte solution was uniformly dropped on the surface of a circular lithium sheet having a diameter of 16 mm until the solvent was completely evaporated. Thereafter, a lithium sheet containing a solid electrolyte protective layer was obtained, and the thickness of the protective layer was 300 nm.
  • the prepared lithium metal sheet was used as a negative electrode to match the nickel-cobalt-manganese positive electrode to the whole battery. After testing, it was found that the lithium-sulfur battery can achieve a coulombic efficiency of 85.0% and a cycle life of 400 cycles.
  • Example 8 A 1,3-dioxolane solution having a mass fraction of 2.0% lithium nitrate and a mass fraction of 10.0% copper fluoride was prepared, and 80 ⁇ L of the electrolyte solution was uniformly added dropwise to a circular lithium sheet having a diameter of 16 mm. On the surface, after the solvent was completely evaporated, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 1 ⁇ m. The prepared lithium metal sheet is used as a negative electrode Matching with the sulfur positive electrode for the whole battery, after testing, the coulombic efficiency of the lithium-sulfur battery can reach 99.9%, and the cycle life can reach 5000 circles.
  • Example 9 A tetraethylene glycol dimethyl ether solution having a mass fraction of 8.0% lithium perchlorate and a mass fraction of 0.5% sodium fluoride was prepared, and 400 ⁇ L of the electrolyte solution was uniformly added dropwise to a circular lithium having a diameter of 16 mm. On the surface of the sheet, after the solvent was completely evaporated, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 80 nm. The prepared lithium metal sheet is used as a negative electrode and a lithium sulfide positive electrode for matching the whole battery. It has been found that the lithium-sulfur battery can achieve a coulombic efficiency of 99.3% and a cycle life of 4,000 cycles.
  • Example 10 A dimethyl sulfoxide solution having a mass fraction of 9.0% lithium hexafluorophosphate and a mass fraction of 3.0% potassium fluoride was prepared, and 100 ⁇ L of the electrolyte solution was uniformly dropped on the surface of a circular lithium sheet having a diameter of 16 mm, to be a solvent. After the natural evaporation was completed, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 500 nm. The prepared lithium metal sheet was used as a negative electrode to match the lithium iron phosphate positive electrode for the whole battery. After testing, the coulombic efficiency of the lithium sulfur battery was 98.0%, and the cycle life was 1000 cycles.
  • Example 11 A vinyl carbonate solution having a mass fraction of 5.0% lithium hexafluoroborate and a mass fraction of 7.0% silver fluoride was prepared, and 90 ⁇ L of the electrolyte solution was uniformly dropped on the surface of a circular lithium sheet having a diameter of 16 mm. After the solvent was completely evaporated, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 150 nm. The prepared lithium metal sheet was used as a negative electrode to match the sulfur positive electrode for the whole battery. After testing, it was found that the lithium-sulfur battery can achieve a coulombic efficiency of 93.0% and a cycle life of 1000 cycles.
  • Example 12 A tetraethylene glycol dimethyl ether solution having a mass fraction of 15.0% lithium hexafluoroarsenate and a mass fraction of 20.0% copper fluoride was prepared, and 500 ⁇ L of the electrolyte solution was uniformly added dropwise to a circle having a diameter of 16 mm. On the surface of the lithium sheet, after the solvent was completely evaporated, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 2 ⁇ m. The prepared lithium metal sheet was used as a negative electrode and the nickel-cobalt-aluminum ternary material positive electrode was matched to the whole battery. After testing, it was found that the lithium-sulfur battery can achieve a coulombic efficiency of 97.0% and a cycle life of 900 cycles.
  • Example 13 A dimethyl sulfoxide solution having a mass fraction of 1.0% fluoroethylene carbonate and a mass fraction of 2.0% sodium fluoride was prepared, and 40 ⁇ L of the electrolyte solution was uniformly added dropwise to a circular lithium sheet having a diameter of 16 mm. On the surface, after the solvent was completely evaporated, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 30 nm. The prepared lithium metal sheet was used as a negative electrode to match the nickel-cobalt-manganese ternary material positive electrode to the whole battery. After testing, the coulombic efficiency of the lithium-sulfur battery was 99.0%, and the cycle life was 1000 cycles.
  • Example 14 A 1,3-dioxolane solution having a mass fraction of 2.0% vinylene carbonate and a mass fraction of 5.0% lithium nitrate was prepared, and 50 ⁇ L of the electrolyte solution was uniformly added dropwise to a circular lithium having a diameter of 16 mm. On the surface of the sheet, after the solvent was completely evaporated, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 250 nm. The prepared lithium metal sheet was used as a negative electrode to match the sulfur positive electrode for the whole battery. After testing, it was found that the lithium-sulfur battery can achieve a coulombic efficiency of 96.0% and a cycle life of 800 cycles.
  • Example 15 A vinyl carbonate solution having a mass fraction of 1.0% lithium hexafluoroarsenate and a mass fraction of 3.0% fluoroethylene carbonate was prepared, and 30 ⁇ L of the electrolyte solution was uniformly added dropwise to a circular lithium wafer having a diameter of 16 mm. On the surface, after the solvent was completely evaporated, a lithium sheet containing a protective layer of a solid electrolyte was obtained, and the thickness of the protective layer was 60 nm. The prepared lithium metal sheet is used as a negative electrode to match the full battery of the lithium iron phosphate material positive electrode. After testing, the coulombic efficiency of the lithium sulfur battery can reach 94.0%, and the cycle life can reach 600 circles.
  • Example 16 A propylene carbonate solution having a mass fraction of 4.0% lithium perchlorate and a mass fraction of 2.0% copper fluoride was prepared, and 80 ⁇ L of the electrolyte solution was uniformly dropped on the surface of a circular lithium sheet having a diameter of 16 mm. After the solvent was completely evaporated, a lithium sheet containing a solid electrolyte protective layer was obtained, and the thickness of the protective layer was 80 nm. The prepared lithium metal sheet was used as a negative electrode to match the sulfur positive electrode for the whole battery. After testing, it was found that the lithium-sulfur battery can achieve a coulombic efficiency of 99.0% and a cycle life of 1500 cycles.

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Abstract

本发明公开了一种锂金属电池的锂负极表面处理方法，属于锂电池技术领域。该方法采用化学方法，将盐类或酯类作为添加剂溶解到有机溶剂中，制成电解质溶液；取电解质溶液与金属锂片反应，使得在锂片表面形成一层固态电解质保护层。本发明的操作方法简单，便于大规模的生产及定量控制；在金属锂表面原位形成的固态电解质层能有效抑制锂枝晶的产生，减少锂源的损失，使得整个电池的库伦效率在没有添加剂的条件下得到明显提高，实现了金属锂负极在电池长续航过程中的稳定和高效，在抑制金属锂枝晶和提高并保持全电池的高库伦效率方面都有明显效果。

Description

一种锂金属电池的锂负极表面处理方法 技术领域
本发明涉及一种锂金属电池的金属锂负极表面处理方法，属于锂金属电池技术领域。
背景技术
21世纪进入移动生活时代，整个社会对于能源的需求变得更高，这也促进了储能领域尤其是电池储能的快速发展。从索尼公司在20世纪90年代研发出了用石墨负极代替金属负极发布第一代商用锂离子电池之后，锂离子电池迅速占领了以笔记本电脑、手机、数码相机等电子产品为主体的高端移动终端市场。随着国家新能源战略发展策略的提出，在全国范围推广普及新能源汽车来遏制内燃机汽车造成的尾气污染，同时也能减少国家对石油的进口依赖。人们对高能量密度的电池期望也就越来越高，商业化的石墨材料用作电池的负极从本征特性上已经决定了其无法满足新能源汽车长续航里程的要求(400Wh kg-1)，科学研究人员又重新把目光聚焦在了以金属锂为负极的锂金属电池领域。金属锂用作负极具有天然的优势，比如最负的电极电势(-3.040V)、极高的理论容量(3850mAh g-1)，这些决定了金属锂电池在高电压、高能量密度电池中都有极大潜力。
金属锂电池自20世纪70年代被提出以来，始终面临着几个未被解决的问题：比如金属锂枝晶的产生，部分枝晶会脱离导电骨架形成无法再被利用的“死锂”，致使库伦效率下降和锂源的损失；此外，锂枝晶的大量产生有可能会刺穿隔膜导致电池的安全问题。解决锂枝晶问题的科学研究也从未停止，目前解决金属锂问题的策略集中在以下几个方面：通过构筑高比表面结构的支撑材料(石墨烯)来减小锂离子脱嵌的局部电流密度(专利号：CN105845891A)；通过自限域的方法来控制锂离子的沉积位点(Small,2014,10,4257)；通过强极性物质的吸附作用来减缓锂离子沉积速率(Adv.Mater.2016,28,2888)；通过电解液添加剂来控制锂离子的均匀沉积(专利号：CN105870502A)通过降低金属锂沉积的过电势诱导锂离子的定向选择性沉积(Nature Energy,2016,1,16010)；在金属锂的表面构建一层固态电解质膜，阻止锂表面与电解液的直接接触，同时能够抑制锂枝晶的产生(Adv.Mater.2016,28,1853)。
发明内容
本发明的目的是提供一种锂金属电池的锂负极表面处理方法，通过在金属锂负极表面原位形成一层稳定的固态电解质保护层，使其可有效抑制锂枝晶的产生，减少锂源的损失，进而提高锂金属电池的锂负极在长续航过程中的寿命。
本发明的技术方案如下：一种锂金属电池的锂负极表面处理方法，其特征在于该方法包括如下步骤：
1)将盐类或酯类作为添加剂溶解到有机溶剂中，制成电解质溶液，其中添加剂的质量分 数为0.01％～20.0％；
2)取电解质溶液与金属锂片反应，使得在锂片表面形成一层保护层，电解质溶液滴加的量为5μLcm-2～1000μLcm-2，在金属锂负极表面原位形成一层固态电解质保护层。
优选地，所述添加剂为碳酸锂、硝酸锂、高氯酸锂、六氟磷酸锂、六氟硼酸锂、六氟砷酸锂、氟化钾、氟化银、氟化铜、氟化钠、碳酸亚乙烯酯和氟代碳酸乙烯酯中的一种或几种。
优选地，所述的有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、四氢呋喃、环丁砜、1,3-二氧戊环、四乙二醇二甲醚和二甲基亚砜中的一种或几种。
本发明所述滴加电解质溶液后获得的锂片表面固态电解质保护膜厚度优选为2nm～200μm。
本发明相比现有技术，具有如下优点及突出性效果：本发明操作方法简单，便于大规模的生产及定量控制；处理后的锂片用作锂金属电池负极时，能提高整个电池的长续航寿命，抑制金属锂枝晶的产生，隔绝电解液与金属锂的大面积接触，减少锂源的损失，使得库伦效率能够稳定在85～99.9％，并且能够同时应用于酯类和醚类电解液体系，推进锂金属电池的产业化进程。
具体实施方式
下面通过几个具体实施例可对本发明的具体实施得到进一步的了解。
本发明提供的一种锂金属电池的金属锂负极表面处理方法，该方法使得金属锂负极表面原位形成一层固态电解质保护层，该固态电解质保护层采用化学反应方法制备。用于制备固态电解质层的前驱电解质溶液包含一定质量分数的盐类添加剂和有机溶剂。盐类添加剂为碳酸锂、硝酸锂、高氯酸锂、六氟磷酸锂、六氟硼酸锂、六氟砷酸锂、氟化钾、氟化银、氟化铜、氟化钠、氟代碳酸乙烯酯中的一种或几种，添加剂的质量分数在0.01％～20.0％。有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、四氢呋喃、环丁砜、1,3-二氧戊环、四乙二醇二甲醚、二甲基亚砜中的一种或几种。电解质溶液滴加在金属锂表面的量为5μL/cm-2～1000μL/cm-2,化学反应法获得的锂片表面固态电解质保护膜的厚度为2nm～200μm。
从以下实施例可进一步理解本发明，但本发明不仅仅局限于以下实施例。
实施例1：配制以质量分数为1％碳酸锂和质量分数为0.5％氟化钠的碳酸乙烯酯溶液，取40μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为2nm。将制备出的金属锂片作为负极与硫正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到99.0％，循环寿命可以达到1000圈。
实施例2：配制以质量分数为0.01％硝酸锂和质量分数为1％氟化钾的碳酸丙烯酯溶 液，取10μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为20μm。将制备出的金属锂片作为负极与磷酸铁锂正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到99.6％，循环寿命可以达到2000圈。
实施例3：配制以质量分数为10.0％高氯酸锂和质量分数为3.0％氟化银的碳酸二甲酯溶液，取1000μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为200μm。将制备出的金属锂片作为负极与镍钴锰三元正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到97.0％，循环寿命可以达到1000圈。
实施例4：配制以质量分数为20.0％六氟磷酸锂和质量分数为5.0％氟化铜的碳酸二乙酯溶液，取2000μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为100μm。将制备出的金属锂片作为负极与硫正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到99.9％，循环寿命可以达到2000圈。
实施例5：配制以质量分数为5.0％六氟硼酸锂和质量分数为0.01％氟化钠的碳酸甲乙酯溶液，取50μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为200nm。将制备出的金属锂片作为负极与镍钴铝正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到95.0％，循环寿命可以达到800圈。
实施例6：配制以质量分数为0.5％六氟砷酸锂和质量分数为0.05％氟化钾的四氢呋喃溶液，取100μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为500nm。将制备出的金属锂片作为负极与磷酸铁锂正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到90.0％，循环寿命可以达到600圈。
实施例7：配制以质量分数为10.0％碳酸锂和质量分数为5.0％氟化银的环丁砜溶液，取60μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为300nm。将制备出的金属锂片作为负极与镍钴锰正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到85.0％，循环寿命可以达到400圈。
实施例8：配制以质量分数为2.0％硝酸锂和质量分数为10.0％氟化铜的1,3-二氧戊环溶液，取80μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为1μm。将制备出的金属锂片作为负极 与硫正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到99.9％，循环寿命可以达到5000圈。
实施例9：配制以质量分数为8.0％高氯酸锂和质量分数为0.5％氟化钠的四乙二醇二甲醚溶液，取400μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为80nm。将制备出的金属锂片作为负极与硫化锂正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到99.3％，循环寿命可以达到4000圈。
实施例10：配制以质量分数为9.0％六氟磷酸锂和质量分数为3.0％氟化钾的二甲基亚砜溶液，取100μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为500nm。将制备出的金属锂片作为负极与磷酸铁锂正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到98.0％，循环寿命可以达到1000圈。
实施例11：配制以质量分数为5.0％六氟硼酸锂和质量分数为7.0％氟化银的碳酸乙烯酯溶液，取90μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为150nm。将制备出的金属锂片作为负极与硫正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到93.0％，循环寿命可以达到1000圈。
实施例12：配制以质量分数为15.0％六氟砷酸锂和质量分数为20.0％氟化铜的四乙二醇二甲醚溶液，取500μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为2μm。将制备出的金属锂片作为负极与镍钴铝三元材料正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到97.0％，循环寿命可以达到900圈。
实施例13：配制以质量分数为1.0％氟代碳酸乙烯酯和质量分数为2.0％氟化钠的二甲基亚砜溶液，取40μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为30nm。将制备出的金属锂片作为负极与镍钴锰三元材料正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到99.0％，循环寿命可以达到1000圈。
实施例14：配制以质量分数为2.0％碳酸亚乙烯酯和质量分数为5.0％硝酸锂的1,3-二氧戊环溶液，取50μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为250nm。将制备出的金属锂片作为负极与硫正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到96.0％，循环寿命可以达到800圈。
实施例15：配制以质量分数为1.0％六氟砷酸锂和质量分数为3.0％氟代碳酸乙烯酯的碳酸乙烯酯溶液，取30μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为60nm。将制备出的金属锂片作为负极与磷酸铁锂材料正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到94.0％，循环寿命可以达到600圈。
实施例16：配制以质量分数为4.0％高氯酸锂和质量分数为2.0％氟化铜的碳酸丙烯酯溶液，取80μL该电解质溶液均匀滴加在直径为16mm的圆形锂片表面，待溶剂自然蒸发完全后得到含有固态电解质保护层的锂片，保护层厚度为80nm。将制备出的金属锂片作为负极与硫正极进行全电池的匹配，经过测试发现，锂硫电池的库伦效率可以达到99.0％，循环寿命可以达到1500圈。

Claims (4)

  1. 一种锂金属电池的锂负极表面处理方法，其特征在于该方法包括如下步骤：
    1)将盐类或酯类作为添加剂溶解到有机溶剂中，制成电解质溶液，其中添加剂的质量分数为0.01％～20.0％；
    2)取电解质溶液与金属锂片反应，使得在锂片表面形成一层保护层，电解质溶液滴加的量为5μLcm-2～1000μLcm-2，在金属锂负极表面原位形成一层固态电解质保护层。
  2. 按照权利要求1所述的一种金属电池的锂负极表面处理方法，其特征在于：所述添加剂为碳酸锂、硝酸锂、高氯酸锂、六氟磷酸锂、六氟硼酸锂、六氟砷酸锂、氟化钾、氟化银、氟化铜、氟化钠、碳酸亚乙烯酯和氟代碳酸乙烯酯中的一种或几种。
  3. 根据权利要求1或2所述的一种金属电池的锂负极表面处理方法，其特征在于:所述的有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、四氢呋喃、环丁砜、1,3-二氧戊环、四乙二醇二甲醚和二甲基亚砜中的一种或几种。
  4. 按照权利要求3所述的一种金属电池的锂负极表面处理方法，其特征在于：滴加电解质溶液后获得的锂片表面固态电解质保护膜厚度为2nm～200μm。
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CN112768651A (zh) * 2021-01-07 2021-05-07 华中科技大学 一种引入硝酸盐到碱金属电池负极的方法及其产物与应用

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