CN115821243A - A method for exciting liquid plasma surface modification of lithium metal - Google Patents
A method for exciting liquid plasma surface modification of lithium metal Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 230000004048 modification Effects 0.000 title claims abstract description 11
- 238000012986 modification Methods 0.000 title claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052751 metal Inorganic materials 0.000 claims abstract description 82
- 239000002184 metal Substances 0.000 claims abstract description 82
- 239000011241 protective layer Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- DEAZEWBZYSWFCA-UHFFFAOYSA-N C(O)(=O)F.C(O)(=O)F.C(O)(=O)F.C=CC Chemical compound C(O)(=O)F.C(O)(=O)F.C(O)(=O)F.C=CC DEAZEWBZYSWFCA-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 150000002641 lithium Chemical class 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
Description
技术领域technical field
本发明涉及一种激发液体等离子体表面改性金属锂的方法，属于金属锂材料加工技术领域。The invention relates to a method for stimulating the surface of liquid plasma to modify lithium metal, which belongs to the technical field of lithium metal material processing.
技术背景technical background
金属锂具有理论比容量高、电位低、密度小、能量密度大等优点，因此是组装新型锂电池的理想负极材料。然而，金属锂在生产和储存过程中，一旦和空气接触，就会被空气腐蚀，和空气中的水、氧、二氧化碳等发生反应，在表面形成氧化锂、碳酸锂、氢氧化锂等杂质，且这些杂质在金属锂表面的分布是不均匀的，会进一步影响其电化学性能的发挥。因此，金属锂的空气稳定性差是阻碍其实际应用的一大难题，是本领域亟待解决的重点难题。Lithium metal has the advantages of high theoretical specific capacity, low potential, low density, and high energy density, so it is an ideal negative electrode material for assembling new lithium batteries. However, during the production and storage process, once metal lithium comes into contact with air, it will be corroded by air, react with water, oxygen, carbon dioxide, etc. in the air, and form impurities such as lithium oxide, lithium carbonate, and lithium hydroxide on the surface. Moreover, the distribution of these impurities on the surface of metal lithium is uneven, which will further affect its electrochemical performance. Therefore, the poor air stability of lithium metal is a major problem hindering its practical application, and it is a key problem to be solved in this field.
等离子体是由电子、离子和未电离的中性粒子构成的，具有一定的能量。通过直流电源可以在金属电极和液体阳极之间形成等离子体，给体系提供能量。此外，与气相等离子体活性粒子相比，液相等离子体活性粒子具有更强的渗透效应，能够与反应物更均匀地接触，从而有利于反应的均匀发生。针对金属锂空气稳定性差的问题，本发明提供一种液体激发等离子体表面改性金属锂的方法，通过液体溶剂两侧的金属电极之间形成的等离子体，为金属锂和液体溶剂之间的反应提供能量，促进反应快速发生，在金属锂表面形成一层均匀致密的保护层，提高金属锂的空气稳定性，同时通过液体溶剂种类的选择，还能进一步提高金属锂的电化学性能。Plasma is composed of electrons, ions and unionized neutral particles and has a certain energy. A plasma can be formed between the metal electrode and the liquid anode through a DC power supply to provide energy to the system. In addition, compared with the gas-phase plasma active particles, the liquid-phase plasma active particles have a stronger penetration effect, and can contact the reactants more uniformly, thereby facilitating the uniform occurrence of the reaction. Aiming at the problem of poor air stability of metal lithium, the present invention provides a method for liquid-excited plasma surface modification of metal lithium, through the plasma formed between the metal electrodes on both sides of the liquid solvent, as the gap between metal lithium and liquid solvent The reaction provides energy, promotes the rapid reaction, forms a uniform and dense protective layer on the surface of lithium metal, and improves the air stability of lithium metal. At the same time, the electrochemical performance of lithium metal can be further improved by selecting the type of liquid solvent.
发明内容Contents of the invention
为了解决上述现有技术中的不足，本发明提供一种快速高效、成本低廉、操作简单的激发液体等离子体表面改性金属锂的方法。In order to solve the deficiencies in the above-mentioned prior art, the present invention provides a method for exciting liquid plasma to modify the surface of lithium metal which is fast, efficient, low in cost and simple in operation.
本发明解决其技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve its technical problems is:
一种激发液体等离子体表面改性金属锂的方法，包括步骤如下：A method for exciting liquid plasma surface modification lithium metal, comprising steps as follows:
S1：在惰性气氛下将金属锂放置在等离子体反应器内；S1: placing lithium metal in a plasma reactor under an inert atmosphere;
S2：加入能够浸没金属锂的有机溶剂，将等离子体反应器密封；S2: adding an organic solvent capable of immersing metallic lithium, and sealing the plasma reactor;
S3：使等离子体反应器内产生等离子体，反应一定时间后得到表面改性金属锂。S3: Generate plasma in the plasma reactor, and obtain surface-modified metal lithium after a certain period of reaction.
作为优选，上述制备方法步骤S1中所述金属锂为粉体、块体、带材等形态，更优选的所述金属锂为锂粉、锂块、锂带、锂片的至少一种。Preferably, the metal lithium in step S1 of the above preparation method is in the form of powder, block, strip, etc. More preferably, the metal lithium is at least one of lithium powder, lithium block, lithium ribbon, and lithium sheet.
作为优选，上述制备方法步骤S1在充满惰性气氛的手套箱中将金属锂放置在等离子体反应器内。Preferably, in step S1 of the above preparation method, metal lithium is placed in a plasma reactor in a glove box filled with an inert atmosphere.
作为优选，上述制备方法步骤S2中加入有机溶剂后对等离子体反应器进行密封。Preferably, the plasma reactor is sealed after adding the organic solvent in step S2 of the above preparation method.
作为优选，上述制备方法步骤S2中所述有机溶剂为碳酸乙烯酯、氟代碳酸乙烯酯、碳酸丙烯酯、三氟碳酸丙烯酯、双三氟乙基碳酸酯等中的至少一种。Preferably, the organic solvent in step S2 of the above preparation method is at least one of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, trifluoropropylene carbonate, bistrifluoroethyl carbonate and the like.
作为优选，上述制备方法步骤S3中通过开启直流电流，使等离子体反应器的处于阳极和阴极之间的电子受到电场力的作用形成等离子体；更优选的所述直流电流功率为10～1000W，反应时间为10～600min。As a preference, in step S3 of the above preparation method, by turning on the direct current, the electrons in the plasma reactor between the anode and the cathode are subjected to an electric field force to form a plasma; more preferably, the direct current power is 10-1000W, The reaction time is 10-600 minutes.
作为优选，上述制备方法步骤S3中所述表面改性金属锂是通过对金属锂表面形成均匀致密保护层进行表面改性，所述均匀致密保护层为碳酸锂、氟化锂、氧化锂等中的一种或多种。Preferably, the surface modified metal lithium in step S3 of the above preparation method is to modify the surface of the metal lithium by forming a uniform and dense protective layer on the surface of the metal lithium, and the uniform and dense protective layer is lithium carbonate, lithium fluoride, lithium oxide, etc. one or more of .
作为优选，上述制备方法步骤S3在室温下进行。Preferably, step S3 of the above preparation method is carried out at room temperature.
作为优选，本发明中所述惰性气氛为氩气。Preferably, the inert atmosphere in the present invention is argon.
作为优选，所述方法具体包括步骤如下：Preferably, the method specifically includes the following steps:
S1：在充满惰性气氛的手套箱中将金属锂放置在等离子体反应器内；S1: Lithium metal is placed in a plasma reactor in a glove box filled with an inert atmosphere;
S2：向等离子体反应器内加入一定量的有机溶剂，使金属锂完全浸没在有机溶剂中，并密封；S2: Add a certain amount of organic solvent into the plasma reactor, so that the metal lithium is completely immersed in the organic solvent, and seal it;
S3：开启直流电源，调节功率，反应一定时间后关闭直流电源，打开密封盖后得到改性金属锂。S3: Turn on the DC power supply, adjust the power, turn off the DC power supply after a certain period of time, and open the sealing cover to obtain the modified lithium metal.
本发明提供一种简便的激发液体等离子体表面改性金属锂的方法：首先将金属锂放置在等离子体反应器内，加入一定量的有机溶剂后密封，开启直流电源后位于液体溶剂两侧的金属电极之间形成等离子体，为有机溶剂与金属锂之间的反应提供能量，在金属锂表面构筑一层均匀致密的保护层。该方法操作简单、成本低廉、快速高效，极具规模化生产的潜力。The invention provides a simple method for stimulating the surface of liquid plasma to modify lithium metal: firstly, metal lithium is placed in a plasma reactor, a certain amount of organic solvent is added and then sealed, and the DC power supply is turned on and located on both sides of the liquid solvent Plasma is formed between the metal electrodes, which provides energy for the reaction between the organic solvent and the lithium metal, and builds a uniform and dense protective layer on the surface of the lithium metal. The method is simple to operate, low in cost, fast and efficient, and has great potential for large-scale production.
与现有技术相比，本发明的有益效果在于：Compared with prior art, the beneficial effect of the present invention is:
本发明通过液体溶剂两侧的金属电极之间形成的等离子体为液体溶剂和金属锂的反应提供能量，促进反应的快速发生，在金属锂表面构筑均匀致密的保护层。均匀致密的保护层能够将金属锂和空气隔绝，从而防止空气对金属锂的腐蚀，此外，通过液体溶剂的种类选择，还可以在金属锂表面构筑有利于其发挥电化学性能的保护层，在提高空气稳定性的同时提高其充放电性能，降低其生产、储存成本，同时避免安全问题的产生。该方法工艺简单，操作简便，快速高效，经济效益显著。In the invention, the plasma formed between the metal electrodes on both sides of the liquid solvent provides energy for the reaction of the liquid solvent and metal lithium, promotes the rapid occurrence of the reaction, and constructs a uniform and dense protective layer on the surface of the metal lithium. A uniform and dense protective layer can isolate metallic lithium from the air, thereby preventing air from corroding metallic lithium. In addition, through the selection of the type of liquid solvent, a protective layer that is conducive to its electrochemical performance can also be constructed on the surface of metallic lithium. Improve the air stability while improving its charge and discharge performance, reduce its production and storage costs, and avoid safety problems. The method has the advantages of simple process, convenient operation, rapidity and high efficiency, and remarkable economic benefit.
附图说明Description of drawings
附图1为未改性金属锂(左)、实施例1改性金属锂(中)和对比例改性金属锂(右)暴露在空气中5min后(上)和30min后(下)的对比图。Accompanying drawing 1 is the comparison of unmodified metal lithium (left), embodiment 1 modified metal lithium (middle) and comparative example modified metal lithium (right) after being exposed to the air for 5min (top) and 30min (bottom) picture.
附图2为实施例1改性金属锂的SEM图。Accompanying
附图3为实施例1改性金属锂的XPS图。Accompanying
附图4为采用实施例1改性金属锂、未改性金属锂和对比例改性金属锂分别组装的三元电池的循环性能对比图。Accompanying
附图5为采用暴露空气后的实施例1改性金属锂、未改性金属锂和对比例改性金属锂分别组装的三元电池的循环性能对比图。Accompanying
附图6为实施例2的XPS谱图。Accompanying
具体实施方式Detailed ways
下面通过实施例，结合附图，对本发明的技术方案进一步阐述说明，但本发明的保护范围不限于此。本发明中所述室温为15-40℃，更优选为25-30℃。The technical solution of the present invention will be further elaborated below through the embodiments, in conjunction with the accompanying drawings, but the protection scope of the present invention is not limited thereto. The room temperature in the present invention is 15-40°C, more preferably 25-30°C.
实施例1：Example 1:
一种激发液体等离子体表面改性金属锂的方法，包括以下步骤：A method for exciting liquid plasma surface modification lithium metal, comprising the following steps:
S1：在充满氩气的手套箱中将长20mm宽15mm的金属锂片放置在等离子体反应器内；S1: Place a metal lithium sheet with a length of 20 mm and a width of 15 mm in a plasma reactor in a glove box filled with argon;
S2：在反应器内加入20mL氟代碳酸乙烯酯使金属锂片完全浸没，密封后将反应器移出手套箱；S2: Add 20mL of fluoroethylene carbonate into the reactor to completely submerge the metal lithium sheet, and move the reactor out of the glove box after sealing;
S3：开启直流电源，调节功率为50W，反应300min后关闭直流电源，打开密封盖后得到表面附有碳酸锂、氟化锂致密保护层的改性金属锂。S3: Turn on the DC power supply, adjust the power to 50W, turn off the DC power supply after 300 minutes of reaction, and open the sealing cover to obtain the modified lithium metal with a dense protective layer of lithium carbonate and lithium fluoride on the surface.
对比例：Comparative example:
S1：在充满氩气的手套箱中将长20mm宽15mm的金属锂片放置在反应器内；S1: Place a metal lithium sheet with a length of 20 mm and a width of 15 mm in the reactor in a glove box filled with argon;
S2：在反应器内加入20mL氟代碳酸乙烯酯使金属锂片完全浸没，密封后将反应器移出手套箱；S2: Add 20mL of fluoroethylene carbonate into the reactor to completely submerge the metal lithium sheet, and move the reactor out of the glove box after sealing;
S3：待反应器内的金属锂和氟代碳酸乙烯酯反应300min后打开密封盖，得到表面附有碳酸锂、氟化锂的改性金属锂。S3: After the metal lithium in the reactor reacts with fluoroethylene carbonate for 300 minutes, open the sealing cover to obtain the modified metal lithium with lithium carbonate and lithium fluoride attached to the surface.
附图1为未改性金属锂(左)、实施例1改性金属锂(中)和对比例改性金属锂(有)暴露在空气中5min后(上)和30min后(下)的对比图。暴露空气5min后实施例1和对比例改性金属锂仍旧保持金属光泽，而未改性金属锂表面变黑；暴露空气30min后对比例改性金属锂和未改性金属锂表面都变黑，完全被氧化腐蚀，而实施例1改性金属锂仍然保持金属光泽，经本发明改性的金属锂的空气稳定性得到明显提升。Accompanying drawing 1 is the comparison of unmodified metal lithium (left), embodiment 1 modified metal lithium (middle) and comparative example modified metal lithium (with) exposed in air for 5 minutes (top) and after 30 minutes (bottom) picture. After 5 minutes of exposure to air, the modified metal lithium of Example 1 and the comparative example still maintained a metallic luster, while the surface of the unmodified lithium metal turned black; after 30 minutes of exposure to the air, the surfaces of the modified metal lithium of the comparative example and the unmodified lithium metal both turned black, Completely oxidized and corroded, while the metal lithium modified in Example 1 still maintains metallic luster, and the air stability of the metal lithium modified by the present invention is significantly improved.
附图2为实施例1改性金属锂的SEM。可以看到实施例1改性金属锂表面均匀分布有保护层产物。Accompanying
附图3为实施例1改性金属锂的XPS。从Li 1s谱图上可以看出，本实施例改性金属锂表面有碳酸锂和氟化锂。因此可知本实施例改性锂表面附有碳酸锂和氟化锂的均匀致密保护层。Accompanying
采用实施例1改性金属锂和未改性金属锂以及对比例改性金属锂分别为负极，与三元正极(NCM811)以及电解液(1M LiPF6/(EC+DMC))组装成电池，附图4为这三种电池的循环性能对比图。实施例1改性金属锂组装的电池循环50圈后容量为180.2mA h g-1，未改性金属锂组装的电池循环50圈后容量为175.5mA h g-1，而对比例改性金属锂组装的电池循环50圈后容量为173.6mA h g-1，实施例1改性金属锂电池不仅克服了现有的对于金属锂进行改性时会造成容量降低的问题，甚至更进一步使得电池发挥了更大的容量，超过未改性金属锂组装的电池容量。Using Example 1 modified metal lithium and unmodified metal lithium and comparative example modified metal lithium as negative electrodes respectively, and ternary positive electrode (NCM811) and electrolyte (1M LiPF 6 /(EC+DMC)) were assembled into batteries, Accompanying drawing 4 is the comparison graph of cycle performance of these three kinds of batteries. Example 1 The battery assembled with modified metal lithium has a capacity of 180.2 mA hg -1 after 50 cycles, the battery assembled with unmodified metal lithium has a capacity of 175.5 mA hg -1 after 50 cycles, while the battery assembled with modified metal lithium in the comparative example The capacity of the battery after 50 cycles is 173.6mA hg -1 . The modified metal lithium battery in Example 1 not only overcomes the existing problem of capacity reduction caused by the modification of metal lithium, but even further enables the battery to play a more advanced role. Large capacity, exceeding the battery capacity assembled by unmodified metal lithium.
附图5为采用暴露空气5min后的实施例1改性金属锂和未改性金属锂以及对比例改性金属锂分别组装的三元电池的循环性能对比图。实施例1改性金属锂暴露空气后组装的电池循环50圈后容量为175.9mA h g-1，仍能稳定循环，且发挥较大的容量，其循环性能与容量值较未暴露空气时未有较大变化，而未改性金属锂暴露空气后组装的电池容量衰减很快，循环50圈后容量仅剩140.9mA h g-1，电化学性能恶化严重，此外对比例改性金属锂暴露空气后组装的电池循环50圈后容量也仅有154.2mA h g-1，且循环稳定性差，电化学性能同样恶化严重。Accompanying drawing 5 is the cycle performance comparison diagram of the ternary batteries respectively assembled with the modified metal lithium and the unmodified metal lithium of Example 1 and the modified metal lithium of the comparative example after being exposed to the air for 5 minutes. Example 1 The battery assembled after the modified metal lithium was exposed to the air had a capacity of 175.9mA hg -1 after 50 cycles, and it could still cycle stably and exert a large capacity. However, the battery capacity of the unmodified metal lithium exposed to the air decays rapidly, and the capacity is only 140.9mA hg -1 after 50 cycles, and the electrochemical performance deteriorates seriously. In addition, the modified metal lithium exposed to the air The capacity of the assembled battery is only 154.2mA hg -1 after 50 cycles, and the cycle stability is poor, and the electrochemical performance is also seriously deteriorated.
实施例2：Example 2:
一种激发液体等离子体表面改性金属锂的方法，包括以下步骤：A method for exciting liquid plasma surface modification lithium metal, comprising the following steps:
S1：在充满氩气的手套箱中将金属锂带卷绕成金属锂卷后放置在等离子体反应器内；S1: In a glove box filled with argon gas, the metal lithium ribbon was wound into a metal lithium roll and placed in the plasma reactor;
S2：在反应器内加入30mL碳酸乙烯酯，使金属锂卷完全浸没，密封后移出手套箱；S2: Add 30mL ethylene carbonate into the reactor to completely submerge the metal lithium coil, seal it and remove it from the glove box;
S3：开启直流电源，调节功率为10W，反应600min后关闭直流电源，打开密封盖后得到表面附有碳酸锂的改性金属锂。S3: Turn on the DC power supply, adjust the power to 10W, turn off the DC power supply after 600 minutes of reaction, and open the sealing cover to obtain the modified lithium metal with lithium carbonate on the surface.
附图6为实施例2的XPS谱图。从Li 1s谱图可以得知，实施例2改性锂表面含有碳酸锂和锂，其中锂是金属锂自身。由此可知，实施例2改性金属锂表面附有碳酸锂保护层。Accompanying drawing 6 is the XPS spectrogram of
实施例3：Example 3:
一种激发液体等离子体表面改性金属锂的方法，包括以下步骤：A method for exciting liquid plasma surface modification lithium metal, comprising the following steps:
S1：在充满氩气的手套箱中将金属锂片放置在等离子体反应器内；S1: Place the lithium metal sheet in the plasma reactor in a glove box filled with argon;
S2：在反应器内加入40mL三氟碳酸丙烯酯，使金属锂粉完全浸没，密封后移出手套箱；S2: Add 40mL propylene trifluorocarbonate into the reactor to fully submerge the metal lithium powder, seal it and remove it from the glove box;
S3：开启直流电源，调节功率为1000W，反应10min后关闭直流电源，打开密封盖后得到表面附有碳酸锂和氟化锂的改性金属锂。S3: Turn on the DC power supply, adjust the power to 1000W, turn off the DC power supply after 10 minutes of reaction, and open the sealing cover to obtain the modified lithium metal with lithium carbonate and lithium fluoride on the surface.
实施例4：Example 4:
一种激发液体等离子体表面改性金属锂的方法，包括以下步骤：A method for exciting liquid plasma surface modification lithium metal, comprising the following steps:
S1：在充满氩气的手套箱中将金属锂片放置在等离子体反应器内；S1: Place the lithium metal sheet in the plasma reactor in a glove box filled with argon;
S2：在反应器内加入50mL双三氟乙基碳酸酯，使金属锂完全浸没，密封后移出手套箱；S2: Add 50mL of bistrifluoroethyl carbonate into the reactor to completely immerse the lithium metal, seal it and remove it from the glove box;
S3：开启直流电源，调节功率为800W，反应30min后关闭直流电源，打开密封盖后得到表面附有碳酸锂和氟化锂的改性金属锂。S3: Turn on the DC power supply, adjust the power to 800W, turn off the DC power supply after 30 minutes of reaction, and open the sealing cover to obtain the modified lithium metal with lithium carbonate and lithium fluoride on the surface.
各实施例的制备参数和性能结果参见表1。See Table 1 for the preparation parameters and performance results of each embodiment.
表1各实施例的制备参数和性能结果Preparation parameters and performance results of each embodiment of table 1
综上所述，本发明的方法得到的改性金属锂能提高空气稳定性，同时改善了锂电池的电化学稳定性，提高了电池的容量；该方法工艺简单，操作简便，快速高效，经济效益显著。In summary, the modified metal lithium obtained by the method of the present invention can improve the air stability, improve the electrochemical stability of the lithium battery, and increase the capacity of the battery; the method is simple in process, easy to operate, fast, efficient, and economical Significant benefits.
以上所述的实施例只是本发明的较佳方案，并非对本发明作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其他的变体及改型。The embodiments described above are only preferred solutions of the present invention, and do not limit the present invention in any form. There are other variations and modifications on the premise of not exceeding the technical solutions described in the claims.
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