CN115842126A - Lithium metal negative electrode protective layer, preparation method thereof and lithium battery comprising same - Google Patents
Lithium metal negative electrode protective layer, preparation method thereof and lithium battery comprising same Download PDFInfo
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- CN115842126A CN115842126A CN202111110258.3A CN202111110258A CN115842126A CN 115842126 A CN115842126 A CN 115842126A CN 202111110258 A CN202111110258 A CN 202111110258A CN 115842126 A CN115842126 A CN 115842126A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 130
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011241 protective layer Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 34
- 239000010410 layer Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 82
- 238000006243 chemical reaction Methods 0.000 description 26
- 230000008021 deposition Effects 0.000 description 17
- 210000001787 dendrite Anatomy 0.000 description 12
- 230000009257 reactivity Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000010574 gas phase reaction Methods 0.000 description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 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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Abstract
The invention discloses a preparation method of a lithium metal negative electrode protective layer, which comprises the following steps: a. placing lithium metal in a reactor, the reactor being provided with a gas inlet and a gas outlet; b. introducing a first gas and a second gas into the reactor, and reacting with lithium metal to generate a protective layer; wherein the first gas is selected from N 2 、CO 2 Or O 2 Is selected from at least one of water vapor or alcohol vapor. The preparation method is simple and feasible, does not need inert atmosphere, is easy for industrial application, and the prepared protective layer has controllable components and structure, can effectively inhibit dendritic crystal growth, reduces side reaction between subsequent lithium and a solvent after contacting with an electrolyte, and achieves the effect of controlling the intermediate phase of the solid electrolyte on the surface of the metallic lithium cathode.
Description
Technical Field
The invention belongs to the technical field of battery cathode materials, particularly relates to a lithium metal cathode protective layer, and particularly relates to a preparation method of the lithium metal cathode protective layer.
Background
The Li metal cathode has the advantages of high energy density and low potential, and is a key material for developing next-generation high-energy-density rechargeable batteries. However, in the deposition process of lithium, dendrite growth due to local electron concentration is likely to occur, side reactions are caused, electrolyte loss and battery capacity attenuation are caused, and even safety problems are caused, so that the application of the lithium negative electrode is seriously hindered. The stability of the lithium metal negative electrode is improved, so that the lithium metal negative electrode still has higher safety and long cycle life in an environment with liquid electrolyte, and the lithium metal negative electrode is a key technology for developing a lithium metal secondary battery.
Current lithium metal protection schemes include: the physical protective layer is formed on the surface of the lithium metal, so that the layer is not easy to damage when the dendrite grows, and the mechanical protection effect is achieved; through regulation and control of the electrolyte formula, a solid electrolyte intermediate phase with good lithium ion conductivity and electronic insulation is formed on the surface of lithium metal, so that supply and demand balance of lithium ions is realized in the deposition process of lithium, and formation of dendritic crystals is avoided; the uniformity of electron distribution is improved, the local current density on the surface of the electrode is reduced, and the deposition overpotential is reduced through the three-dimensional current collector.
CN109244370A discloses a method for preparing a secondary lithium metal battery cathode vapor protective film, which generates a protective film by heating a precursor and a solvent to react on the surface of a lithium material, and the obtained lithium cathode surface has high ion conductivity and chemical stability, and can improve the growth of lithium dendrite. However, the patent limits reactants, mainly comprises iodine simple substance and carbon disulfide solvent, and the generated surface protective layer has a single component structure, mainly comprises LiI, and has a limited effect of inhibiting lithium dendrite; the reaction conditions are strictly limited, the operation needs to be carried out in a closed environment, and the industrial application is not easy.
CN111293299A discloses a modified metal lithium negative electrode battery and a preparation method thereof, and the invention provides a method for improving the stability of a lithium metal negative electrode by obtaining a lithium acetate passive film through the reaction of acetic acid steam and lithium, so that the growth of lithium dendrites is inhibited. The protection effect generated by the method is completely based on the in-situ reaction of lithium acetate on the surface of lithium metal, but the lithium acetate has poor stability in the air, so the method still has severe limitation on the preparation conditions, needs to be operated in a glove box, and limits the amplification feasibility of the process; lithium acetate itself has very low ionic conductivity (10) -9 S cm -1 ) The interface impedance of the negative electrode can be increased, the polarization of the battery is increased, and the performance of the battery is not favorably improved.
Therefore, it is required to develop a simple and easy-to-apply method for preparing a lithium metal negative electrode protective layer.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: although the Li metal negative electrode has the advantages of high energy density and low potential, dendritic crystal growth due to local electron concentration is easy to occur, side reaction is caused, electrolyte loss and battery capacity attenuation are caused, a protective film needs to be formed on the surface of the Li metal negative electrode to inhibit dendritic crystal growth, and the existing protective layer forming process conditions are harsh and are not easy to apply industrially.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a preparation method of a lithium metal negative electrode protection layer, which is simple in preparation method, free of inert atmosphere and easy for industrial application, and the prepared protection layer has controllable components and structure, can effectively inhibit dendritic crystal growth, reduces side reactions between subsequent lithium and a solvent after contacting with an electrolyte, and achieves the effect of controlling a solid electrolyte mesophase on the surface of a metal lithium negative electrode.
The preparation method of the lithium metal negative electrode protection layer according to the embodiment of the invention comprises the following steps:
a. placing lithium metal in a reactor, the reactor being provided with a gas inlet and a gas outlet;
b. introducing a first gas and a second gas into the reactor, and reacting with lithium metal to generate a protective layer;
wherein the first gas is selected from N 2 、CO 2 Or O 2 At least one of water vapor or alcohol vapor.
According to the advantages and technical effects brought by the preparation method of the lithium metal negative electrode protection layer, 1, in the embodiment of the invention, a first gas with low reactivity with lithium and a second gas with high reactivity with lithium are introduced in the reaction process to react with the lithium metal, the reaction between the lithium metal and the gas is promoted by utilizing the synergistic effect between the two gases, the second gas with reactivity with lithium is taken as an accelerant, the reaction between the lithium and the low-activity first gas is accelerated, a protection layer with controllable components and thickness is formed on the surface of the lithium metal, the subsequent side reaction between the lithium and an electrolyte is effectively inhibited, the components of an intermediate phase of a solid electrolyte are regulated, and the effect of inhibiting the growth of lithium dendrites is realized; 2. according to the method provided by the embodiment of the invention, the reactant is subjected to vaporization treatment, and the chemical reaction between lithium metal and the reactant can be more uniformly generated in a gas phase reaction mode; 3. the method provided by the embodiment of the invention adopts a gas phase reaction, can realize effective control, has strong operability, does not need an inert atmosphere environment, has a simple process and low requirement on the environment, is beneficial to industrial application, and has a wide prospect.
In some embodiments, the alcohol has a carbon number of from C1 to C12, and preferably, the alcohol has a carbon number of from C2 to C5.
In some embodiments, the volumetric flow ratio of the first gas to the second gas is 1.
In some embodiments, the volumetric flow ratio of the first gas to the second gas is 1.
In some embodiments, the protective layer is made to a thickness of 50nm to 5 μm.
In some embodiments, in step b, the reaction time is 20 to 60min.
In some embodiments, in step a, the reactor is placed in a drying chamber, the humidity of the drying chamber is 0.4% to 0.6%, where the percentage refers to volume percentage.
In some embodiments, in step a, the ambient temperature of the reactor is 20-35 ℃.
The embodiment of the invention also provides a lithium metal negative electrode protective layer which is prepared by the method provided by the embodiment of the invention. The lithium metal negative electrode protection layer provided by the embodiment of the invention can effectively inhibit the growth of lithium dendrites, has all the advantages brought by the preparation method of the lithium metal negative electrode protection layer provided by the embodiment of the invention, and is not described again.
The embodiment of the invention also provides a lithium battery which comprises the lithium metal negative electrode protective layer. The lithium battery provided by the embodiment of the invention has all the advantages brought by the lithium metal negative electrode protection layer provided by the embodiment of the invention, and details are not repeated herein.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The preparation method of the lithium metal negative electrode protective layer according to the embodiment of the invention comprises the following steps:
a. placing lithium metal in a reactor, the reactor being provided with a gas inlet and a gas outlet;
b. introducing a first gas and a second gas into the reactor, and reacting with lithium metal to generate a protective layer;
wherein the first gas is selected from N 2 、CO 2 Or O 2 The second gas is at least one selected from water vapor or alcohol vapor, the alcohol vapor may be monohydric alcohol or polyhydric alcohol, and the number of carbon atoms of the alcohol is C1-C12, preferably C1-C5.
The reaction involved in the method of the embodiment of the present invention is as follows:
a second gas reaction equation:
2Li+2H 2 O-->2LiOH+H 2
2Li+2ROH→2LiOR+H 2 wherein R is alkyl;
reacting the second gas with Li metal to form a protective layer structure with pores;
the first gas reaction formula:
2Li+O 2 -->2Li 2 O
6Li+N 2 -->2Li 3 N
2LiOH+CO 2 -->Li 2 CO 3 +H 2 O
2LiOR+CO 2 -->Li 2 CO 3 +ROR
according to the preparation method of the lithium metal negative electrode protection layer provided by the embodiment of the invention, the first gas with lower reactivity with lithium and the second gas with higher reactivity with lithium are introduced to react with lithium metal in the reaction process, and the first gas and the second gas are utilized to react with lithiumThe synergistic effect between the two gases promotes the reaction between the lithium metal and the gases. The second gas has high reactivity to lithium and can rapidly corrode the surface of lithium metal, so that the reaction area between lithium and the first gas is increased, the reaction process between lithium and the first gas is promoted, and CO is adopted 2 When the first gas is used, the reaction process of the second gas is that lithium reacts with the first gas CO 2 The second gas with reactivity to lithium is used as an accelerant, the reaction between the lithium and the first gas with low activity is accelerated, a protective layer with controllable components and thickness is formed on the surface of the lithium metal, the side reaction between the subsequent lithium and the electrolyte is effectively inhibited, the components of the intermediate phase of the solid electrolyte are regulated, and the effect of inhibiting the growth of lithium dendrites is realized. According to the method provided by the embodiment of the invention, the reactant is subjected to vaporization treatment, and the chemical reaction between lithium metal and the reactant can be more uniformly generated in a gas phase reaction mode. The method provided by the embodiment of the invention adopts a gas phase reaction, can realize effective control, has strong operability, does not need an inert atmosphere environment, has a simple process and lower requirements on the environment, is beneficial to industrial application, and has wide prospects.
In some embodiments, the volumetric flow ratio of the first gas to the second gas is 1. In the embodiment of the invention, the flow ratio between the first gas and the second gas is preferably selected, if the second gas is too much, the protective layer formed by the second gas is too thick, which is not beneficial to the reaction between the first gas and lithium and influences the optimization of the components of the protective layer, and if the dosage of the second gas is too little, the corrosion area on the surface of lithium metal is not enough, and the promotion effect on the reaction between the first gas and the lithium metal cannot be exerted.
In some embodiments, the resulting protective layer is 50nm-5 μm thick, such as 50nm, 100nm, 500nm, 1um, 2um, 3um, 4um, 5um, and the like. In the method of the embodiment of the invention, the thickness of the protective layer is optimized, if the protective layer is too thin, the growth of the lithium dendrite cannot be effectively inhibited, the protection effect is poor, and if the formed protective layer is too thick, the impedance of the lithium battery is too large.
In some embodiments, in step a, the reactor is placed in a drying chamber, preferably, the humidity of the drying chamber is 0.4% to 0.6%; the ambient temperature of the reactor is 20-35 ℃, such as 20 ℃, 25 ℃, 30 ℃, 35 ℃ and the like; in the step b, the reaction time is 20-60min, such as 20min, 30min, 40min, 50min, 60min and the like. According to the method provided by the embodiment of the invention, the reactor is placed in the drying room for reaction, so that the influence of humidity on lithium metal can be controlled, the quantitative reaction of the second gas and lithium is effectively ensured, and the structure of the protective layer is further optimized.
The embodiment of the invention also provides a lithium metal negative electrode protective layer which is prepared by the method provided by the embodiment of the invention. The lithium metal negative electrode protection layer provided by the embodiment of the invention can effectively inhibit the growth of lithium dendrites, has all the advantages brought by the preparation method of the lithium metal negative electrode protection layer provided by the embodiment of the invention, and is not described again.
The embodiment of the invention also provides a lithium battery which comprises the lithium metal negative electrode protective layer. The lithium battery provided by the embodiment of the invention has all the advantages brought by the lithium metal negative electrode protection layer provided by the embodiment of the invention, and details are not repeated herein.
The present invention will be described in detail with reference to examples.
Example 1
30 x 30cm was placed in a drying chamber with a humidity of 0.5% (referring to the volume percentage of water vapor in the air) 3 The box reactor, the box reactor sets up an air inlet and a gas outlet, places steam generator in air inlet department, and to the gaseous reactant direct aeration entering box reactor that is the normal temperature, to the liquid reactant that is the normal temperature, through the mode production steam entering box of heating, gas gets into the reactor through the air inlet, through gas outlet discharge reactor. The environmental temperature in the reaction process is controlled to be 20-35 ℃.
Ventilating the box reactor before reaction, and controlling the first gas CO 2 Gas flow rate of 1L/min, second gas H 2 O steam flow of 0.1L/min, ventilating for 15min, cutting lithium metal foil into 10 x 10cm 2 The shape of the lithium ion battery is that the lithium ion battery is placed in the center of the reactor, and after the first gas and the second gas are continuously introduced to react for 30min, a protective layer is formed on the surface of the lithium metal foil, wherein the thickness of the protective layer is 200nm.
The lithium metal foil with the protective layer prepared in the embodiment is transferred into a glove box, a disc with the diameter of 12mm is punched, the lithium foil disc is used as an anode and a cathode to assemble a symmetrical battery, and 60 mu L of electrolyte (1M LiPF) 6 EC/DMC/DEC (1 -2 The lithium deposition capacity was controlled to 1mAh cm -2 . After 100 weeks of cycling, the average value of the over-potential of lithium deposition of the battery is 60mV, and no short circuit phenomenon occurs.
Example 2
The same process as in example 1, except that the first gas CO 2 The flow rate of the gas is 1L/min, and the second gas H 2 The O steam flow rate is 0.5L/min.
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of the lithium deposition overpotential of the battery was 80mV, and no short circuit occurred.
Example 3
The same procedure as in example 1, except that the first gas was N 2 ，
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of over-potential for lithium deposition of the battery was 100mV, and no short circuit occurred.
Example 4
The same procedure as in example 1 was followed, except that the second gas was ethanol vapor.
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of the overpotential for lithium deposition of the battery was 115mV, and no short circuit occurred.
Example 5
The same procedure as in example 1, except that the first gas was O 2 。
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of lithium deposition overpotential of the battery was 90mV, and no short circuit occurred.
Example 6
The same procedure as in example 1, except that the first gas was N 2 And the second gas is ethanol vapor.
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of over-potential for lithium deposition of the battery was 100mV, and no short circuit occurred.
Example 7
The same procedure as in example 1, except that the first gas was O 2 And the second gas is ethanol vapor.
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of lithium deposition overpotential of the battery was 120mV, and no short circuit occurred.
Example 8
The same procedure as in example 1, except that the first gas was O 2 And the second gas is ethylene glycol vapor.
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of lithium deposition overpotential of the battery was 130mV, and no short circuit occurred.
Comparative example 1
Punching lithium metal foil without protective layer into 12mm diameter disc, assembling into symmetrical battery with the lithium foil disc as positive and negative electrodes, adding 60 μ L electrolyte (1M LiPF) 6 EC/DMC/DEC (1 -2 The lithium deposition capacity was controlled to 1mAh cm -2 . After 40 cycles, the average over-potential for lithium deposition of the cell was 200mV and a short circuit occurred.
Comparative example 2
The same procedure as in example 1, except that CO was introduced as the first gas only 2 The flow rate of the gas was controlled to 1.1L/min.
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of the overpotential for lithium deposition of the battery was 190mV, and short-circuiting occurred.
Comparative example 3
The same process as in example 1, except that the first gas CO 2 The flow rate of the gas is 1L/min, and the second gas H 2 The O steam flow is 0.04L/min.
The test was carried out in the same manner as in example 1, and after 100 cycles, the average value of lithium deposition overpotential of the battery was 160mV, and short circuit occurred.
In the embodiments 1-8 of the present invention, the first gas and the second gas are reacted with lithium metal to form the protective layer, so that the growth of lithium dendrites is effectively inhibited, the overpotential for lithium deposition of the battery can be controlled at a low level after 100 cycles, and short circuit does not occur. Especially, in example 1, the overpotential can be controlled to 60mv after 100 cycles by using the water vapor as the second gas, because the water vapor has higher reactivity than the alcohol vapor and has better promoting effect on the subsequent reaction of the first gas with Li. In comparative example 1, no protective layer was formed on the surface of the lithium metal, the overpotential for lithium deposition of the battery was 200mV and short circuit occurred after 40 cycles, and in comparative example 2, the second gas, water vapor, was not introduced, and only the first gas, CO, was used without the promoter due to the lower activity of the first gas 2 An effective protective layer cannot be formed, a short circuit phenomenon occurs, and after 100 cycles, the lithium deposition overpotential of the battery reaches 190mV. Therefore, in the embodiment of the invention, the second gas with higher activity is introduced in the reaction process, so that the reaction between the first gas and Li is effectively promoted, an effective protective layer is formed on the surface of lithium metal, and the growth of lithium dendrite is inhibited.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a lithium metal negative electrode protection layer is characterized by comprising the following steps:
a. placing lithium metal in a reactor, the reactor being provided with a gas inlet and a gas outlet;
b. introducing a first gas and a second gas into the reactor, and reacting with lithium metal to generate a protective layer;
wherein the first gas is selected from N 2 、CO 2 Or O 2 Is selected from at least one of water vapor or alcohol vapor.
2. The method for preparing a lithium metal negative electrode protective layer according to claim 1, wherein the number of carbon atoms of the alcohol is C1 to C12, and preferably, the number of carbon atoms of the alcohol is C2 to C5.
3. The method for preparing a lithium metal negative electrode protective layer according to claim 1, wherein the volume flow ratio of the first gas to the second gas is 1.
4. The method for producing a lithium metal negative electrode protective layer according to claim 3, wherein a volume flow ratio of the first gas to the second gas is 1.
5. The method of claim 1, wherein the thickness of the protective layer is 50nm to 5 μm.
6. The method for preparing the lithium metal negative electrode protective layer according to claim 1, wherein the reaction time in the step b is 20 to 60min.
7. The method for preparing the lithium metal negative electrode protective layer according to claim 1, wherein in the step a, the reactor is placed in a drying room, and the humidity of the drying room is 0.4-0.6%.
8. The method for preparing a lithium metal anode protective layer according to claim 1, wherein the ambient temperature of the reactor in the step a is 20 to 35 ℃.
9. A lithium metal negative electrode protective layer, characterized in that it is obtained by the method according to any one of claims 1 to 8.
10. A lithium battery comprising the lithium metal negative electrode protective layer of claim 9.
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