CN114583108A - Lithium alloy negative electrode film, preparation method thereof and secondary lithium metal battery - Google Patents
Lithium alloy negative electrode film, preparation method thereof and secondary lithium metal battery Download PDFInfo
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- CN114583108A CN114583108A CN202210162398.3A CN202210162398A CN114583108A CN 114583108 A CN114583108 A CN 114583108A CN 202210162398 A CN202210162398 A CN 202210162398A CN 114583108 A CN114583108 A CN 114583108A
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- 229910000733 Li alloy Inorganic materials 0.000 title claims abstract description 92
- 239000001989 lithium alloy Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011888 foil Substances 0.000 claims abstract description 83
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- 238000000034 method Methods 0.000 claims abstract description 41
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
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- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052787 antimony Inorganic materials 0.000 claims description 2
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052732 germanium Inorganic materials 0.000 claims description 2
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 34
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
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- 239000000203 mixture Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
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- 238000013112 stability test Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910008405 Li-Zn Inorganic materials 0.000 description 2
- 229910007049 Li—Zn Inorganic materials 0.000 description 2
- 229910000979 O alloy Inorganic materials 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- -1 cobalt nitride Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
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- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
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- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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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
- H01M4/134—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium alloy negative electrode film, a preparation method thereof and a secondary lithium metal battery, wherein the lithium alloy negative electrode film comprises a base foil and an alloy film layer arranged on the base foil, the components of the alloy film layer at least comprise lithium metal and M material, the M material is metal or inorganic nonmetal, and the mass ratio of the M material to the lithium metal is (0.01-50): 100. the lithium alloy negative electrode film prepared by the method is flat and smooth, has no wrinkle defect and burr, has better electrochemical performance, and can remarkably improve the cycle performance of a lithium metal battery; the improved preparation method is simple, safe and efficient, is easy to realize large-scale production, and can be used for liquid, semi-solid, quasi-solid and all-solid lithium metal batteries.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a lithium alloy negative electrode film, a preparation method thereof and a secondary lithium metal battery.
Background
In recent years, electric vehicles and 3C electronic devices have been rapidly developed, and a higher requirement is placed on the energy density of a battery, and lithium metal has a theoretical specific capacity of 3860mAh/g and an extremely low oxidation-reduction potential (-3.045V vs. nhe), so that the lithium metal directly attracts a wide attention of researchers as a negative electrode material. However, the lithium metal negative electrode is subjected to non-uniform deposition-dissolution in the charging and discharging process, so that the lithium dendrite grows uncontrollably, the lithium dendrite reacts with an electrolyte to consume the electrolyte, and a diaphragm is easy to pierce, so that the battery is short-circuited.
At present, researchers utilize different process methods to prepare lithium alloy cathodes to inhibit the growth of lithium dendrites, Yongming Sun et al prepare tin-copper composite belts by sputtering tin layers on bare copper foils by a magnetron sputtering technology, and then uniformly coat lithium metal liquid on the tin-copper composite belts by a coating technology to prepare ultrathin Li-Sn electrodes. However, the magnetron sputtering conditions are harsh and the process is complex, which is not suitable for industrial production. The method needs to use lithium metal liquid transfer coating, and is not beneficial to the large-scale production of the thin film electrode. Some companies prepare the lithium metal negative electrode material by laser welding the current collector and the lithium metal, the preparation process of the method has high requirement, and the laser welding is not beneficial to electron transfer between the lithium metal and the current collector. In other companies, metal lithium is deposited on a current collector by using an electroplating method, and serious problems that metal distribution is uneven, part of burrs occur on the surface of a film and the like easily occur when the film is prepared by using the electroplating method.
The magnetron sputtering process has high requirement, the preparation process is complex and is not beneficial to industrialization, the safety problem of the transfer step of the molten transfer alloy liquid has high requirement, the steps are complicated, and the large-scale production is not facilitated. The electroplating method easily causes the problems of uneven metal distribution, burrs on the surface of the film and the like. At present, commercial lithium metal films are mainly rolled, but lithium metal is soft and easily generates wrinkle defects after rolling, so that the electrochemical performance of the lithium metal films is influenced. Therefore, it is important to develop a method that will not cause wrinkle defect and burr of the lithium alloy negative electrode film, and the preparation method should ensure the excellent cycle performance of the prepared lithium metal battery.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the lithium alloy negative electrode film, the preparation method thereof and the secondary lithium metal battery.
The method is realized by the following technical scheme:
the lithium alloy negative electrode film comprises a base foil and an alloy film layer arranged on the base foil, wherein the alloy film layer at least comprises lithium metal and an M material, the M material is metal or inorganic nonmetal, and the mass ratio of the M material to the lithium metal is (0.01-50): 100, if the mass ratio of the M material to the lithium metal is lower than the range, the significance for improving the performance of the lithium negative electrode film is avoided; if the mass ratio of the M material to the lithium metal is higher than this range, the content of active lithium metal is too low, which affects the specific capacity of the lithium alloy negative electrode thin film.
Further, the M material is one or more of elementary sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, vanadium, chromium, iron, cobalt, nickel, copper, zinc, tin, boron, aluminum, gallium, indium, silver, germanium, lead, antimony, bismuth, and fluoride, chloride, bromide, iodide, sulfide and oxide of the above elementary substances.
Further, the base foil is copper foil, aluminum foil, stainless steel foil, polyimide film, carbon-coated copper foil, carbon-coated aluminum foil, carbon-coated stainless steel foil, carbon-coated polyimide film, graphene film or carbon fiber film, copper foam, nickel foam, iron foam, titanium foam, stainless steel mesh.
The invention also provides a preparation method of the lithium alloy negative electrode film, which comprises the following steps:
preparing a lithium metal alloy liquid, coating the lithium metal alloy liquid on the substrate foil, and then curing and rolling to obtain a lithium alloy negative electrode film;
the cloth moving speed of the base foil is 0.1 cm-10 m/min, so that cracking or bubbles caused by too fast moving can be prevented, and the uniformity and compactness of a formed film are controlled; the step of preparing the lithium metal alloy liquid comprises the steps of placing lithium metal and an M material in a trough, wherein the heating temperature in the trough is 200-600 ℃, the rotating speed of a mechanical stirrer in the trough is 1-10000 r/min, and the stirring time is 1-10 hours.
Specifically, the curing is carried out through 1-10 levels of air-blast drying ovens, and the temperature in each level of drying oven is 30-300 ℃.
Specifically, the rolling rate during rolling is 0.1% -60%, the density of the lithium alloy negative electrode film can be further ensured through rolling, and different densities can be controlled through different rolling rates. The more compact the lithium alloy negative electrode film is, the more favorable the deposition of lithium ions is, the more favorable the internal conduction of the film is, and the specific capacity of the lithium alloy negative electrode film is improved.
Further, a doctor blade coating method is adopted, and the method comprises the following specific steps:
under the conditions of an environment dew point temperature of-100-0 ℃ and a nitrogen, argon or air atmosphere, placing lithium metal and M material at a trough, heating the trough at a temperature of 200-600 ℃, heating and melting to obtain Li-M alloy liquid, wherein the rotating speed of a mechanical stirrer in the trough is 1-10000 r/min, and the stirring time is 1-10 hours. The distance between the surface of the scraper and the base foil is 0.1-1000 mu M, the heating temperature of the scraper is 200-600 ℃, and the scraper is heated to prevent the Li-M alloy liquid from being solidified on the scraper due to low temperature, so that the Li-M alloy liquid cannot be uniformly coated. The cloth moving speed of the base foil is 0.1 cm-10M/min, the Li-M alloy liquid is coated on the base foil, the temperature of a roller below a scraper is 200-600 ℃, the temperature of the roller is controlled to be 200-600 ℃, the flatness of the surface of the negative electrode film can be further ensured, the alloy liquid is prevented from being rapidly cooled and solidified to cause surface cracks, the alloy liquid is solidified through a 1-10-level blast drying box, the temperature in a drying box at each level is 30-300 ℃, the alloy liquid is rolled through a hot roller, the temperature of the hot roller is 30-300 ℃, the rolling rate is 0.1-60%, and the lithium alloy negative electrode film is prepared.
Further, according to the requirement, the Li-M alloy liquid can be coated on one side or two sides of the base foil.
Further, an extrusion coating method is adopted, and the method comprises the following specific steps:
under the conditions that the environment dew point temperature is-100-0 ℃ and a gas atmosphere exists, placing lithium metal and an M material at a material groove, heating the material groove at 200-600 ℃, heating and melting to obtain a Li-M alloy liquid, wherein the rotating speed of a mechanical stirrer in the material groove is 1-10000 r/min, the stirring time is 1 min-10 h, conveying the Li-M alloy liquid to a slit discharge port through extrusion by utilizing the rotation of a screw, coating the Li-M alloy liquid on a base foil material, the temperature of a first roller after coating is 200-600 ℃, solidifying the Li-M alloy liquid through a 1-10-grade blast drying box, the temperature in each grade of drying boxes is 30-300 ℃, rolling is carried out through a hot roller, the temperature of the hot roller is 30-300 ℃, and the rolling rate is 0.1-60%, and obtaining a lithium alloy negative electrode film;
wherein the rotating speed of the screw is 1-10000 r/min, the gap of the slit discharge port is 1-1000 μm, the vertical distance between the slit discharge port and the foil is 1-10000 μm, and the heating temperature of the screw motion area and the slit discharge port is 200-600 ℃.
Further, the gas atmosphere is air, nitrogen or argon. Meanwhile, the environmental dew point temperature is-100-0 ℃, and the higher the dew point temperature is, the higher the water vapor content in the air is, the more humid the air is, and on the contrary, the drier the air is, so the high and low dew point temperature can indicate the humidity degree of the air. The dew point temperature is also specified to ensure that the coating of lithium metal can be carried out under such conditions, and the ambient atmosphere does not chemically react with the lithium metal.
Further, according to the requirement, the Li-M alloy liquid can be coated on one side or two sides of the base foil.
The roll nip in the present invention is: (thickness difference before and after rolling divided by thickness before rolling). times.100%.
The invention also provides a secondary lithium metal battery which comprises the lithium alloy negative electrode film.
Further, the secondary lithium metal battery may be a liquid lithium metal battery, a semi-solid lithium metal battery, a quasi-solid lithium metal battery, or a solid lithium metal battery.
Has the advantages that:
according to the invention, the M material is introduced into the lithium metal liquid, the M material can obviously reduce the contact angle between the lithium alloy liquid and the surface of the substrate, and the formed Li-M alloy liquid has good wetting property on the substrate material, so that the coating uniformity and continuity of the alloy film are facilitated.
The lithium alloy negative electrode film is successfully prepared by a simple scraper coating technology and an extrusion coating method, the preparation scheme is simple, safe and efficient, the problems of high process requirements, complex steps and the like of the existing method can be avoided, and the large-scale production of the lithium alloy film is facilitated. Meanwhile, the lithium alloy negative electrode film prepared by the two methods cannot cause problems of wrinkle defects, burrs and the like in the rolling process, so that the lithium alloy film electrode prepared by the method has faster lithium ion transportation and a more stable interface. The alloy components can ensure uniform and compact deposition of lithium metal, reduce side reactions of the lithium metal and electrolyte, improve the coulombic efficiency of the secondary lithium metal battery, reduce the volume expansion of the secondary lithium metal battery in the charging and discharging processes, and further improve the cycle performance of the battery; inhibit the growth of lithium dendrites and improve the cycle performance and safety of the lithium metal battery. The preparation method of the lithium alloy cathode material provided by the invention is simple and efficient, is easy to realize large-scale production, and provides important technical guidance for commercial application of the lithium metal cathode material.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing a lithium alloy negative electrode film according to the present invention;
FIG. 2 is a schematic diagram of a doctor blade process for preparing a lithium alloy negative electrode film;
FIG. 3 is a schematic diagram of a lithium alloy negative electrode film prepared by an extrusion coating method;
FIG. 4 is a limit current density test of a symmetrical cell in a liquid lithium battery system of example 1;
FIG. 5 is a limit current density test of a symmetrical cell in a liquid lithium battery system of example 2;
FIG. 6 is a limit current density test of a symmetrical cell in a liquid lithium battery system of example 3;
FIG. 7 shows the current density of 1mA cm for a symmetrical cell in a liquid lithium battery system of example 1-2Testing the lower cycle stability;
FIG. 8 shows the current density of 1mA cm for a symmetrical cell in a liquid lithium battery system of example 2-2Testing the lower cycle stability;
FIG. 9 shows the current density of 1mA cm for a symmetrical cell in a liquid lithium battery system of example 3-2Testing the lower cycle stability;
FIG. 10 shows the current density of 1mA cm for a symmetrical cell in a liquid lithium battery system of example 6-2Testing the lower cycle stability;
FIG. 11 is a scanning electron microscope image of the thin film electrode prepared in example 1 before cycling;
FIG. 12 shows the current density of 1mA cm for a symmetrical cell in a liquid lithium battery system of example 1-2Scanning electron microscopy after a lower cycle of 100 cycles;
fig. 13 is a cycle stability test of example 1 in a Li | | | NCM622 full cell application in a liquid lithium battery system.
Reference numerals are as follows:
1-a base foil; 2-Li-M alloy liquid; 3-a scraper; 4-a trough; 5-drying oven; 6-roller; 7-extruding machine; 8-hot rolling; 9-a valve; 10-lithium alloy negative electrode film.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Comparative examples
a) Taking 0.0045g of metal lithium, and melting the metal lithium in a trough for 30 minutes at 300 ℃ to obtain lithium metal liquid;
b) uniformly coating lithium metal liquid on the surface of copper foil by using a scraper to prepare a lithium metal negative electrode film;
c) and (3) taking the lithium metal negative electrode film to carry out material characterization and liquid battery assembly test.
Example 1 (blade coating method)
The utility model provides a lithium alloy negative pole film, includes the base foil to and set up the alloy rete on the base foil, the base foil is the copper foil, and the composition of alloy rete includes lithium metal, aluminium metal and calcium fluoride powder, and its mass ratio is 20: 1: 1.
fig. 1 is a schematic flow diagram of a preparation method provided by the invention, and fig. 2 is a schematic diagram of a lithium alloy negative electrode film prepared by a doctor blade coating method, wherein a trough (4) is provided with a valve (9), the flow of a Li-M alloy liquid is controlled by controlling the valve (9), a doctor blade (3) is positioned above a roller (6), a base foil (1) is contacted with the Li-M alloy liquid (2) in the trough (4) by the rotation of the roller (6), then the base foil contacted with the Li-M alloy liquid is conveyed to the doctor blade (3), the doctor blade (3) uniformly coats the Li-M alloy liquid (2) on the base foil (1), and then the Li-M alloy liquid is solidified by an oven (5) and rolled by a hot roller (8), so as to obtain the lithium alloy negative electrode film (10).
The preparation method comprises the following steps:
a) the environmental dew point temperature is-50 ℃, and the protective gas is argon;
b) placing 0.1g of metallic lithium, 0.005g of aluminum particles and 0.005g of calcium fluoride powder at a material groove, setting the heating temperature in the material groove to be 300 ℃, setting the rotating speed of a mechanical stirrer in the material groove to be 4000 revolutions per minute and stirring for 1 hour to form Li-Al-CaF2Alloy liquid A;
c) adjusting the distance between the surface of the scraper and the copper foil to be 50 mu m, setting the heating temperature of the scraper to be 270 ℃, and setting the temperature of a roller below the scraper to be 300 ℃;
d) setting the cloth-moving speed of the copper foil of the substrate foil to be 1 m/min, and enabling the copper foil to uniformly contact Li-Al-CaF2Coating the single side of the alloy liquid A by a scraper to obtain a lithium alloy film B;
e) passing the coated lithium alloy film B through a first roller at the temperature of 200 ℃ to obtain a film C;
f) then, the film C passes through a 5-stage blast drying oven, and the temperature in each stage of drying oven is set to be 60 ℃, so that a film D is obtained;
g) and rolling the film D through a hot roller, wherein the temperature of the hot roller is 100 ℃, and the rolling rate is 30%, so that the lithium alloy negative electrode film is obtained.
Example 2 (blade coating method)
The utility model provides a lithium alloy negative pole film, includes the base foil to and set up the alloy rete on the base foil, the base foil is the copper foil, and the composition of alloy rete includes lithium metal, silver metal and cuprous chloride, and its mass ratio is 20: 1: 1.
the preparation method comprises the following steps:
a) the environmental dew point temperature is-25 ℃, and the protective gas is argon;
b) placing 0.1g of metal lithium, 0.005g of silver and 0.005g of cuprous chloride powder at a trough, setting the heating temperature in the trough to be 350 ℃, setting the rotating speed of a mechanical stirrer in the trough to be 4000 revolutions per minute, and stirring for 1 hour to form Li-Ag-CuCl alloy liquid A;
c) adjusting the distance between the surface of the scraper and the copper foil to be 100 mu m, setting the heating temperature of the scraper to be 300 ℃, and setting the temperature of a roller below the scraper to be 350 ℃;
d) setting the cloth feeding speed of the substrate copper foil to be 5 m/min, enabling the copper foil to uniformly contact the Li-Ag-CuCl alloy liquid A, and obtaining a lithium alloy film B after single-side coating by a scraper;
e) passing the coated lithium alloy film B through a first roller at the temperature of 230 ℃ to obtain a film C;
f) then, the film C passes through a 5-stage blast drying oven, and the temperature in each stage of drying oven is set to be 50 ℃, so that a film D is obtained;
g) and rolling the film D through a hot roller, wherein the temperature of the hot roller is 30 ℃, and the rolling rate is 10%, so that the lithium alloy negative electrode film is obtained.
Example 3 (extrusion coating method)
The utility model provides a lithium alloy negative pole film, includes the base foil to and set up the alloy rete on the base foil, the base foil is carbon-coated stainless steel foil, and the composition of alloy rete includes lithium metal and potassium bromide, and the mass ratio is 5: 1.
referring to fig. 3, fig. 3 is a schematic diagram of a lithium alloy negative electrode film prepared by an extrusion coating method, a material tank (4) is provided with a valve (9), the flow of a Li-M alloy liquid is controlled by controlling the valve (9), the Li-M alloy liquid is coated on a base foil (1) by an extruder (7), and then the Li-M alloy liquid passes through a roller (6), is solidified by an oven (5) and is rolled by a hot roller (8), and the lithium alloy negative electrode film (10) is obtained.
The preparation method comprises the following steps:
a) the environment dew point temperature is-15 ℃, and the gas atmosphere is air;
b) placing 0.1g of lithium metal and 0.02g of potassium bromide powder at a trough, setting the heating temperature in the trough to be 350 ℃, setting the rotating speed of a mechanical stirrer in the trough to be 4000 revolutions per minute, and stirring for 1 hour to form Li-KBr alloy liquid A;
c) setting the rotating speed of a screw of an extruder to be 3000 r/min, setting the gap of an extrusion slit to be 10 μm, setting the vertical distance between a slit discharge port and the carbon-coated stainless steel foil to be 200 μm, setting the heating temperature of a screw movement area and the slit discharge port to be 400 ℃, setting the cloth feeding speed of the carbon-coated stainless steel foil to be 1 m/min, conveying Li-KBr alloy liquid A to the discharge slit through extrusion by utilizing the rotation of the screw, and uniformly coating the single surface of the Li-KBr alloy liquid A on the carbon-coated stainless steel foil to obtain a lithium alloy film B;
d) passing the coated lithium alloy film B through a first roller at the temperature of 230 ℃ to obtain a film C;
e) then, the film C passes through a 10-stage blast drying oven, and the temperature in each stage of drying oven is set to be 80 ℃, so that a film D is obtained;
f) and rolling the film D through a hot roller, wherein the temperature of the hot roller is 50 ℃, and the rolling rate is 30%, so that the lithium alloy negative electrode film is obtained.
Example 4 (extrusion coating method)
The utility model provides a lithium alloy negative pole film, includes the base foil to and set up the alloy rete on the base foil, the base foil is carbon-coated stainless steel foil, and the composition of alloy rete includes lithium metal and iron iodide, and its mass ratio is 4: 1.
the preparation method comprises the following steps:
a) the environmental dew point temperature is-35 ℃, and the protective gas is argon;
b) placing 0.1g of lithium metal and 0.025g of ferric iodide at a trough, setting the heating temperature in the trough to be 400 ℃, setting the rotating speed of a mechanical stirrer in the trough to be 4000 revolutions per minute, and stirring for 1 hour to form Li-FeI3Alloy liquid A;
c) setting the rotation speed of a screw of an extruder at 1000 rpm, extruding a slit at 5 μm, setting the vertical distance between a slit discharge port and the carbon-coated stainless steel foil at 40 μm, the heating temperature of a screw motion area and the slit discharge port at 300 ℃, setting the cloth-moving speed of the carbon-coated stainless steel foil at 5 m/min, and rotating the screw to drive Li-FeI3Conveying the alloy liquid A to a discharging slit through extrusion, and uniformly coating one side of the alloy liquid A on a carbon-coated stainless steel foil to obtain a lithium alloy film B;
d) passing the coated lithium alloy film B through a first roller at the temperature of 300 ℃ to obtain a film C;
e) then, the film C passes through a 5-stage blast drying oven, and the temperature in each stage of drying oven is set to be 100 ℃, so that a film D is obtained;
f) and rolling the film D through a hot roller, wherein the temperature of the hot roller is 80 ℃, and the rolling rate is 10%, so that the lithium alloy negative electrode film is obtained.
Example 5 (extrusion coating method)
The lithium alloy negative electrode film comprises a base foil and an alloy film layer arranged on the base foil, wherein the base foil is a carbon-coated stainless steel foil, the alloy film layer comprises lithium metal and zinc metal, and the mass ratio of the lithium metal to the zinc metal is 10: 3.
the preparation method comprises the following steps:
a) the environment dew point temperature is-20 ℃, and the gas atmosphere is air;
b) placing 0.1g of metallic lithium and 0.03g of zinc particles at a trough, setting the heating temperature in the trough to be 350 ℃, setting the rotating speed of a mechanical stirrer in the trough to be 4000 revolutions per minute, and stirring for 1 hour to form Li-Zn alloy liquid A;
c) setting the rotating speed of a screw of an extruder at 5000 revolutions per minute, setting the gap of an extrusion slit at 30 micrometers, setting the vertical distance between a slit discharge port and a base foil at 40 micrometers, heating the heating temperature of a screw moving area and the slit discharge port at 500 ℃, setting the cloth feeding speed of the base foil at 8 m/minute, and conveying the Li-Zn alloy liquid A to the discharge slit by extrusion through the rotation of the screw to uniformly coat the single surface of the discharge slit on the carbon-coated stainless steel foil to obtain a lithium alloy film B;
d) passing the coated lithium alloy film B through a first roller at the temperature of 400 ℃ to obtain a film C;
e) then, the film C passes through a 60-stage blast drying oven, and the temperature in each stage of drying oven is set to be 150 ℃, so that a film D is obtained;
f) and rolling the film D through a hot roller, wherein the temperature of the hot roller is 100 ℃, and the rolling rate is 25%, so that the lithium alloy negative electrode film is obtained.
Example 6 (blade coating method)
The lithium alloy negative electrode film comprises a base foil and an alloy film layer arranged on the base foil, wherein the base foil is a stainless steel foil, the alloy film layer comprises lithium metal, aluminum and lithium oxide, and the mass ratio of the lithium metal to the aluminum oxide is 20: 1: 1.
the preparation method comprises the following steps:
a) the environment dew point temperature is-50 ℃, and the gas atmosphere is argon;
b) 0.1g of metallic lithium, 0.005g of aluminum and 0.005g of lithium oxide powder are placed in a material groove, the heating temperature in the material groove is set to be 350 ℃, the rotating speed of a mechanical stirrer in the material groove is 8000 revolutions per minute, and the stirring time is 0.5 hour, so that Li-Al-Li is formed2O alloy liquid A;
c) adjusting the distance between the surface of the scraper and the stainless steel foil to be 5 mu m, setting the heating temperature of the scraper to be 270 ℃, and setting the temperature of a roller below the scraper to be 300 ℃;
d) setting the cloth-moving speed of the stainless steel foil as the base at 5 m/minThe copper foil is uniformly contacted with Li-Al-Li2Coating the single side of the O alloy liquid A by a scraper to obtain a lithium alloy film B;
e) passing the coated lithium alloy film B through a first roller at the temperature of 250 ℃ to obtain a film C;
f) then, the film C passes through a 10-stage air blast drying oven, and the temperature in each stage of drying oven is set to be 80 ℃, so that a film D is obtained;
g) and rolling the lithium alloy film D through a hot roller, wherein the temperature of the hot roller is 50 ℃, and the rolling rate is 20%, so that the lithium alloy negative electrode film is obtained.
Example 7 (blade coating method)
The utility model provides a lithium alloy negative pole film, includes the base foil to and set up the alloy rete on the base foil, the base foil is the carbon fiber foil, and the composition of alloy rete includes lithium metal and sodium chloride, and its mass ratio is 10: 1.
the preparation method comprises the following steps:
a) the environment dew point temperature is 0 ℃, and the gas atmosphere is argon;
b) placing 0.1g of metal lithium and 0.01g of sodium chloride powder at a trough, setting the heating temperature in the trough to be 150 ℃, setting the rotating speed of a mechanical stirrer in the trough to be 2000 r/min, and stirring for 3 hours to form Li-NaCl alloy liquid A;
c) adjusting the distance between the surface of the scraper and the carbon fiber foil to be 1000 mu m, setting the heating temperature of the scraper to be 200 ℃, and setting the temperature of a roller below the scraper to be 300 ℃;
d) setting the cloth feeding speed of the substrate carbon fiber foil to be 1 cm/min, enabling the copper foil to uniformly contact the alloy liquid A, and coating the single side of the alloy liquid A by a scraper to obtain a lithium alloy film B;
e) passing the coated lithium alloy film B through a first roller at the temperature of 200 ℃ to obtain a film C;
f) then, the film C passes through a 2-stage blast drying oven, and the temperature in each stage of drying oven is set to be 60 ℃, so that a film D is obtained;
g) and rolling the film D through a hot roller, wherein the temperature of the hot roller is 50 ℃, and the rolling rate is 10%, so that the lithium alloy negative electrode film is obtained.
Example 8 (blade coating method)
A lithium alloy negative electrode film comprises a base foil and an alloy film layer arranged on the base foil, wherein the base foil is a graphene foil, the alloy film layer comprises lithium metal and cobalt nitride metal in a mass ratio of 100: 1.
The preparation method comprises the following steps:
a) the environment dew point temperature is-60 ℃, and the gas atmosphere is argon;
b) 10g of metal lithium and 0.1g of cobalt nitride particles are placed at a trough, the heating temperature in the trough is set to be 800 ℃, the rotating speed of a mechanical stirrer in the trough is 4000 revolutions per minute, and the stirring time is 1 hour, so that the Li-Co is formed3N2Alloy liquid A;
c) adjusting the distance between the surface of the scraper and the graphene foil to be 100 mu m, setting the heating temperature of the scraper to be 300 ℃, and setting the temperature of a roller below the scraper to be 300 ℃;
d) setting the cloth feeding speed of the substrate graphene foil to be 1 m/min, enabling the copper foil to uniformly contact the alloy liquid A, and coating the single side of the alloy liquid A by a scraper to obtain a lithium alloy film B;
e) passing the coated lithium alloy film B through a first roller at the temperature of 500 ℃ to obtain a film C;
f) then, the film C passes through a 10-stage blast drying oven, and the temperature in each stage of drying oven is set to be 200 ℃, so that a film D is obtained;
g) and rolling the film D through a hot roller, wherein the temperature of the hot roller is 50 ℃, and the rolling rate is 5%, so that the lithium alloy negative electrode film is obtained.
Experimental examples Performance test
(1) Limiting current density test
The lithium alloy negative electrode films of examples 1 to 3 were subjected to a limiting current density test in a liquid lithium battery system. The test method comprises the following steps: firstly, the current density of the symmetrical battery is 0.1mA cm-2Constant current charging and discharging are sequentially carried out for 30 minutes as a cycle, and the activation is carried out by charging and discharging for 10 cycles under the current density; at a secondary current density of 0.25mA cm-2Base number, in 0.25mA cm-2Step sizes at current densities of 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 1.75, 2, respectively.0、2.25、2.5、2.75、3.0、3.25、3.5、3.75、4.0、4.25、4.5、4.75、5.0、5.25、5.5、5.75、6.0、6.25、6.5、6.75、7.0、7.25、7.5、7.75、8.0、8.25、8.5、8.75、9.0、9.25、9.5、9.75、10.0mA cm-2The charge and discharge were each carried out for 30 minutes and cycled 10 times at each current density.
FIGS. 4 to 6 show the results of the tests, and it can be seen that example 1 (Li-Al-CaF)2) The limiting current density in the liquid system is 2.25mA cm-2Example 2(Li-Ag-CuCl) in a liquid System the limiting Current Density is 2.0mA cm-2Example 3(Li-KBr) in liquid System the limiting Current Density is 2.25mA cm-2. The results show that in the comparative example, at a current density of 0.25mA cm-2In the case of the lithium alloy negative electrode thin film of examples 1 to 3, under a large current, the lithium alloy negative electrode thin film can reduce Li by rapidly increasing the polarization voltage and causing the lithium dendrites to pierce the electrolyte and the diaphragm to cause a rapid decrease in the polarization voltage and short-circuit of the battery+Thereby inducing Li+Uniform deposition, inhibiting the growth of lithium dendrites and promoting Li+Nucleation and crystallization are carried out, nucleation potential energy is reduced, polarization voltage is reduced, lithium dendrite is still not generated by deposition and separation of high-capacity lithium ions, and long-term stability of battery operation is guaranteed.
(2) Test for cycling stability
At a current density of 1mA cm-2The lithium alloy negative electrode films of examples 1 to 3 and 6 were subjected to a cycle stability test in a symmetrical battery of a liquid lithium battery system.
FIGS. 7 to 10 show the test results (light color in the figure indicates the data of the comparative example, and black color indicates the data of the example), and it can be seen that example 1 (Li-Al-CaF)2) In a liquid system, the current density is 1mA cm-2The time cycle duration is 160 hours; example 2(Li-Ag-CuCl) in a liquid System, Current Density 1mA cm-2The time cycle duration is 90 hours; example 3(Li-KBr) in a liquid System, Current Density 1mA cm-2The time cycle duration is 180 hours; example 6 Current Density 1mA cm in a liquid System-2The time cycle duration was 130 hours. In the comparative example, the polarization voltage of the symmetrical battery is gradually increased in the circulation process, and lithium dendrites pierce the diaphragm and the electrolyte to cause a circuit short circuit in 20 hours of circulation, so that the lithium alloy negative electrode film prepared by the invention can reduce Li+Thereby inducing Li+Uniform deposition, inhibiting growth of lithium dendrite, and promoting Li+Nucleation and crystallization are carried out, nucleation potential energy is reduced, and polarization voltage is reduced.
(3) Characterization of
In order to further determine the cycling stability of the film electrode, the shape change of the lithium alloy negative electrode film before and after cycling is researched by utilizing a scanning electron microscope picture, as shown in fig. 11 and 12, the result shows that after cycling, the lithium alloy negative electrode film prepared by the invention forms a compact protective layer on the surface, and can reduce Li+Thereby inducing Li+The lithium alloy negative electrode film prepared by the invention can inhibit the growth of lithium dendrites and promote Li+Nucleation and crystallization are carried out, nucleation potential energy is reduced, and polarization voltage is reduced.
(4) Cycling stability test in full cell applications
The lithium alloy negative electrode thin films of comparative example and example 1 were placed in a Li | | | NCM622 full cell in a liquid lithium battery system for cycle stability testing.
As a result, as shown in fig. 13, in the Li | | NCM622 full cell, the capacity of example 1 can still maintain 98% of the initial capacity after 500 cycles of charging and discharging, while the capacity of the comparative example is only 67% of the initial capacity after 500 cycles, which proves that the lithium alloy film prepared by the method of the present invention has good cycle stability in the commercial NCM622 positive electrode full cell, and the present invention further accelerates the process of the commercial application of the lithium alloy negative electrode.
The data figures can prove that the lithium alloy film material prepared by different preparation methods has the characteristics of flatness, smoothness and the like, the surface of the electrode is flat and smooth, and uniform lithium ion flux deposition is favorably realized; secondly, by introducing other metallic/non-metallic materials to form alloys, Li can be reduced+Nucleation potential ofCan thereby induce Li+The lithium alloy negative electrode film prepared by the invention can inhibit the growth of lithium dendrites and promote Li+Nucleation and crystallization are carried out, nucleation potential energy is reduced, and polarization voltage is reduced. The film has simple preparation process and diversified preparation process. The method has important guiding significance for the application of the commercial negative electrode of the lithium metal material with high capacity and high stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The lithium alloy negative electrode film is characterized by comprising a base foil and an alloy film layer arranged on the base foil, wherein the alloy film layer at least comprises lithium metal and M material, the M material is metal or inorganic nonmetal, and the mass ratio of the M material to the lithium metal is (0.01-50): 100.
2. the lithium alloy negative electrode film according to claim 1, wherein the M material is one or more of elemental sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, vanadium, chromium, iron, cobalt, nickel, copper, zinc, tin, boron, aluminum, gallium, indium, silver, germanium, lead, antimony, bismuth, and fluoride, chloride, bromide, iodide, sulfide, and oxide thereof.
3. The lithium alloy negative electrode film according to claim 1, wherein the base foil is a copper foil, an aluminum foil, a stainless steel foil, a polyimide film, a carbon-coated copper foil, a carbon-coated aluminum foil, a carbon-coated stainless steel foil, a carbon-coated polyimide film, a graphene film or a carbon fiber film, a copper foam, a nickel foam, an iron foam, a titanium foam, a stainless steel mesh.
4. The method for preparing the lithium alloy negative electrode film according to any one of claims 1 to 3, comprising:
preparing a lithium metal alloy liquid, coating the lithium metal alloy liquid on the substrate foil, and then curing and rolling to obtain a lithium alloy negative electrode film;
the method comprises the following steps of preparing a lithium metal alloy solution, wherein the cloth feeding speed of a base foil is 0.1-10M/min, and the step of preparing the lithium metal alloy solution comprises the steps of placing lithium metal and an M material in a trough, wherein the heating temperature in the trough is 200-600 ℃, the rotating speed of a mechanical stirrer in the trough is 1-10000 rpm, and the stirring time is 1-10 hours.
5. The preparation method of the lithium alloy negative electrode film as claimed in claim 4, wherein the curing is performed by 1-10 stages of air-blowing drying oven, and the temperature in each stage of drying oven is 30-300 ℃.
6. The method of preparing the lithium alloy negative electrode film according to claim 4, wherein a rolling ratio at the time of rolling is 0.1 to 60%.
7. The preparation method of the lithium alloy negative electrode film according to claim 4, which is characterized in that a doctor blade coating method is adopted, and the method comprises the following specific steps:
placing lithium metal and M material at a trough under the conditions that the environmental dew point temperature is-100-0 ℃ and the atmosphere of nitrogen, argon or air, heating the trough at 200-600 ℃, the rotating speed of a mechanical stirrer in the trough is 1-10000 r/min, the stirring time is 1-10 min, heating and melting to obtain Li-M alloy liquid, the distance between the surface of a scraper and the base foil is 0.1-1000 mu M, the heating temperature of the scraper is 200-600 ℃, the cloth-moving speed of the base foil is 0.1-10M/min, coating the Li-M alloy liquid on the base foil, the temperature of a roller below the scraper is 200-600 ℃, curing is carried out through a 1-10-level blowing drying box, the temperature in each level of drying boxes is 30-300 ℃, rolling is carried out through a hot roller, the temperature of the hot roller is 30-300 ℃, and the rolling rate is 0.1-60%, and preparing the lithium alloy negative electrode film.
8. The preparation method of the lithium alloy negative electrode film according to claim 4, which is characterized in that an extrusion coating method is adopted, and the method comprises the following specific steps:
placing lithium metal and an M material at a trough under the conditions of an environment dew point temperature of-100-0 ℃ and a nitrogen, argon or air atmosphere, heating and melting to obtain a Li-M alloy liquid, wherein a mechanical stirrer in the trough has the rotation speed of 1-10000 rpm and the stirring time of 1 min-10 h, conveying the Li-M alloy liquid to a slit discharge outlet by extruding through the rotation of a screw, coating the Li-M alloy liquid on a base foil, and solidifying through a 1-10-grade blowing drying box at the temperature of 200-600 ℃ after coating, wherein the temperature in each grade of drying boxes is 30-300 ℃, rolling is carried out through a hot roller, the temperature of the hot roller is 30-300 ℃, and the rolling rate is 0.1-60% to obtain a lithium alloy negative electrode film;
wherein the rotating speed of the screw is 1-10000 r/min, the gap of the slit discharge port is 1-1000 μm, the vertical distance between the slit discharge port and the foil is 1-10000 μm, and the heating temperature of the screw movement area and the slit discharge port is 200-600 ℃.
9. A secondary lithium metal battery comprising the lithium alloy negative electrode film according to any one of claims 1 to 3 or the lithium alloy negative electrode film produced by the production method according to any one of claims 4 to 8.
10. The secondary lithium metal battery of claim 9, wherein the secondary lithium metal battery is a liquid lithium metal battery, a semi-solid lithium metal battery, a quasi-solid lithium metal battery, or a solid lithium metal battery.
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