CN117802334A - High-magnification long-service-life metal lithium composite anode material, preparation method thereof and lithium metal battery - Google Patents
High-magnification long-service-life metal lithium composite anode material, preparation method thereof and lithium metal battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 152
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 129
- 239000002184 metal Substances 0.000 title claims abstract description 129
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000010405 anode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims description 62
- 229910000733 Li alloy Inorganic materials 0.000 claims description 60
- 239000001989 lithium alloy Substances 0.000 claims description 60
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- 229910045601 alloy Inorganic materials 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 46
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
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- 229910003002 lithium salt Inorganic materials 0.000 description 10
- 159000000002 lithium salts Chemical class 0.000 description 10
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000011165 3D composite Substances 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003003 Li-S Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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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
Abstract
The invention discloses a high-magnification long-life metal lithium composite anode material, a preparation method thereof and lithium goldBelongs to the technical field of lithium batteries. In order to overcome the problems in the prior art, the invention utilizes a two-dimensional linear mismatch degree equation to screen Al which meets the mismatch degree requirement and heterogeneous nucleation condition with metal lithium 2 Y、AlB 2 、Al 2 The Yb alloy is regulated and controlled in proportion, high-temperature smelting is adopted for compounding, the size of metal lithium crystal grains and grain boundary components in the crystallization process are regulated and controlled, fine crystal grains are realized, the number of grain boundaries is increased, more active sites are induced to generate, the migration capacity of lithium ions is improved, and the rate performance is improved; meanwhile, components at the grain boundary are regulated and controlled, so that the grain boundary is passivated, and the electrochemical circulation stability is improved; and as the crystal grains are obviously thinned, dislocation among the metal lithium anode materials is improved, so that the mechanical strength of the metal lithium anode materials is obviously improved; the electrochemical performance, mechanical performance, service life, safety performance and the like of the battery are greatly improved.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a high-rate long-life metal lithium composite anode material, a preparation method thereof and a lithium metal battery.
Background
With the increasing severity of energy shortage and environmental pollution problems, lithium metal batteries (Li-S, li-O 2 Etc.) are widely studied as a clean energy source. The metal lithium cathode has extremely high theoretical specific capacity (3860 mAh.g -1 ) And extremely negative potentials (-3.040V vs. standard hydrogen electrode) are considered the most potential negative electrode materials.
However, commercial applications of lithium metal anodes still present a number of challenges, including: (1) The high activity of the metallic lithium causes the metallic lithium to easily react with the electrolyte, which leads to continuous consumption of the electrolyte and the metallic lithium negative electrode; (2) Uneven lithium deposition during electrochemical cycling causes lithium dendrite growth, eventually causing the separator to be pierced, resulting in cell shorting and serious safety accidents; (3) The great change of the volume of the lithium metal anode in the process of extraction and intercalation causes pulverization of the electrode and damages a Solid Electrolyte Interface (SEI), thereby generating dead lithium and promoting the reaction of electrolyte and lithium metal; (4) Poor mechanical strength and low rate performance, and can not maintain the structural stability of the material under high rate discharge, and the difficulty in preparing ultrathin lithium strips; the above problems have a critical impact on commercial applications of lithium metal batteries.
In recent years, researchers have come to many ways to modify the problems of metallic lithium cathodes, including: the method for regulating and controlling electrolyte additives, adopting solid electrolyte membrane, current collector modification, metal lithium surface coating protective film, metal lithium alloying treatment and the like can not fundamentally solve the problems of metal lithium negative pole dendrite growth, volume expansion and the like.
CN201811182577.3 discloses a metal lithium alloy electrode material, a preparation method and application thereof, which introduces the advantages of reducing side reactions between a metal lithium negative electrode and an electrolyte, improving coulombic efficiency and realizing high safety and long cycle at the same time by alloying Li with Al, zn and Ag. CN201910552753.6 extracting the purified alkali metal-containing aqueous phase with a complex extraction organic phase, and separating the liquid to obtain an alkali metal-rich organic phase; washing the obtained alkali metal salt-rich organic phase with a washing liquid, and then carrying out electrolysis to obtain the metal lithium alloy. CN201910329991.0 provides a three-dimensional composite metal lithium negative electrode, a preparation method, a lithium metal battery and a lithium sulfur battery. The three-dimensional porous structure conductor can be any one of foamy copper, three-dimensional porous copper-zinc alloy and three-dimensional porous copper-silver alloy, is immersed into a metal lithium liquid with the temperature of 310-900 ℃, the immersion time and the temperature are controlled, and then the three-dimensional porous structure conductor is taken out and cooled to obtain the three-dimensional composite metal lithium cathode, so that the generation of lithium dendrites and the change of volume caused in the battery cycle process are inhibited, and the commercialized application of the metal lithium cathode is facilitated. CN109167029a proposes a silicon nitride modified metal lithium negative electrode material of a lithium sulfur battery and a preparation method thereof, a silicon nitride nanowire is obtained by high-temperature nitridation after hydrolysis of tetraethoxysilane, and metal lithium is loaded inside the silicon nitride nanowire by carbothermal reduction, and the prepared metal lithium negative electrode material is stacked on the surface of a lithium metal phase by the silicon nitride nanowire to form a three-dimensional reticular coating layer, so that irreversible loss of lithium metal and damage to a diaphragm are reduced. However, these methods are not suitable for industrial implementation, and have certain drawbacks in terms of improving the rate performance of the metal lithium material layer and inhibiting the side reaction with the electrolyte.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention utilizes a two-dimensional linear mismatch degree equation to screen out alloy materials which meet the mismatch degree requirement and heterogeneous nucleation condition with metal lithium, then regulates and controls the proportion, and combines the alloy materials with pure metal lithium in a high-temperature smelting mode, and regulates and controls the grain size and grain boundary components of the metal lithium in the crystallization process, thereby realizing the metal lithium alloy cathode material with fine grains. The number of grain boundaries is further increased, more active sites are induced to be generated, so that the lithium ion migration capacity is improved, and the rate performance is improved; and meanwhile, components at the grain boundary are regulated and controlled, so that the original grain boundary with higher activity with the electrolyte is passivated, the structural stability in the charge and discharge process is improved, and the electrochemical cycling stability of the lithium metal anode is further improved. In addition, as the crystal grains are obviously thinned, dislocation among the lithium metal anode materials is improved, and thus, the mechanical strength of the lithium metal anode materials is obviously improved. The metal lithium composite anode material prepared by the method obviously improves the mechanical strength, the electrochemical multiplying power performance and the cycle performance of the metal lithium anode, and obviously improves the problem of lithium dendrite, so that the safety performance of the battery is greatly improved.
The invention firstly provides a preparation method of a high-rate long-life metal lithium composite anode material, which comprises the following steps:
A. heating an alloy reaction furnace to 300-1200 ℃ in an inert atmosphere, adding metal lithium into the reaction furnace to be fully melted, heating to 800-1200 ℃, adding an alloy intermediate phase, and continuously stirring; in the step A, the addition amount of the alloy intermediate phase is 0.1-20% of the mass of the metallic lithium; in the step A, the alloy intermediate phase is Al 2 Y、AlB 2 Or Al 2 At least one of Yb;
B. after the metal lithium and the alloy intermediate phase are fully mixed by stirring at high temperature, carrying out ultrasonic treatment to uniformly mix the materials;
C. casting under the ultrasonic treatment condition to obtain an alloy ingot, then adopting stepped cooling, controlling the cooling rate to be 3-5 ℃/min before 300 ℃, subsequently controlling the cooling rate to be 15-20 ℃/min, removing a surface oxide layer after cooling, and then heating to 60-150 ℃ for heat preservation, and cooling to room temperature to obtain the lithium alloy ingot;
D. and C, extruding the lithium alloy ingot obtained in the step C, controlling the extrusion thickness to be 100-300 microns, and then rolling the metal lithium alloy strip in multiple passes to obtain the metal lithium composite anode material with the thickness of 10-50 microns.
In the preparation method, in the step A, the addition amount of the alloy intermediate phase is 0.5-10% of the mass of the metallic lithium.
In the preparation method, in the step A, the temperature is kept at 300-1200 ℃ for 0.5-2 h, so that the metal lithium is fully melted.
In the preparation method, in the step A, the continuous stirring time is 0.5-4 h.
In the preparation method, in the step B, the ultrasonic treatment time is 0.2-2 h.
Wherein, in the step C, the temperature is kept between 60 and 150 ℃ for 1 to 6 hours.
In the preparation method, the steps A to C are all carried out under inert atmosphere.
In the above preparation method, in the step D, the multi-pass rolling is: the rolling pass is controlled to be 2-5 times, and the rolling reduction of each rolling is controlled to be 20-50%.
The invention also provides a high-rate long-life metal lithium composite anode material which is prepared by adopting the method.
The invention also provides a lithium metal battery, which takes the metal lithium composite anode material as an anode.
The invention has the beneficial effects that:
the invention utilizes a two-dimensional linear mismatch degree equation to screen out alloy materials which meet the mismatch degree requirement and heterogeneous nucleation condition with metal lithium, al 2 Y、AlB 2 、Al 2 The Yb alloy intermediate phase and the metal lithium form heterogeneous nuclei, and the heterogeneous nuclei are preferentially crystallized to provide oriented nucleation sites for the molten metal lithium, so that the grain size of the metal lithium is refined; the highest activity at the metal lithium grain boundary (lithium ion elution and intercalation activity)Sex and reactivity), grain boundary number is increased after grain refinement, so that ion migration capacity of the metal lithium in a charging and discharging process is improved, and electrochemical rate performance of the metal lithium cathode is further enhanced; metallic lithium at Al 2 Y、AlB 2 、Al 2 Heterogeneous nucleation around Yb alloy intermediate phase, crystal growth, thereby making Al 2 Y、AlB 2 、Al 2 Yb alloy intermediate phase fills up the grain boundary due to Al 2 Y、AlB 2 、Al 2 The Yb alloy intermediate phase has higher stability, inhibits side reaction between the metal lithium phase and the electrolyte, and improves the structural stability of the material; at the same time Al 2 Y、AlB 2 、Al 2 The Yb has higher adsorption energy on lithium ions, and anchors the deposition process of the metal lithium, so that the cycle stability of the metal lithium cathode is improved; after the crystal grains are obviously refined, dislocation on the surface of the metal lithium material is increased, the mechanical strength of the lithium cathode is enhanced, the preparation of an ultrathin lithium belt is facilitated, and the belt breakage risk in the rolling process is reduced.
Metallic lithium and a small amount of Al 2 Y、AlB 2 、Al 2 The Yb alloy intermediate phase is alloyed, so that the multiplying power performance, the circulating stability, the mechanical performance and the corrosion resistance of the metal lithium composite anode material are enhanced while the capacity requirement is met, the lithium ion elution process is optimized, and the application of the metal lithium anode material in primary batteries and secondary batteries is facilitated.
Drawings
Fig. 1 is a graph showing the comparison of the grain size and distribution of a pure metallic lithium anode and a modified composite anode.
Fig. 2 is a graph comparing cycle performance of a pure metallic lithium anode with that of a modified composite anode.
Fig. 3 is a graph comparing the rate performance of a pure metallic lithium anode with that of a modified composite anode.
Fig. 4 is a graph showing the mechanical strength comparison of a pure metallic lithium anode and a modified composite anode.
Detailed Description
Specifically, the preparation method of the high-rate long-life metal lithium composite anode material comprises the following steps:
A. heating an alloy reaction furnace to 300-1200 ℃ in an inert atmosphere, adding metal lithium into the reaction furnace to be fully melted, heating to 800-1200 ℃, adding an alloy intermediate phase, and continuously stirring; in the step A, the addition amount of the alloy intermediate phase is 0.1-20% of the mass of the metallic lithium; in the step A, the alloy intermediate phase is Al 2 Y、AlB 2 Or Al 2 At least one of Yb;
B. after the metal lithium and the alloy intermediate phase are fully mixed by stirring at high temperature, carrying out ultrasonic treatment to uniformly mix the materials;
C. casting under the ultrasonic treatment condition to obtain an alloy ingot, then adopting stepped cooling, controlling the cooling rate to be 3-5 ℃/min before 300 ℃, subsequently controlling the cooling rate to be 15-20 ℃/min, removing a surface oxide layer after cooling, and then heating to 60-150 ℃ for heat preservation, and cooling to room temperature to obtain the lithium alloy ingot;
D. and C, extruding the lithium alloy ingot obtained in the step (generally in an extruder), controlling the extrusion thickness to be 100-300 microns, and then carrying out multi-pass rolling on the metal lithium alloy strip to obtain the metal lithium composite anode material with the thickness of 10-50 microns.
In the step A of the invention, because the metallic lithium has high reactivity, the reaction furnace is generally required to be dried in a vacuum environment of 60-120 ℃ for 2-10 hours, water is removed in advance, and the reaction of the water and the metallic lithium in the high temperature at the rear end is avoided, so that impurities are generated.
In the step A, an alloy reaction furnace is heated to 300-1200 ℃, and the temperature is kept for 0.5-2 h, so that the metal lithium added into the reaction furnace is fully melted. If the temperature of the molten metal lithium is lower, the temperature is required to be increased to 800-1200 ℃ later, and then an alloy intermediate phase is added; the temperature of the molten metal lithium is 800-1200 ℃, and the temperature is not required to be raised.
The invention obtains the alloy material which can meet the mismatch degree requirement and heterogeneous nucleation condition with the metal lithium through screening, al 2 Y、AlB 2 、Al 2 The Yb alloy intermediate phase and the metallic lithium form heterogeneous nuclei; and e.g. Al 2 Ca,AlMg 2 Such alloys are not suitable.
In step A of the present invention, it is necessary to control the amount of alloy intermediate phase. Preferably, the addition amount of the alloy intermediate phase is controlled to be 0.5-10% of the mass of the metallic lithium, and the obtained anode material has more excellent performance.
In the step A, after the alloy intermediate phase is added, the continuous stirring time is controlled to be 0.5-4 h, so that the metal lithium and the alloy intermediate phase are melted and alloyed.
In step B of the present invention, although the materials can be sufficiently mixed by stirring at high temperature, the inventors found that segregation and sedimentation easily occur when casting is directly performed. Therefore, in order to ensure that the lithium metal alloy liquid in the whole reaction kettle is uniformly mixed during casting, ultrasonic treatment is also required by adopting equipment such as a ring ultrasonic instrument and the like. In the step B, the ultrasonic treatment time is 0.2-2 h.
In the step C, the ultrasonic wave only ensures that the alloy lithium liquid entering the casting nozzle is uniformly mixed before the mixed alloy material is cast, and the casting mold is not subjected to the ultrasonic wave when casting is performed.
In the step C of the invention, the temperature reduction program is controlled: the temperature is reduced by adopting a temperature reduction speed of 5 ℃/min before 300 ℃ (namely 300 ℃ -1200 ℃), so that the early-stage alloy intermediate phases are uniformly distributed in the whole metal lithium melt (the melting point of the alloy intermediate phases is higher than that of the metal lithium) in the prior nucleation process, and the alloy intermediate phases are prevented from being clustered together to form a certain concentrated area; when the temperature is lowered below 300 ℃ to room temperature, the temperature is lowered at a cooling rate of 20 ℃/min, because the alloy intermediate phase is completely nucleated and distributed in the whole melt at the moment, the rapid cooling can ensure heterogeneous nucleation growth of the metal lithium phase along the crystal grains of the alloy intermediate phase, thereby realizing the purpose of grain refinement.
In the step C, after casting, the temperature is raised to 60-150 ℃ again for heat preservation, so that the metal lithium alloy ingot is subjected to secondary annealing treatment, the crystallinity of a metal lithium phase is further improved, and meanwhile, the internal stress of the material is released. In the step C, the temperature is kept at 60-150 ℃ for 1-6 h.
In the invention, the steps A to C are all carried out under inert atmosphere; step D is generally carried out in a drying room, and the dew point is controlled to be between-45 ℃ and-60 ℃.
In the step D, a lithium alloy ingot is put into an extruder for extrusion, an extrusion die is controlled, the extrusion thickness is controlled to be 100-300 microns, the metal lithium alloy strip is rolled for multiple times, the rolling pass is controlled to be 2-5 times, the rolling reduction of each rolling is controlled to be 20-50%, the thickness is finally 10-50 microns, and the metal lithium composite anode is obtained by slicing.
The invention also provides a high-rate long-life metal lithium composite anode material which is prepared by adopting the method.
The invention also provides a lithium metal battery, which takes the metal lithium composite anode material as an anode.
The present invention will be described in further detail by way of examples, which are not intended to limit the scope of the invention.
Example 1
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 800 ℃ under argon atmosphere, preserving heat for 2 hours, adding metal lithium into the reaction furnace for full melting, and adding 2wt.% of Al 2 B, continuously stirring for 1h; after the metals are fully mixed, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; casting under the ultrasonic treatment condition to obtain a lithium alloy ingot, cooling in a stepped way (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃, preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, the lithium salt is 1.0M LiTFSI and S positive plate are adopted, and the solvent DME is as follows: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Example 2
Drying alloy reaction furnace at 80deg.C under vacuum for 5 hr, heating to 1000deg.C under argon atmosphere, maintaining for 2 hr, adding metal lithium into the reaction furnace, melting, adding 2wt.% AlB 2 And 1wt.% Al 2 Y, stirring continuously for 1h; after the metals are fully mixed, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; casting under the ultrasonic treatment condition to obtain a lithium alloy ingot, cooling in a stepped way (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃, preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, the lithium salt is 1.0M LiTFSI and S positive plate are adopted, and the solvent DME is as follows: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Example 3
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 1000 ℃ under argon atmosphere, preserving heat for 2 hours, adding metal lithium into the reaction furnace for full melting, and adding 2wt.% of Al 2 Yb, stirring continuously for 1h; after the metals are fully mixed, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; casting under the ultrasonic treatment condition to obtain a lithium alloy ingot, cooling in a stepped way (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃, preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for carrying outExtruding, controlling an extruding die, and controlling the extruding thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, the lithium salt is 1.0M LiTFSI and S positive plate are adopted, and the solvent DME is as follows: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Example 4
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 1100 ℃ under argon atmosphere, preserving heat for 2 hours, adding metal lithium into the reaction furnace for full melting, and adding 2wt.% of Al 2 Yb and 1wt.% Al 2 Y, stirring continuously for 1h; after the metals are fully mixed, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; casting under the ultrasonic treatment condition to obtain a lithium alloy ingot, cooling in a stepped way (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃, preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, a 2032 button cell was assembled with an S positive plate using 1.0M LiTFSI as lithium salt and solvent DME: dol=1:1 as electrolyte, followed by electrochemical performance testing.
Example 5
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 1200 ℃ under argon atmosphere, preserving heat for 2 hours, adding metal lithium into the reaction furnace for full melting, and adding 2wt.% of Al 2 Yb and 2wt.% Al 2 Y, stirring continuously for 1h; to fully mix the metalAfter the mixing, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; casting under the ultrasonic treatment condition to obtain a lithium alloy ingot, cooling in a stepped way (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 120 ℃ and preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, the lithium salt is 1.0M LiTFSI and S positive plate are adopted, and the solvent DME is as follows: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Example 6
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 1200 ℃ under argon atmosphere, preserving heat for 2 hours, adding metal lithium into the reaction furnace for full melting, and adding 0.5wt.% Al 2 Y, stirring continuously for 1h; after the metals are fully mixed, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; casting under the ultrasonic treatment condition to obtain a lithium alloy ingot, cooling in a stepped way (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 120 ℃ and preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, the lithium salt is 1.0M LiTFSI and S positive plate are adopted, and the solvent DME is as follows: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Example 7
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 1200 ℃ under argon atmosphere, preserving heat for 2 hours, adding metal lithium into the reaction furnace for full melting, and adding 5wt.% of Al 2 Yb and 5wt.% Al 2 Y, stirring continuously for 1h; after the metals are fully mixed, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; casting under the ultrasonic treatment condition to obtain a lithium alloy ingot, cooling in a stepped way (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 120 ℃ and preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, the lithium salt is 1.0M LiTFSI and S positive plate are adopted, and the solvent DME is as follows: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Comparative example 1
In an inert atmosphere glove box, a pure metal lithium sheet is adopted as a cathode material, and 1.0M LiTFSI is adopted as lithium salt and a solvent DME is adopted as an S anode sheet: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Comparative example 2
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 800 ℃ under argon atmosphere, preserving heat for 2 hours, adding metal lithium into the reaction furnace for full melting, and adding 2wt.% of Al 2 Ca, stirring continuously for 1h; after the metals are fully mixed, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; under ultrasonic treatment conditionsCasting to obtain lithium alloy ingot, cooling in a stepped mode (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing the surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 120 ℃ and preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, the lithium salt is 1.0M LiTFSI and S positive plate are adopted, and the solvent DME is as follows: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Comparative example 3
Drying alloy reaction furnace at 80deg.C under vacuum for 5 hr, heating to 800deg.C under argon atmosphere, maintaining for 2 hr, adding metal lithium into the reaction furnace, melting, and adding 2wt.% AlMg 2 Stirring is continued for 1h; after the metals are fully mixed, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min, so that the materials are uniformly mixed; casting under the ultrasonic treatment condition to obtain a lithium alloy ingot, cooling in a stepped way (the cooling rate is controlled to be 5 ℃/min before 300 ℃ and the subsequent cooling rate is controlled to be 20 ℃/min), and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 120 ℃ and preserving heat for 4 hours, and cooling to room temperature; putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 200 micrometers; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be 50%, and the thickness of the metal lithium alloy belt is 25 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
In an inert atmosphere glove box, the lithium salt is 1.0M LiTFSI and S positive plate are adopted, and the solvent DME is as follows: dol=1: 1 is an electrolyte, and 2032 button cell is assembled and then subjected to electrochemical performance testing.
Table 1 electrochemical cycle performance data sheet
| Sample of | Multiplying power | Cycle number | Capacity retention rate |
| Comparative example 1 | 0.5C | 100 | 75％ |
| Comparative example 2 | 0.5C | 100 | 73％ |
| Comparative example 3 | 0.5C | 100 | 67％ |
| Example 3 | 0.5C | 100 | 92％ |
| Example 4 | 0.5C | 100 | 84％ |
Fig. 1 is a graph showing the comparison of the grain size and distribution of a pure metallic lithium anode and a modified composite anode. As can be seen from the electron microscope scan of FIG. 1, li-Al 2 The grain size of Yb is obviously smaller than that of pure metal lithium, which leads to obviously increased number of grain boundaries, and the addition of the intermediate phase of the alloy achieves the effect of heterogeneous nucleation, thereby reducing the grain size.
Electrochemical cycling stability, rate capability and mechanical strength of the pure metallic lithium electrode, metallic lithium composite negative electrode were compared in fig. 2, 3 and 4. As is apparent from fig. 2, the alloying treatment improves the side reaction between the lithium metal negative electrode and the electrolyte to some extent, and improves the structural stability of the material in the charge and discharge processes, thereby improving the cycle stability of the battery and enabling the battery to have longer cycle life. Fig. 3 shows a significant improvement in electrochemical rate performance of the lithium metal composite anode material. Meanwhile, fig. 4 compares the difference of the grain sizes of the refined lithium metal negative electrode in the mechanical strength, and the alloy intermediate screened by adopting the two-dimensional linear mismatch degree equation has a great influence on the growth nucleation of the lithium metal, so that the grain size of the lithium metal negative electrode is obviously reduced, the surface dislocation of the lithium metal negative electrode is increased, and the high mechanical strength is realized. Therefore, the composite alloy negative electrode prepared by the alloying means is an effective way capable of prolonging the cycle life of the battery and enhancing the multiplying power performance and the mechanical strength.
Claims (10)
1. The preparation method of the high-rate long-life metal lithium composite anode material is characterized by comprising the following steps of: the method comprises the following steps:
A. heating an alloy reaction furnace to 300-1200 ℃ in an inert atmosphere, adding metal lithium into the reaction furnace to be fully melted, heating to 800-1200 ℃, adding an alloy intermediate phase, and continuously stirring; in the step A, the addition amount of the alloy intermediate phase is 0.1-20% of the mass of the metallic lithium; in the step A, the alloy intermediate phase is Al 2 Y、AlB 2 Or Al 2 At least one of Yb;
B. after the metal lithium and the alloy intermediate phase are fully mixed by stirring at high temperature, carrying out ultrasonic treatment to uniformly mix the materials;
C. casting under the ultrasonic treatment condition to obtain an alloy ingot, then adopting stepped cooling, controlling the cooling rate to be 3-5 ℃/min before 300 ℃, subsequently controlling the cooling rate to be 15-20 ℃/min, removing a surface oxide layer after cooling, and then heating to 60-150 ℃ for heat preservation, and cooling to room temperature to obtain the lithium alloy ingot;
D. and C, extruding the lithium alloy ingot obtained in the step C, controlling the extrusion thickness to be 100-300 microns, and then rolling the metal lithium alloy strip in multiple passes to obtain the metal lithium composite anode material with the thickness of 10-50 microns.
2. The method for preparing the high-rate long-life metal lithium composite anode material according to claim 1, which is characterized in that: in the step A, the addition amount of the alloy intermediate phase is 0.5-10% of the mass of the metallic lithium.
3. The method for preparing the high-rate long-life metal lithium composite anode material according to claim 1, which is characterized in that: in the step A, the temperature is kept at 300-1200 ℃ for 0.5-2 h, so that the metal lithium is fully melted.
4. The method for preparing the high-rate long-life metal lithium composite anode material according to claim 1, which is characterized in that: in the step A, the continuous stirring time is 0.5-4 h.
5. The method for preparing the high-rate long-life metal lithium composite anode material according to claim 1, which is characterized in that: in the step B, the ultrasonic treatment time is 0.2-2 h.
6. The method for preparing the high-rate long-life metal lithium composite anode material according to claim 1, which is characterized in that: in the step C, the temperature is kept at 60-150 ℃ for 1-6 h.
7. The method for preparing the high-rate long-life metal lithium composite anode material according to claim 1, which is characterized in that: all steps A to C are carried out under inert atmosphere.
8. The method for preparing a high-rate long-life metallic lithium composite anode material according to any one of claims 1 to 7, characterized by: in the step D, the multi-pass rolling is: the rolling pass is controlled to be 2-5 times, and the rolling reduction of each rolling is controlled to be 20-50%.
9. The high-rate long-life metal lithium composite anode material prepared by adopting the method of claim 1.
10. Lithium metal battery, its characterized in that: a negative electrode made of the metal lithium composite negative electrode material according to claim 9.
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