CN116632180A - High-strength high-rate discharge lithium alloy composite anode material, preparation method and application - Google Patents
High-strength high-rate discharge lithium alloy composite anode material, preparation method and application Download PDFInfo
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- CN116632180A CN116632180A CN202310542101.0A CN202310542101A CN116632180A CN 116632180 A CN116632180 A CN 116632180A CN 202310542101 A CN202310542101 A CN 202310542101A CN 116632180 A CN116632180 A CN 116632180A
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- 229910001316 Ag alloy Inorganic materials 0.000 description 1
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- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
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- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C24/00—Alloys based on an alkali or an alkaline earth metal
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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
- 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
- H01M4/13—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/36—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 application discloses a lithium alloy composite negative electrode material with high strength and high rate discharge, a preparation method and application thereof, wherein metallic lithium and a metallic element Al, mg, zn, ca are fully melted and mixed at low temperature; adding transition metal or at least two elements in rare earth metal, or adding mixed elements of the transition metal and the rare earth metal, fully melting and mixing at high temperature, cooling and ultrasonically mixing; casting to obtain a lithium alloy ingot, heating the lithium alloy ingot to 60-150 ℃, preserving heat for 1-6 hours, and then cooling to room temperature, wherein the process is repeated for at least 2 times; and (3) preparing the lithium alloy ingot into a lithium alloy belt, and slicing to obtain the composite metal lithium anode. According to the application, a small amount of common metals, transition metals or lanthanide rare earth metals are migrated to the grain boundary by utilizing the segregation principle, so that the grain boundary activity is reduced, the side reaction between the lithium anode material and the electrolyte is reduced, the structural stability of the material is improved, and the mechanical strength and the rate capability of the material are improved.
Description
Technical Field
The application relates to a negative electrode material obtained by compounding metal lithium, common metal, transition metal or rare earth metal, and provides a preparation method thereof.
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 metallic lithium anode material has a 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 metallic lithium anode materials 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, resulting in 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) The mechanical strength is poor, the structural stability of the material under high-rate discharge can not be maintained, and the difficulty in preparing an ultrathin lithium belt can be overcome; the above problems have a critical impact on commercial applications of lithium metal batteries.
With the increasing demand of high energy density of lithium ion batteries, numerous researchers focus on lithium metal anode materials, and although the energy density is improved to a certain extent, the cycle life and the safety of the lithium ion batteries are still important problems to be solved. In the charge and discharge process, lithium dendrite is formed due to uneven deposition of lithium ions, and when serious, the lithium dendrite penetrates through a diaphragm to directly link positive and negative electrodes to form a short circuit, so that thermal runaway is caused to cause safety accidents; particularly, under high current density, the dendrite growth and volume expansion effect of lithium are more serious, so that the requirement of high-rate charge and discharge in a battery system can not be met by taking metal lithium as a cathode material. In addition, metallic lithium is liable to undergo side reactions with the electrolyte to generate "dead lithium" which reduces the battery capacity and deteriorates the cycle stability thereof.
In recent years, researchers have come to improve the series of problems of metallic lithium cathodes in many ways, including: regulating electrolyte additive, adopting solid electrolyte membrane, current collector modification, coating protective film on the surface of metal lithium, alloying metal lithium and other methods. Some related art techniques for improving the performance of metallic lithium alloy negative electrode materials are listed below:
patent CN111048744a discloses a metal lithium alloy electrode material, a preparation method and application thereof, wherein Li and Al, zn and Ag form an alloy to reduce side reactions between a metal lithium anode and an electrolyte, improve coulombic efficiency, and realize the advantages of high safety and long cycle. The purified alkali metal-containing aqueous phase is extracted by a composite extraction organic phase in the patent CN110564965A, and the alkali metal-rich organic phase is obtained by separating the liquid; washing the obtained alkali metal salt-rich organic phase with a washing liquid, and then carrying out electrolysis to obtain the metal lithium alloy. Patent CN110112367A provides a three-dimensional composite metal lithium negative electrode, a preparation method, a lithium metal battery and a lithium sulfur battery, wherein a three-dimensional porous conductor (which can be any of foam 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 composite metal lithium negative electrode is obtained by taking out and cooling, so that the generation of lithium dendrites and the volume change caused in the battery circulation process are inhibited, and the commercialized application of the metal lithium negative electrode is facilitated. Patent CN109167029a proposes a silicon nitride modified metal lithium negative electrode material of a lithium sulfur battery and a preparation method thereof, wherein silicon nitride nanowires are obtained by high-temperature nitridation after hydrolysis of tetraethoxysilane, and metal lithium is loaded inside the silicon nitride nanowires 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 nanowires to form a three-dimensional reticular coating layer, so that irreversible loss of lithium metal and damage to a diaphragm are reduced.
The problems of dendrite growth, volume expansion and the like of the metal lithium negative electrode cannot be fundamentally solved by the technology, so that the electrochemical cycle performance of the metal lithium negative electrode cannot be fundamentally improved.
Disclosure of Invention
The application overcomes the defects of the prior art, and provides a high-strength and high-rate discharge lithium alloy composite anode material and an implementation mode of a preparation method thereof, so that the problems of dendrite growth, volume expansion and the like of a metal lithium anode can be expected to be solved.
In order to solve the technical problems, one embodiment of the present application adopts the following technical scheme:
a preparation method of a lithium alloy composite anode material with high strength and high rate discharge comprises the following steps:
(1) Fully melting and mixing metallic lithium and metallic element Al, mg, zn, ca under the protection of inert atmosphere and under the first temperature condition to obtain a first molten liquid; the Li content is 80-98wt.%, and the Al, mg, zn, ca content is less than or equal to 5wt.%, respectively; the first temperature condition is less than 700 ℃;
(2) Adding at least two elements in the transition metal Y, zr, nb, mo, tc, ru, rh, pd, ag, cd, or adding at least two elements in the rare earth metal La, ce, nd, pr, gd and Er, or adding the mixed elements of the transition metal and the rare earth metal, and fully melting and mixing under a second temperature condition to obtain a second molten liquid; the control amount of each transition metal or rare earth metal element is 0.01-3wt.%, and the total amount of the transition metal and the rare earth metal is not more than 5wt.%; the second temperature condition is more than or equal to 700 ℃;
(3) Cooling the second molten liquid to below 200 ℃, and then performing ultrasonic treatment to uniformly mix;
(4) Casting to obtain a lithium alloy ingot, cooling and removing a surface oxide layer; then heating the obtained lithium alloy ingot to 60-150 ℃, preserving heat for 1-6 hours, and then cooling to room temperature, and repeating the process for at least 2 times;
(5) And (3) preparing the lithium alloy ingot into a lithium alloy belt, and slicing to obtain the composite metal lithium anode.
The more detailed technical scheme is that the following operation modes can be adopted for the steps:
step (1), drying an alloy reaction furnace for 2-10 hours in a vacuum environment at 60-120 ℃, then heating the alloy reaction furnace to 300-650 ℃ under an argon atmosphere, preserving heat for 0.5-2 hours, adding metal lithium into the reaction furnace, fully melting the metal lithium, and adding a certain amount of metal elements Al, mg, zn, ca; the element content is controlled as follows: li (80-98 wt.%), al (0.5-5 wt.%), mg (0.5-5 wt.%), zn (0.5-5 wt.%), ca (0.05-5 wt.%); preferably Al, mg, zn, ca is present in an amount of 1.5-2wt.%, 1-1.5wt.%, 0.4-0.6wt.%, 0.2-0.6wt.%, respectively; continuously stirring for 0.5-2h after Al, mg, zn, ca is added, so that all metal elements are melted and mixed uniformly as much as possible to obtain a first molten liquid; the metal elements Li, al, mg, zn, ca are all percentages by mass of the total alloy cathode material, and the total percentage of the metal elements Al, mg, zn, ca is controlled to ensure that enough active lithium exists, so that the requirement of positive and negative electrode capacity ratio (N/P) can be met when the active lithium is matched with the positive electrode capacity, and the full battery assembly is met;
the alloy reaction furnace is dried for 2-10h under the vacuum environment of 60-120 ℃, and then is heated to 300-650 ℃ under the argon atmosphere for 0.5-2h, so that the alloy reaction furnace is kept absolute dry before smelting, no moisture exists, and meanwhile, the alloy reaction furnace is heated to 300-650 ℃ in advance, so that the metal lithium can quickly enter into a molten liquid state after being added, the alloy preparation process is shortened, and the production efficiency is improved.
The application utilizes alloying means to carry out primary smelting on common metal elements such as magnesium, aluminum, zinc, calcium and the like, thereby improving the mechanical strength of the material; it is generally desirable to add more than two common metallic elements, including but not limited to Al, mg, zn, ca, and in order to obtain better mechanical strength, the present application preferably employs four common metallic elements, each Al, mg, zn, ca, to participate in primary smelting. The three metal elements of Al, mg and Zn are alloyed with lithium to improve the diffusion coefficient of lithium ions, and meanwhile, ca is added to play a role in refining grains. Therefore, alloying these metals with lithium can achieve a synergistic effect that improves the electrochemical properties and mechanical strength of the material.
Step (2), after the several metals in the step (1) are fully mixed, adding a certain amount of transition metal and/or rare earth metal, wherein the transition metal is Y, zr, nb, mo, tc, ru, rh, pd, ag, cd, the rare earth metal is at least two of La, ce, nd, pr, gd and Er, the control amount of each transition metal or rare earth metal element is 0.01-3wt.%, and the total amount of the transition metal and the rare earth metal is not more than 5wt.%; adding transition metal and/or rare earth metal, and then continuously heating and stirring at 700-1000 ℃ for 0.5-2h to fully mix to obtain a second molten liquid; preferably, the mixture is heated and stirred continuously for 1 to 1.5 hours at the temperature of between 700 and 900 ℃ for complete mixing; the total ratio of transition metal and rare earth metal is controlled to ensure that enough active lithium exists, and the positive and negative electrode capacity ratio (N/P) requirement can be met when the lithium ion battery is subjected to capacity matching with the positive electrode, so that the full battery assembly is met.
Several preferred combinations of transition metals and/or rare earth metals are provided below:
(1) the transition metal and/or rare earth metal combined elements are Nb and Ag, and the content of Nb and Ag in the composite metal lithium anode is 0.2-0.3wt.% and 0.2-0.3wt.%, respectively.
(2) The transition metal and/or rare earth metal combined elements are Nb and Cd, and the content of Nb and Cd in the composite metal lithium anode is 0.2-0.3wt.% and 0.2-0.3wt.%, respectively.
(3) The transition metal and/or rare earth metal combined element is La, ce, and the contents of La and Ce in the composite metal lithium anode are respectively 0.08-0.12wt.% and 0.08-0.12wt.%.
(4) The transition metal and/or rare earth metal combined elements are Nd and Ce, and the content of Nd and Ce in the composite metal lithium anode is 0.08-0.12wt.% and 0.15-0.25wt.% respectively.
(5) The transition metal and/or rare earth metal combined elements are La and Nd, and the contents of La and Nd in the composite metal lithium anode are 0.2-0.3wt.% and 0.2-0.3wt.%, respectively.
The lithium anode material is prepared by taking lithium element as a main element, and the content of the lithium element reaches 80-98wt.%, so that the positive-negative capacity ratio of the battery is ensured, and then other metal elements are added into the lithium material to modify the lithium anode material.
The transition metal and the rare earth metal are doped after common metal elements are mixed in lithium, and do not form alloy phases with lithium and common metals in the technology of the application, but only play roles in improving supercooling degree of materials in a cooling process in a high-temperature smelting process and a cooling process so as to inhibit grain growth and refine grain structures (as shown in figure 1), thereby further enhancing ion conductivity and mechanical strength of the whole lithium anode material. Because the reactivity of the metal lithium material at the grain boundary is highest, segregation occurs in the cooling process after the transition metal and the rare earth element are added, the grain boundary is occupied by the transition metal, the rare earth metal and the alloy phase, and the reactivity at the grain boundary of the metal lithium negative electrode can be reduced, so that the side reaction between the metal lithium negative electrode and the electrolyte is slowed down, the corrosion resistance of the metal lithium negative electrode to the electrolyte is enhanced, and the structural stability of the material is finally improved.
Step (3), when the second molten liquid is cooled to below 200 ℃, the alloy reaction kettle is subjected to ultrasonic treatment in an annular ultrasonic instrument, the ultrasonic vibration frequency of the ultrasonic treatment is 15-30 kHz, and the ultrasonic treatment time is 10-60min so as to uniformly mix; the purpose of the ultrasonic treatment is to uniformly mix the various elements in the second melt, which if not done may result in non-uniform composition of the material during final formation and poor uniformity of material properties.
Step (4), casting to obtain a lithium alloy ingot after ultrasonic treatment is finished, and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 60-150 ℃, preserving heat for 1-6 hours, and then cooling to room temperature, and repeating the process for at least 2 times; the application heats the lithium alloy ingot to 60-150 ℃ for heat preservation, cooling and repeating, so as to strengthen the crystallinity of the metal lithium belt. In the process, the metal lithium is fully alloyed with elements such as Al, ca, zn and the like, and the multiple annealing treatments are beneficial to enhancing the alloying structure, so that the mechanical strength of the composite anode material is enhanced. In the prior art, a metal lithium ingot is obtained by a rapid cooling mode, the metal lithium can not be completely crystallized in the process, and the fact that diffraction peaks are weaker due to weak crystallinity can be found in the process of testing XRD.
Step (5), putting the lithium alloy ingot into an extruder for extrusion, controlling an extrusion die, and controlling the extrusion thickness to be 100-300 micrometers to obtain a lithium alloy belt; rolling the metal lithium alloy belt in multiple passes, wherein the rolling reduction of each rolling is controlled to be between 10 and 80 percent, and the lithium alloy belt with the thickness of 10 to 50 microns is obtained; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
The broken strip and the edge running in the preparation process of the metal lithium alloy strip are not beneficial to the preparation of the thin lithium strip, the metal lithium alloy strip is rolled in multiple passes, the broken strip and the edge running in the process of severely stretching and deforming the lithium strip can be reduced by controlling the rolling reduction of each pass, meanwhile, the thickness of the metal lithium strip can be more uniform through the multiple passes of rolling, the influence caused by rebound is reduced, and the technology is commonly used in the field.
Alloying metal lithium and a small amount of other metal elements, so that the positive and negative electrode capacity ratio is ensured to be met when the full battery is assembled, the mechanical strength, the ion conductivity and the corrosion resistance of the metal lithium composite negative electrode material are enhanced while the active lithium content is controlled to meet the capacity requirement of the full battery, and the application of the metal lithium composite negative electrode material in primary batteries and secondary batteries is facilitated; li in metallic lithium + Diffusion rate in pure lithium (5.69×10) -11 cm 2 s -1 ) Far lower than Li in alloying materials + Diffusion coefficients such as Li-Mg, li-A1 and Li-Zn have high Li + Diffusion coefficient (10) -8 ～10 -6 cm 2 s -1 ) The method comprises the steps of carrying out a first treatment on the surface of the Therefore, the diffusion of lithium ions in the electrode can be promoted by utilizing the metal lithium alloy phase, so that the metal lithium is nucleated and grown in the electrode, and meanwhile, the metal element Ca capable of refining grains is added for alloying treatment to further increaseThe ionic conductivity of the material is strong, so that the rate capability of the lithium metal anode is improved; the alloying element is added to reduce the activity of the metal lithium, thereby being beneficial to enhancing the corrosion resistance of the metal lithium anode, reducing the side reaction with electrolyte and enhancing the structural stability and the cycle stability of the anode material. The mechanical strength of the lithium metal negative electrode can be obviously enhanced by doping a small amount of transition metal or lanthanide rare earth metal, and meanwhile, the extensibility of the lithium metal negative electrode is not influenced (the better the extensibility is, the thinner the lithium metal belt can be made), so that the lithium metal negative electrode has a pushing effect on the research of the ultrathin lithium metal belt. In conclusion, the composite metal lithium anode material obtained by the method is greatly improved in safety and cycle life, and is beneficial to the later research and application of the metal lithium anode.
Compared with the prior art, the application has at least the following beneficial effects:
according to the application, a small amount of common metals, transition metals or lanthanide rare earth metals are migrated to the grain boundary by utilizing the segregation principle, so that the grain boundary activity is reduced, the side reaction between the lithium anode material and the electrolyte is reduced, and the structural stability of the material is improved.
The application enhances the mechanical strength of the lithium cathode by utilizing alloying means, reduces the risk of breakage in the calendaring process, and can prepare the ultrathin lithium belt with the thickness of 10-50 micrometers.
The composite anode material prepared by the application obviously improves the mechanical strength, high-rate performance and corrosion resistance of the metal lithium anode, and obviously improves the problem of lithium dendrite, so that the cycle performance of the battery is greatly improved.
Drawings
FIG. 1 is a schematic diagram of an alloyed grain refinement.
Fig. 2 is a graph comparing electrochemical cycle performance of assembled full cells.
Fig. 3 a is a dendrite growth chart of comparative example 1 and b is a dendrite growth chart of example 5.
FIGS. 4a and c show the XRD patterns of the volume expansion of comparative example 1 and example 5, respectively, before cycling; b. d is the volume expansion XRD patterns after cycling of comparative example 1 and example 5, respectively.
Fig. 5 shows the rate performance of examples 1, 3, and 5 at discharge rates of 0.1C,0.5C,1C, and 5C.
Fig. 6 is an XRD pattern before and after the heat treatment of example 6 of the present application.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
Comparative example 1
In comparison with example 5, this example uses only two conventional metals to modify lithium, and no rare earth metal.
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 600 ℃ under argon atmosphere, preserving heat for 2 hours, adding metal lithium into the reaction furnace for full melting, adding 1.5wt.% of Mg and 0.5wt.% of Zn, and continuously stirring for 1 hour; placing the alloy reaction kettle in an annular ultrasonic instrument, wherein the ultrasonic treatment time of 20kHz is 30min so as to uniformly mix; casting to obtain a lithium alloy ingot after ultrasonic treatment is finished, and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃ and preserving heat for 4 hours, and then repeating the process for 2 times at 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 30 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
Comparative example 2
Only three conventional metals of 1.5% al, 1.5% mg and 1.0% zn were used without using calcium, and the other is the same as in example 5.
Comparative example 3
Only 4% calcium was used, and three conventional metals of Al, mg and Zn were not used, except that the same as in example 5 was used.
Comparative example 4
The rare earth metal was used only with 0.50% la, not Nd, and the other was the same as in example 5.
Example 1
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 600 ℃ under argon atmosphere, preserving heat for 2 hours, adding 2wt.% of Al, 1.5wt.% of Mg, 0.5wt.% of Zn and 0.5wt.% of Ca into the reaction furnace for full melting, and continuously stirring for 1 hour; after the above several metals are fully mixed, adding 0.25wt.% Nb and 0.25wt.% Ag, and continuously heating and stirring at 800 ℃ for 1h to fully mix; when the mixed melt is cooled to 200 ℃, the alloy reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min at 20kHz to lead the mixture to be uniform; casting to obtain a lithium alloy ingot after ultrasonic treatment is finished, and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃ and preserving heat for 4 hours, and then repeating the process for 2 times at 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 30 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
Example 2
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 600 ℃ under argon atmosphere, preserving heat for 2 hours, adding 2wt.% of Al, 1wt.% of Mg, 0.5wt.% of Zn and 0.25wt.% of Ca into the reaction furnace after the metal lithium is fully melted, and continuously stirring for 1 hour; after the above several metals are fully mixed, adding 0.25wt.% Nb and 0.25wt.% Cd, and continuously heating and stirring at 800 ℃ for 1h to fully mix; when the mixed melt is cooled to 200 ℃, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min at 20kHz to lead to uniform mixing; casting to obtain a lithium alloy ingot after ultrasonic treatment is finished, and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃ and preserving heat for 4 hours, and then repeating the process for 2 times at 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 30 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
Example 3
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 600 ℃ under argon atmosphere, preserving heat for 2 hours, adding 2wt.% of Al, 1.5wt.% of Mg, 0.5wt.% of Zn and 0.5wt.% of Ca into the reaction furnace for full melting, and continuously stirring for 1 hour; after the above metals are fully mixed, 0.1wt.% La and 0.1wt.% Ce are added, and the mixture is continuously heated and stirred for 1h at 800 ℃ for fully mixing; when the mixed melt is cooled to 200 ℃, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min at 20kHz to lead to uniform mixing; casting to obtain a lithium alloy ingot after ultrasonic treatment is finished, and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃ and preserving heat for 4 hours, and then repeating the process for 2 times at 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 30 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
Example 4
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 400 ℃ under argon atmosphere, preserving heat for 2 hours, adding 2wt.% of Al, 1.5wt.% of Mg, 0.5wt.% of Zn and 0.5wt.% of Ca into the reaction furnace for full melting, and continuously stirring for 1 hour; after the above several metals are fully mixed, 0.1wt.% Nd and 0.2wt.% Ce are added, and the mixture is continuously heated and stirred for 1h at 800 ℃ for fully mixing; when the mixed melt is cooled to 200 ℃, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min at 20kHz to lead to uniform mixing; casting to obtain a lithium alloy ingot after ultrasonic treatment is finished, and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃ and preserving heat for 4 hours, and then repeating the process for 2 times at 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 30 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
Example 5
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 600 ℃ under argon atmosphere, preserving heat for 2 hours, adding 1.5wt.% Al, 1.5wt.% Mg, 0.5wt.% Zn and 0.5wt.% Ca into the reaction furnace after the metal lithium is fully melted, and continuously stirring for 1 hour; after the above metals are fully mixed, 0.25wt.% La and 0.25wt.% Nd are added, and the mixture is continuously heated and stirred for 1h at 900 ℃ for fully mixing; when the mixed melt is cooled to 200 ℃, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min at 20kHz to lead to uniform mixing; casting to obtain a lithium alloy ingot after ultrasonic treatment is finished, and removing a surface oxide layer after cooling; then heating the obtained lithium alloy ingot to 110 ℃ and preserving heat for 4 hours, and then repeating the process for 2 times at 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 30 microns; and finally, slicing by using a slicer to obtain the composite metal lithium cathode suitable for the assembled battery.
The dendrite growth pattern was obtained using an in situ microscope test method, as shown in fig. 3, in example 5, the dendrite growth amount was small, and the dendrite growth of comparative example 1 was significantly higher.
Obtaining volume expansion XRD patterns by adopting a scanning electron microscope test method, wherein a and c are the volume expansion XRD patterns before the circulation of comparative examples 1 and 5 respectively as shown in figure 4; b. d is the volume expansion XRD patterns of comparative examples 1 and 5 after cycling, respectively; comparing a, b shows that comparative example 1 has a significantly higher volume expansion than example 5.
In an inert atmosphere glove box, use LiNi 0.8 Co 0.1 Mn 0.1 O 2 As the electrode positive electrode sheet, EC (ethylene carbonate) was used: DEC (diethyl carbonate): DMC (carbon)Dimethyl acid) =1:1:1 (volume ratio) as electrolyte, a 2032 button cell was assembled using the composite lithium metal anodes prepared in examples 1, 3, 5, followed by a rate performance test. The rate performance was demonstrated at discharge rates of 0.1C,0.5C,1C and 5C, and it is apparent from fig. 5 that example 5 has a higher specific discharge capacity at different discharge rates. Therefore, the adoption of the alloying means can obviously improve the multiplying power performance of the metal lithium anode material. The capacity retention rates of the examples and comparative examples are shown in table 1.
Table 1 elemental composition and capacity retention rates of examples and comparative examples
As seen from the capacity retention rates of examples 1 to 5 in table 1, the combination of four common metal elements and two rare earth metals is the best for Li anode modification, and the capacity retention rates are generally 90% or more; as can be seen from the elemental composition comparison and the capacity retention of example 1 and example 4, when the same combination of 4 common metal elements is employed, the two rare earth metals are different in combination, and the capacity retention of the resulting anode material is somewhat different. Fig. 2 is a graph showing comparison of electrochemical cycle performance of a full cell assembled using the negative electrode materials of comparative example 1, example 3, and example 5, and it can be seen from fig. 2 that the retention rates of examples 3 and 5 are high after 200 cycles, whereas the capacity retention rate of comparative example 1 is rapidly decreased during cycles.
Samples of the negative electrode materials of examples and comparative examples were passed through a roll to 30 μm, then slit into 12cm long strips of 2cm wide, and tested for tensile strength using a universal tester, and the test results are shown in table 2.
Table 2 tensile strength of negative electrode materials obtained in examples and comparative examples
As can be seen from the tensile strengths of examples 1 to 5 in table 2, the combination of four common metal elements and two rare earth metals has the best effect of modifying the Li anode, and the tensile strength reaches 3.5MPa or more; as can be seen from the elemental composition comparisons and tensile strengths of examples 1 and 4, when the same combination of 4 common metal elements is employed, the two rare earth metals are different in combination, and the resulting anode material also has a certain difference in tensile strength.
Example 6
Drying the alloy reaction furnace for 5 hours in a vacuum environment at 80 ℃, then heating the alloy reaction furnace to 600 ℃ under argon atmosphere, preserving heat for 2 hours, adding 1.5wt.% Al, 1.5wt.% Mg, 0.5wt.% Zn and 0.5wt.% Ca into the reaction furnace after the metal lithium is fully melted, and continuously stirring for 1 hour; after the above metals are fully mixed, 0.25wt.% La and 0.25wt.% Nd are added, and the mixture is continuously heated and stirred for 1h at 900 ℃ for fully mixing; when the mixed melt is cooled to 200 ℃, the smelting reaction kettle is placed in an annular ultrasonic instrument, and the ultrasonic treatment time is 30min at 20kHz to lead to uniform mixing; casting to obtain a lithium alloy ingot after ultrasonic treatment is finished, and removing a surface oxide layer after cooling; measuring the crystallinity of the material (namely the crystallinity of the material before heating), then heating the obtained lithium alloy ingot to 110 ℃, preserving heat for 4 hours, and then repeating the process for 2 times at room temperature; the material crystallinity (i.e., the material crystallinity after heating) was again measured. Fig. 6 shows XRD patterns before and after the heat treatment of the present example, and as is clear from fig. 6, diffraction peaks are significantly enhanced after the heat treatment, indicating that the crystallinity of the material after the heat treatment is significantly enhanced.
Although the application has been described herein with reference to illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure. More specifically, various modifications and improvements may be made to the component parts and/or arrangements of the subject combination layout within the scope of the disclosure. In addition to variations and modifications in the component parts and/or arrangements, other uses will be apparent to those skilled in the art.
Claims (10)
1. The preparation method of the lithium alloy composite anode material with high strength and high rate discharge is characterized by comprising the following steps of:
(1) Fully melting and mixing metallic lithium and metallic element Al, mg, zn, ca under the protection of inert atmosphere and under the first temperature condition to obtain a first molten liquid; the first temperature condition is less than 700 ℃;
(2) Adding at least two elements in the transition metal Y, zr, nb, mo, tc, ru, rh, pd, ag, cd, or adding at least two elements in the rare earth metal La, ce, nd, pr, gd and Er, or adding the mixed elements of the transition metal and the rare earth metal, and fully melting and mixing under a second temperature condition to obtain a second molten liquid; the second temperature condition is more than or equal to 700 ℃;
(3) Cooling the second molten liquid to below 200 ℃, and then performing ultrasonic treatment to uniformly mix;
(4) Casting to obtain a lithium alloy ingot, heating the lithium alloy ingot to 60-150 ℃, preserving heat for 1-6 hours, and then cooling to room temperature, wherein the process is repeated for at least 2 times;
(5) Preparing a lithium alloy ingot into a lithium alloy belt, and slicing to obtain a composite metal lithium anode, wherein the Li content is 80-98wt.% and the Al, mg, zn, ca content is respectively less than or equal to 5wt.%; the control amount of each transition metal or rare earth metal element is 0.01-3wt.%, respectively, and the total amount of transition metal and rare earth metal is not more than 5wt.%.
2. The method for preparing a lithium alloy composite negative electrode material for high-intensity and high-rate discharge according to claim 1, wherein the elements added in the step (2) are Nb and Ag, and the content of Nb and Ag in the composite metal lithium negative electrode is 0.2-0.3wt.% and 0.2-0.3wt.%, respectively.
3. The method for preparing a high-strength high-rate discharge lithium alloy composite negative electrode material according to claim 1, wherein the elements added in the step (2) are Nb and Cd, and the content of Nb and Cd in the composite metal lithium negative electrode is 0.2-0.3wt.% and 0.2-0.3wt.%, respectively.
4. The method for preparing a lithium alloy composite negative electrode material with high strength and high rate discharge according to claim 1, wherein the elements added in the step (2) are La and Ce, and the content of La and Ce in the composite metal lithium negative electrode is 0.08-0.12wt.% and 0.08-0.12wt.%, respectively.
5. The method for preparing a lithium alloy composite negative electrode material with high strength and high rate discharge according to claim 1, wherein the elements added in the step (2) are Nd and Ce, and the content of Nd and Ce in the composite metal lithium negative electrode is 0.08-0.12wt.% and 0.15-0.25wt.%, respectively.
6. The method for preparing a lithium alloy composite negative electrode material for high-intensity and high-rate discharge according to claim 1, wherein the elements added in the step (2) are La and Nd, and the content of La and Nd in the composite metal lithium negative electrode is 0.2-0.3wt.% and 0.2-0.3wt.%, respectively.
7. The method for producing a lithium alloy composite negative electrode material for high-intensity, high-rate discharge according to any one of claims 2 to 6, wherein the content of Al, mg, zn, ca in the composite metal lithium negative electrode is 1.5 to 2wt.%, 1 to 1.5wt.%, 0.4 to 0.6wt.%, 0.2 to 0.6wt.%, respectively, and the balance is a Li transition metal or a rare earth element.
8. The method for preparing a lithium alloy composite negative electrode material for high-intensity and high-rate discharge according to claim 7, wherein the first temperature condition is 300-650 ℃ and the second temperature condition is 700-900 ℃.
9. The lithium alloy composite negative electrode material with high strength and high rate discharge obtained by the preparation method of claim 8.
10. The use of the high-strength, high-rate discharge lithium alloy composite negative electrode material according to claim 9, characterized in that an ultra-thin lithium strip having a thickness of 10-50 μm is prepared as a negative electrode assembly battery.
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