CN115976500B - Lithium-based high-entropy alloy coating, preparation method and metal lithium battery - Google Patents
Lithium-based high-entropy alloy coating, preparation method and metal lithium battery Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 112
- 239000000956 alloy Substances 0.000 title claims abstract description 112
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 101
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012530 fluid Substances 0.000 claims abstract description 70
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- 238000000713 high-energy ball milling Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
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- 239000007789 gas Substances 0.000 description 27
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- 230000000052 comparative effect Effects 0.000 description 10
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- 238000011065 in-situ storage Methods 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 210000001787 dendrite Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
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- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910000636 Ce alloy Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910015243 LiMg Inorganic materials 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- -1 hydroxy acid esters Chemical class 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000642 polymer Polymers 0.000 description 2
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- 238000004808 supercritical fluid chromatography Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- FKZLAFQXOCKZOC-UHFFFAOYSA-N cerium lithium Chemical compound [Li][Ce] FKZLAFQXOCKZOC-UHFFFAOYSA-N 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
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- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of batteries, in particular to a lithium-based high-entropy alloy coating, a preparation method and a metal lithium battery. The preparation method of the alloy coating comprises the steps of mixing supercritical fluid and high-entropy alloy powder to obtain fluid for preparing the high-entropy alloy coating; and reacting the fluid for preparing the high-entropy alloy coating with metal lithium to form the lithium-based high-entropy alloy coating. By exerting the synergistic effect of the lithium-based high-entropy alloy layer, the high-entropy alloy layer simultaneously shows good fracture toughness, thermal stability, corrosion resistance, lithium affinity and interfacial stability, and has high lithium ion diffusion coefficient and low reactivity.
Description
Technical Field
The invention relates to the field of batteries, in particular to a lithium-based high-entropy alloy coating, a preparation method and a metal lithium battery.
Background
Along with the rapid development of new energy automobiles and energy storage fields, higher requirements are put on the energy density and safety of secondary batteries. Graphite has very stable electrochemical properties and is widely used in various fields. Although graphite cathode based on the embedded reaction principle has excellent stability, the theoretical specific capacity is only 375mAhg < -1 >, and the cathode specific capacity utilization level of the commercial lithium ion battery is close to the theoretical specific capacity, so that in order to realize the requirement of a high-energy-density battery, the research on cathode materials with high theoretical specific capacity is particularly important. Among the existing lithium ion battery anode materials, the lithium metal anode has extremely high theoretical specific capacity (3860 mAhg-1), the lowest electrode potential (-3.04 Vvs standard hydrogen electrode) and the lowest density of metal family (0.59 gcm-3). The lithium metal lithium cathode is used as a holy cup electrode in the field of batteries, and the energy density of the lithium metal lithium cathode is approximately 10 times higher than that of a traditional graphite cathode. However, the intrinsic high reaction interfacial activity and chemical/electrochemical instability of the lithium ion battery directly lead to defects of dendrite growth, low coulomb efficiency, short cycle life and the like, which prevent the practical application of the lithium metal in the secondary battery. The interface regulation and control of the metal lithium to passivate the metal lithium and improve the interface stability is the key point of the research of researchers.
In the prior art, although the lithium-sulfur secondary battery with the lithium-magnesium alloy as the negative electrode plays an effective role in inducing lithium ions to uniformly deposit and avoiding lithium dendrite growth, a large number of parallel cracks appear in the LiMg alloy after a bending test, and when the LiMg alloy is applied to the secondary battery as the negative electrode, the lithium-magnesium alloy is difficult to bear the defects of volume expansion/shrinkage, cracks and the like in the continuous deposition/stripping process of the lithium ions, so that the cycling stability of the battery is not facilitated. The surface of lithium metal is treated by adopting fluoride solution of rare earth element cerium, and an interface alloying protective film containing lithium cerium alloy on the surface is obtained by an in-situ means; however, the method involves organic solvents, which can cause environmental pollution; in addition, the method for forming the film on the surface of the metal lithium through the solution is not easy to control, and large-scale application is difficult to realize; finally, the function of the Li-Ce alloy layer is only to accelerate electron transfer at the interface, but not to improve the lithium ion diffusion coefficient of the interface layer, and not to alleviate the problem of uneven lithium deposition from the perspective of the lithium-based alloy layer.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a lithium-based high-entropy alloy coating, which comprises the following steps:
mixing the supercritical fluid with the high-entropy alloy powder to obtain a fluid for preparing the high-entropy alloy coating;
and reacting the fluid for preparing the high-entropy alloy coating with metal lithium to form the lithium-based high-entropy alloy coating.
Further, mixing the supercritical fluid with the high-entropy alloy powder to obtain a fluid for preparing the high-entropy alloy coating comprises:
forming a supercritical fluid from a precursor gas of the supercritical fluid, and mixing the supercritical fluid with the high-entropy alloy powder to obtain the fluid for preparing the high-entropy alloy coating.
Further, the reacting the fluid for preparing the high-entropy alloy coating with lithium metal to form a lithium-based high-entropy alloy coating comprises:
and flowing the fluid for preparing the high-entropy alloy coating into the high-pressure reaction kettle in which the metal lithium is placed for reaction to obtain the lithium-based high-entropy alloy coating.
Further, the high-entropy alloy powder is SnaAlbIncGed, wherein 0.2 is more than or equal to a is more than or equal to 0.23,0.2, b is more than or equal to 0.37,0.3, c is more than or equal to 0.5, d is more than or equal to 0.1 and more than or equal to 0.15, and a+b+c+d=1;
and/or the supercritical fluid is one or more of CO2, CO, NH3 or CF 4.
Further, the high-entropy alloy powder is obtained through high-energy ball milling.
Further, the conditions for high energy ball milling include: the ball material mass ratio is 3-4:1, the ball milling time is 10-30 h, and the rotating speed is 250-500 rpm; further, the ball milling mode is as follows: the first direction is rotated for 10-30min, stopped for 5-20min, and the second direction is rotated for 10-30min, stopped for 5-20min.
Further, the conditions for obtaining the fluid for preparing the high-entropy alloy coating are: the temperature is-150-160 ℃, the pressure is 1-90MPa, the rotating speed is 5-800 rad/min, and the time is 15min-12h;
and/or the lithium-based high-entropy alloy coating conditions are: the temperature is 0-180 ℃, the pressure is 0-70MPa, the time is 15min-6h, and the rotating speed is 5-800 rad/min.
Also provided is a lithium-based high-entropy alloy coating, including LiSnaAlbIncGed coatings, wherein 0.2 is greater than or equal to a is greater than or equal to 0.23,0.2, b is greater than or equal to 0.37,0.3, c is greater than or equal to 0.5, d is greater than or equal to 0.1 and greater than or equal to 0.15, and a+b+c+d=1.
Also provides a metal lithium battery comprising the lithium-based high-entropy alloy coating.
The beneficial effects of this patent are as follows:
the lithium-based high-entropy alloy layer LiSnAlInGe prepared by the method can solve the problems of poor fracture toughness, poor thermal stability, poor chemical stability and low lithium ion diffusion coefficient of a binary lithium alloy coating; in addition, the invention also generates the lithium-based high-entropy alloy layer on the lithium surface in situ by means of a supercritical fluid method, thereby relieving the problem of uneven lithium deposition caused by poor uniformity of the alloy layer and the defect of easy falling off in the battery cycle process. The preparation process has the characteristics of high controllability, small pollution and simple preparation. The high-entropy alloy layer which is tightly adhered to the surface of lithium metal and has good lithium affinity, lithium ion conductivity, corrosion resistance and strong toughness can be obtained, the metal lithium can be effectively passivated, the lithium ion is induced to be uniformly deposited, and the structural integrity of the metal lithium and the high-entropy alloy layer is maintained in the repeated deposition/stripping process of the lithium ion.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate and do not limit the invention.
FIG. 1 is a schematic structural view of a lithium-based high-entropy alloy layer preparation apparatus according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
The invention provides a preparation method of a lithium-based high-entropy alloy coating, which comprises the following steps: mixing the supercritical fluid with the high-entropy alloy powder to obtain a fluid for preparing the high-entropy alloy coating, wherein the fluid is used for preparing the high-entropy alloy coating; and reacting the fluid for preparing the high-entropy alloy coating with metal lithium to form the lithium-based high-entropy alloy coating.
According to the method, the lithium-based high-entropy alloy layer is generated on the surface of lithium in situ by means of the supercritical fluid method, so that the problem of uneven lithium deposition caused by poor uniformity of the alloy layer and the defect of easy falling off in the battery circulation process are relieved. The preparation process has the characteristics of high controllability, small pollution and simple preparation.
In another embodiment of the present invention, the preparation of the supercritical fluid is further included before the supercritical fluid is mixed with the high-entropy alloy powder to obtain the fluid for preparing the high-entropy alloy coating, and the preparation method of the supercritical fluid includes: the gas (precursor of the supercritical fluid) is heated and pressurized to form the supercritical fluid.
The supercritical fluid and the high-entropy alloy powder are mixed to obtain the fluid for preparing the high-entropy alloy coating, namely the formed supercritical fluid and the high-entropy alloy powder are mixed under the conditions of temperature rise and pressure to form the fluid for preparing the high-entropy alloy coating.
Specifically, for convenience and simplification of the preparation steps, the preparation process of the fluid for preparing the high-entropy alloy coating includes: and (3) introducing the gas in the gas storage unit into a high-pressure reaction kettle in which the high-entropy alloy powder is placed, and reacting the gas with the high-entropy alloy powder after forming a supercritical fluid in the high-pressure reaction kettle to obtain the fluid for preparing the high-entropy alloy coating.
Of course, the gas in the gas storage unit may be first formed into a supercritical fluid in an environment such as another autoclave, and then the supercritical fluid may be introduced into the autoclave in which the high-entropy alloy powder is placed to react.
In another embodiment of the present invention, the reacting the fluid for preparing the high entropy alloy coating with metallic lithium to form a lithium-based high entropy alloy coating comprises:
and flowing the fluid for preparing the high-entropy alloy coating into the high-pressure reaction kettle in which the metal lithium is placed for coating, so as to obtain the lithium-based high-entropy alloy coating.
The alloy powder and the metal lithium are placed in different high-pressure reaction kettles, so that the reaction of the fluid for preparing the high-entropy alloy coating and the metal lithium is facilitated, the reaction is more complete, and the formed alloy layer is more uniform and has no cracks.
In another embodiment of the invention, the high entropy alloy powder is SnaAlbIncGed, wherein 0.2. Gtoreq.a. 0.23,0.2. Gtoreq.b.gtoreq. 0.37,0.3. Gtoreq.c.gtoreq.0.5, 0.1. Gtoreq.d.gtoreq.0.15, and a+b+c+d=1.
The LiSnAlInGe high-entropy alloy layer formed by the method has a cocktail effect, and the interaction among the five components enables the high-entropy alloy layer to show more excellent characteristics than any single component, so that the high-entropy alloy layer simultaneously shows good fracture toughness, thermal stability, corrosion resistance, lithium philicity and interface stability, and has high lithium ion diffusion coefficient and low reactivity.
In another embodiment of the present invention, the supercritical fluid is CO 2 、CO、NH 3 Or CF (CF) 4 One or more of the following.
The supercritical fluid has wide source and low price, and is more beneficial to the realization of industrialization.
In another embodiment of the present invention, the high-entropy alloy powder is obtained by high-energy ball milling. The Sn powder, the Al powder, the In powder and the Ge powder can be mechanically alloyed by high-energy ball milling.
In another embodiment of the present invention, the conditions for high energy ball milling include: the ball material mass ratio is 3-4:1, the ball milling time is 10-30 h, and the rotating speed is 250-500 rpm; further, the ball milling mode is as follows: the first direction is rotated for 10-30min, stopped for 5-20min, and the second direction is rotated for 10-30min, stopped for 5-20min, and the process is repeated for a plurality of times until all the powder becomes alloy phase.
When the ball milling conditions are out of the above range, an effective alloy phase cannot be formed.
In another embodiment of the present invention, the high-entropy alloy powder is formed under the following conditions: the temperature is-150-160 ℃, the pressure is 1-90MPa, the rotating speed is 5-800 rad/min, and the reaction time is 15min-12h.
Under this condition, the gas may be converted into a supercritical state, and the solvent action is achieved by the supercritical state to dissolve and disperse the reactant (coating material), and the coating material reacts. The reaction time is the time after the coating material reacts.
The formation conditions of the high-entropy alloy powder coating are as follows: the temperature is 0-180 ℃, the pressure is 0-70MPa, the time is 15min-6h, and the rotating speed is 5-800 rad/min.
When the parameter is outside the above range, the coating property of lithium will be affected, resulting in uneven or incomplete coating thereof.
In another embodiment of the present invention, the lithium is a lithium sheet or a lithium strip.
An embodiment of the present invention provides a device for preparing the above-mentioned lithium-based high-entropy alloy coating, as shown in fig. 1, including: a gas storage unit 1 for storing a gas; a first autoclave 5, the first autoclave 5 being used for generating a supercritical fluid and a fluid for preparing a high-entropy alloy coating; and a second autoclave 12, wherein the second autoclave 12 is used for placing and coating a material to be coated; wherein, the gas storage unit 1 can be respectively communicated with the first autoclave 5 and the second autoclave 12, and the first autoclave 5 can be communicated with the second autoclave 12.
The device can be used for coating various material substrates, taking coated metallic lithium as an example, the metallic lithium can be placed in a second high-pressure reaction kettle 12, a coating material (high-entropy alloy powder) is placed in a first high-pressure reaction kettle 5, and gas of a gas storage unit can enter the first high-pressure reaction kettle 12 and the second high-pressure reaction kettle 12 respectively through fluid pipelines; after the gas enters a first high-pressure reaction kettle to form supercritical, under the action of the supercritical fluid serving as a solvent, the high-entropy alloy powder in the first reaction kettle forms fluid for preparing the high-entropy alloy coating, and the fluid for preparing the high-entropy alloy coating can enter a second high-pressure reaction kettle 12 through a fluid pipeline to react with the metal lithium to form the lithium-based high-entropy alloy coating.
The coating device disclosed by the invention is simple and easy to purchase, industrialization is easy to realize, and the modified metallic lithium anode prepared by the device has excellent interfacial compatibility stability, can effectively inhibit growth of lithium/sodium dendrite, and has excellent long-cycle performance when applied to all-solid-state batteries.
In another embodiment of the present invention, the first autoclave 5 includes a material placing chamber 8, a first rotating shaft 9, and a mesh drum 7, the mesh drum 7 is disposed in the first autoclave 5 through the first rotating shaft 9, the material placing chamber 8 is disposed in the mesh drum 7, and the first rotating shaft 9 can rotate the mesh drum 7 and the material placing chamber 8 when rotating.
Specifically, the first rotating shaft 9 is disposed at the bottom of the first autoclave 5, and the mesh drum 7 is coaxially connected to the first rotating shaft 9 through the first rotating shaft 9. When the first rotating shaft 9 rotates, the mesh drum 7 and the material placing cavity 8 are driven to rotate simultaneously, so that the high-entropy alloy powder in the material placing cavity 8 also rotates together.
In another embodiment of the present invention, the mesh of the mesh drum 7 is 500 to 2500 mesh.
The mesh in the range can lead the material to be dispersed uniformly, the particles to be fine, the coating effect to be better, and the coating to be more uniform.
In another embodiment of the present invention, the second autoclave 12 includes a second rotating shaft 13 and a stage 14, where the second rotating shaft 13 is connected to the stage 14, and when rotating, the second rotating shaft can drive the stage 14 to rotate.
Specifically, the second rotating shaft 13 is disposed at the bottom of the second autoclave 12, the stage 14 is disposed at a side of the second rotating shaft 13 away from the bottom of the autoclave 12, and when the second rotating shaft 13 rotates, the stage 14 rotates together, thereby driving the metallic lithium placed on the stage 14 to rotate together.
In another embodiment of the present invention, a first pipeline valve 4 is connected between the gas storage unit 1 and the second autoclave 12. The first pipe valve 4 can control the communication and non-communication between the gas storage unit 1 and the second autoclave 12. When the first pipeline valve 4 is opened, the gas storage unit 1 is communicated with the second high-pressure reaction kettle 12, and when the first pipeline valve 4 is closed, the gas storage unit 1 is not communicated with the second high-pressure reaction kettle 12.
In another embodiment of the present invention, a second pipeline valve 11 is connected between the first autoclave 5 and the second autoclave 12. The second pipeline valve 11 can control the communication between the first autoclave 5 and the second autoclave 12. When the second pipeline valve 11 is opened, the first high-pressure reaction kettle 5 is communicated with the second high-pressure reaction kettle 12, and when the second pipeline valve 11 is opened, the first high-pressure reaction kettle 5 is not communicated with the second high-pressure reaction kettle 12.
In another embodiment of the invention, the apparatus further comprises a hydraulic pump 2 for pumping the gas in the gas storage unit 1 into the autoclave 5 or 12.
In another embodiment of the present invention, the apparatus further comprises pressure gauges 6 respectively disposed on the first autoclave 5 and the second autoclave 12 for monitoring and displaying the pressure in the autoclaves.
In another embodiment of the present invention, the apparatus further comprises an air outlet 15, which is disposed on the second autoclave 12, for discharging the air in the second autoclave.
Another embodiment of the invention also provides a lithium-based high-entropy alloy coating, comprising a SnaAlbIncGed coating, wherein 0.2 is greater than or equal to a 0.23,0.2, b is greater than or equal to 0.37,0.3, c is greater than or equal to 0.5, d is greater than or equal to 0.1 and greater than or equal to 0.15, and a+b+c+d=1.
The invention also provides a metal lithium battery, which comprises the lithium-based high-entropy alloy coating.
In another embodiment, the metal lithium battery further comprises a positive electrode material, wherein the positive electrode material is lithium iron phosphate, lithium manganese phosphate, lithium cobalt phosphate, carbon-coated lithium iron phosphate or a ternary layered electrode material.
In another embodiment, the lithium metal battery further comprises an electrolyte material comprising an electrolyte solution comprising carbonates, ethers, and/or hydroxy acid esters, and a solid electrolyte comprising a polymer, oxide, and/or sulfide solid electrolyte.
In another embodiment, the positive electrode material and the negative electrode material (i.e., the metal lithium of the coating layer) are mixed according to the mass ratio of 50-95 parts: 50-95 parts.
In order to more clearly demonstrate the preparation method of the present application, the following examples and comparative examples are described.
Example 1
According to Sn, al, in, ge, the atomic ratio is 0.21:0.27:0.41:0.11 weighing Sn powder, al powder, in powder and Ge powder, and mixing to obtain raw material powder;
carrying out high-energy ball milling treatment on the raw material powder in an argon protective atmosphere, wherein the ball material mass ratio is 3.5:1, the ball milling time is 20h, the rotating speed is 300rpm, and the ball milling mode is set as follows: clockwise for 20min, stopping for 10min, anticlockwise for 20min, stopping for 10min, and reciprocating so as to mechanically alloy to obtain high-entropy alloy powder Sn 0.21 Al 0.27 In 0.41 Ge 0.11 ；
Placing the above high entropy alloy powder in supercritical fluid reaction device shown in figure 1, introducing CO into gas storage unit at 7.3MPa and 31.2deg.C 2 And (3) entering a first high-pressure reaction kettle and changing the powder into a supercritical fluid, so that the high-entropy alloy powder in the first high-pressure reaction kettle is uniformly mixed with the supercritical fluid. In a second high-pressure reaction kettle, high-entropy alloy powder Sn 0.21 Al 0.27 In 0.41 Ge 0.11 The metal lithium reacts spontaneously with the metal lithium in a supercritical fluid atmosphere, and the specific reaction conditions are as follows: the temperature is 30 ℃, the pressure is 0.1MPa, the time is 2 hours, and the rotating speed is 500rad/min.
In-situ generation of lithium-based high-entropy alloy coating Sn on surface of lithium sheet 0.21 Al 0.27 In 0.41 Ge 0.11 。
And opening the reaction kettle, taking out the metal lithium protected by the lithium-based high-entropy alloy layer, and cutting into a proper size. In an argon glove box, liFePO4 electrode sheet was used as the positive electrode, using a commercial ether electrolyte (1 mliffsi dissolved in DOL to DME volume ratio=1:1), the amount of electrolyte was 50 μl. Celgard2325 was used as a diaphragm, button cells were prepared in button molds, sealed with a sealer, and stored in a glove box for testing, and the test results are shown in Table 1.
Example 2:
the atomic ratio of Sn powder, al powder, in powder, ge powder was replaced with 0.2:0.32:0.38:0.1; the high-energy ball milling treatment conditions are replaced by: ball material mass ratio is 3.8:1, ball milling time is 25h, rotation speed is 320rpm, the ball milling machine rotates for 10 minutes in the first direction, stops for 5 minutes, rotates for 10 minutes in the second direction, and stops for 5 minutes; the gas is replaced by CO; placing the high-entropy alloy powder into a supercritical fluid reaction device, and introducing gas CO into the supercritical fluid reaction device at the pressure of 3.5MPa and the temperature of-140.2 ℃ to change the gas CO into the supercritical fluid, so that the high-entropy alloy powder and the supercritical fluid are uniformly mixed; the conditions to obtain the fluid used to prepare the high entropy alloy coating are replaced by: -140.2 ℃, 3.5MPa pressure, 5rad/min rotational speed; the reaction conditions of the second reaction kettle and lithium are as follows: the pressure is 0.1MPa, the temperature is 30 ℃, the time is 1h, and the rotating speed is 700rad/min; the electrolyte was replaced with a 1M lithium hexafluorophosphate (LiPF 6) solution in a volume ratio of Ethylene Carbonate (EC)/diethyl carbonate (DEC) =1:1, otherwise the same as in example 1, and the test results are shown in table 1.
Example 3:
the atomic ratio of Sn powder, al powder, in powder, ge powder was replaced with 0.23:0.29:0.33:0.15; the high-energy ball milling treatment conditions are replaced by: ball material mass ratio is 3.7:1, ball milling time is 25h, rotation speed is 250rpm, the first direction is rotated for 30 minutes, stopping for 20 minutes, the second direction is rotated for 30 minutes, stopping for 20 minutes; gas substitution to NH 3 The method comprises the steps of carrying out a first treatment on the surface of the The method comprises the steps of carrying out a first treatment on the surface of the Introducing gas NH at 11.3MPa and 135.2 deg.C 3 Changing into supercritical fluid, and uniformly mixing the high-entropy alloy powder with the supercritical fluid. The reaction condition of the second reaction kettle and lithium is that the pressure is 0.1MPa, the temperature is 30 ℃, the time is 2 hours, and the rotating speed is 600rad/min; the positive electrode is replaced by LiNi 0.8 Co 0.1 Mn 0.1 O 2 The electrolyte is replaced by PVDF-HFP/LiTFSI polymer solid electrolyte; otherwise, the test results are shown in Table 1, which is the same as in example 1.
Example 4:
the atomic ratio of Sn powder, al powder, in powder, ge powder was replaced with 0.2:0.2:0.5:0.1; the high-energy ball milling treatment conditions are replaced by: ball material mass ratio is 4:1, ball milling time is 30h, and rotating speed is 500rpm; placing the high-entropy alloy powder into a supercritical fluid reaction device, and introducing gas CF under the conditions of 3.739MPa and 45.6 DEG C 4 Changing into supercritical fluid, and uniformly mixing the high-entropy alloy powder with the supercritical fluid; the reaction conditions of the second reaction kettle and lithium are as follows: the pressure is 0.1MPa, the temperature is 30 ℃, the time is 1.5 hours, and the rotating speed is 650rad/min; the electrolyte is replaced by PEO/LLZTO/LiTFSI composite solid electrolyte; otherwise, the test results are shown in Table 1, which is the same as in example 1.
Comparative example 1
Li symmetric cells were assembled to test electrochemical stability using bare lithium (uncoated) 16.0mm in diameter as the working electrode. The Li symmetric battery was tested under constant current charge/discharge conditions at room temperature. The electrolyte was the same as in example 1. The specific test results are shown in Table 1.
Comparative example 2
The atomic ratio of Sn powder, al powder, in powder, ge powder was replaced with 0.5:0.1:0.2:0.2, other steps and parameters were the same as in example 1. The specific test results are shown in Table 1.
Comparative example 3
Mechanically alloying powder Sn 0.21 Al 0.27 In 0.41 Ge 0.11 Dissolving in anhydrous acetonitrile serving as an inert solvent, heating and stirring at 100 ℃ at a rotating speed of 500rad/min for 12 hours to obtain uniformly mixed slurry. The slurry is dripped on a lithium sheet, a doctor blade is used for coating on the lithium sheet through a tape casting method, and after the alloy powder and the metallic lithium spontaneously react to form a lithium-based alloy layer in situ, the lithium-based alloy layer is dried at room temperature for 24 hours. After the solvent is thoroughly evaporated, the surface of the lithium sheet is covered with a lithium-based high-entropy alloy coating LiSn0.21Al0.27In0.41Ge0.11. All of the above operations were carried out in a glove box (O) 2 <0.1ppm，H 2 O<0.1 ppm).
Comparative example 4
The reaction conditions of the first autoclave were replaced with: the temperature is 160 ℃ below zero, the pressure is 0.5MPa, the rotating speed is 3rad/min, and the reaction time is 10min; other steps and parameters were the same as in example 1. The specific test results are shown in Table 1.
Comparative example 5
The reaction conditions of the second autoclave were replaced with: the pressure is 80MPa, the temperature is 200 ℃, the time is 5min, and the rotating speed is 2rad/min; other steps and parameters were the same as in example 1. The specific test results are shown in Table 1.
Comparative example 6
The conditions of the high-energy ball milling are replaced by: ball mass ratio 2, ball milling time 5h, rotational speed 100rpm; other steps and parameters were the same as in example 1. The specific test results are shown in Table 1.
The products of examples and comparative examples were tested and the results are shown in table 1.
Table 1 properties of examples and comparative examples
As can be seen from the above table, the performance of the battery anode prepared by the examples of the present application is far superior to that of the comparative example.
Although the embodiments of the present invention are described above, the embodiments are only used for facilitating understanding of the present invention, and are not intended to limit the present invention. Any person skilled in the art can make any modification and variation in form and detail without departing from the spirit and scope of the present disclosure, but the scope of the present disclosure is to be determined by the appended claims.
Claims (6)
1. The preparation method of the lithium-based high-entropy alloy coating is characterized by comprising the following steps of:
mixing the supercritical fluid with the high-entropy alloy powder to obtain a fluid for preparing the high-entropy alloy coating;
reacting the fluid for preparing the high-entropy alloy coating with lithium metal to form a lithium-based high-entropy alloy coating;
wherein the high-entropy alloy powder is Sn a Al b IncGe d Wherein 0.2.gtoreq.a.gtoreq. 0.23,0.2.gtoreq.b.gtoreq. 0.32,0.33.gtoreq.c.gtoreq.0.5, 0.1.gtoreq.d.gtoreq.0.15, a+b+c+d=1;
the conditions for obtaining the fluid for preparing the high-entropy alloy coating are as follows: forming a supercritical fluid from a precursor gas of the supercritical fluid, mixing the supercritical fluid with the high-entropy alloy powder at a temperature of-150-160 ℃, a pressure of 1-90MPa, a rotating speed of 5-800 rad/min and a time of 15min-12h;
the conditions for obtaining the lithium-based high-entropy alloy coating are as follows: and (3) flowing the fluid for preparing the high-entropy alloy coating into a high-pressure reaction kettle in which metal lithium is placed for reaction, wherein the temperature is 0-180 ℃, the pressure is 0-70MPa, the time is 15min-6h, and the rotating speed is 5-800 rad/min.
2. The method of claim 1, wherein the supercritical fluid is CO 2 、CO、NH 3 Or CF (CF) 4 One or more of the following.
3. The method of claim 1, wherein the high-entropy alloy powder is obtained by high-energy ball milling.
4. The method of claim 3, wherein the high energy ball milling conditions include: the ball material mass ratio is 3-4:1, the ball milling time is 10-30 h, and the rotating speed is 250-500 rpm; further, the ball milling mode is as follows: the first direction is rotated for 10-30min, stopped for 5-20min, and the second direction is rotated for 10-30min, stopped for 5-20min.
5. A lithium-based high-entropy alloy coating prepared by the preparation method of any one of claims 1 to 4.
6. A metallic lithium battery comprising the lithium-based high-entropy alloy coating of claim 5.
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