CN113113680A - Partially etched MAX material and preparation method and application thereof - Google Patents

Partially etched MAX material and preparation method and application thereof Download PDF

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CN113113680A
CN113113680A CN202110382533.0A CN202110382533A CN113113680A CN 113113680 A CN113113680 A CN 113113680A CN 202110382533 A CN202110382533 A CN 202110382533A CN 113113680 A CN113113680 A CN 113113680A
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lithium
partially etched
max
etched max
stainless steel
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冯金奎
魏传亮
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Shandong University
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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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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 belongs to the technical field of lithium ion batteries, and particularly relates to a material, and a preparation method and application thereof. And an interlayer pit in the partially etched MAX material is used as a 'host' of the metallic lithium, and a lithium-philic 'A' layer remained between the partially etched MAX layers is used as a nucleating agent, so that the uniform deposition of the lithium between the layers is induced, the volume expansion of the electrode is relieved, and the stability of the metallic lithium cathode is finally improved. And the interlayer pits in the MAX which are partially etched are used as hosts of the metal lithium, so that the deposition and distribution of the lithium are more uniform, and the volume expansion effect of the electrode in the charging and discharging processes is relieved.

Description

Partially etched MAX material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a material, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Lithium metal batteries are considered to be one of the most promising energy storage devices due to their higher energy density. Lithium metal batteries employ metallic lithium as the negative electrode material. Metallic lithium is widely used as a negative electrode materialAdvantages include high theoretical specific capacity (3860mAh/g), ultra-low electrochemical potential (-3.04V/vs. standard hydrogen electrode), light weight (0.534 g/cm)3) Good conductivity, etc. However, the metallic lithium negative electrode has some problems such as growth of lithium dendrite, large volume expansion effect, unstable Solid Electrolyte Interface (SEI), high chemical reactivity, and the like. These problems severely hamper the use of metallic lithium negative electrodes in lithium metal batteries.
Currently, researchers have proposed many strategies for modifying lithium metal anodes, such as designing three-dimensional current collectors, designing "hosts" for lithium metal, membrane modification, electrolyte modification, designing artificial SEI, using nucleating agents, and the like. These methods improve the stability of the lithium metal negative electrode to some extent. However, the inventors have studied and found that: many modification strategies reported at present are single, only a certain problem of the lithium metal negative electrode is considered, and the deposition process and the electrochemical performance stability of the lithium metal negative electrode cannot be comprehensively improved. However, most of the methods reported at present are based on MXene loading, modification and structural design, the preparation process is complex, and the characteristics of MAX materials cannot be fully utilized. In addition, when lithium is deposited on the surface of the accordion-shaped MXene material, the lithium is preferentially deposited on the surface or the edge of the lamellar structure, and is difficult to deposit in the interlayer internal area, so that uneven lithium deposition and growth of lithium dendrites are easily caused, and the stability of the metal lithium negative electrode is reduced.
Disclosure of Invention
In order to solve the problems of complex MAX etching process and poor effect in the prior art, the invention provides a partially etched MAX material and a preparation method and application thereof.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, a partially etched MAX material is provided, wherein the partially etched MAX material is of a lamellar structure, and the lamellar structure is provided with pits and is free of through holes.
In a second aspect, the present invention provides a method for preparing a partially etched MAX material, comprising: and partially etching the MAX material by adopting an etching method to ensure that the sheet layer is provided with pits and has no through holes.
In a third aspect of the present invention, there is provided a highly stable lithium metal anode material comprising: lithium metal, a current collector and the partially etched MAX material of claim 1.
In a fourth aspect of the present invention, a method for preparing a high-stability lithium metal negative electrode material is provided, which includes: and coating the partially etched MAX material on a current collector, and depositing metal lithium on the current collector coated with the partially etched MAX.
In a fifth aspect of the invention, an application of the partially etched MAX material and/or the high-stability metallic lithium negative electrode material in a lithium battery, an electric vehicle, a smart grid, and a mobile energy storage device is provided.
In a sixth aspect of the invention, a lithium battery is provided comprising a partially etched MAX material and/or a highly stable metallic lithium anode material.
In a seventh aspect of the invention, an electric vehicle is provided comprising a partially etched MAX material and/or a highly stable metallic lithium negative electrode material.
In an eighth aspect of the invention, a smart grid is provided, which comprises a partially etched MAX material and/or a high-stability metallic lithium negative electrode material.
In a ninth aspect, the invention provides a mobile energy storage device, comprising a partially etched MAX material and/or a high stable metallic lithium negative electrode material.
One or more embodiments of the present invention have the following advantageous effects:
(1) the invention adopts the interlayer pits in the MAX which are partially etched as the 'hosts' of the metal lithium, so that the deposition and distribution of the lithium are more uniform, and the volume expansion effect of the electrode in the charging and discharging process is relieved.
(2) The MAX material forms a multilayer structure through incomplete etching, atoms (such as Al, Ga, Si and the like) of a weaker 'A' layer are combined in the MAX phase and are etched, because the MAX phase is incompletely etched, pits are only generated on a lamellar structure, through holes do not appear, the 'A' layer with lithium affinity remained in the pits between layers is used as a nucleating agent, and the uniform and compact deposition of lithium in the holes is induced, so that the deposition of lithium can be realized in the inner area between the layers, and the lithium is prevented from being deposited only on the surface or the edge of the lamellar structure.
(3) The invention adopts functional groups (such as-O, -OH, -F and the like) in the partially etched MAX to regulate and control ion flow and stabilize an interface, and inhibits the growth of lithium dendrite. Wherein the-O and-OH functional groups have lithium affinity, can reduce the nucleation barrier of lithium, induce uniform ion flow in the lithium deposition process and inhibit the growth of lithium dendrites. F can form LiF with lithium, and can be used as an artificial SEI layer to improve the interface stability of the lithium metal cathode.
(4) The invention comprehensively considers the inherent problems of the metallic lithium cathode and synthesizes the metallic lithium cathode material with good safety, high stability and long cycle life.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a schematic flow chart of the preparation of high-stability lithium metal anode materials in examples 1 to 11 of the present invention.
FIG. 2 shows Ti in comparative example and example 1 of the present invention3AlC2MAX obtained by partial etching after 0.5h of HF etching and Ti obtained by 25h of HF etching3C2X-ray diffraction pattern of MXene.
Fig. 3 is a scanning electron microscope image of a MAX of a partial etching obtained by etching for 0.5h in embodiment 1 of the present invention.
FIG. 4 is a scanning electron microscope image of the deposition profile of lithium on a partially etched MAX electrode in accordance with embodiment 1 of the present invention.
FIG. 5 shows Ti obtained by etching with HF for 25 hours in comparative example of the present invention3C2Scanning electron microscope image of MXene.
FIG. 6 shows a comparative example of the present invention in which lithium is Ti3C2Scanning electron microscope images of deposition morphology on MXene electrodes.
FIG. 7 shows the results of the present invention in which lithium is present in Ti in comparative example and example 13C2Coulombic efficiency plots of deposition/lift-off process on MXene electrode and partially etched MAX electrode.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
MXene, an emerging two-dimensional material, is etched from MAX phase, where M represents a transition metal in the early stages of the periodic Table (e.g., Ti, V, Nb, Mo, Cr, Zr, Ta, Hf, Sc, etc.), A represents an element belonging to groups 13-16 of the periodic Table (e.g., Al, Si, Sn, Ge, etc.), and X represents an element C or N. The MXene reported at present is obtained by completely etching the element A in the MAX phase, has the problems of complex synthesis, long etching time, more etchant dosage, high cost, great environmental pollution and the like, and has been widely applied to stabilizing the metallic lithium cathode. In addition, when lithium is deposited on the surface of the accordion-shaped MXene material, the lithium is preferentially deposited on the surface or the edge of the lamellar structure, and is difficult to deposit in the interlayer internal area, so that uneven lithium deposition and growth of lithium dendrites are easily caused, and the stability of the metal lithium negative electrode is reduced.
In order to solve the problems of complex MAX etching process, difficult lithium deposition and poor effect in the prior art, the invention provides a partially etched MAX material and a preparation method and application thereof.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, a partially etched MAX material is provided, wherein the partially etched MAX material is of a lamellar structure, and the lamellar structure is provided with pits and is free of through holes.
The invention uses the pits existing among the layers of the partially etched MAX material as the 'hosts' of the metallic lithium cathode, and relieves the volume expansion effect of the electrode in deposition/stripping. The remaining lithium-philic "a" layer between the partially etched MAX material layers was used as a nucleating agent to induce uniform dense deposition of lithium in the pits between the layers. In the process of depositing the metallic lithium, because the alloying potential of the layer A and the metallic lithium is higher than the lithium deposition potential, the metallic lithium preferentially generates an alloying reaction with the layer A remained between the layers to generate a lithium-based alloy, then the metallic lithium continuously grows on the alloy, and finally the metallic lithium fills pits between the layers to grow on the surface or the edge of the lamellar structure. In addition, functional groups in the partially etched MAX material can further regulate ion flow and improve an interface, and generation of lithium dendrites is inhibited. Under the synergistic effect of the positive effects, the stability of the metallic lithium negative electrode is obviously improved.
Whereas for a fully etched MAX (i.e., MXene) a porous structure is formed on the sheet because the "a" layer is fully etched. Due to the absence of the lithium-philic "a" layer, under the effect of the "tip effect", lithium deposition is difficult to preferentially deposit into the pores between the layers, but rather to the MXene surface layer or edge region, thereby causing uneven lithium deposition and a larger electrode volume expansion effect.
The MAX material is selected from Ti3AlC2、Ti2AlC、V2AlC、Ti2AlN、Ta4AlC3、Nb4AlC3、Mo2Ga2C、Ti3SiC2Any one of them.
In a second aspect, the present invention provides a method for preparing a partially etched MAX material, comprising: and partially etching the MAX material by adopting an etching method to ensure that the sheet layer is provided with pits and has no through holes.
Preferably, the etching method includes any one of a fluorine-based aqueous solution etching method, an alkali etching method, an electrochemical etching method, an anhydrous etching method, a hydrothermal etching method, a molten salt etching method, and the like;
in the invention, the etching method is not particularly limited as long as the etching effect can be achieved, and part of the element of the layer A is stripped or etched.
Preferably, the etchant is selected from the group consisting of HF, LiF, NH4HF2、KHF2、NaOH、H2O2One or more of HCl;
preferably, the etchant is selected from HF and NH4HF2；
Preferably, the mass fraction of the etching agent is 5% -40%, preferably 40%;
preferably, the dosage of the etching agent is 5-50 mL;
preferably, the ratio of the MAX material to the etchant is 0.5g:5-15ml, preferably 0.5g:10 ml;
preferably, the temperature of the water bath in the etching method is 30-80 ℃;
preferably, the etching time of the water bath in the etching method is 0.1-1 h.
During the partial etching process of the solution, the type and concentration of the etchant can affect the etching effect, if the concentration is too high or the dosage is too much, the material is easily etched completely, a through hole is generated, a pit structure cannot be formed for depositing lithium, and the distribution of lithium and the electrochemical performance of the material are further affected.
Similarly, when the water bath etching time is too long or the temperature is too high in the etching method, the MAX material can be completely etched, through holes are formed in the formed lamellar structure, a lithium-philic 'A' layer does not exist, lithium cannot be uniformly deposited, and the electrochemical performance is affected.
In a third aspect of the present invention, there is provided a highly stable lithium metal anode material comprising: lithium metal, a current collector and the partially etched MAX material of claim 1.
Preferably, the loading of the partially etched MAX powder on the current collector is between 0.1 and 5mg/cm2Preferably 2mg/cm2(ii) a Too little loading can result in too few "hosts" being provided for the metallic lithium, affecting the uniform deposition of lithium, and being not conducive to the exertion of electrochemical properties.
Preferably, the current collector is any one of copper foil, copper mesh, copper foam, iron foil, carbon cloth and carbon paper.
In a fourth aspect of the present invention, a method for preparing a high-stability lithium metal negative electrode material is provided, which includes: and coating the partially etched MAX material on a current collector, and depositing metal lithium on the current collector coated with the partially etched MAX.
The lithium deposition is carried out in an inert atmosphere, wherein the inert atmosphere is argon, nitrogen, hydrogen-argon mixed gas, helium, vacuum atmosphere and the like, the oxygen content of the lithium deposition is less than 0.1ppm, and the moisture content of the lithium deposition is less than 0.1 ppm.
The lithium deposition current is 0.1-10mA/cm2Preferably 0.5 to 10mA/cm2More preferably 5mA/cm2。
The lithium deposition capacity is 0.1-20mAh/cm2Preferably 0.5-20mAh/cm2More preferably 15mAh/cm2。
In the MXene material formed by complete etching, if the lithium deposition current is too high or the deposition capacity is too large, lithium is only deposited at the edges of the lamella and cannot penetrate into the inner area between the lamellas. In the invention, pits are generated between layers by incompletely etching the MAX material, and the lithium-philic A layer is remained as a nucleating agent to induce uniform and compact deposition of lithium in interlayer holes, so that lithium can be uniformly deposited even under higher deposition current or larger deposition capacity, and the preparation efficiency and effect are improved. If the MAX material is not etched, no lamellar structure is generated, large-area pits and a lithium-affinity A layer are not generated, and the difficulty of uniform lithium deposition is higher.
The method further comprises a step of drying after the partially etched MAX material is coated on the current collector, wherein the drying temperature is 50-100 ℃.
The anode matched with the high-stability metal lithium cathode material comprises any one of lithium iron phosphate, a ternary material, lithium cobaltate, lithium manganate, a lithium-rich manganese-based material and the like.
In a fifth aspect of the invention, an application of the partially etched MAX material and/or the high-stability metallic lithium negative electrode material in a lithium battery, an electric vehicle, a smart grid, and a mobile energy storage device is provided.
The electrolyte of the lithium battery is ether, ester or nitrile.
In a sixth aspect of the invention, a lithium battery is provided comprising a partially etched MAX material and/or a highly stable metallic lithium anode material.
In a seventh aspect of the invention, an electric vehicle is provided comprising a partially etched MAX material and/or a highly stable metallic lithium negative electrode material.
In an eighth aspect of the invention, a smart grid is provided, which comprises a partially etched MAX material and/or a high-stability metallic lithium negative electrode material.
In a ninth aspect, the invention provides a mobile energy storage device, comprising a partially etched MAX material and/or a high stable metallic lithium negative electrode material.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
Preparation and application of a partially etched MAX stabilized metallic lithium anode material comprising the following steps (fig. 1):
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, thus obtaining the partially etched MAX powder, wherein the X-ray diffraction spectrum and the scanning electron microscope spectrum of the partially etched MAX powder are respectively shown as figure 2 and figure 3.
The X-ray diffraction pattern showed that the partially etched MAX material prepared in this example was compared to the fully etched MXene material with Ti3AlC2The peaks of (a) are almost identical and the peak intensity is reduced. The partially etched MAX material has already been created as a layered structure with pits.
(4) And (3) uniformly mixing the partially etched MAX powder obtained in the step (3) and the PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil current collector, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2The scanning electron micrograph after deposition is shown in FIG. 4. As can be seen, lithium is uniformly distributed on the surface, edges and inside of the lamellar structure, and no aggregated or large-area plate-hardened lithium deposits occur.
The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 2
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g V2The AlC MAX powder was slowly added in several portions to a teflon beaker containing 10mL HF etchant solution (40% by mass). At the addition of V2The process of AlC powder needs to be stirred by magnetic force continuously.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 3
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3SiC2The MAX powder was slowly added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3SiC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode and electricityAn electrolyte and a membrane.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 4
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a Teflon beaker containing 30mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 5
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a Teflon beaker containing 50mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte, taking the partially etched MAX electrode plate in the step (4) as one electrode, and taking metal lithium as metal lithiumTo the electrodes, CR2032 type button cells were assembled in an inert atmosphere. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 6
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at the temperature of 60 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of the partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 7
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at the temperature of 80 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) Mixing the partially etched MAX powder obtained in the step (3) with PVAnd uniformly mixing the DF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying the copper foil in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 8
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.2h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 9
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.8h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium iron phosphate anode, and assembling the lithium iron phosphate anode and the partially etched MAX stable metal lithium cathode into a high-energy-density lithium metal battery by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 10
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3AlC2MAX powder SlowThe mixture was added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a ternary material anode, and assembling the lithium metal battery with high energy density by using a CR2032 button cell in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Example 11
The preparation and application of the partially etched MAX stable metallic lithium anode material comprise the following steps:
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 0.5h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out, and the partially etched MAX powder is obtained.
(4) And (4) uniformly mixing the partially etched MAX powder obtained in the step (3) and a PVDF binder in an NMP solvent according to the mass ratio of 9:1, then coating the mixture on a copper foil, and drying in vacuum to obtain the partially etched MAX electrode slice. The loading of partially etched MAX powder on the copper foil was 2mg/cm2。
(5) In 1M-LiPF6And (4) assembling the CR2032 button cell in an inert atmosphere in-EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte by taking the partially etched MAX electrode plate in the step (4) as one electrode and metallic lithium as a counter electrode. Then, the button cell is controlled by charging and discharging equipment, electrochemical deposition of lithium is carried out on the partially etched MAX electrode, and the deposition current is 0.2mA/cm2The deposition amount is 0.2mAh/cm2'. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate, a partially etched MAX electrode, electrolyte and a diaphragm.
(6) And (4) disassembling the button cell deposited with the lithium in the step (5) in an inert atmosphere to obtain the partially etched MAX stable metallic lithium cathode.
(7) Matching the partially etched MAX stable metal lithium cathode obtained in the step (6) with a lithium-rich manganese-based material anode, and assembling a CR2032 button cell into a high-energy-density lithium metal battery in an inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring sheet (stainless steel), a positive electrode, a metallic lithium negative electrode stabilized by partially etched MAX, electrolyte and a diaphragm.
Comparative example
The implementation of the comparative example mainly comprises the following steps:
(1) 0.5g of Ti3AlC2The MAX powder was slowly added in portions to a polytetrafluro beaker containing 10mL of HF etchant solution (40% by mass). After adding Ti3AlC2Magnetic stirring is required continuously during the powder process.
(2) And (3) putting the polytetrafluoroethylene beaker in the step (1) into a water bath kettle at 40 ℃, magnetically stirring for 25h, and finishing etching.
(3) And (3) centrifugally washing the etched sample in the step (2) until the pH is close to neutral. Then filtering and vacuum drying are carried out to obtain the completely etched Ti3C2MXene powder, its X-ray diffraction pattern and scanning electron microscope pattern are shown in FIG. 2 and FIG. 5 respectively.
X-ray diffraction pattern shows that compared with Ti3AlC2The strength of characteristic peaks of the MAX material and the MXene material is further reduced, even some characteristic peaks disappear, and therefore some atoms are completely etched to form through holes, and no lithium-philic sites exist.
MXene is displayed by a scanning electron microscope atlas to have a more obvious lamellar structure, and the lamellar structure is provided with larger through holes.
(4) Ti obtained in the step (3)3C2Mixing MXene powder and PVDF binder uniformly in NMP solvent at a mass ratio of 9:1, then coating on copper foil, and drying in vacuum to obtain Ti3C2MXene electrode slice. Ti3C2The loading capacity of MXene powder on the copper foil is 2mg/cm2。
(5) In 1M-LiPF6EC/DEC (1:1v/v) -10 wt% FEC liquid electrolyte, with Ti in step (4)3C2The MXene electrode plate is used as one electrode, the metal lithium is used as a counter electrode, and the CR2032 button cell is assembled in an inert atmosphere. Then controlling the button cell by using a charging and discharging device at Ti3C2Electrochemical lithium deposition and current deposition are carried out on MXene electrodeIs 0.2mA/cm2The deposition amount is 0.2mAh/cm2The scanning electron micrograph after deposition is shown in FIG. 6. As can be seen from the figure, lithium is only deposited on the MXene surface to form a larger plate-shaped morphology, which indicates that the uniformity of lithium deposition on the MXene surface is inferior to that of example 1, and the formed plate-shaped lithium layer prevents lithium from being deposited inside the lamellar structure, so that the electrical performance is also inferior to that of example 1.
The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a lithium plate and Ti3C2MXene electrode, electrolyte and diaphragm.
(6) Disassembling the button cell deposited with lithium in the step (5) in inert atmosphere to obtain Ti3C2MXene-based metal lithium negative electrodes.
(7) Ti obtained in the step (6)3C2MXene-based metal lithium cathode is matched with lithium iron phosphate anode, and the high-energy density lithium metal battery is assembled by using CR2032 button cell in inert atmosphere. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a spring plate (stainless steel), a positive electrode and Ti3C2MXene-based metal lithium negative electrode, electrolyte and diaphragm.
Performance testing
(1) The coulombic efficiency of the partially etched MAX electrode was tested with a charge and discharge device (nover CT-4008) using the button cell assembled in example 1 as an example. Also, as a comparison, Ti was also tested3C2The above performance of the MXene electrode (comparative) is shown in FIG. 7. At a current density of 0.5mA/cm2The capacity is 0.5mAh/cm2Under the condition of (3), the coulombic efficiency ratio of the partially etched MAX electrode is Ti3C2The coulombic efficiency of the MXene electrode needs to be more stable and can be maintained for up to 80 circles. And Ti3C2The coulombic efficiency of the MXene electrode fluctuates up and down after 30 circles, and the stability is poor. The above results show that the partially etched MAX can increase the stability of the lithium metal cathode, improve the cycle stability and prolong the life thereof.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The MAX material is characterized in that the MAX material is of a lamellar structure, and pits are formed in the lamellar structure and are not provided with through holes.
2. The partially etched MAX material of claim 1, wherein the MAX material is selected from Ti3AlC2、Ti2AlC、V2AlC、Ti2AlN、Ta4AlC3、Nb4AlC3、Mo2Ga2C、Ti3SiC2Any one of them.
3. A method of preparing a partially etched MAX material according to claim 1 or 2, comprising: partially etching the MAX material by using an etching method to enable the sheet layer to be provided with pits and have no through holes;
preferably, the etching method includes any one of a fluorine-based aqueous solution etching method, an alkali etching method, an electrochemical etching method, an anhydrous etching method, a hydrothermal etching method, a molten salt etching method, and the like;
preferably, the etchant is selected from the group consisting of HF, LiF, NH4HF2、KHF2、NaOH、H2O2One or more of HCl;
preferably, the etchant is selected from HF and NH4HF2；
Preferably, the mass fraction of the etching agent is 5% -40%, preferably 40%;
preferably, the dosage of the etching agent is 5-50 mL;
preferably, the ratio of the MAX material to the etchant is 0.5g:5-15ml, preferably 0.5g:10 ml;
preferably, the temperature of the water bath in the etching method is 30-80 ℃;
preferably, the etching time of the water bath in the etching method is 0.1-1 h.
4. A highly stable metallic lithium negative electrode material, comprising: lithium metal, a current collector and the partially etched MAX material of claim 1;
preferably, the loading of the partially etched MAX powder on the current collector is between 0.1 and 5mg/cm2；
Preferably, the current collector is any one of copper foil, copper mesh, copper foam, iron foil, carbon cloth and carbon paper.
5. The method for preparing the high-stability lithium metal anode material of claim 4, comprising the following steps: coating the partially etched MAX material of claim 1 on a current collector, and then depositing lithium metal onto the partially etched MAX coated current collector;
preferably, the lithium deposition current is 0.1-10mA/cm2；
Preferably, the lithium deposition capacity is 0.1-20mAh/cm2。
6. Use of the partially etched MAX material of claim 1 or 2 and/or the highly stable metallic lithium negative electrode material of claim 4 in lithium batteries, electric vehicles, smart grids, mobile energy storage devices.
7. A lithium battery comprising a partially etched MAX material according to claim 1 or 2 and/or a highly stable metallic lithium negative electrode material according to claim 4.
8. An electric vehicle comprising a partially etched MAX material according to claim 1 or 2 and/or a highly stable metallic lithium negative electrode material according to claim 4.
9. A smart grid comprising the partially etched MAX material of claim 1 or 2 and/or the high stability lithium metal anode material of claim 4.
10. A mobile energy storage device, comprising the partially etched MAX material of claim 1 or 2 and/or the highly stable metallic lithium negative electrode material of claim 4.
CN202110382533.0A 2021-04-09 2021-04-09 Partially etched MAX material and preparation method and application thereof Pending CN113113680A (en)

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CN115548342A (en) * 2022-10-19 2022-12-30 山东省科学院新材料研究所 3D TiC composite material and preparation method and application thereof
CN115548342B (en) * 2022-10-19 2023-05-12 山东省科学院新材料研究所 3D TiC composite material and preparation method and application thereof
CN116425160A (en) * 2023-04-21 2023-07-14 四川金时新能科技有限公司 Nb (Nb) alloy 4 C 3 T x MXene material and rapid preparation method thereof

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Application publication date: 20210713