CN114899362A - Three-dimensional lithium metal negative electrode material with solid electrolyte interface and preparation method thereof - Google Patents

Three-dimensional lithium metal negative electrode material with solid electrolyte interface and preparation method thereof Download PDF

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CN114899362A
CN114899362A CN202210539310.5A CN202210539310A CN114899362A CN 114899362 A CN114899362 A CN 114899362A CN 202210539310 A CN202210539310 A CN 202210539310A CN 114899362 A CN114899362 A CN 114899362A
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dimensional
lithium metal
lithium
negative electrode
solid electrolyte
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谌伟民
喻发全
曹文珠
路咪
王岩
邹璐
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Wuhan Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/64—Carriers or collectors
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a three-dimensional lithium metal negative electrode material with an artificial Solid Electrolyte Interface (SEI), which is prepared by coating g-C on a three-dimensional carbon material in situ 3 N 4 Then carrying out high-temperature standing reaction to form Li in situ 3 N artificial solid electrolyte interface film. The invention has the advantages ofThe scale is designed, the lithium-philic coating is compounded on the three-dimensional conductive main body, and an SEI film can be generated on the surface of the electrode in situ on the basis of ensuring the effective combination of the lithium metal and the carbon material to form Li 3 CC/Li at N-solid electrolyte interface 3 A N lithium metal negative electrode material; the local current density on the surface of the lithium metal negative electrode can be effectively reduced, the growth of lithium dendrites caused by the continuous deposition of lithium ions on the surface of the electrode can be avoided, and the problems of lithium source loss and the like caused by natural SEI can be effectively avoided; the feasibility of the lithium metal battery in practical application is improved.

Description

Three-dimensional lithium metal negative electrode material with solid electrolyte interface and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to a three-dimensional lithium metal negative electrode material with a solid electrolyte interface and a preparation method thereof.
Background
With the development of society, the current lithium ion battery taking graphite as a negative electrode can not meet the requirement of people on high energy density of the battery; to solve this problem, a higher specific capacity of the negative electrode material needs to be used instead of graphite. The lithium metal has ultrahigh theoretical specific capacity (3860mAh g -1 ) The lower oxidation-reduction potential (-3.04V vs standard hydrogen electrode) is the most promising ideal cathode material at present. However, the lithium metal negative electrode has low coulombic efficiency and short cycle life along with the growth of lithium dendrite and serious volume expansion problem in the charge-discharge cycle process, and even causes safety problem, thereby limiting the development and application of the lithium metal negative electrode. Therefore, how to inhibit the growth of lithium dendrites and alleviate the volume expansion effect of lithium metal is a hot spot of current academic research.
In order to solve the above-mentioned problem of limiting the development of lithium metal negative electrode applications, there have been some research reports, such as: on one hand, the high-conductivity three-dimensional carbon material or metal material is adopted as a main framework of the lithium metal negative electrode, so that the specific surface area of the electrode can be increased, the lithium ion current can be uniformly dispersed, and the volume expansion effect of the lithium metal negative electrode in the charge-discharge cycle process can be relieved, but the design strategy is often hindered by the incompatibility of the three-dimensional conductive material and the lithium metal; on the other hand, the artificial SEI film for conducting ions and blocking electrons is prepared on the surface of the lithium metal cathode in situ, the strategy can avoid the problem of lithium source consumption caused by the generation of natural SEI to a certain extent, and prevent electrons from accumulating on the surface of the electrode and attracting lithium ions to deposit on the surface of the electrode to form lithium dendrites, but poor contact between the non-in-situ prepared SEI film and lithium metal increases the internal impedance of the battery, the two-dimensional artificial SEI film prepared in situ can crack under the condition of high current, and the problems of reduced electronic conductivity, increased battery impedance and the like are brought, so that the effective charge-discharge cycle of the lithium metal battery under the condition of high current density is limited.
In conclusion, the three-dimensional lithium metal negative electrode material with the artificial solid electrolyte interface has a wide application prospect in the development of future energy storage, and further explores the lithium metal negative electrode material with the artificial solid electrolyte interface, which can regulate and control the uniform deposition of lithium ions, inhibit the growth of lithium dendrites and relieve the volume expansion effect of lithium metal, and has an important significance in promoting the lithium metal negative electrode to realize a commercial application target.
Disclosure of Invention
The invention aims to solve the problems and the defects of the prior art and provides a three-dimensional lithium metal negative electrode material with a solid electrolyte interface, which is prepared by firstly modifying the surface of a three-dimensional carbon material with g-C 3 N 4 Then reacted with molten lithium to form lithium bearing Li 3 CC/Li of N solid electrolyte interface 3 A N lithium metal negative electrode material; the local current density on the surface of the lithium metal negative electrode can be effectively reduced, and the growth of lithium dendrite caused by the continuous deposition of lithium ions on the surface of the electrode is avoided; meanwhile, the problems of lithium source loss and the like caused by natural SEI can be effectively avoided, and the performance of the lithium metal battery is further improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
three-dimensional lithium metal negative electrode material (CC/Li) with solid electrolyte interface 3 N lithium metal negative electrode material) by first g-C a three-dimensional carbon material 3 N 4 Loading, putting in molten lithium, and standing at high temperature.
In the above scheme, the surface of the three-dimensional lithium metal negative electrode material contains Li 3 Gradient layer of N, Li 3 The content of N is gradually decreased from top to bottom (from the surface to the three-dimensional carbon material substrate), and the upper surface is deep purple high-concentration Li 3 N layer with silvery white and light purple on the lower surfaceDistributed low concentration of Li 3 N layers (see fig. 3). Li 3 The formation of the N gradient constitutes the formation of the electron conduction gradient. The structure effectively reduces the local current density on the surface of the lithium metal cathode, can guide lithium ions to be preferentially deposited below an artificial solid electrolyte interface, and avoids the growth of lithium dendrites caused by the continuous deposition of the lithium ions on the surface of the electrode.
In the scheme, the three-dimensional carbon material can be conductive carbon cloth, foam carbon, graphene foam, a carbon nanotube film, a biomass carbon film or the like.
In the scheme, the three-dimensional carbon material is in a wafer structure with the diameter of 8-20 mm.
In the above scheme, the g-C 3 N 4 The loading step comprises: firstly, carrying out oxidation treatment (oxygen-containing group modification) on a three-dimensional carbon material by adopting acid liquor, and then soaking the obtained carbon material in g-C 3 N 4 Carrying out water bath reaction in the precursor solution, drying and calcining to obtain g-C 3 N 4 Coated three-dimensional carbon material CC @ g-C 3 N 4 。
In the above scheme, the g-C 3 N 4 The precursor can be selected from urea, cyanamide, dicyandiamide, melamine and the like; g-C 3 N 4 The concentration of the precursor solution is 0.1-5 mol/L.
In the scheme, the high-temperature standing reaction temperature is 200-350 ℃, and the time is 0-3 h.
Preferably, the high-temperature standing reaction time is 0.5-3 h.
The preparation method of the three-dimensional lithium metal negative electrode material with the solid electrolyte interface specifically comprises the following steps:
1) cleaning and drying the three-dimensional carbon material; then soaking in acid liquor, heating for reaction, cleaning and drying;
2) soaking the three-dimensional carbon material obtained by oxidation treatment in the step 1) in g-C 3 N 4 Performing water bath reaction in the precursor solution (promoting the interaction of nitrogen-containing groups at the edge of the precursor and oxygen-containing groups on the three-dimensional carbon material to uniformly distribute the precursor on the surface of the three-dimensional carbon material) Drying; then calcining the mixture under the protective atmosphere to obtain g-C 3 N 4 Coated three-dimensional carbon Material (CC @ g-C) 3 N 4 )；
3) Under a protective atmosphere, the obtained g-C 3 N 4 The coated three-dimensional carbon material is placed in molten lithium for lithium metal perfusion, and high-temperature standing reaction is carried out, so that the three-dimensional lithium metal negative electrode material (CC/Li) with a solid electrolyte interface is obtained 3 N lithium metal negative electrode material).
In the scheme, the acid solution is preferably a mixed acid solution; the mixed acid solution is preferably a mixed solution of sulfuric acid and nitric acid.
In the scheme, the mixed acid solution is formed by mixing sulfuric acid and nitric acid according to the volume ratio of 1 (1-5), wherein the concentration of the sulfuric acid is 70-98 wt%, and the concentration of the nitric acid is 10-60 wt%.
In the scheme, the heating reaction temperature in the step 1) is 120-180 ℃, and the time is 8-24 h.
In the scheme, the drying temperature in the steps 1) to 3) is 40-80 ℃, and the drying time is 8-24 h.
In the scheme, the water bath reaction temperature in the step 2) is 50-80 ℃, and the time is 2-6 h.
In the scheme, the calcining temperature is 500-600 ℃, and the time is 2-4 h.
In the scheme, the adopted protective atmosphere can be nitrogen or argon and the like.
In the scheme, the temperature of the molten lithium is 200-350 ℃.
In the scheme, the mass ratio of the three-dimensional carbon material to the molten lithium is 1: 1-5.
The invention first makes use of g-C 3 N 4 Carrying out surface modification on the three-dimensional carbon material subjected to oxidation treatment to prepare g-C 3 N 4 A uniformly coated three-dimensional carbon material; then mixing it with molten lithium and reacting it with a catalyst at elevated temperature 3 N 4 Li produced by reaction with molten lithium 3 The N gradually migrates to the upper surface of the electrode along with the extension of the standing time; due to Li 3 Low electron conductivity of N: (<10 - 12 Scm -1 ) High ionic conductivity (10) -3 ～10 -4 S cm -1 )，Li 3 The formation of the N gradient forms an electronic conduction gradient; the surface of the electrode at one side close to the diaphragm in the obtained three-dimensional lithium metal negative electrode material is uniform and compact and is made of Li 3 The artificial solid electrolyte membrane formed by N can play good roles of ion conduction and electron resistance; the side far away from the diaphragm is made of three-dimensional carbon-based lithium metal, and good electronic conductivity can be shown, so that the function of attracting lithium ions to be preferentially deposited is achieved. The structure can effectively reduce the local current density on the surface of the lithium metal negative electrode, guide lithium ions to be preferentially deposited below an artificial solid electrolyte interface, and avoid the growth of lithium dendrites caused by the continuous deposition of the lithium ions on the surface of the electrode.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention uses three-dimensional conductive carbon material as the base material for lithium deposition, and firstly coats a layer of g-C uniformly on the surface 3 N 4 Carrying out lithium-philic modification treatment; then utilizing g-C under high temperature conditions 3 N 4 Chemically react with molten lithium to form Li 3 N, and Li during high-temperature standing 3 N can spontaneously migrate to the upper surface, and the in-situ load of the artificial SEI film on the lithium metal negative electrode material can be realized; compared with the traditional means for inhibiting the lithium dendrites, the method has the advantages that the lithium-philic coating is compounded on the three-dimensional conductive main body through multi-scale design, and an SEI film can be generated in situ on the surface of the electrode on the basis of ensuring the effective combination of lithium metal and a carbon material; the obtained artificial SEI film has good mechanical property, excellent ion-conducting and electron-blocking effects, and the electrons are mainly distributed in Li 3 Below the N solid electrolyte membrane, lithium ions are effectively guided to be deposited below an electrode/electrolyte interface, and the growth of lithium dendrites caused by the deposition of the lithium ions on the electrode/electrolyte interface is avoided;
2) the in-situ preparation method of the SEI film can further promote the formation of Li 3 N graded layer due to Li 3 N has the advantages of high ionic conductivity and low electronic conductivity, and the concentration gradient of N can effectively regulate and control the electronic distribution of the three-dimensional lithium metal current collector and avoidThe accumulation of electrons on the surface of the SEI film is avoided, so that lithium ions are guided to tend to deposit below the SEI film, and the growth of lithium dendrites is effectively inhibited.
3) On the premise of effectively improving the problems of dendritic crystal growth and volume expansion effect of the lithium metal battery, the invention can also effectively avoid the problem of lithium source loss caused by natural SEI, and can improve the feasibility of the lithium metal battery in practical application.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the round carbon cloth obtained in step 1);
FIG. 2 shows CC @ g-C obtained in example 1 of the present invention 3 N 4 Scanning Electron Microscope (SEM) images of (a);
FIG. 3 shows CC @ g-C obtained in example 1 of the present invention 3 N 4 And pure three-dimensional carbon cloth and pure g-C as described in comparative example 1 3 N 4 A Fourier infrared spectrogram (FT-IR) diagram of (A);
FIG. 4 shows CC/Li obtained in example 1 of the present invention 3 X-ray diffraction (XRD) patterns of N and CC/Li obtained in comparative example 1;
FIG. 5 shows CC/Li obtained in example 1 3 N real object diagram;
FIG. 6 shows CC/Li obtained in examples 1-2 of the present invention 3 N, CC/Li obtained in comparative example 1 and commercial lithium metal foil in comparative example 2 are respectively equal to commercial LiFePO 4 And the positive electrode material is assembled into a lithium storage cycle rate performance diagram of the lithium metal battery in a matching way.
Detailed Description
The present invention is further described in detail in the following description of specific embodiments and the accompanying drawings, which are included to illustrate the invention and not to limit the scope of the invention, and various equivalent modifications of the invention which fall within the limits of the appended claims after reading the present invention.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
Three-dimensional lithium metal negative electrode material (CC/Li) with solid electrolyte interface 3 N), the preparation method comprises the following steps:
1) ultrasonically cleaning a round carbon cloth (about 5mg) with the diameter of 8mm by using ethanol and deionized water respectively, and drying in an oven (drying at 60 ℃ for 12h) after cleaning; preparing a mixed acid solution of nitric acid and sulfuric acid according to a volume ratio of 4:1 (the concentration of the nitric acid is 50 wt%, the concentration of the sulfuric acid is 98 wt%), placing the dried carbon cloth in the mixed acid solution, transferring the mixed acid solution into a reaction kettle to perform a solvothermal reaction (reaction at 120 ℃ for 10 hours), cleaning the carbon cloth with deionized water for 3 times after the hydrothermal reaction, and placing the carbon cloth in an oven again to dry (drying at 60 ℃ for 12 hours);
2) placing the carbon cloth obtained by the treatment in the step 1) in a urea solution with the concentration of 0.2M, carrying out water bath reaction (water bath at 80 ℃ for 2h), and drying in an oven (drying at 60 ℃ for 12 h); then placing the mixture into a tubular furnace for high-temperature calcination; wherein the atmosphere of argon/nitrogen is adopted, the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, and the calcining time is 2h, so that CC @ g-C is obtained 3 N 4 ；
3) For CC @ g-C obtained in step 2) 3 N 4 Pouring molten lithium (argon atmosphere, oxygen content is less than or equal to 0.01ppm, water content is less than or equal to 0.01ppm, temperature is 350 ℃), after the molten lithium (about 10mg) completely infiltrates the carbon cloth, continuously standing for 1h at 350 ℃, and cooling to room temperature to obtain the electrode material CC/Li 3 N (noted as CC/Li 3 N-1h)。
In this example, the round carbon cloth obtained in step 1) and CC @ g-C obtained in step 2) 3 N 4 See fig. 1 and 2, respectively. It can be seen that the obtained g-C is comparable to the untreated carbon cloth fiber 3 N 4 Are uniformly distributed on the surface of the carbon cloth fiber.
Example CC @ g-C obtained in step 2) 3 N 4 And pure Carbon Cloth (CC) and pure g-C 3 N 4 The Fourier infrared spectrum of (A) is shown in FIG. 3, and CC @ g-C can be seen 3 N 4 g-C is obvious 3 N 4 Has an absorption peak of g-C 3 N 4 Successful loading provides strong evidence on CC.
CC/Li obtained in this example 3 The X-ray diffraction pattern of N is shown in FIG. 4, and it can be seen that the resulting product is mainly composed ofComprising C, Li and Li 3 Three phases of N, proving g-C 3 N 4 Reaction with lithium metal to form Li 3 N。
CC/Li obtained in this example 3 The physical diagram of N is shown in FIG. 5, and it can be seen that the upper surface of the obtained electrode material is dark purple and presents high concentration of Li 3 N is distributed; the lower surface is light purple and presents low Li concentration 3 N is distributed; further proves that the CC/Li obtained by the invention 3 N surface can form Li 3 A gradient layer of N, and Li 3 The content of N is gradually decreased from top to bottom.
The CC/Li obtained in the example 3 N electrode material and commercial LiFePO 4 The electrochemical performance test of the full cell assembled by matching the positive electrode material is carried out, and the result is shown in figure 6. After the three-dimensional carbon skeleton and the artificial solid electrolyte membrane SEI are introduced, the effective capacity of the battery is improved.
Example 2
Three-dimensional lithium metal negative electrode material (CC/Li) with solid electrolyte interface 3 N), the preparation method comprises the following steps:
1) ultrasonically cleaning a round carbon cloth (about 5mg) with the diameter of 8mm by using ethanol and deionized water respectively, and drying in an oven (drying at 60 ℃ for 12h) after cleaning; preparing a mixed acid solution of nitric acid and sulfuric acid according to a volume ratio of 4:1 (the concentration of the nitric acid is 50 wt%, the concentration of the sulfuric acid is 98 wt%), placing the dried carbon cloth in the mixed acid solution, transferring the mixed acid solution into a high-pressure reaction kettle to perform a solvothermal reaction (reaction at 120 ℃ for 10 hours), cleaning the carbon cloth for 3 times by using deionized water after the hydrothermal reaction, and placing the carbon cloth in an oven again to dry (drying at 60 ℃ for 12 hours);
2) placing the carbon cloth obtained by the treatment in the step 1) in a urea solution with the concentration of 0.2M, carrying out water bath reaction (water bath at 80 ℃ for 2h), and drying in an oven (drying at 60 ℃ for 12 h); then placing the mixture into a tubular furnace for high-temperature calcination; wherein, the atmosphere of argon/nitrogen is adopted, the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, the calcining time is 2h, and CC @ g-C is obtained 3 N 4 。
3) For CC @ g-C obtained in step 2) 3 N 4 Molten lithium infusion (argon atmosphere, oxygen content)Less than or equal to 0.01ppm, the water content less than or equal to 0.01ppm and the temperature of 350 ℃), keeping standing for 0h at 350 ℃ after the molten lithium (about 10mg) is completely soaked in the carbon cloth, and cooling to room temperature to obtain the electrode material CC/Li 3 N (noted as CC/Li 3 N-0h)。
Example 3
Three-dimensional lithium metal negative electrode material (CC/Li) with solid electrolyte interface 3 N), the preparation method comprises the following steps:
1) ultrasonically cleaning a round carbon cloth (about 5mg) with the diameter of 8mm by using ethanol and deionized water respectively, and drying in an oven (drying at 60 ℃ for 12h) after cleaning; preparing a mixed acid solution of nitric acid and sulfuric acid according to a volume ratio of 4:1 (the concentration of the nitric acid is 50 wt%, the concentration of the sulfuric acid is 98 wt%), placing the dried carbon cloth in the mixed acid solution, transferring the mixed acid solution into a high-pressure reaction kettle to perform a solvothermal reaction (reaction at 120 ℃ for 10 hours), cleaning the carbon cloth for 3 times by using deionized water after the hydrothermal reaction, and placing the carbon cloth in an oven again to dry (drying at 60 ℃ for 12 hours);
2) placing the carbon cloth obtained by the treatment in the step 1) in a urea solution with the concentration of 0.2M, carrying out water bath reaction (water bath at 80 ℃ for 2h), and drying in an oven (drying at 60 ℃ for 12 h); then placing the mixture into a tubular furnace for high-temperature calcination; wherein, the atmosphere of argon/nitrogen is adopted, the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, the calcining time is 2h, and CC @ g-C is obtained 3 N 4 。
3) For CC @ g-C obtained in step 2) 3 N 4 Pouring molten lithium (argon atmosphere, oxygen content is less than or equal to 0.01ppm, water content is less than or equal to 0.01ppm, temperature is 350 ℃), after the molten lithium (about 10mg) completely infiltrates the carbon cloth, continuously standing for 0.5h at 350 ℃, and cooling to room temperature to obtain the electrode material CC/Li 3 N (noted as CC/Li 3 N-0.5h)。
Example 4
Three-dimensional lithium metal negative electrode material (CC/Li) with solid electrolyte interface 3 N), the preparation method comprises the following steps:
1) ultrasonically cleaning a round carbon cloth (about 5mg) with the diameter of 8mm by using ethanol and deionized water respectively, and drying in an oven (drying at 60 ℃ for 12h) after cleaning; preparing a mixed acid solution of nitric acid and sulfuric acid according to a volume ratio of 4:1 (the concentration of the nitric acid is 50 wt%, the concentration of the sulfuric acid is 98 wt%), placing the dried carbon cloth in the mixed acid solution, transferring the mixed acid solution into a high-pressure reaction kettle to perform a solvothermal reaction (reaction at 120 ℃ for 10 hours), cleaning the carbon cloth for 3 times by using deionized water after the hydrothermal reaction, and placing the carbon cloth in an oven again to dry (drying at 60 ℃ for 12 hours);
2) placing the carbon cloth obtained by the treatment in the step 1) in a urea solution with the concentration of 0.2M, carrying out water bath reaction (water bath at 80 ℃ for 2h), and drying in an oven (drying at 60 ℃ for 12 h); then placing the mixture into a tubular furnace for high-temperature calcination; wherein, the atmosphere of argon/nitrogen is adopted, the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, the calcining time is 2h, and CC @ g-C is obtained 3 N 4 。
3) For CC @ g-C obtained in step 2) 3 N 4 Pouring molten lithium (argon atmosphere, oxygen content is less than or equal to 0.01ppm, water content is less than or equal to 0.01ppm, temperature is 350 ℃), after the molten lithium (about 10mg) completely infiltrates the carbon cloth, continuously standing for 1.5h at 350 ℃, and cooling to room temperature to obtain the electrode material CC/Li 3 N (noted as CC/Li 3 N-1.5h)。
Example 5
Three-dimensional lithium metal negative electrode material (CC/Li) with solid electrolyte interface 3 N), the preparation method comprises the following steps:
1) ultrasonically cleaning a round carbon cloth (about 5mg) with the diameter of 8mm by using ethanol and deionized water respectively, and drying in an oven (drying at 60 ℃ for 12h) after cleaning; preparing a mixed acid solution of nitric acid and sulfuric acid according to a volume ratio of 4:1 (the concentration of the nitric acid is 50 wt%, the concentration of the sulfuric acid is 98 wt%), placing the dried carbon cloth in the mixed acid solution, transferring the mixed acid solution into a high-pressure reaction kettle to perform a solvothermal reaction (reaction at 120 ℃ for 10 hours), cleaning the carbon cloth for 3 times by using deionized water after the hydrothermal reaction, and placing the carbon cloth in an oven again to dry (drying at 60 ℃ for 12 hours);
2) placing the carbon cloth obtained by the treatment in the step 1) in a urea solution with the concentration of 0.2M, carrying out water bath reaction (water bath at 80 ℃ for 2h), and drying in an oven (drying at 60 ℃ for 12 h); then placing the mixture into a tubular furnace for high-temperature calcination; wherein the atmosphere of argon/nitrogen is adopted, and the calcining temperature is 50 DEGThe temperature rise rate is 5 ℃/min at 0 ℃, the calcination time is 2h, and CC @ g-C is obtained 3 N 4 。
3) For CC @ g-C obtained in step 2) 3 N 4 Pouring molten lithium (argon atmosphere, oxygen content is less than or equal to 0.01ppm, water content is less than or equal to 0.01ppm, temperature is 350 ℃), after the molten lithium (about 10mg) completely infiltrates the carbon cloth, continuously standing for 2h at 350 ℃, and cooling to room temperature to obtain the electrode material CC/Li 3 N (noted as CC/Li 3 N-2h)。
Example 6
Three-dimensional lithium metal negative electrode material (CC/Li) with solid electrolyte interface 3 N), the preparation method comprises the following steps:
1) ultrasonically cleaning a round carbon cloth (about 5mg) with the diameter of 8mm by using ethanol and deionized water respectively, and drying in an oven (drying at 60 ℃ for 12h) after cleaning; preparing a mixed acid solution of nitric acid and sulfuric acid according to a volume ratio of 4:1 (the concentration of the nitric acid is 50 wt%, the concentration of the sulfuric acid is 98 wt%), placing the dried carbon cloth in the mixed acid solution, transferring the mixed acid solution into a high-pressure reaction kettle to perform a solvothermal reaction (reaction at 120 ℃ for 10 hours), cleaning the carbon cloth for 3 times by using deionized water after the hydrothermal reaction, and placing the carbon cloth in an oven again to dry (drying at 60 ℃ for 12 hours);
2) placing the carbon cloth obtained by the treatment in the step 1) in a urea solution with the concentration of 0.2M, carrying out water bath reaction (water bath at 80 ℃ for 2h), and drying in an oven (drying at 60 ℃ for 12 h); then placing the mixture into a tubular furnace for high-temperature calcination; wherein, the atmosphere of argon/nitrogen is adopted, the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, the calcining time is 2h, and CC @ g-C is obtained 3 N 4 。
3) For CC @ g-C obtained in step 2) 3 N 4 Pouring molten lithium (argon atmosphere, oxygen content is less than or equal to 0.01ppm, water content is less than or equal to 0.01ppm, temperature is 350 ℃), after the molten lithium (about 10mg) completely infiltrates the carbon cloth, continuously standing for 3h at 350 ℃, and cooling to room temperature to obtain the electrode material CC/Li 3 N (noted as CC/Li 3 N-3h)。
Comparative example 1
A three-dimensional lithium metal anode material CC/Li is prepared by the following steps:
1) ultrasonically cleaning a round carbon cloth (about 5mg) with the diameter of 8mm by using ethanol and deionized water respectively, and drying in an oven (drying at 60 ℃ for 12h) after cleaning;
2) and (2) performing molten lithium (about 10mg) infusion (argon atmosphere, oxygen content is less than or equal to 0.01ppm, water content is less than or equal to 0.01ppm and 350 ℃) on the carbon cloth obtained in the step 1), and cooling the carbon cloth to room temperature after lithium metal completely infiltrates the carbon cloth to obtain the electrode material CC/Li.
Comparative example 2
Commercial lithium sheets with a thickness of 100 μm and a diameter of 8mm were used as the lithium metal negative electrode material.
The lithium metal anode materials obtained in examples 1-2 and comparative examples 1-2 were respectively mixed with commercial LiFePO 4 The anode material is assembled in a matching way to be used for carrying out electrochemical performance test on the anode material and a full cell (argon atmosphere, oxygen content is less than or equal to 0.01ppm, and water content is less than or equal to 0.01ppm), and the result is shown in figure 6.
FIG. 6 shows CC/Li obtained in examples 1 to 2 3 N, CC/Li obtained in comparative example 1, commercial lithium metal foil and commercial LiFePO described in comparative example 2 4 The lithium storage cycle rate performance diagram of the lithium metal battery assembled by the positive electrode material in a matching way can be seen as follows: pure lithium metal has serious capacity loss under the condition of high rate because the SEI film formed spontaneously is unstable; furthermore, it can be seen by comparing example 1 and example 2 that the invention is achieved by the CC @ g-C for pouring molten lithium 3 N 4 The high-temperature standing reaction is carried out, so that the rate capability (especially the specific capacity below 2C rate) and the cycling stability of the obtained battery (the high specific capacity can be still maintained after the battery is cycled for more than 35 times at 0.2C) can be further effectively improved.
The upper and lower limit values and interval values of the raw materials, the reaction temperature and the time can all realize the invention, and the examples are not necessarily listed here.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. A three-dimensional lithium metal negative electrode material with a solid electrolyte interface is characterized in that the three-dimensional carbon material is subjected to g-C 3 N 4 Loading, putting in molten lithium, and standing at high temperature.
2. The three-dimensional lithium metal anode material according to claim 1, wherein the surface thereof comprises Li 3 Gradient layer of N, Li 3 The content of N decreases from top to bottom.
3. The three-dimensional lithium metal anode material according to claim 1, wherein the three-dimensional carbon material is a conductive carbon cloth, a carbon foam, a graphene foam, a carbon nanotube film, or a biomass carbon film.
4. The three-dimensional lithium metal anode material of claim 1, wherein the g-C is 3 N 4 The loading step comprises: oxidizing a three-dimensional carbon material by using acid liquor, and soaking the obtained carbon material in g-C 3 N 4 Carrying out water bath reaction in the precursor solution, drying and calcining to obtain g-C 3 N 4 Coated three-dimensional carbon material CC @ g-C 3 N 4 。
5. The three-dimensional lithium metal anode material of claim 4, wherein the g-C is 3 N 4 The precursor is urea, cyanamide, dicyandiamide or melamine; g-C 3 N 4 The concentration of the precursor solution is 0.1-5 mol/L.
6. The three-dimensional lithium metal anode material as claimed in claim 1, wherein the reaction temperature of the high temperature standing is 200-350 ℃ and the reaction time is 0-3 h.
7. The method for preparing the three-dimensional lithium metal anode material with the solid electrolyte interface as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
1) cleaning and drying the three-dimensional carbon material; then soaking in acid liquor, carrying out heating reaction, cleaning and drying;
2) soaking the three-dimensional carbon material obtained by the treatment of the step 1) in g-C 3 N 4 Carrying out water bath reaction in the precursor solution, and drying; then calcining the mixture under the protective atmosphere to obtain g-C 3 N 4 A coated three-dimensional carbon material;
3) under a protective atmosphere, the obtained g-C 3 N 4 And (3) placing the coated three-dimensional carbon material in molten lithium for lithium metal perfusion, and performing high-temperature standing reaction to obtain the three-dimensional lithium metal negative electrode material with a solid electrolyte interface.
8. The preparation method according to claim 1, wherein the calcination temperature is 500 to 600 ℃ and the calcination time is 2 to 4 hours.
9. The method according to claim 1, wherein the temperature of the molten lithium is 200 to 350 ℃.
10. The method according to claim 1, wherein the mass ratio of the three-dimensional carbon material to the molten lithium is 1:1 to 5.
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