CN114122332A - Method for preparing three-dimensional metal lithium cathode by using MOFs (metal-organic frameworks) derivatives - Google Patents

Method for preparing three-dimensional metal lithium cathode by using MOFs (metal-organic frameworks) derivatives Download PDF

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CN114122332A
CN114122332A CN202111409635.3A CN202111409635A CN114122332A CN 114122332 A CN114122332 A CN 114122332A CN 202111409635 A CN202111409635 A CN 202111409635A CN 114122332 A CN114122332 A CN 114122332A
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lithium
metal
dimensional
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batteries
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魏涛
陆佳豪
张琪
孙成
周艳艳
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Jiangsu University of Science and 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a method for preparing a three-dimensional lithium metal cathode by using MOFs derivatives. Preparing a metal organic framework material; mixing the pretreated three-dimensional porous framework and the metal organic framework material to enable the metal organic framework material to uniformly grow on the three-dimensional porous framework; then the mixture is transferred into a muffle furnace for carbonization; and then pouring the molten liquid metal lithium onto the whole framework to obtain the novel three-dimensional metal lithium cathode. The electrode can be applied to liquid lithium batteries and lithium-oxygen and lithium-sulfur solid batteries with high energy density, effectively reduces local current density, inhibits the growth of lithium dendrites, and improves the safety and the service life of the batteries. The lithium ion battery can effectively deal with the volume expansion of the lithium cathode, improve the interface stability of the electrode/electrolyte, the electrochemical performance of the electrode and the like, can be applied to metal batteries with higher energy density, such as three-dimensional metal sodium cathodes, zinc cathodes, potassium cathodes and the like, and further promotes the research and development and practice steps of high-safety power batteries.

Description

Method for preparing three-dimensional metal lithium cathode by using MOFs (metal-organic frameworks) derivatives
Technical Field
The invention belongs to the technical field of lithium ion battery preparation, and particularly relates to a method for preparing a three-dimensional metal lithium cathode by using MOFs derivatives.
Background
In recent years, increasingly higher requirements are put on the energy density and safety of lithium ion batteries in the fields of miniature electronic equipment, energy storage equipment, new energy automobiles and the like so as to meet the social demands. The traditional lithium ion battery taking a carbon material as a negative electrode cannot meet the requirement of the current society on energy density, and the current trend is to take metal lithium as the negative electrode.
In order to satisfy a safe high specific energy power battery, a lithium metal battery is a necessary trend. Since the metallic lithium negative electrode has the highest energy density (3860 mAh/g) and the lowest potential (-3.04 v. vs. standard hydrogen electrode), metallic lithium has an absolute advantage as a negative electrode material for lithium batteries. However, during the charging and discharging processes, the lithium negative electrode has many disadvantages of volume expansion, dead lithium phenomenon, growth of lithium dendrite, high reaction with electrolyte, etc., which seriously affect the electrochemical performance and safety of the battery. On one hand, lithium ions in different positions cause non-uniform nucleation of lithium in an electrochemical process, which aggravates growth of lithium dendrites and causes safety problems such as internal short circuit. On the other hand, lithium metal anodes undergo severe volume expansion and contraction during cycling, while a Solid Electrolyte Interface (SEI) film is continuously reconstructed, resulting in a decrease in coulombic efficiency and a shortened cycle life.
Therefore, how to alleviate or improve the above-mentioned problems with lithium negative electrodes allows lithium metal negative electrodes to be optimized to serve safe power cells. In the face of the dilemma of lithium metal negative electrodes, a series of schemes, namely an artificial SEI film, an electrolyte, an additive, a solid electrolyte, a three-dimensional negative electrode structure and the like, are proposed at present, wherein the design of the three-dimensional negative electrode structure is a hot spot at present and is a scheme which is hopeful to solve the defects of the lithium negative electrode most. At present, common three-dimensional mesh substrate materials (such as foamed nickel, foamed copper and carbon cloth) are poor in lithium affinity, and by means of rolling, electron deposition, atomic deposition, thermal spraying and the like, the three-dimensional mesh substrate materials are combined with strong lithium affinity groups, the lithium affinity of the substrate is changed, and therefore three-dimensional lithium cathode structures with good lithium affinity and stable electrochemical performance are designed, and finally lithium ions can be uniformly deposited.
Metal Organic Frameworks (MOFs) are coordination polymer materials which have been developed rapidly in recent decades. The material is obtained by self-assembly of metal ions and organic ligands, has high specific surface area, riches adjustable pore channel structures and a modifiable surface. Among various MOFs materials full of Linglan, a part of MOFs such as Cu-MOFs, Al-MOFs, Co-MOFs, Mn-MOFs and the like and derived materials thereof show certain advantages in the aspects of electrolyte transmission and alleviation of volume change problems generated by a lithium cathode in a long-term circulation process due to high specific surface area and rich and adjustable channels. The MOFs can be converted into MOFs derivative materials by means of heat treatment and the like by taking the MOFs as a sacrificial template. MOFs derived materials generally include: carbon materials, metal composite materials, carbon/metal composite materials. Compared with MOFs, the MOFs derivative material generally has better conductivity and stability, and has better application prospect in batteries.
Disclosure of Invention
With the rapid development of electric vehicles and portable electronic products, the demand for high specific energy secondary batteries is more and more urgent. Lithium metal is considered to be one of the ideal negative electrode materials for next-generation high specific energy batteries with its extremely high theoretical specific capacity and extremely low electrode potential. However, practical application of lithium metal negative electrodes is limited by problems such as growth of lithium dendrites and volume expansion.
Aiming at the defects of the prior art, the invention provides a method for preparing a three-dimensional metallic lithium cathode by using MOFs derivatives, which further reduces the pore diameter of a three-dimensional porous framework and homogenizes the pore diameter distribution by means of physical or chemical means, and then combines with a lithium-philic material to form the lithium-philic porous framework. The lithium-philic porous framework can reduce the nucleation energy barrier of lithium, induce the uniform nucleation of lithium and more effectively regulate and control the lithium deposition behavior.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a method for preparing a three-dimensional metallic lithium cathode by using MOFs derivatives comprises the following steps:
s1, preparing a metal organic framework material:
dissolving 1mmol of metal salt in 15-30ml of organic solvent, adding 3-5mmol of organic ligand, magnetically stirring for 20-30min, and synthesizing metal organic framework material by solvothermal method or standing method;
s2, mixing the pretreated three-dimensional porous framework and the metal organic framework material, and uniformly growing the metal organic framework material on the three-dimensional porous framework by a soaking or hydrothermal method;
s3, placing the three-dimensional porous skeleton full of the metal organic framework material in a muffle furnace, carbonizing in nitrogen or air, and generating a metal oxide which is a metal organic framework derivative material and is a lithium-philic material after carbonization;
s4, melting of metal lithium: placing the lithium metal on a stainless steel sheet in a glove box filled with argon, and heating to 350 ℃ to obtain molten liquid lithium metal;
and S5, pouring liquid metal lithium on the whole framework to prepare the three-dimensional metal lithium cathode.
The improvement is that the metal salt in step S1 is one or a mixture of copper nitrate, aluminum nitrate, cobalt nitrate, tin nitrate, manganese nitrate and zinc nitrate.
The improvement is that the organic solvent in step S1 is one or a mixture of methanol, absolute ethanol, dimethylformamide and dimethylacetamide.
The improvement is that the organic ligand in step S1 is one or a mixture of more of terephthalic acid, biphenyldicarboxylic acid, trimesic acid, 2-methylimidazole, and 1H-1,2, 3-triazole.
The three-dimensional porous skeleton in step S2 is one of nickel foam, copper foam, carbon cloth, and melamine sponge.
As a modification, the preprocessing in step S2 includes: sequentially treating with acetone, anhydrous alcohol, and deionized water by ultrasonic treatment for 10-15 min.
Has the advantages that:
compared with the prior art, the method for preparing the three-dimensional metallic lithium cathode by utilizing the MOFs derivatives has the following advantages:
1. the three-dimensional porous skeleton has a higher specific surface area, and can remarkably reduce the local current density of a negative electrode, so that the initial nucleation time point of lithium dendrites is delayed; meanwhile, the growth of lithium can be limited in the pores, and the volume expansion of the metal lithium generated in the charge and discharge process is relieved;
2. the deposition of metallic lithium on an unmodified framework is easy to form lithium dendrites, but the deposition is uniform on the three-dimensional porous framework of the overgrown metal-organic framework derived material of the invention;
3. the three-dimensional metal lithium cathode can be applied to all-solid-state lithium batteries with higher energy density and lithium-oxygen and lithium-sulfur batteries, can be expanded to metal batteries such as three-dimensional metal sodium cathodes, Zn cathodes and potassium cathodes, and further promotes the research and development and practice steps of high-safety power batteries.
Drawings
Fig. 1 is a flow chart of a three-dimensional metallic lithium negative electrode prepared in example 1;
fig. 2 is an SEM image comparing a three-dimensional metallic lithium negative electrode prepared in example 1 with a general lithium negative electrode;
FIG. 3 is a test chart of a symmetric lithium battery using the three-dimensional lithium metal negative electrode prepared in example 1 as the positive and negative electrodes;
fig. 4 is a battery test chart using the three-dimensional lithium metal negative electrode prepared in example 1 as a negative electrode and lithium iron phosphate as a positive electrode.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1 preparation of three-dimensional metallic lithium negative electrode:
the adopted metal salt is cobalt nitrate, the organic solvent is methanol, the organic ligand is 2-methylimidazole, and the three-dimensional porous framework is foamed nickel.
S1, dissolving 1mmol of cobalt nitrate hexahydrate (0.291 g) in 25ml of methanol, and placing the obtained solution on a magnetic stirrer for stirring for 5-10 min;
s2, weighing 4mmol of 2-methylimidazole (0.328 g), adding the 2-methylimidazole into the solution of S1, continuously stirring uniformly, and standing for 24 hours to obtain a methanol solution containing the metal organic framework material ZIF-67;
s3, pretreatment of the foamed nickel: respectively putting the foamed nickel into 5-10ml of acetone, 5-10ml of absolute ethyl alcohol and 5-10ml of deionized water, performing ultrasonic treatment for 10-15min respectively, and then putting the foamed nickel into a vacuum drying oven at 60 ℃ for drying for 1-2 h;
s4, soaking the pretreated foamed nickel in a methanol solution containing ZIF-67;
s5, placing the obtained mixed solution on a magnetic stirrer to stir for 20-30min to obtain a uniform solution; finally, standing the obtained uniform solution for 24 hours to finally obtain the foamed nickel material overgrowing with ZIF-67;
s6, placing the foamed nickel material overgrown with the ZIF-67 in a muffle furnace, raising the temperature to 350 ℃ at a heating rate of 3 ℃/min for carbonization, and carrying out Scanning Electron Microscope (SEM) test on the carbonized material to obtain a result shown in figure 2;
s7, placing the carbonized ZIF-67@ Ni foam material obtained in the step S6 into a glove box, then placing a lithium sheet into a battery case, placing carbonized foam nickel above the lithium sheet, placing the lithium sheet on a heating table at the temperature of 300-350 ℃, and carrying out a lithium melting process;
and S8, observing that the surface of the foamed nickel is completely covered by silvery white liquid lithium, and finishing the preparation of the three-dimensional metal lithium cathode.
Example 2 testing of Battery Performance of three-dimensional metallic lithium negative electrodes
S1, preparing a lithium iron phosphate electrode slice: firstly, N-methylpyrrolidone (NMP) is used as a solvent, and LiFePO is adopted4Conductive carbon black/binder PVDF (mass ratio of 8:1: 1) to prepare a lithium iron phosphate electrode slurry. Uniformly stirring the obtained slurry for 20-30 min; using a scraper toThe resulting homogeneous slurry was coated on an aluminum current collector, followed by vacuum drying at 120 ℃ for 12 h.
S2, filling argon into the glove box (H)20、O2All the contents are less than 0.1 ppm), respectively preparing a lithium symmetrical battery and a full battery according to the sequence of a composite metal lithium negative electrode/a commercial diaphragm/a composite metal lithium negative electrode and lithium iron phosphate/a commercial diaphragm membrane/a composite metal lithium negative electrode, and placing the batteries on a blue battery tester for testing at normal temperature. The test results are shown in fig. 3 and 4, respectively.
Further, FIG. 3 shows that a symmetric lithium battery can be operated at 0.2mA/cm2The next continuous operation lasts for more than 800 hours, and no obvious lithium dendrite growth occurs. This indicates that the three-dimensional metallic lithium negative electrode can achieve uniform lithium deposition and extraction, and plays a crucial role in inhibiting the growth of lithium dendrites and alleviating volume changes generated during the lithium deposition/extraction process. The test results of the full cell are shown in fig. 4, and the three-dimensional lithium metal cathode and LiFePO are used4The capacity retention rate of the full battery assembled by matching the positive electrode is 99.3 percent after the full battery is cycled for 100 circles under the multiplying power of 0.2C.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple changes or equivalent substitutions of technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.

Claims (6)

1. A method for preparing a three-dimensional metallic lithium cathode by using MOFs derivatives is characterized by comprising the following steps:
s1, preparing a metal organic framework material: dissolving 1mmol of metal salt in 15-30ml of organic solvent, adding 3-5mmol of organic ligand, magnetically stirring for 20-30min, and synthesizing metal organic framework material by solvothermal method or standing method;
s2, mixing the pretreated three-dimensional porous framework and the metal organic framework material, and uniformly growing the metal organic framework material on the three-dimensional porous framework by a soaking or hydrothermal method;
s3, placing the three-dimensional porous skeleton full of the metal organic framework material in a muffle furnace, carbonizing in nitrogen or air, and generating a metal oxide which is a metal organic framework derivative material and is a lithium-philic material after carbonization;
s4, melting of metal lithium: placing the lithium metal on a stainless steel sheet in a glove box filled with argon, and heating to 350 ℃ to obtain molten liquid lithium metal;
and S5, pouring liquid metal lithium on the whole framework to obtain the three-dimensional metal lithium cathode.
2. The method as claimed in claim 1, wherein the metal salt in step S1 is one or more selected from copper nitrate, aluminum nitrate, cobalt nitrate, tin nitrate, manganese nitrate, and zinc nitrate.
3. The method of claim 1, wherein the organic solvent in step S1 is one or more selected from methanol, absolute ethanol, dimethylformamide, and dimethylacetamide.
4. The method for preparing the three-dimensional metallic lithium cathode by using the MOFs derivatives according to claim 1, wherein the organic ligand in the step S1 is one or a mixture of more of terephthalic acid, diphenyldicarboxylic acid, trimesic acid, 2-methylimidazole and 1H-1,2, 3-triazole.
5. The method of claim 1, wherein the three-dimensional porous skeleton in step S2 is one of nickel foam, copper foam, carbon cloth, and melamine sponge.
6. The method for preparing the three-dimensional metallic lithium anode by using the MOFs derivatives according to claim 1, wherein the step of preprocessing in the step S2 is: sequentially treating with acetone, anhydrous alcohol, and deionized water by ultrasonic treatment for 10-15 min.
CN202111409635.3A 2021-11-25 2021-11-25 Method for preparing three-dimensional metal lithium cathode by using MOFs (metal-organic frameworks) derivatives Pending CN114122332A (en)

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CN114335443A (en) * 2022-03-09 2022-04-12 安徽盟维新能源科技有限公司 Composite lithium metal negative electrode, preparation method thereof and lithium metal battery
CN114665098A (en) * 2022-04-29 2022-06-24 重庆大学 Composite lithium metal negative electrode material, preparation method thereof and metal lithium battery
CN114975892A (en) * 2022-05-15 2022-08-30 北京化工大学 Preparation method of self-supporting liquid alloy electrode
CN115000355A (en) * 2022-06-06 2022-09-02 中汽创智科技有限公司 Three-dimensional metal lithium-oxide composite negative electrode, and preparation method and application thereof

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CN110212200A (en) * 2019-05-30 2019-09-06 江汉大学 A kind of battery, compound cathode of lithium and preparation method thereof
CN110649267A (en) * 2019-08-20 2020-01-03 北京泰丰先行新能源科技有限公司 Composite metal lithium cathode, preparation method and metal lithium battery
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