CN107732204B - Metal lithium composite material and preparation method thereof, and multilayer metal lithium composite material and preparation method thereof - Google Patents

Metal lithium composite material and preparation method thereof, and multilayer metal lithium composite material and preparation method thereof Download PDF

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CN107732204B
CN107732204B CN201710958308.0A CN201710958308A CN107732204B CN 107732204 B CN107732204 B CN 107732204B CN 201710958308 A CN201710958308 A CN 201710958308A CN 107732204 B CN107732204 B CN 107732204B
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lithium
macroporous
metal
porous carbon
composite material
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CN107732204A (en
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邓伟
朱文华
周旭峰
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 provides a preparation method of a metal lithium composite material, which comprises the following steps: s1) soaking the first macroporous material in the solution to obtain a soaked macroporous material; the solution contains a porous carbon material and/or a porous carbon material precursor; s2) drying the soaked macroporous material, and then carrying out annealing treatment to obtain a treated material; s3) loading metallic lithium into and/or on the surface of the treated material to obtain a metallic lithium composite material. Compared with the prior art, the invention utilizes the porous carbon material to construct a multilevel pore channel structure in the pores of the macroporous material, thereby constructing a multilevel contact interface between the electrolyte and the metal lithium, and simultaneously, the metal lithium is divided and constrained in a micron-scale space, thus being beneficial to the full reaction and deposition of the metal lithium; the multilevel structure provides a three-dimensional path for the conduction of electrons, inhibits the growth of dendritic crystal of metal lithium, and ensures that the metal lithium composite material has higher specific capacity, better rate performance and better cycling stability.

Description

Metal lithium composite material and preparation method thereof, and multilayer metal lithium composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a metal lithium composite material and a preparation method thereof, and a multilayer metal lithium composite material and a preparation method thereof.
Background
The lithium ion battery is widely applied to the fields of mobile equipment, electric automobiles and the like, and higher requirements are put forward on the energy density and the power density of the lithium ion battery. The development and research of the anode material are gradually perfected, and the method has great prospect for improving the overall performance of the lithium ion battery and researching the high-performance anode material. Lithium metal is often considered as the final negative electrode material of lithium ion batteries due to its advantages of high specific capacity, light weight, low potential, etc.
However, lithium metal hinders its further development due to its reactivity and inevitable dendrites during charging and discharging. In the past, most of research focuses on the modification of the electrolyte, and it is also a commonly used technical solution to form a stable SEI film on the surface of lithium metal to hinder the growth of dendrites, or to passivate and modify the surface of lithium metal to prepare a stable passivation film. In recent years, due to the development of nanomaterials and assembly technologies, a plurality of materials can be made into a self-supporting matrix material with a porous structure, metal lithium can be loaded in the porous material matrix in different modes, and the conventional metal lithium foil electrode is dispersed in the porous matrix to enhance the reversible capacity of the electrode in the deposition and stripping processes.
During the deposition of metallic lithium, the interface of the electrolyte with the metallic lithium is the primary reaction site. However, in the conventional research process of the metal lithium, the metal lithium in a bulk phase is adopted as a research model, so that the interface between the electrolyte and the metal lithium is limited in the stripping and deposition processes of the metal lithium. On one hand, in the existing lithium metal composite material, the size of the lithium metal is still hundreds of microns or even centimeters, the size of the dispersed/compounded lithium metal cannot be reduced to the micron level, so that the lithium metal is not greatly different from the bulk lithium metal in the reaction process, and the function of a matrix skeleton in guiding deposition is weakened; on the other hand, the existing metal lithium is compounded in a material matrix, almost completely fills the whole matrix material, and no redundant electrolyte infiltration interface is left, so that although the metal lithium is compounded in the porous matrix, other electrolyte interfaces except the surface metal lithium/electrolyte cannot be constructed, and thus the metal lithium can not be greatly distinguished from bulk lithium in the stripping and deposition processes.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a lithium metal composite material and a preparation method thereof, and a multi-layer lithium metal composite material and a preparation method thereof, wherein the lithium metal composite material has a high specific capacity, a good rate capability and a good cycle performance.
The invention provides a preparation method of a metal lithium composite material, which comprises the following steps:
s1) soaking the first macroporous material in the lithium-philic nanometer material solution to obtain a soaked macroporous material; the lithium-philic nano material solution contains a lithium-philic nano material and a porous carbon material and/or a porous carbon material precursor;
s2) drying the soaked macroporous material, and then carrying out annealing treatment to obtain a treated material;
s3) loading metallic lithium into and/or on the surface of the treated material to obtain a metallic lithium composite material.
The invention also provides a preparation method of the multilayer metal lithium composite material, which comprises the following steps:
s1) soaking the first macroporous material in the lithium-philic nanometer material solution to obtain a soaked macroporous material; the lithium-philic nano material solution contains a lithium-philic nano material and a porous carbon material and/or a porous carbon material precursor;
s2) drying the soaked macroporous material, and then carrying out annealing treatment to obtain a treated material;
s3) loading metal lithium into the interior and/or on the surface of the treated material to obtain a metal lithium composite material;
s4) compounding the second macroporous material on the surface of the lithium metal composite material to obtain the multilayer lithium metal composite material.
Preferably, the first macroporous material and the second macroporous material are each independently selected from a metal foam material, a graphene oxide foam material,One or more of a polymer foam material, activated carbon fiber cloth, carbonized sponge and carbonized trees; the pore diameters of the first macroporous material and the second macroporous material are respectively 0.01-1.0 mm independently; the porosity is independently 30-90%; the through hole rates are respectively and independently 100-95 percent; the bulk densities are respectively and independently 0.05-0.9 mg/cm3。
Preferably, the porous carbon material and/or porous carbon material precursor is selected from one or more of graphene oxide, graphene, reduced graphene oxide, carbon nanotubes, bacterial cellulose, carbonized cotton cloth, metal organic framework compounds, porous carbon and graphene hollow spheres; the concentration of the porous carbon material and/or the porous carbon material precursor in the lithium-philic nano material solution is 0.025-5 wt%.
Preferably, the mass of the porous carbon material and/or the porous carbon material precursor is 5-95% of the mass of the first macroporous material.
Preferably, the soaking temperature in the step S1) is 40-80 ℃; the soaking time is 5-20 h;
the step S2) is freeze drying; the temperature of the freeze drying is-100 ℃ to-60 ℃; the freeze drying time is 10-30 h;
the temperature of the annealing treatment in the step S2) is 500-1000 ℃; the annealing time is 0.5-10 h.
Preferably, the mass of the lithium-philic nano material is 0.5-10% of that of the first macroporous material; the lithium-philic nano material is selected from one or more of zinc acetate, silicon, zinc oxide, tin, silicon dioxide and silicon monoxide.
Preferably, the step S3) is specifically:
heating and melting the metal lithium in a protective atmosphere to obtain metal lithium liquid;
and placing the treated material on the metal lithium liquid to obtain the metal lithium composite material.
The present invention also provides a lithium metal composite material, comprising:
a composite material; the composite material comprises a first macroporous material and a porous carbon material; the porous carbon material has a hierarchical pore structure built within pores of a first macroporous material;
the composite material is internally and/or externally loaded with metallic lithium.
The present invention also provides a multilayer metallic lithium composite material comprising:
a composite material; the composite material comprises a first macroporous material and a porous carbon material; the porous carbon material has a hierarchical pore structure built within pores of a first macroporous material;
the composite material is internally and/or externally loaded with metallic lithium;
and a second macroporous material is compounded on the surface of the composite material.
The invention provides a preparation method of a metal lithium composite material, which comprises the following steps: s1) soaking the first macroporous material in the lithium-philic nanometer material solution to obtain a soaked macroporous material; the lithium-philic nano material solution contains a lithium-philic nano material and a porous carbon material and/or a porous carbon material precursor; s2) drying the soaked macroporous material, and then carrying out annealing treatment to obtain a treated material; s3) loading metallic lithium into and/or on the surface of the treated material to obtain a metallic lithium composite material. Compared with the prior art, the invention utilizes the porous carbon material to construct a multilevel pore channel structure in the pores of the macroporous material, thereby constructing a multilevel contact interface between the electrolyte and the metal lithium, and simultaneously, the metal lithium is divided and constrained in a micron-scale space, thus being beneficial to the full reaction and deposition of the metal lithium; the multilevel structure of the composite material provides a three-dimensional path for the conduction of electrons, and provides a foundation for the dispersion of current of the metal lithium under high rate, so that the growth of dendritic crystals of the metal lithium is inhibited, and the metal lithium composite material has higher specific capacity, better rate performance and better cycling stability.
Drawings
FIG. 1 is a scanning electron micrograph of a treated material obtained in example 1 of the present invention;
FIG. 2 is a graph of voltage versus time performance for a lithium symmetric cell of example 1 in accordance with the present invention;
FIG. 3 is a SEM photograph of the treated material obtained in example 2 of the present invention;
fig. 4 is a graph of voltage time performance of a lithium symmetric battery in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a metal lithium composite material, which comprises the following steps: s1) soaking the first macroporous material in the lithium-philic nanometer material solution to obtain a soaked macroporous material; the lithium-philic nano material solution contains a lithium-philic nano material and a porous carbon material and/or a porous carbon material precursor; s2) drying the soaked macroporous material, and then carrying out annealing treatment to obtain a treated material; s3) loading metallic lithium into and/or on the surface of the treated material to obtain a metallic lithium composite material.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
Soaking the first macroporous material in the lithium-philic nanometer material solution; the first macroporous material is a macroporous material well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of a metal foam material, a graphene foam material, a polymer foam material, activated carbon fiber cloth, a carbonized sponge, and a carbonized tree are preferred; the aperture of the first macroporous material is preferably 0.01-1.0 mm, more preferably 0.02-1.0 mm, and still more preferably 0.02-0.5 mm; the porosity of the first macroporous material is preferably 30-90%; the through-hole rate of the first macroporous material is preferably 100-95%; the preferred volume density of the first macroporous material is 0.05-6 mg/cm3(ii) a The lithium-philic nano material solution comprises the lithium-philic nano materialMixing the raw materials with a porous carbon material and/or a porous carbon material precursor; the porous carbon material is a porous carbon material well known to those skilled in the art, and is not particularly limited; the porous carbon material precursor is a precursor which can form the porous carbon material at high temperature and is well known to those skilled in the art, and is not particularly limited; the porous carbon material and/or porous carbon material precursor is preferably one or more of graphene oxide, graphene, reduced graphene oxide, carbon nano tubes, bacterial cellulose, carbonized cotton cloth, metal organic framework compounds, porous carbon and graphene hollow spheres; when the porous carbon material and/or the porous carbon material precursor is/are a material which can be dispersed in water solution, such as one or more of graphene oxide, bacterial cellulose and a metal organic framework compound, the lithium-philic nano material solution is preferably a water solution; when the porous carbon material and/or the porous carbon material precursor cannot be dispersed in the aqueous solution, the solvent of the lithium-philic nanomaterial solution is preferably one or more of ethanol, methanol, N-methylpyrrolidone (NMP) and Dimethylformamide (DMF), and more preferably ethanol and/or NMP; the concentration of the porous carbon material and/or the porous carbon material precursor in the lithium-philic nano material solution is preferably 0.025-5 wt%; when the solution contains the porous carbon material, the concentration of the porous carbon material is more preferably 0.025-1 wt%; when the solution only contains the porous carbon material precursor, the concentration of the porous carbon material precursor is preferably 0.5-5 wt%; the mass of the porous carbon material and/or the porous carbon material precursor is preferably 5-95%, more preferably 10-90%, and even more preferably 30-80% of the mass of the first macroporous material; the lithium-philic nanomaterial is not particularly limited, but is preferably one or more of zinc acetate, silicon, zinc oxide, tin oxide, magnesium acetate, silicon dioxide and silicon monoxide; the mass of the lithium-philic nano material is preferably 0.5-10% of that of the first macroporous material. The lithium affinity of the added lithium affinity nano material can be utilized, so that the immersion speed of the metal lithium is accelerated, the metal lithium can be inhibited from filling the whole composite material, the immersion path of the electrolyte is increased, and the construction of the electrolyte/metal is facilitatedThe lithium interface and the lithium-philic nanometer material can also provide affinity sites for the surface property change of the metal lithium. The lithium-philic nanometer material can be attached to the macroporous material in different morphological structures, and can be one or more of needle-rod-shaped, spherical and sheet-shaped.
The soaking temperature is preferably 40-80 ℃, more preferably 50-70 ℃, further preferably 55-65 ℃ and most preferably 60 ℃; the soaking time is preferably 5-20 h, more preferably 8-16 h, still more preferably 10-14 h, and most preferably 12-14 h. And after soaking, preferably cooling and taking out to obtain the soaked macroporous material.
Drying the soaked macroporous material; the drying method is not particularly limited as long as it is a method well known to those skilled in the art, and freeze-drying is preferable in the present invention; the temperature of the freeze drying is preferably-100 ℃ to-60 ℃, more preferably-90 ℃ to-60 ℃, and further preferably-80 ℃ to-60 ℃; the freeze drying time is preferably 10-30 h, more preferably 15-30 h, still more preferably 20-30 h, and most preferably 24-28 h.
After drying, carrying out annealing treatment to obtain a treated material; the annealing treatment is preferably carried out in a protective atmosphere; the protective atmosphere is not particularly limited as long as it is known to those skilled in the art, and argon is preferred in the present invention; the annealing treatment temperature is preferably 500-1000 ℃, more preferably 600-900 ℃, further preferably 650-850 ℃, and most preferably 800 ℃; the time of the annealing treatment is preferably 0.5-10 hours, more preferably 2-8 hours, and still more preferably 3-5 hours. The porous carbon material constructs a multi-level pore structure in the macroporous material, reduces the size of the original pore structure and enables the composite area of the metal lithium to be micron.
Loading metal lithium into the interior and/or on the surface of the treated material to obtain a metal lithium composite material; the method of loading is not particularly limited as long as it is well known to those skilled in the art, and the present invention is preferably carried out according to the following method: heating and melting the metal lithium in a protective atmosphere to obtain metal lithium liquid; and placing the treated material on the metal lithium liquid to obtain the metal lithium composite material. The heating and melting temperature is preferably 200-400 ℃, more preferably 250-350 ℃, and further preferably 300 ℃; the mass of the metallic lithium is preferably 10% to 400%, more preferably 100% to 150% of the mass of the material after treatment.
According to the invention, a multi-stage pore channel structure is constructed in pores of a macroporous material by using a porous carbon material, so that a multi-stage contact interface of electrolyte and metal lithium is constructed, and the metal lithium is divided and bound in a micron-scale space, so that sufficient reaction and deposition of the metal lithium are facilitated; the multilevel structure of the composite material provides a three-dimensional path for the conduction of electrons, and provides a foundation for the dispersion of current of the metal lithium under high rate, so that the growth of dendritic crystals of the metal lithium is inhibited, and the metal lithium composite material has higher specific capacity, better rate performance and better cycling stability; the preparation method provided by the invention is simple and feasible, and is beneficial to large-scale production.
The invention also provides a metal lithium composite material prepared by the method, which comprises the following steps: a composite material; the composite material comprises a first macroporous material and a porous carbon material; the porous carbon material has a hierarchical pore structure built within pores of a first macroporous material; the composite material is internally and/or externally loaded with metallic lithium; the lithium-philic nanometer material is preferably also attached to the inner part and/or the surface of the composite material.
According to the invention, a multi-stage structure is constructed by using a porous carbon material in the macroporous material, so that the dispersion size of the metal lithium is improved, the complete reaction capability of the metal lithium is increased, and meanwhile, the constructed multi-stage structure is used for limiting and guiding the deposition of the metal lithium, so that sufficient electrons are provided for the glass of the metal lithium, and thus, the highly reversible metal lithium composite material is obtained, and the growth of surface dendrites and the accumulation of dead lithium are weakened.
The first macroporous material, the porous carbon material, the lithium-philic nanomaterial and the metallic lithium are the same as those described above, and are not described herein again.
The invention also provides a preparation method of the multilayer metal lithium composite material, which comprises the following steps: s1) soaking the first macroporous material in the lithium-philic nanometer material solution to obtain a soaked macroporous material; the lithium-philic nano material solution contains a lithium-philic nano material and a porous carbon material and/or a porous carbon material precursor; s2) drying the soaked macroporous material, and then carrying out annealing treatment to obtain a treated material; s3) loading metal lithium into the interior and/or on the surface of the treated material to obtain a metal lithium composite material; s4) compounding the second macroporous material on the surface of the lithium metal composite material to obtain the multilayer lithium metal composite material.
The steps S1) to S3) are the same as above, and are not described herein again.
Compounding a second macroporous material on the surface of the metal lithium composite material to obtain a multilayer metal lithium composite material; the second macroporous material is a macroporous material well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of a metal foam material, a graphene foam material, a polymer foam material, activated carbon fiber cloth, a carbonized sponge, and a carbonized tree are preferred; the aperture of the second macroporous material is preferably 0.01-1.0 mm, more preferably 0.05-0.5 mm, and still more preferably 0.005-0.3 mm; the porosity is preferably 30-90%; the through hole rate is preferably 100-95%; the preferred volume density is 0.05-0.9 mg/cm3(ii) a The thickness of the second macroporous material is preferably 10-50 μm, and more preferably 20-30 μm; the compounding method is not particularly limited as long as it is a method well known to those skilled in the art, and a method of press compounding is preferably used in the present invention; the pressurizing pressure is preferably 1-10 MPa, and more preferably 5-6 MPa; the second macroporous material is preferably compounded on the surface of the lithium metal composite material loaded with the lithium metal. The second macroporous material is a surface barrier layer in the multilayer metal lithium composite material.
The invention loads a metal lithium material on a substrate with a hierarchical pore channel to form a metal lithium composite material, constructs a surface barrier layer on the basis of the metal lithium composite material, thereby restricting the size of the metal lithium to a micron level, constructs a multilevel electrolyte/metal lithium interface and a surface multifunctional barrier structure, guides and limits metal lithium dendrites, and obtains the multilayer metal lithium composite material with high multiplying power and high stability.
The invention also provides a multilayer metal lithium composite material prepared by the method, which comprises the following steps: a composite material; the composite material comprises a first macroporous material and a porous carbon material; the porous carbon material has a hierarchical pore structure built within pores of a first macroporous material; the composite material is internally and/or externally loaded with metallic lithium; and a second macroporous material is compounded on the surface of the composite material.
The invention also provides an application of the metal lithium composite material or the multilayer metal lithium composite material as a metal lithium negative electrode material.
In order to further illustrate the present invention, a lithium metal composite and a method for preparing the same, a multi-layer lithium metal composite and a method for preparing the same, which are provided by the present invention, are described in detail below with reference to examples.
The reagents used in the following examples are all commercially available.
Example 1
1.1 adding 40mL of 10mg/mL graphite oxide solution into 160mL of deionized water solution, carrying out ultrasonic treatment in 200W water bath for 2h to obtain 2.0mg/mL graphene oxide solution, adding 4.0g of zinc acetate into the graphene oxide solution, and stirring the solution for 2 h.
1.2 foam copper substrate (aperture 0.5mm, porosity 30%, through-hole porosity 95%, bulk density 0.2 mg/cm)3) Soaking in the graphene oxide solution, placing in a 60 ℃ oven for 12h, cooling, and taking out the soaked material.
1.3 freezing the soaked materials in liquid nitrogen, and freeze-drying in a vacuum environment (the temperature of freeze-drying is-100 ℃) for 24 hours, and then taking out a sample. And then placing the sample in an argon protective atmosphere, and carrying out annealing treatment at 800 ℃ for 4h to obtain the treated material.
1.4 placing the metallic lithium (100 percent of the mass of the processed material) in an argon protection atmosphere to heat to 300 ℃, then placing the material on the molten metallic lithium liquid, and after 2 minutes, loading the metallic lithium in the material to obtain the metallic lithium composite material.
1.5 foam of neat graphene (thickness 50 μm, bulk density) at a pressure of 2MPa0.5mg/cm3) And loading the composite material on the surface of the metal lithium composite material to obtain the multilayer metal lithium composite material.
1.6 the obtained lithium metal composite material is assembled into a lithium symmetric battery (namely, the lithium metal composite material and the lithium metal composite material are assembled into a button battery), and the area current density is 2mA cm-2Specific area capacity of 1mAh cm-2The conditions of (1) were tested in cycles.
The treated material obtained in example 1 was analyzed by a scanning electron microscope, and a scanning electron micrograph thereof is shown in fig. 1.
The voltage and time stability obtained from the cycling test is shown in figure 2.
Example 2
2.1 taking 80mL of graphene solution stripped by a high-quality solvent of 9mg/mL, adding the graphene solution into 160mL of deionized water solution, carrying out ultrasonic treatment in a 200W water bath for 1h to obtain 3.0mg/mL of graphene solution, adding 6.0g of silicon dioxide nano particles into the graphene solution, and stirring the solution for 1 h.
2.2 the activated carbon fiber cloth (aperture range is 0.05-0.2 mm, the diameter of a single fiber is 10 mu m, the through hole rate is 100 percent, and the volume density is 5mg/cm3) Soaking in the graphene solution, placing in an oven at 80 ℃ for 10h, cooling, and taking out the soaked material.
2.3 freezing the soaked materials in liquid nitrogen, and freeze-drying in a vacuum environment (the temperature of freeze-drying is-60 ℃) for 24 hours, and taking out the sample. And then placing the sample in an argon protective atmosphere, and carrying out annealing treatment at 600 ℃ for 3h to obtain the treated material.
2.4 putting the metal lithium (200% of the processed material mass) in an argon protection atmosphere to heat to 300 ℃, then putting the material on the molten metal lithium liquid, and after 1 minute, loading the metal lithium in the material to obtain the metal lithium composite material.
2.5 under the pressure of 5MPa, pure activated carbon fiber cloth (the aperture range is 0.05-0.2 mm, the diameter of a single fiber is 10 mu m, the through hole rate is 100 percent, and the volume density is 5mg/cm3) Loading on the surface of the lithium metal composite material to obtain multiple layersA lithium metal composite.
2.6 assembling the obtained lithium metal composite material into a lithium symmetric battery (namely assembling the lithium metal composite material and the lithium metal composite material into a button battery), and carrying out lithium symmetric battery under the condition that the area current density is 5mA cm-2Specific area capacity of 1mAh cm-2The conditions of (1) were tested in cycles.
The treated material obtained in example 2 was analyzed by a scanning electron microscope, and a scanning electron micrograph thereof is shown in fig. 3.
The stability of the voltage and time obtained by the cycling test is shown in fig. 4.
Example 3
3.1 taking 80mL of 1.0mg/mL bacterial cellulose alcoholic solution, adding 3.0g of zinc oxide nano particles into the bacterial cellulose alcoholic solution, and stirring the solution for 10 hours.
3.2 carbonizing the tree substrate (aperture 0.02mm, through-hole rate 100%, volume density 3 mg/cm)3) Soaking in the bacterial cellulose alcoholic solution, placing in an oven at 80 deg.C for 10h, cooling, and taking out the soaked material.
3.3 freezing the soaked materials in liquid nitrogen, and freeze-drying in a vacuum environment (the temperature of freeze-drying is-80 ℃) for 20 hours, and then taking out the sample. And then placing the sample in an argon protective atmosphere, and carrying out annealing treatment at 1000 ℃ for 8h to obtain the treated material.
And 3.4, placing the metal lithium (400 percent of the mass of the processed material) in an argon protection atmosphere, heating to 360 ℃, placing the material on molten metal lithium liquid, and after 5 minutes, loading the metal lithium into the material to obtain the metal lithium composite material.
3.5 pure nickel foam (pore diameter 0.5mm, porosity 80%, porosity 95%, bulk density 0.4 mg/cm) was pressed under 9MPa3) And loading the composite material on the surface of the metal lithium composite material to obtain the multilayer metal lithium composite material.
3.6 assembling the obtained lithium metal composite material into a lithium symmetric battery (namely assembling the lithium metal composite material and the lithium metal composite material into a button battery), and carrying out lithium symmetric battery under the condition that the area current density is 10mA cm-2Specific area capacity of 0.5mAh cm-2The conditions of (1) were tested in cycles.
Example 4
4.1 taking 120mL of 5.0mg/mL carbon nanotube solution, adding 3.0g of tin oxide nanoparticles into the carbon nanotube solution, and stirring the solution for 8 h.
4.2 mixing the polymer foam substrate (aperture range is 0.1-0.2 mm, the through hole rate is 100%, and the volume density is 6 mg/cm)3) Soaking in the carbon nano solution, placing in an oven at 80 ℃ for 6h, cooling, and taking out the soaked material.
4.3 freezing the soaked materials in liquid nitrogen, and then freeze-drying in a vacuum environment (the temperature of freeze-drying is-70 ℃) for 30h, and taking out a sample. And then placing the sample in an argon protective atmosphere, and carrying out annealing treatment at 1000 ℃ for 3h to obtain the treated material.
4.4 putting the metal lithium (50 percent of the mass of the processed material) in an argon protection atmosphere to heat to 280 ℃, then putting the material on the molten metal lithium liquid, and after 10 minutes, loading the metal lithium in the material to obtain the metal lithium composite material.
4.5 pure carbonized Cotton cloth (thickness 20 μm, bulk density 0.2 mg/cm) was pressed under 3MPa3) And loading the composite material on the surface of the metal lithium composite material to obtain the multilayer metal lithium composite material.
4.6 assembling the obtained lithium metal composite material into a lithium symmetric battery (namely assembling the lithium metal composite material and the lithium metal composite material into a button battery), and carrying out lithium symmetric battery under the condition that the area current density is 2mA cm-2Specific area capacity of 5mAh cm-2The conditions of (1) were tested in cycles.
Example 5
5.1 taking 200mL of 1.0mg/mL graphene hollow sphere alcohol solution, adding 2.0g of tin oxide and magnesium acetate into the graphene hollow sphere alcohol solution, and stirring the solution for 8 hours.
5.2 foaming graphene (pore diameter of 0.2mm, porosity of 90%, porosity of 95%, bulk density of 0.05 mg/cm)3) Soaking in the graphene hollow sphere alcohol solution, placing in an oven at 80 ℃ for 6h, and coolingHowever, the soaked material was removed.
And 5.3, freezing the soaked materials in liquid nitrogen, and then freeze-drying in a vacuum environment (the temperature of freeze-drying is-50 ℃) for 10 hours, and taking out a sample. And then placing the sample in an argon protective atmosphere, and carrying out annealing treatment at 500 ℃ for 1h to obtain the treated material.
And 5.4, placing the metal lithium (300 percent of the mass of the processed material) in an argon protection atmosphere to be heated to 350 ℃, then placing the material on molten metal lithium liquid, and after 2 minutes, loading the metal lithium into the material to obtain the metal lithium composite material.
5.5 pure graphene foam (pore size 0.2mm, porosity 90%, through-hole porosity 95%, bulk density 0.05 mg/cm) was pressed at 1MPa3) And loading the composite material on the surface of the metal lithium composite material to obtain the multilayer metal lithium composite material.
5.6 assembling the obtained lithium metal composite material into a lithium symmetric battery (namely assembling the lithium metal composite material and the lithium metal composite material into a button battery), and carrying out lithium symmetric battery under the condition that the area current density is 5mA cm-2Specific area capacity of 3mAh cm-2The conditions of (1) were tested in cycles.

Claims (8)

1. A method of making a multi-layer metallic lithium composite, comprising:
s1) soaking the first macroporous material in the lithium-philic nanometer material solution to obtain a soaked macroporous material; the lithium-philic nano material solution contains a lithium-philic nano material and a porous carbon material and/or a porous carbon material precursor;
s2) drying the soaked macroporous material, and then carrying out annealing treatment to obtain a treated material;
s3) loading metal lithium into the interior and/or on the surface of the treated material to obtain a metal lithium composite material;
s4) compounding the second macroporous material on the surface of the lithium metal composite material to obtain the multilayer lithium metal composite material.
2. According to claimThe preparation method of claim 1, wherein the first macroporous material and the second macroporous material are each independently selected from one or more of a metal foam material, a graphene foam material, a polymer foam material, activated carbon fiber cloth, a carbonized sponge and a carbonized tree; the pore diameters of the first macroporous material and the second macroporous material are respectively 0.01-1.0 mm independently; the porosity is independently 30-90%; the through hole rates are respectively and independently 100-95 percent; the bulk densities are respectively and independently 0.05-0.9 mg/cm3。
3. The preparation method according to claim 1, wherein the porous carbon material and/or porous carbon material precursor is selected from one or more of graphene oxide, graphene, reduced graphene oxide, carbon nanotubes, bacterial cellulose, carbonized cotton cloth, metal organic framework compounds, porous carbon and graphene hollow spheres; the concentration of the porous carbon material and/or the porous carbon material precursor in the lithium-philic nano material solution is 0.025-5 wt%.
4. The production method according to claim 1, wherein the mass of the porous carbon material and/or the porous carbon material precursor is 5% to 95% of the mass of the first macroporous material.
5. The preparation method according to claim 1, wherein the temperature for soaking in the step S1) is 40-80 ℃; the soaking time is 5-20 h;
the step S2) is freeze drying; the temperature of the freeze drying is-100 ℃ to-60 ℃; the freeze drying time is 10-30 h;
the temperature of the annealing treatment in the step S2) is 500-1000 ℃; the annealing time is 0.5-10 h.
6. The preparation method according to claim 1, wherein the mass of the lithium-philic nano-material is 0.5-10% of the mass of the first macroporous material; the lithium-philic nano material is selected from one or more of zinc acetate, silicon, zinc oxide, tin, silicon dioxide and silicon monoxide.
7. The preparation method according to claim 1, wherein the step S3) is specifically:
heating and melting the metal lithium in a protective atmosphere to obtain metal lithium liquid;
and placing the treated material on the metal lithium liquid to obtain the metal lithium composite material.
8. A multi-layered lithium metal composite prepared by the preparation method of any one of claims 1 to 7, comprising:
a composite material; the composite material comprises a first macroporous material and a porous carbon material; the porous carbon material has a hierarchical pore structure built within pores of a first macroporous material;
the composite material is internally and/or externally loaded with metallic lithium;
and a second macroporous material is compounded on the surface of the composite material.
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