CN112968174B - Lithium-philic alloy modification layer, composite lithium negative electrode material, and preparation methods and applications of lithium-philic alloy modification layer and composite lithium negative electrode material - Google Patents

Lithium-philic alloy modification layer, composite lithium negative electrode material, and preparation methods and applications of lithium-philic alloy modification layer and composite lithium negative electrode material Download PDF

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CN112968174B
CN112968174B CN202110201911.0A CN202110201911A CN112968174B CN 112968174 B CN112968174 B CN 112968174B CN 202110201911 A CN202110201911 A CN 202110201911A CN 112968174 B CN112968174 B CN 112968174B
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lithium
alloy
negative electrode
philic
composite
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CN112968174A (en
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李晶泽
阮瑾
陈涛
王子豪
王志红
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University of Electronic Science and Technology of China
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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
    • H01M4/38—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • H01M2004/026—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 lithium-philic alloy modification layer, a composite lithium cathode material, and a preparation method and application thereof, and belongs to the technical field of batteries. According to the invention, a dissimilar element M is added into molten metal lithium to obtain molten lithium alloy Li-M, then the molten lithium alloy Li-M is contacted with the surface of a metal material N, a lithium-philic alloy modification layer at least containing elements M and N is spontaneously formed on the surface of the metal material N, the lithium-philic alloy modification layer induces liquid lithium alloy and/or liquid lithium to be adsorbed on the surface of the metal material N, and then the metal material N is cooled to room temperature to obtain a three-layer structure containing a metal material N framework layer, a lithium-philic alloy modification layer and a Li-M lithium alloy/metal lithium layer, and a solid composite lithium anode material containing at least three components, so that the preparation problems of the existing composite lithium anode material and the problems of dendritic crystal growth, electrode volume expansion and structure pulverization in the circulation process are solved.

Description

Lithium-philic alloy modification layer, composite lithium negative electrode material, and preparation methods and applications of lithium-philic alloy modification layer and composite lithium negative electrode material
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method and application thereof.
Background
The negative electrode material of the battery is one of the main factors influencing the energy density of the battery, and the negative electrode of the commercial lithium ion battery is mainly based on a carbon material. Because the carbon material is limited by a graphitized structure, the theoretical specific capacity of the carbon material is only 372mAh/g, which is one of the main factors for restricting the further improvement of the energy density of the lithium ion battery. The theoretical specific capacity of the pure lithium negative electrode material can reach 3860mAh/g, and the pure lithium negative electrode material has ultralow electrochemical potential (-3.040V vs. standard hydrogen electrode) and ultralow mass density (0.53 g/cm) 3 ) It is an ideal negative electrode material of high-energy density secondary lithium battery. But is extremely active due to the chemical properties of lithium metal and the absence of pores in the electrode itselfThe rapid growth of lithium dendrites and large volume change of electrodes during the circulation process are caused, lithium and Electrolyte are continuously consumed along with repeated rupture and repair of a Solid Electrolyte interface (Solid Electrolyte interface) film, partial lithium is inactivated, dead lithium is generated, the circulation efficiency is reduced, and lithium dendrites even penetrate through a diaphragm to cause short circuit of a battery, so that the safety problem is caused.
In order to solve the problems of dendritic crystal growth, volume change and the like of a lithium metal negative electrode, a framework material and metal lithium are compounded together in the prior art, and the obtained composite lithium negative electrode material is a hotspot of current research. The technical scheme mainly has the following advantages: (1) the three-dimensional structure formed by the framework material can provide space for lithium deposition, and volume change generated in the lithium deposition/lithium stripping process is eliminated or reduced; (2) the high specific surface area of the three-dimensional framework can effectively reduce the current density, thereby reducing lithium dendrites; (3) the three-dimensional framework itself and its porous structure may be Li + The transmission of ions provides a fast channel, reducing internal resistance.
However, the above technical solutions still have a series of problems. For example, generally, the framework material has poor wettability with lithium, and even exhibits a lithium-phobic characteristic, so that the surface of the framework material needs to be modified to prepare a layer of lithium-philic substance, and then metal lithium can be compounded with the lithium-philic substance to obtain the composite lithium negative electrode. Common materials of the modification layer are poor in electronic conductivity, such as oxides and sulfides, and hinder electronic transmission to a certain extent, so that the rate performance of the battery is poor. At present, typical methods for preparing the lithium-philic modification layer include chemical deposition, electrochemical deposition, atomic layer deposition, joule heating, and the like. However, the electrochemical deposition method requires lithium plating in an electrolytic cell, the atomic layer deposition requires expensive and complicated equipment and takes a long time, the joule heating method has high energy consumption and poor controllability, and after a lithium-philic modification layer is formed, all the methods also require an additional process to perform lithium recombination, so that the composite lithium negative electrode can be finally obtained. In the prior art, the method for preparing the lithium-philic layer on the surface of the framework material and obtaining the composite lithium cathode has complex process, needs at least two steps and is difficult to realize commercial production.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a lithium-philic alloy modification layer, a composite lithium negative electrode material, a preparation method and an application thereof, which can effectively solve the problems of lithium dendrite growth, electrode volume expansion and structure pulverization in the circulation process of the existing composite lithium negative electrode material, and complex preparation method and high cost of the existing composite lithium negative electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a lithium-philic alloy modification layer, which is prepared by the following method: contacting the molten lithium alloy Li-M with the surface of the metal material N to spontaneously form a lithium-philic alloy modification layer on the surface of the metal material N; wherein M is a different element different from the metal material N, and the lithium-philic alloy modification layer contains M and N.
Further, M is one or more of Na, Mg, Ca, Sr, Ba, Cr, Mn, Mo, Ni, Cu, Zn, B, Al, Ga, Ge, In, Si, Sn, Pb, Ag or Sb elements.
Further, the component of the metal material N is one or more of Cu, Zn, Al, Ti, Ni or Fe, the material form is one-dimensional, two-dimensional, three-dimensional or a mixture thereof, and the structure is a three-dimensional network structure or a three-dimensional foam cavity structure formed by interweaving particles, fibers and sheets; wherein the size of the cavity in the three-dimensional foam cavity structure is 10 nm-500 mu m, and the thickness of the three-dimensional network structure and the three-dimensional skeleton in the three-dimensional foam cavity structure is 1 mu m-500 mu m.
Further, the metal material N is a copper wire, a zinc wire, an aluminum wire, a nickel wire, an iron wire, a titanium wire, an iron-nickel alloy wire, a stainless steel wire, a copper foil, a zinc foil, an aluminum foil, a nickel foil, an iron foil, a titanium foil, an iron-nickel alloy foil, a stainless steel foil, a copper foam, a zinc foam, a nickel foam, an aluminum foam, an iron foam, a titanium foam, an iron-nickel foam, or a stainless steel foam.
The invention also provides a composite lithium negative electrode material containing the lithium-philic alloy modification layer.
Further, the composite lithium negative electrode material structure comprises a metal material N framework layer, a lithium-philic alloy modification layer and a Li-M lithium alloy/metal lithium layer.
The invention also provides a preparation method of the composite lithium negative electrode material, which comprises the following steps:
step (1): melting the metal lithium into liquid state to obtain molten metal lithium;
step (2): adding a dissimilar element M into the molten lithium metal obtained in the step (1) to obtain a molten lithium alloy Li-M;
and (3): contacting the molten lithium alloy Li-M obtained in the step (2) with the surface of a metal material N to obtain a molten composite lithium negative electrode material in situ;
and (4): and (4) cooling the molten state composite lithium negative electrode material obtained in the step (3) to room temperature to obtain the composite lithium negative electrode material.
Furthermore, the melting temperature of the lithium metal in the step (1) is 200-800 ℃.
Further, in the step (2), the molar ratio of the dissimilar element M to lithium is 1:2 to 200, preferably 1: 50.
Further, the time for cooling the molten state composite lithium negative electrode material to room temperature in the step (4) is 1-600 minutes.
The invention also provides application of the composite lithium negative electrode material in preparing a lithium battery negative electrode or a lithium battery.
The invention has the following advantages:
1. the invention provides a lithium-philic alloy modification layer, which is formed spontaneously on the surface of a metal material N by contacting molten lithium alloy Li-M with the surface of the metal material N, and has a thickness of nanometer magnitude;
2. the invention provides a composite lithium negative electrode material which comprises a metal material N framework layer, a lithium-philic alloy modification layer and a Li-M lithium alloy/metal lithium layer. The metal material N framework layer has outstanding mechanical properties, can prevent the structural collapse problem of the negative electrode in the charge-discharge cycle process, and provides extra space for accommodating lithium deposition; the metal material N framework layer and the lithium-philic alloy modification layer have good conductivity, and the rate performance is improved; the lithium-philic alloy modification layer is conformally present on the surface of the metal material N and is uniformly distributed, so that the lithium-philic alloy modification layer plays a key role in the preparation stage of the composite lithium cathode material, and has high affinity to lithium in the battery cycle process, so that lithium atoms are induced to be uniformly deposited, the growth of lithium dendrites is reduced, the coulomb efficiency of the battery is greatly improved, the cycle life is prolonged, and the lithium-philic alloy modification layer has practical application value in the aspect of preparing a lithium battery cathode or a lithium battery;
3. the invention provides a preparation method of a composite lithium negative electrode material, which comprises the steps of adding a dissimilar element M into molten metal lithium to obtain a molten lithium alloy Li-M, contacting the molten lithium alloy Li-M with the surface of a metal material N, spontaneously forming a lithium-philic alloy modification layer at least containing the elements M and N on the surface of the metal material N, inducing liquid lithium alloy and/or liquid lithium to be adsorbed on the surface of the metal material by the lithium-philic alloy modification layer, cooling to room temperature, and obtaining a three-layer structure containing a metal material N framework layer, a lithium-philic alloy modification layer and a Li-M lithium alloy/metal lithium layer and a solid composite lithium negative electrode material containing at least three components; the method has the obvious characteristics of simplicity, convenience and low cost, and the lithium-philic alloy modification layer and the composite lithium anode material are obtained in one step.
Drawings
FIG. 1 is a schematic diagram showing the evolution of the three-layer structure of the metal material N-framework layer, the lithium-philic alloy modification layer and the Li-M lithium alloy/metal lithium layer in the material preparation process;
FIG. 2 is an SEM photograph of a Mg-Li alloy in a molten state contacting a copper foam skeleton for different times in example 1 of the present invention;
FIG. 3 is an XRD pattern of a Mg-Li alloy in a molten state contacting a copper foam skeleton for various times in example 1 of the present invention;
FIG. 4 shows that in example 1 of the present invention, Cu is present on the surface 2 SEM sectional view, element distribution diagram and corresponding XRD diagram of the copper framework of the Mg alloy modification layer;
FIG. 5 shows a symmetrical cell of the present invention in Experimental example 1 at (a)1mA cm -2 And (b)5mA cm -2 A constant current cycle time-voltage curve chart is shown;
fig. 6 is a graph showing the discharge capacity and coulombic efficiency at 0.5C as a function of cycle number in a lithium-iron phosphate battery system according to experimental example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be purely exemplary of the invention and are not intended to be limiting.
Example 1
The embodiment 1 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material and a preparation method thereof, and specifically comprises the following steps:
putting the metallic lithium into a stainless steel crucible in an external environment with a dew point of-50 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 400 ℃ to enable the metallic lithium to be in a molten state; then adding metallic magnesium (Mg) to metallic lithium in a molten state to form a molten lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of the foam copper cavity structure, and is cooled to room temperature within 2min, so that a solid composite lithium negative electrode material containing at least three components and a three-layer structure of a metal material Cu framework layer, a Mg-Cu lithium-philic alloy modification layer and a Li-Mg lithium alloy/metal lithium layer can be obtained, and the evolution schematic diagram in the preparation process of the composite lithium negative electrode material is shown in figure 1; wherein the molar ratio of metal Mg to metal lithium is 1:50, and the cavity size of the foam copper cavity structure material is 10-200 μm.
Example 2
This example 2 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in example 1 only in that: the foam copper cavity structure material in example 1 was replaced with copper foil, and the remaining parameters were the same.
Example 3
This embodiment 3 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in embodiment 1 only in that: the foam copper cavity structure material in example 1 was replaced with a copper wire network, and the remaining parameters were the same.
Example 4
The embodiment 4 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material and a preparation method thereof, and specifically includes the following steps:
putting metallic lithium into a stainless steel crucible in an external environment with a dew point of-55 ℃ and an oxygen content of less than 10ppm, and placing the crucible on a heating table with a temperature of 500 ℃ to enable the metallic lithium to be in a molten state; then adding metallic calcium (Ca) to the metallic lithium in a molten state to form a molten lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of an aluminum wire, and is cooled to room temperature within 1min, so that a solid composite lithium negative electrode material containing at least three components and having a three-layer structure of a metal material Al framework layer, a Ca-Al lithium-philic alloy modification layer and a Li-Ca lithium alloy/metal lithium layer can be obtained; wherein the molar ratio of the metal Ca to the molten metal lithium is 1: 200.
Example 5
This example 5 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which are different from those of example 4 only in that: the aluminum wire in example 4 was replaced with an aluminum foil, and the remaining parameters were the same.
Example 6
This embodiment 6 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in embodiment 4 only in that: replacing the aluminum wire in the embodiment 4 with a foamed aluminum cavity structure material, wherein the other parameters are the same; wherein the cavity size of the foamed aluminum cavity structure material is 10 μm.
Example 7
This embodiment 7 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which specifically includes the following steps:
putting the metallic lithium into a stainless steel crucible in an external environment with a dew point of-45 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 450 ℃ to enable the metallic lithium to be in a molten state; then adding metallic strontium (Sr) to metallic lithium in a molten state to form a molten lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of an aluminum wire, and the aluminum wire is cooled to room temperature within 60min, so that a solid composite lithium negative electrode material containing at least three components and having a three-layer structure of a metal material Al framework layer, a Sr-Al lithium-philic alloy modification layer and a Li-Sr lithium alloy/metal lithium layer can be obtained; wherein the molar ratio of the metal Sr to the molten metal lithium is 1: 2.
In this embodiment 7, the aluminum wire may be replaced with an aluminum foil or a foamed aluminum cavity structure material in the preparation method of the lithium-philic alloy modification layer and the composite lithium negative electrode material; wherein the cavity size of the foamed aluminum cavity structure material is 500 mu m.
This example 7 provides a lithium battery negative electrode and a lithium battery, which are different from the example 4 only in that: the composite lithium negative electrode material in example 4 was replaced with the composite lithium negative electrode material prepared in example 7, and the remaining steps and parameters were the same.
Example 8
This example 8 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material and a preparation method thereof, which are different from those of example 7 only in that: the metal strontium (Sr) in example 7 was replaced with the metal barium (Ba), and the remaining parameters and steps were the same.
Example 9
This embodiment 9 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which specifically includes the following steps:
putting the metal lithium into a stainless steel crucible in an external environment with a dew point of-50 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 800 ℃ to ensure that the metal lithium is in a molten state; then adding metallic chromium (Cr) to metallic lithium in a molten state to form a molten lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of a nickel wire, and the nickel wire is cooled to room temperature within 600min, so that a solid composite lithium negative electrode material containing a three-layer structure of a metal material Ni framework layer, a Cr-Ni lithium-philic alloy modification layer and a Li-Cr lithium alloy/metal lithium layer and containing at least three components can be obtained; wherein the molar ratio of the metal Cr to the molten metal lithium is 1: 50.
In the preparation method of the lithium-philic alloy modification layer and the composite lithium negative electrode material of this embodiment 9, the nickel wire may be replaced by a nickel foil or a foam nickel cavity structure material; wherein the cavity size of the foam nickel cavity structure material is 100 μm.
Example 10
This embodiment 10 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which specifically includes the following steps:
putting the metallic lithium into a stainless steel crucible in an external environment with a dew point of-50 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 700 ℃ to enable the metallic lithium to be in a molten state; then adding metal manganese (Mn) into the molten metal lithium to form a molten lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of a nickel wire, and the nickel wire is cooled to room temperature within 40min, so that a solid composite lithium negative electrode material containing a three-layer structure of a metal material Ni framework layer, a Mn-Ni lithium-philic alloy modification layer and a Li-Mn lithium alloy/metal lithium layer and containing at least three components can be obtained; wherein the molar ratio of the metal Mn to the molten metal lithium is 1: 50.
In the preparation method of the lithium-philic alloy modification layer and the composite lithium negative electrode material in this embodiment 10, the nickel wire may be replaced by a nickel foil or a foam nickel cavity structure material; wherein the cavity size of the foam nickel cavity structure material is 100 mu m.
Example 11
This embodiment 11 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which specifically includes the following steps:
putting the metallic lithium into a stainless steel crucible in an external environment with a dew point of-50 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 800 ℃ to enable the metallic lithium to be in a molten state; then adding metallic molybdenum (Mo) to metallic lithium in a molten state to form a molten state lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of the iron wire and cooled to room temperature within 24min, and the solid composite lithium negative electrode material containing at least three components and a three-layer structure of a metal material Fe framework layer, a Mo-Fe lithium-philic alloy modification layer and a Li-Mo lithium alloy/metal lithium layer can be obtained; wherein the molar ratio of the metal Mo to the molten metal lithium is 1: 50.
In this embodiment 11, the lithium-philic alloy modification layer and the composite lithium negative electrode material may be made of a nickel wire with a cavity structure of iron foil or foam iron; wherein the cavity size of the foam iron cavity structure material is 100 μm.
Example 12
This embodiment 12 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which specifically includes the following steps:
putting the metallic lithium into a stainless steel crucible in an external environment with a dew point of-50 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 350 ℃ to enable the metallic lithium to be in a molten state; then adding metallic zinc (Zn) to the metallic lithium in a molten state to form a molten state lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of a copper wire and cooled to room temperature within 3min, so that a solid composite lithium negative electrode material containing at least three components and a three-layer structure of a Cu framework layer, a Zn-Cu lithium-philic alloy modification layer and a Li-Zn lithium alloy/metal lithium layer can be obtained; wherein the molar ratio of the metal Zn to the molten metal lithium is 1: 5.
In the preparation method of the lithium-philic alloy modification layer and the composite lithium negative electrode material in this embodiment 12, the copper wire may be replaced by a copper foil or a foam copper cavity structure material; wherein the cavity size of the foam copper cavity structure material is 100 μm.
Example 13
This example 13 provides a composite lithium negative electrode material and a method for preparing the same, which are different from those of example 11 only in that: the metal molybdenum (Mo) in example 11 was replaced by metal aluminum (Al), and the remaining steps and parameters were the same.
Example 14
This embodiment 14 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which specifically includes the following steps:
putting the metallic lithium into a stainless steel crucible in an external environment with a dew point of-50 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 800 ℃ to enable the metallic lithium to be in a molten state; then adding metallic boron (B) to metallic lithium in a molten state to form a molten state lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of a titanium wire, and the titanium wire is cooled to room temperature within 3min, so that a solid composite lithium negative electrode material containing a three-layer structure of a metal material Ti framework layer, a B-Ti lithium-philic alloy modification layer and a Li-B lithium alloy/metal lithium layer and containing at least three components can be obtained; wherein the molar ratio of the metal B to the molten metal lithium is 1: 50.
In the preparation method of the lithium-philic alloy modification layer and the composite lithium negative electrode material in this embodiment 14, the titanium wire may be replaced by a titanium foil or a titanium foam cavity structure material; wherein the cavity size of the titanium foam cavity structure material is 200 μm.
Example 15
This example 15 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in example 12 in that: the metal zinc (Zn) in example 12 was replaced with metal tin (Sn), the molar ratio of metal tin (Sn) to molten metal lithium was 1:200, and the remaining steps and parameters were the same, to obtain a solid-state composite lithium negative electrode material containing at least three components, which had a three-layer structure of a metal material Cu skeleton layer, a Sn-Cu lithium-philic alloy modification layer, and a Li-Sn lithium alloy/metal lithium layer.
Example 16
This example 16 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in example 12 in that: the metal zinc (Zn) in example 12 was replaced with metal germanium (Ge), the cooling time was 10 minutes, and the remaining steps and parameters were the same, to obtain a solid composite lithium negative electrode material containing at least three components, which had a three-layer structure of a metallic material Cu skeleton layer, a Ge-Cu lithium-philic alloy modification layer, and a Li-Ge lithium alloy/metallic lithium layer.
Example 17
This example 17 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in example 12 in that: the metal zinc (Zn) In example 12 was replaced with metal indium (In), the cooling time was 5 minutes, and the remaining steps and parameters were the same, to obtain a solid composite lithium negative electrode material containing at least three components and having a three-layer structure of a metal material Cu skeleton layer, an In-Cu lithium-philic alloy modification layer, and a Li-In lithium alloy/metal lithium layer.
Example 18
This example 18 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in example 11 in that: the metal molybdenum (Mo) in example 11 was replaced with a heterogeneous material silicon (Si), and the remaining steps and parameters were the same, to obtain a solid-state composite lithium negative electrode material having a three-layer structure including a metallic material Fe skeleton layer, a Si-Fe lithium-philic alloy modification layer, and a Li-Si lithium alloy/metallic lithium layer, and including at least three components.
Example 19
This embodiment 19 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which specifically includes the following steps:
putting the metallic lithium into a stainless steel crucible in an external environment with a dew point of-50 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 300 ℃ to enable the metallic lithium to be in a molten state; then adding metallic lead (Pb) to the metallic lithium in a molten state to form a molten lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of a zinc wire, and is cooled to room temperature within 3min, so that a solid composite lithium negative electrode material containing a three-layer structure of a metal material Zn framework layer, a Pb-Zn lithium-philic alloy modification layer and a Li-Pb lithium alloy/metal lithium layer and containing at least three components can be obtained; wherein the molar ratio of the metallic lead (Pb) to the molten metallic lithium is 1: 150.
In the preparation method of the lithium-philic alloy modification layer and the composite lithium negative electrode material in this embodiment 19, the zinc wire may be replaced by a zinc foil or a foam zinc cavity structure material; wherein the cavity size of the foam zinc cavity structure material is 100 μm.
Example 20
This example 20 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in example 12 in that: the metal zinc (Zn) in example 12 was replaced with metal silver (Ag), the cooling time was 2 minutes, the molar ratio of metal silver (Ag) to molten metal lithium was 1:35, and the remaining steps and parameters were the same, to obtain a solid composite lithium negative electrode material comprising at least three components, a three-layer structure of a metallic material Cu skeleton layer, an Ag-Cu lithium-philic alloy modification layer, and a Li-Ag lithium alloy/metal lithium layer.
Example 21
This embodiment 21 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which specifically includes the following steps:
putting the metallic lithium into a stainless steel crucible in an external environment with a dew point of-50 ℃ and an oxygen content of less than 10ppm, and placing the stainless steel crucible on a heating table with a temperature of 500 ℃ to enable the metallic lithium to be in a molten state; then adding metallic copper (Cu) to metallic lithium in a molten state to form a molten state lithium alloy; finally, the obtained molten lithium alloy is contacted with the surface of the iron-nickel alloy wire, and the iron-nickel alloy wire is cooled to room temperature within 20min, so that a solid composite lithium negative electrode material which comprises a three-layer structure of a metal material Fe/Ni framework layer, a Cu-Fe/Ni lithium-philic alloy modification layer and a Li-Cu lithium alloy/metal lithium layer and at least three components can be obtained; wherein the molar ratio of the metal Cu to the molten metal lithium is 1: 2.
In this embodiment 21, the iron-nickel alloy wire in the preparation method of the lithium-philic alloy modification layer and the composite lithium negative electrode material may be replaced by an iron-nickel alloy foil or a foam iron-nickel alloy cavity structure material; wherein the cavity size of the foam iron-nickel alloy cavity structure material is 100 mu m.
Example 22
This example 22 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material and a preparation method thereof, which are different from those of example 11 only in that: the metal molybdenum (Mo) in example 11 was replaced with metal gallium (Ga), the temperature of the heating stage was 200 ℃, and the cooling time to room temperature was 2 minutes, to obtain a solid-state composite lithium negative electrode material having a three-layer structure of a metallic material Fe skeleton layer, a Ga-Fe lithium-philic alloy modification layer, and a Li-Ga lithium alloy/metallic lithium layer, and comprising at least three components.
Example 23
This example 23 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which are different from those in example 7 only in that: the metal strontium (Sr) in example 7 was replaced with metal sodium (Na), the temperature of the heating stage was 250 ℃, and the cooling time to room temperature was 1 minute, to obtain a solid-state composite lithium anode material having a three-layer structure of an Al skeleton layer, a Na-Al lithium-philic alloy modification layer, and a Li-Na lithium alloy/metal lithium layer, which is a metal material, and containing at least three components.
Example 24
This example 24 provides a lithium-philic alloy modification layer, a composite lithium negative electrode material, and a preparation method thereof, which are different from those in example 12 only in that: the metal zinc (Zn) in example 12 was replaced with metal antimony (Sb), and the heating stage temperature was 400 ℃, so that a solid-state composite lithium anode material comprising at least three components and having a three-layer structure of a Cu skeleton layer containing a metal material, a Sb-Cu lithium-philic alloy modification layer, and a Li-Sb lithium alloy/metal lithium layer was obtained.
Example 25
This example 25 provides a lithium-philic alloy modification layer, a lithium composite negative electrode material, and a preparation method thereof, which are different from those in example 12 only in that: the metal zinc (Zn) in example 12 was replaced with a mixture of metal tin (Sn) and metal zinc (Zn), and the heating stage temperature was 500 ℃, to obtain a solid-state composite lithium anode material having a three-layer structure of a Cu skeleton layer of a metal material, a Sn/Zn-Cu lithium-philic alloy modification layer, and a Sn/Zn-Li lithium alloy/metal lithium layer, and containing at least three components.
Experimental example 1
In order to examine the performance of the composite lithium negative electrode material prepared in the present invention, the composite lithium negative electrode material obtained in example 1 was subjected to a Scanning Electron Microscope (SEM) test and an X-ray fluorescence diffraction (XRD) test, and the results of the tests are shown in fig. 2 and 3, whereby it was found that Cu was spontaneously formed on the surface of the copper skeleton 2 Mg layer and inducing adsorption of Li-Mg alloy/Li layer. Wherein, FIG. 2 is an SEM photograph of a Mg-Li alloy in a molten state contacting a copper foam skeleton for various times in example 1 of the present invention, and the white line in FIG. 2 represents 20 μm; FIG. 3 is an XRD pattern of a Mg-Li alloy in a molten state contacting a copper foam skeleton for various times in example 1 of the present invention.
In experimental example 1, the composite lithium negative electrode material obtained in example 1 was applied to a Li-Li symmetric battery system, and a Li-Li symmetric battery was assembled in a glove box filled with argon gas and without water and oxygen. The specific process is as follows: using 1mol/L LiPF 6 A dibasic ester electrolyte system dissolved in a volume ratio EC: DEC ═ 1:1, a composite lithium cathode material with the diameter of 10mm is taken as an electrode, Celgard 2325 with the diameter of 19mm is taken as a diaphragm, a symmetrical battery is assembled and packaged in a CR 2032 button cell for constant current charge and discharge test, the current density is 1mA/cm 2 The charging and discharging curves obtained for 1 hour each are shown in FIG. 5, and it can be seen that Cu-Cu was used 2 Composite lithium negative electrode with Mg-LiCu/Li three-layer structure and lithium-magnesium alloy(Mg-Li) and lithium foil (Li) assembled batteries have significantly improved cycle life.
In this experimental example 1, the composite lithium negative electrode material obtained in example 1 was applied to a lithium-iron phosphate (LFP) battery system, and a lithium-iron phosphate battery was assembled in a glove box which was anhydrous and oxygen-free and filled with argon gas. The specific process is as follows: using 1mol/L LiPF 6 The lithium ion battery is dissolved in a dibasic ester electrolyte system with the volume ratio EC: DEC being 1:1, a composite lithium cathode material with the diameter of 15mm is taken as a cathode, Celgard 2325 with the diameter of 19mm is taken as a diaphragm, a lithium iron phosphate electrode slice with the diameter of 10mm is taken as an anode, the lithium ion battery is packaged in a CR 2032 button cell, and a constant current charge and discharge test is carried out under the multiplying power of 0.5C, and the result is shown in figure 6. As can be seen from FIG. 6, Cu-Cu was used 2 Compared with a battery assembled by lithium-magnesium alloy (Mg-Li) and lithium foil (Li), the composite lithium cathode with the Mg-LiCu/Li three-layer structure has the advantages that the discharge capacity and the capacity retention rate are remarkably improved, and the problems of dendritic crystal growth, electrode volume expansion and structure pulverization of lithium in the circulation process of the conventional composite lithium cathode material can be effectively solved.
It will be understood that the foregoing is illustrative and explanatory only and that various modifications, additions and substitutions for the specific embodiments described may be made by those skilled in the art without inventive faculty, and remain within the scope of the invention.

Claims (7)

1. The composite lithium negative electrode material is characterized in that the structure of the composite lithium negative electrode material comprises a metal material N framework layer, a lithium-philic alloy modification layer M-N and a Li-M lithium alloy layer;
the lithium-philic alloy modification layer is prepared by the following method: contacting the molten lithium alloy Li-M with the surface of the metal material N to spontaneously form a lithium-philic alloy modification layer on the surface of the metal material N; wherein M is a dissimilar element different from the metal material N, and the lithium-philic alloy modification layer consists of M and N; the molar ratio of M to lithium is 1: 2-200; the heterogeneous element M is one or more of Na, Mg, Ca, Sr, Ba, Cr, Mn, Mo, Ni, Cu, Zn, B, Al, Ga, Ge, In, Si, Sn, Pb, Ag and Sb; the metal material N comprises one or more of Cu, Zn, Al, Ti, Ni and Fe.
2. The composite lithium negative electrode material of claim 1, wherein the material form of the metal material N is one-dimensional, two-dimensional, three-dimensional or a mixture thereof, and the structure of the metal material N is a three-dimensional network structure or a three-dimensional foam cavity structure formed by interweaving particles, fibers and sheets; the size of a cavity in the three-dimensional foam cavity structure is 10 nm-500 mm, and the thickness of three-dimensional frameworks in the three-dimensional network structure and the three-dimensional foam cavity structure is 1 mm-500 mm.
3. The composite lithium negative electrode material according to claim 1 or 2, wherein the metal material N is a copper wire, a zinc wire, an aluminum wire, a nickel wire, an iron wire, a titanium wire, an iron-nickel alloy wire, a copper foil, a zinc foil, an aluminum foil, a nickel foil, an iron foil, a titanium foil, an iron-nickel alloy foil, a copper foam, a zinc foam, a nickel foam, an aluminum foam, an iron foam, a titanium foam, or an iron-nickel foam.
4. The method for preparing the composite lithium negative electrode material according to any one of claims 1 to 3, characterized by specifically comprising the steps of:
step (1): melting the metal lithium into liquid state to obtain molten metal lithium;
step (2): adding a dissimilar element M into the molten lithium metal obtained in the step (1) to obtain a molten lithium alloy Li-M;
and (3): contacting the molten lithium alloy Li-M obtained in the step (2) with the surface of a metal material N to obtain a molten composite lithium negative electrode material in situ;
and (4): and (4) cooling the molten state composite lithium negative electrode material obtained in the step (3) to room temperature to obtain the composite lithium negative electrode material.
5. The method for preparing the composite lithium negative electrode material according to claim 4, wherein the melting temperature of the metallic lithium in the step (1) is 200 ℃ to 800 ℃.
6. The method for preparing the lithium composite anode material according to claim 4, wherein the time for cooling the molten lithium composite anode material to room temperature in the step (4) is 1-600 minutes.
7. Use of the composite lithium negative electrode material of any one of claims 1 to 3 for the preparation of a negative electrode for a lithium battery.
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