CN112768637A - Composite lithium metal negative electrode and preparation method thereof - Google Patents
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Abstract
The invention discloses a composite lithium metal cathode and a preparation method thereof, wherein the method comprises the following steps: carrying out surface modification on the three-dimensional framework material to obtain a framework material with a lithium-philic surface; sequentially stacking solid lithium and the framework material with the lithium-philic surface in an inert atmosphere to obtain a composite material; and preheating the composite material to 40-170 ℃, and then pressing to obtain the composite lithium metal cathode. The preparation method of the embodiment of the invention breaks through the conventional thought of the prior art, and the lithium metal with a certain stacking mode is injected into the three-dimensional framework by utilizing the modes of low-temperature preheating and pressurization to complete the hot-pressing preparation of the composite lithium metal, so that the temperature is lower, the energy consumption is low, and the safety is high.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage materials, in particular to a composite lithium metal negative electrode and a preparation method thereof.
Background
Lithium ion batteries have become an important electrochemical energy storage system nowadays, and are widely applied in the fields of electronic products, electric tools, new energy automobiles and energy storage power stations. The existing preparation technology basically limits the energy density of commercial batteries, and great challenges exist in further improving the energy density. Lithium metal has the lowest potential (-3.04V) and extremely high theoretical specific capacity (3860mAh/g), and is an ideal negative electrode material. The graphite cathode of the traditional lithium ion battery is replaced by lithium metal, so that the energy density of the battery can be remarkably and rapidly improved; meanwhile, a next generation of novel electrochemical energy storage system of a lithium-free anode can be developed. Although lithium metal has many advantages, in actual use, the characteristics of lithium dendrite growth, rapid reaction with electrolyte and great volume change exist, which leads to low coulombic efficiency, large interface resistance, short cycle life of the battery and even safety accidents caused by short circuit caused by dendrite.
At present, researchers adopt methods such as electrolyte optimization and introduction of a manual protection interface and a three-dimensional framework, and the like, so that the cycle performance of a lithium metal negative electrode is remarkably improved; comparison document 1: the publication number is 'CN 108365200A', the name is 'a preparation method of a composite lithium metal negative pole', and the preparation method of the composite lithium metal negative pole is disclosed, which is mainly characterized in that solid lithium metal is poured into a three-dimensional framework after being melted at a high temperature of more than 190 ℃. This technique has the following problems: firstly, the energy consumption problem is that after high-temperature heating, the composite lithium metal is cooled to generate a large amount of irreversible heat loss; secondly, the safety problem is that a certain potential safety hazard exists at a high temperature of more than 190 ℃, the activity of the lithium metal is further improved under the high-temperature condition, and the fire is easy to occur; finally, the production efficiency is a problem, and the production rate is necessarily reduced by high temperature.
Therefore, how to develop a composite lithium metal negative electrode and a preparation method thereof, which solve the high temperature problem in the prior art, so as to reduce energy consumption and improve the safety of the preparation process, is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a composite lithium metal cathode and a preparation method thereof, which have the advantages of low temperature, low energy consumption and high safety.
In order to achieve the above object, an embodiment of the present invention provides a method for preparing a composite lithium metal anode, including:
carrying out surface modification on the three-dimensional framework material to obtain a framework material with a lithium-philic surface;
sequentially stacking solid lithium and the framework material with the lithium-philic surface in an inert atmosphere to obtain a composite material;
and preheating the composite material to 40-170 ℃, and then pressing to obtain the composite lithium metal cathode.
Further, the surface modification includes at least one of chemical modification and plating modification;
the chemical modification comprises at least one of oxidation, nitridation, fluorination, phosphorization, and vulcanization;
the plating modification includes at least one of a clad metal layer and a modified metal layer, the metal layer including at least one of zinc, magnesium, silver, gold, silicon, nickel, gallium, tin, indium, germanium, aluminum, titanium, and molybdenum, the modified metal layer including at least one of an oxide, a sulfide, a fluoride, a nitride, and a chloride of a metal atom contained in the metal layer.
Further, the three-dimensional framework material is at least one of a metal material, stainless steel and a carbon material, the metal material is at least one of copper, zinc, molybdenum, nickel and aluminum, and the carbon material is at least one of graphene, carbon nanotubes, carbon fibers, carbon cloth and carbon paper.
Further, the three-dimensional skeleton material has a shape of one of a layer, a net, and a foam.
Further, the preheating temperature is 80-150 ℃.
Further, the solid lithium includes at least one of a lithium foil, a lithium ribbon, and a lithium powder.
Further, the stacking of the solid lithium and the framework material with the lithium-philic surface in sequence specifically includes:
and sequentially stacking N solid lithium and M framework materials with lithium-philic surfaces, wherein N is M +/-1, M is more than or equal to 1, and N is more than or equal to 1.
Further, the pressing pressure is 5-60 MPa, and the pressing time is 0.5-30 min.
Further, the mass fraction of the solid lithium in the composite lithium metal negative electrode is 10% to 95%.
The embodiment of the invention also provides the composite lithium metal cathode prepared by the method.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the composite lithium metal negative electrode and the preparation method thereof provided by the embodiment of the invention, solid lithium and a framework material with a lithium-philic surface are sequentially stacked in an inert atmosphere to obtain a composite material; and preheating the composite material to 40-170 ℃, and then pressing to obtain the composite lithium metal cathode. According to the embodiment of the invention, the lithium metal with a certain stacking mode is injected into the three-dimensional framework by using low-temperature preheating and pressurizing modes, so that the hot-pressing preparation of the composite lithium metal is completed, and the method has the advantages of low temperature, low energy consumption and high safety. The prepared composite lithium metal negative electrode has a three-dimensional framework, and can realize the homogenization of current and the storage of lithium metal; the composite lithium metal has flexibility and can be used as a component of a flexible device; the composite lithium metal has strong adhesive force with the framework and can not fall off; the full battery assembled by taking the composite lithium metal as the negative electrode has the coulombic efficiency of over 98 percent in a commercial carbonate electrolyte, the cycle life is obviously prolonged, and the lithium metal side has no dendritic crystal growth and negative electrode pulverization phenomena.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a flowchart of a method for manufacturing a composite lithium metal negative electrode according to embodiment 1 of the present invention;
fig. 2 is a schematic diagram of several different relative positions of lithium metal and a three-dimensional skeleton in a composite lithium metal negative electrode provided in embodiment 1 of the present invention;
fig. 3 is a scanning electron microscope photograph of a lithium composite metal negative electrode provided in embodiment 1 of the present invention.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the embodiments of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that the present embodiments and examples are illustrative of the present invention and are not to be construed as limiting the present invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention belong. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the examples of the present invention are commercially available or can be obtained by an existing method.
The embodiment of the invention provides a preparation method of a composite lithium metal negative electrode, which has the following general idea:
according to an exemplary embodiment of the present invention, there is provided a method of manufacturing a composite lithium metal anode, the method including:
s1, carrying out surface modification on the three-dimensional framework material to obtain a framework material with a lithium-philic surface;
as an alternative embodiment, the surface modification includes at least one of chemical modification and plating modification;
the chemical modification comprises at least one of oxidation, nitridation, fluorination, phosphorization, and vulcanization;
the plating modification includes at least one of a clad metal layer and a modified metal layer, the metal layer including at least one of zinc, magnesium, silver, gold, silicon, nickel, gallium, tin, indium, germanium, aluminum, titanium, and molybdenum, the modified metal layer including at least one of an oxide, a sulfide, a fluoride, a nitride, and a chloride of a metal atom contained in the metal layer.
As an alternative embodiment, the three-dimensional framework material is at least one of a metal material, stainless steel and a carbon material, the metal material is at least one of copper, zinc, molybdenum, nickel and aluminum, and the carbon material is at least one of graphene, carbon nanotubes, carbon fibers, carbon cloth and carbon paper. The three-dimensional skeleton material is in one of a layered shape, a net shape and a foam shape.
S2, stacking solid lithium and the framework material with the lithium-philic surface in sequence in an inert atmosphere to obtain a composite material;
as an alternative embodiment, the solid lithium comprises at least one of a lithium foil, a lithium ribbon, and a lithium powder. The thickness range of each solid lithium is 20-400 mu m.
As an alternative embodiment, the stacking solid lithium and the framework material with a lithium-philic surface in sequence specifically includes:
and sequentially stacking N solid lithium and M framework materials with lithium-philic surfaces, wherein N is M +/-1, M is more than or equal to 1, and N is more than or equal to 1.
S3, preheating the composite material to 40-170 ℃, and then pressing to obtain the composite lithium metal cathode.
As an optional embodiment, the pressing pressure is 5-60 MPa, and the pressing time is 0.5-30 min. Too little or too short a pressure may present incomplete recombination, and too long a pressure is not necessary much. The two are matched with each other to achieve the effect of complete compounding. Preferably, the pressing pressure: 5-30 MPa, pressing time: 5-25 min.
As an alternative embodiment, the mass fraction of the solid lithium in the lithium composite metal negative electrode is 10% to 95%. The energy density can be improved within the range of 10-95%;
reasons for pressing after preheating to 40-170 ℃: the method is favorable for achieving the effect of completely compounding the solid lithium and the framework material with the lithium-philic surface, and if the preheating temperature is lower than 40 ℃, the solid lithium cannot be compounded into the framework material; if the preheating temperature is higher than 170 ℃, the solid lithium and the pressing die can be adhered; in a preferred embodiment, the preheating temperature is 80-150 ℃.
The embodiment of the invention also provides the composite lithium metal cathode prepared by the method. The prepared full battery assembled by the composite lithium metal negative electrode has the advantages that the coulombic efficiency is up to more than 98 percent in commercial carbonate electrolytes, the cycle life is obviously prolonged, and the phenomena of dendritic crystal growth and negative electrode pulverization do not exist on the lithium metal side.
According to the composite lithium metal cathode and the preparation method thereof provided by the embodiment of the invention, the conventional thought of the prior art is broken through, lithium metal with a certain stacking mode is injected into the three-dimensional framework in a low-temperature preheating and pressurizing mode, the hot-pressing preparation of the composite lithium metal is completed, the temperature is low, the energy consumption is low, and the safety is high. The prepared composite lithium metal negative electrode has a three-dimensional framework, and can realize the homogenization of current and the storage of lithium metal; the composite lithium metal has flexibility and can be used as a component of a flexible device; the composite lithium metal has strong adhesive force with the framework and can not fall off; the full battery assembled by taking the composite lithium metal as the negative electrode has the coulombic efficiency of over 98 percent in a commercial carbonate electrolyte, the cycle life is obviously prolonged, and the lithium metal side has no dendritic crystal growth and negative electrode pulverization phenomena.
The following will describe in detail a method for manufacturing a composite lithium metal negative electrode according to the present application with reference to examples and experimental data.
Example 1
Carbon fibers are prepared and carbonized using an electrospinning device. The carbonized fiber is put into ammonia water and is subjected to hydrothermal reaction at 180 ℃ for 10 hours, so that the surface of the fiber is aminated to have the lithium-philic property. Subsequently, a lithium foil having a thickness of 50 μm was coated on the surface of the carbon fiber after the previous treatment. It was preheated at 40 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 5min under the condition that the pressure is 20MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium iron phosphate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 0.5C, the full battery is stably circulated for 800 weeks, and the capacity retention rate is 70%. After the battery was disassembled, no dendrite and powdering phenomenon were observed.
Example 2
Carbon fibers are prepared and carbonized using an electrospinning device. And plating a layer of metal silver on the surface of the carbonized fiber by using magnetron sputtering equipment to ensure that the carbonized fiber has the lithium affinity. Subsequently, a lithium foil having a thickness of 100 μm was spread between two pieces of the carbon fiber after pretreatment. It was preheated at 120 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 12min under the condition that the pressure is 10MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium iron phosphate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 1C, the full battery is stably circulated for 600 weeks, and the capacity retention rate is 75%. After the battery was disassembled, no dendrite and powdering phenomenon were observed.
Example 3
A commercial 200-mesh copper net is subjected to heat treatment in air at 150 ℃ for 2 hours, so that the surface of the commercial 200-mesh copper net is oxidized and has lithium-philic characteristics. Subsequently, two sheets of lithium foil having a thickness of 50 μm were coated on both sides of the copper mesh after the previous treatment. It was preheated at 100 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 20min under the condition that the pressure is 20MPa, and obtaining the composite lithium metal. And (3) forming a full battery by the composite lithium metal negative electrode and the ternary nickel-cobalt-manganese positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 1C, the full battery is stably circulated for 400 weeks, and the capacity retention rate is 80%. After the battery was disassembled, no dendrite and powdering phenomenon were observed.
Example 4
Putting commercial nickel foam into an electroplating bath, wherein the electroplating solution is a silver nitrate solution, and electroplating a silver layer on the surface of the nickel foam, wherein the surface of the nickel foam has lithium-philic property. Subsequently, two sheets of lithium foil having a thickness of 100 μm were coated on both sides of the previously treated nickel foam. It was preheated at 160 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 25min under the condition that the pressure is 30MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium cobaltate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 1C, the full battery is stably circulated for 800 weeks, and the capacity retention rate is 80%. After the battery was disassembled, no dendrite and powdering phenomenon were observed.
Example 5
The surface of a commercial 150-mesh copper mesh is coated with a layer of zinc sulfide, and the lithium affinity of the copper mesh is improved through the reaction between the zinc sulfide and lithium metal. Subsequently, two sheets of lithium foil having a thickness of 50 μm were coated on both sides of the copper mesh after the previous treatment. It was preheated at 100 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 15min under the condition that the pressure is 30MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium iron phosphate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 0.5C, the full battery is stably cycled for 800 weeks, and the capacity retention rate is 73%. After the battery was disassembled, no dendrite and powdering phenomenon were observed.
Example 6
Preparing graphene into a film, soaking the film in a melamine solution, standing for 2 hours, and taking out and drying. After drying, the mixture is thermally treated for 2 hours at 400 ℃ in the protection of argon atmosphere. Subsequently, a lithium foil having a thickness of 50 μm was placed between the two pretreated graphene thin films. It was preheated at 120 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 25min under the condition that the pressure is 30MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium iron phosphate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 1C, the full battery is stably circulated for 700 weeks, and the capacity retention rate is 80%. After the battery was disassembled, no dendrite and powdering phenomenon were observed.
Example 7
And (3) soaking the carbon cloth in a zinc acetate solution with the concentration of 1 mol per liter for one hour, drying, and then carrying out heat treatment for 30min at 200 ℃ in an atmospheric environment. Commercial lithium powder was then spread evenly on both sides of the carbon cloth. It was preheated at 150 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 14min under the condition that the pressure is 15MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium iron phosphate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 1C, the full battery is stably circulated for 700 weeks, and the capacity retention rate is 75%. After the battery was disassembled, no dendrite and powdering phenomenon were observed.
Comparative example 1
Carbon fibers are prepared and carbonized using an electrospinning device. The carbonized fiber is put into ammonia water and is subjected to hydrothermal reaction at 180 ℃ for 10 hours, so that the surface of the fiber is aminated to have the lithium-philic property. Subsequently, a lithium foil having a thickness of 50 μm was coated on the surface of the carbon fiber. It was preheated at 30 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 20min under the condition that the pressure is 20MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium iron phosphate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 1C, the full battery is stably circulated for 200 weeks, and the capacity retention rate is 65%. After the battery was disassembled, the negative electrode was pulverized.
Comparative example 2
Carbon fibers were prepared using an electrospinning device and carbonized (without lithium-philic treatment). Subsequently, a lithium foil having a thickness of 50 μm was coated on the surface of the carbon fiber. It was preheated at 175 ℃ to temperature stability while preheating the press. After the preheating is finished, pressing for 5min under the condition that the pressure is 20MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium iron phosphate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 1C, the full battery is stably circulated for 250 weeks, and the capacity retention rate is 60%. After the battery was disassembled, the negative electrode was pulverized.
Comparative example 3
Carbon fibers are prepared and carbonized using an electrospinning device. Subsequently, a lithium foil having a thickness of 50 μm was coated on the surface of the carbon fiber. It was preheated at 150 ℃ to a temperature stable while preheating the press. After the preheating is finished, pressing for 20min under the condition that the pressure is 20MPa, and obtaining the composite lithium metal. And (3) forming a full battery by using the composite lithium metal negative electrode and the lithium iron phosphate positive electrode, and taking 1M lithium hexafluorophosphate-diethyl carbonate-vinyl carbonate as electrolyte. Under the multiplying power of 1C, the full battery is stably circulated for 200 weeks, and the capacity retention rate is 60%. After the battery was disassembled, the negative electrode was pulverized.
Experimental example 1
For the sake of comparison, the relevant process parameters of the composite lithium metals of examples 1 to 7 and comparative examples 1 to 2 are listed in table 1.
TABLE 1
| Group of | Surface modification | Preheating temperature deg.C | Pressing pressure MPa | Pressing time min |
| Example 1 | Surface amination | 40 | 20 | 5 |
| Example 2 | Plating a layer of metallic silver | 120 | 5 | 12 |
| Example 3 | Surface oxidation | 100 | 20 | 20 |
| Example 4 | Plating a layer of metallic silver | 170 | 30 | 25 |
| Example 5 | The surface is coated with a layer of zinc sulfide | 100 | 30 | 15 |
| Example 6 | Surface melamine soaking | 120 | 30 | 25 |
| Example 7 | Soaking in |
150 | 15 | 14 |
| Comparative example 1 | Surface amination | 30 | 20 | 20 |
| Comparative example 2 | / | 175 | 20 | 5 |
| Comparative example 3 | / | 150 | 20 | 20 |
The performance of the full cell composed of the composite lithium metal negative electrode of examples 1 to 7 and comparative examples 1 to 3 and the lithium iron phosphate positive electrode is shown in table 2.
TABLE 2
| Group of | Stable cycle time | Capacity retention ratio% | Dendrite and pulverization phenomena |
| Example 1 | 0.5C multiplying power, 800 weeks | 70％ | Is free of |
| Example 2 | Under the magnification of 1C, 600 weeks | 75％ | Is free of |
| Example 3 | Under the magnification of 1C, 400 weeks | 80％ | Is free of |
| Example 4 | 1C multiplying power, 800 weeks | 80％ | Is free of |
| Example 5 | 0.5C multiplying power, 800 weeks | 73％ | Is free of |
| Example 6 | 1C multiplying power, 700 weeks | 80％ | Is free of |
| Example 7 | 1C multiplying power, 700 weeks | 75％ | Is free of |
| Comparative example 1 | Under the magnification of 1C, 200 weeks | 65％ | Is provided with |
| Comparative example 2 | At 1C magnification, 250 weeks | 60％ | Is provided with |
| Comparative example 3 | Under the magnification of 1C, 200 weeks | 60％ | Is provided with |
From the data in table 2, it can be seen that:
in comparative example 1, even if the lithium-philic treatment is performed, the heating temperature is 30 ℃ which is less than the range of 40 ℃ to 170 ℃ in the embodiment of the present invention, there are disadvantages that the combination of lithium and the framework material is not firm, and a complete composite material cannot be formed, and the cycle performance of the battery is not good;
in comparative example 2, no lithium-philic treatment was performed, the heating temperature was 175 ℃ which is greater than the range of 40 ℃ to 170 ℃ in the example of the present invention, and the disadvantage of poor bonding of lithium with the framework material existed;
in comparative example 3, no lithium-philic treatment was performed, the heating temperature was 150 ℃, and in the range of 40 ℃ to 170 ℃ in the example of the present invention, there were disadvantages that lithium was not firmly bonded to the framework material and a complete composite material could not be formed, and the cycle performance of the battery was not good at the same time;
in examples 1 to 7, the prepared composite lithium metal is used as a full cell assembled by a negative electrode, and in a commercial carbonate electrolyte, the coulombic efficiency is as high as more than 98%, the cycle life is remarkably prolonged, and the lithium metal side has no dendritic growth and negative electrode pulverization phenomena.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the embodiments of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments of the present invention without departing from the spirit or scope of the embodiments of the invention. Thus, if such modifications and variations of the embodiments of the present invention fall within the scope of the claims of the embodiments of the present invention and their equivalents, the embodiments of the present invention are also intended to encompass such modifications and variations.
Claims (10)
1. A method of making a composite lithium metal anode, the method comprising:
carrying out surface modification on the three-dimensional framework material to obtain a framework material with a lithium-philic surface;
sequentially stacking solid lithium and the framework material with the lithium-philic surface in an inert atmosphere to obtain a composite material;
and preheating the composite material to 40-170 ℃, and then pressing to obtain the composite lithium metal cathode.
2. The method of claim 1, wherein the surface modification comprises at least one of chemical modification and plating modification;
the chemical modification comprises at least one of oxidation, nitridation, fluorination, phosphorization, and vulcanization;
the plating modification includes at least one of a clad metal layer and a modified metal layer, the metal layer including at least one of zinc, magnesium, silver, gold, silicon, nickel, gallium, tin, indium, germanium, aluminum, titanium, and molybdenum, the modified metal layer including at least one of an oxide, a sulfide, a fluoride, a nitride, and a chloride of a metal atom contained in the metal layer.
3. The method of claim 1, wherein the three-dimensional framework material is at least one of a metal material, stainless steel and a carbon material, the metal material is at least one of copper, zinc, molybdenum, nickel and aluminum, and the carbon material is at least one of graphene, carbon nanotubes, carbon fibers, carbon cloth and carbon paper.
4. The method of claim 1, wherein the three-dimensional framework material is in one of a layered, a mesh, and a foam shape.
5. The method for preparing the composite lithium metal negative electrode according to claim 1, wherein the preheating temperature is 80-150 ℃.
6. The method of claim 1, wherein the solid lithium comprises at least one of a lithium foil, a lithium ribbon, and a lithium powder.
7. The method for preparing a composite lithium metal negative electrode according to claim 1, wherein the step of sequentially stacking solid lithium and the framework material with a lithium-philic surface comprises:
and sequentially stacking N solid lithium and M framework materials with lithium-philic surfaces, wherein N is M +/-1, M is more than or equal to 1, and N is more than or equal to 1.
8. The method for preparing the composite lithium metal negative electrode according to claim 1, wherein the pressing pressure is 5-60 MPa, and the pressing time is 0.5-30 min.
9. The method of claim 1, wherein the mass fraction of solid lithium in the lithium metal composite negative electrode is 10% to 95%.
10. A composite lithium metal negative electrode prepared by the method of any one of claims 1 to 9.
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