Metallic lithium-carbon nanotube composite, method for producing the same, negative electrode, and battery

Abstract

This invention provides a composite formed from a mesh-like skeletal material having a lithium affinity modified layer and metallic lithium, as well as a method for producing the same and its use. [Solution] The method of the present invention enables the industrial production of a composite of a mesh-like skeletal material having a strong lithium affinity modification layer and metallic lithium, and the metallic lithium and carbon material in the manufactured composite are completely impregnated, with no layering and no voids inside the material. The conductive three-dimensional carbon skeletal structure inside the composite provides a reserve space for the deposition of metallic lithium and can mitigate the volume expansion of the metallic lithium anode, and the conductive ability of the carbon skeletal structure can lower the current density on the electrode surface and reduce the generation and growth of lithium dendrites, and electrodes manufactured with this composite have a stable structure and are advantageous for manufacturing electrodes with a long cycle life.

Description

Technical Field

[0001] The present invention belongs to the field of novel material technology, and particularly relates to a composite formed of a network skeleton material having a strong lithium affinity modification layer and metallic lithium, a method for manufacturing the same, and use thereof.

Background Art

[0002] Conventionally, the energy density of lithium-ion batteries has already reached the limit of the battery system, and it has become an urgent task to seek a new battery system with a high energy density.

[0003] As the metal material with the lowest density, metallic lithium has always been an essential material for producing lightweight alloys and metallic lithium batteries. Particularly in the field of new energy, metallic lithium has many advantages such as a high specific capacity (3860 mAh / g) and the most negative chemical potential (-3.04 V vs H / H + ), etc., and thus has the potential to be a single component, that is, a metallic lithium negative electrode, and plays a decisive role in improving the energy density of the battery. However, a normal metallic lithium negative electrode has problems of volume expansion and lithium dendrite during the battery cycle, and one of the causes of lithium dendrite breakage is also due to the breakage of the dendrite root caused by the change in the electrode volume. To solve this problem, a common method is to fabricate a metallic lithium negative electrode having a three-dimensional conductive skeleton structure, reduce the volume expansion of the metallic lithium negative electrode, and reduce the local current density on the electrode surface. The three-dimensional skeleton structure can provide a reserve space for metallic lithium to deposit. When metallic lithium deposits into the reserve space, the electrode will not expand in the reserve space. In addition, due to the conductive performance of the three-dimensional skeleton structure, the current density on the electrode surface can be reduced, and the generation of dendrites can be effectively reduced. Therefore, by fabricating a metallic lithium strip having a conductive three-dimensional skeleton structure, the expansion of the metallic lithium negative electrode can be alleviated and the dendrites can be reduced.

[0004] Conventionally, there are two processes for combining a conductive three-dimensional skeletal structure with metallic lithium. One involves combining metallic lithium and the three-dimensional skeletal structure by mechanical pressure, but the resulting metallic lithium strip clearly shows layering and undergoes some degree of fracture to the skeletal structure. The other involves depositing metallic lithium onto the three-dimensional skeletal structure by electrodeposition to obtain a metallic lithium strip with a three-dimensional skeletal structure, but this method is inefficient and difficult to implement on a large scale.

[0005] Therefore, it is necessary to develop a process for manufacturing metallic lithium composites with a three-dimensional skeletal structure that can be produced on a large scale. [Overview of the project]

[0006] To address the above-mentioned problems, the inventors of this application provide a composite (sometimes referred to as a lithium-carbon composite or lithium-carbon composite material) formed from a (three-dimensional) mesh-like skeletal material having a (strong) lithium affinity modification layer and metallic lithium, as well as a method for manufacturing the same and its use. By this method, a composite of a (three-dimensional) mesh-like skeletal (carbon) material having a strong lithium affinity modification layer and metallic lithium can be manufactured industrially, and in the manufactured composite, metallic lithium and carbon material are completely impregnated, the interior of the composite is not layered, and there are no voids. The conductive three-dimensional carbon skeletal structure (with voids) inside the composite provides a preliminary space for the deposition of metallic lithium, thereby mitigating volume expansion when used as a metallic lithium anode. Furthermore, the conductive ability of the carbon skeletal structure reduces the current density on the electrode surface, thereby reducing the generation and growth of lithium dendrites. Electrodes fabricated using this composite have a stable structure and are advantageous for manufacturing electrodes with a long cycle life.

[0007] Specifically, according to one aspect of the present invention, a composite is provided which is formed of a (three-dimensional) network-like skeletal material having a lithium affinity modified layer and metallic lithium, the composite comprising a porous framework and metallic lithium filling the voids of the porous framework. The porous framework is a (porous) mesh-like framework having a lithium affinity modified layer, formed by the entanglement of composite carbon materials (i.e., carbon framework materials). The composite carbon material comprises a crystalline carbon material and an amorphous carbon coating layer covering the surface of the crystalline carbon material. The amorphous carbon coating layer constitutes the lithium affinity modification layer (i.e., the amorphous carbon coating layer is defined as the lithium affinity modification layer).

[0008] In this invention, a crystalline carbon material refers to a material in which the carbon atoms constituting the material are arranged regularly according to certain rules (microscopic structure), while an amorphous material refers to a material in which atoms are arranged regularly at close range and irregularly at long range, and is also called an amorphous material.

[0009] The schematic structure of the lithium-carbon composite material of the present invention is as shown in Figure 1, and consists of a porous framework and metallic lithium 1 that fills the voids of the porous framework (by immersion, infiltration, and deposition). In particular, the porous framework is formed by the entanglement of composite carbon material, and this composite carbon material includes an internal crystalline carbon material 2 and an external amorphous carbon coating layer 3.

[0010] In some embodiments, the porosity of the porous framework is 15% to 85%, and the size of the voids is in the range of 5 nanometers (nm) to 90 nm.

[0011] In some embodiments, the crystalline carbon material includes at least one of carbon nanotubes, graphene, carbon fibers, carbon-based metal oxide fibers, and carbon-based covalent organic fibers.

[0012] In some embodiments, the composite carbon material is fibrous.

[0013] In some embodiments, the amorphous carbon coating layer is a carbonization product of an organic material blended with a crystalline carbon material, wherein the organic material is selected from the group consisting of organic binders, organic fillers, and crosslinking agents, and the thickness of the amorphous carbon coating layer is in the range of 10 nm to 600 nm.

[0014] In some embodiments, the organic binder is selected from the group consisting of polyvinyl alcohol, polyvinylidene fluoride, polybutene styrene, polystyrene, polycarboxylated cellulose, cyanoacrylate, polyacrylic acid, cyclodextrin, cyclic ether derivatives, polyurethane, methacrylate, epoxy resin, vinyl acetate polymer, polyimide, organofluoropolymer, organosiloxane, polyethylene glycol, polyethylene, polyvinyl chloride, polypropylene, glycerin, ethylparaben and its derivatives, monosaccharide or polysaccharide polymers.

[0015] In some embodiments, the organic filler is selected from the group consisting of plastic fine particles (polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), etc.), benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, calcium propionate, and dehydroacetate.

[0016] In some embodiments, the crosslinking agent is selected from the group consisting of a polymer obtained by bonding allyl curese or pentaerythritol allyl ether to acrylic acid, benzoyl peroxide, diethylenetriamine, sodium borate hydrate, cellulose derivatives, and isothiazolinone.

[0017] In some embodiments, the lithium-carbon composite material is in the form of a strip, the thickness of the lithium-carbon strip is 1 micron (μm) to 1000 microns, and the width of the lithium-carbon strip is 5 millimeters (mm) to 1 meter (m).

[0018] In some embodiments, the thickness of the external amorphous carbon coating layer is 10 nm to 600 nm.

[0019] In some embodiments, the amorphous carbon coating layer further contains nano metal particles, and the nano metal particles are embedded in or on the surface of the amorphous carbon coating layer.

[0020] In some embodiments, the size range of the nano metal particles is 5 nm to 800 nm, and they are dispersedly embedded in the external amorphous carbon coating layer.

[0021] According to another aspect of the present invention, a method for manufacturing the above composite is provided, and the method includes the following steps.

[0022] Step 1: Uniformly mix an organic binder, a filler, a cross-linking agent, and a solvent. The filler includes a crystallized carbon material, any organic filler, and an inorganic filler.

[0023] Step 2: Perform preliminary drying to remove the solvent from the mixture obtained in Step 1.

[0024] Step 3: Under the protection of an inert gas atmosphere, heat the material obtained in Step 2 at a temperature within the range of 300 °C to 1200 °C (carbonization treatment), and obtain a porous skeleton after cooling.

[0025] Step 4: Immerse the porous skeleton obtained in Step 3 in molten lithium to obtain a composite of a network-shaped skeleton material having a strong lithium affinity modification layer and metallic lithium.

[0026] In some embodiments, the mass ratio of the organic binder, the filler, the cross-linking agent, and the solvent is (4 to 15 parts):(10 to 30 parts):(0.01 to 20 parts):(20 to 400 parts).

[0027] In some embodiments, the mass ratio of the crystallized carbon material in the filler is 15% to 100%, for example, 15% to .5%>.

[0028] In some embodiments, the organic binder is selected from the group consisting of polyvinyl alcohol, polyvinylidene fluoride, polybutene styrene, polystyrene, polycarboxylated cellulose, cyanoacrylate, polyacrylic acid, cyclodextrin, cyclic ether derivatives, polyurethane, methacrylate, epoxy resin, vinyl acetate polymer, polyimide, organofluoropolymer, organosiloxane, polyethylene glycol, polyethylene, polyvinyl chloride, polypropylene, glycerin, ethyl paraben and its derivatives, monosaccharides or polysaccharide polymers.

[0029] In some embodiments, the organic filler is selected from the group consisting of plastic fine particles (PP, PET, PS), benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, calcium propionate, dehydroacetate.

[0030] In some embodiments, the inorganic filler is selected from the group consisting of metal nanoparticles, metal oxides, metal nitrides, calcium carbonate, magnesium hydrous silicate, mica, hydrated silica, silica.

[0031] In some embodiments, the crosslinking agent is selected from the group consisting of a polymer polymer in which allyl sucrose or pentaerythritol allyl ether is bonded to acrylic acid, benzoyl peroxide, diethylenetriamine, sodium borate hydrate, cellulose derivatives, isothiazolinone.

[0032] In some embodiments, the solvent is selected from the group consisting of water, tetrachloroethylene, toluene, turpentine oil, acetone, methyl acetate, ethyl acetate, pentane, n-hexane, cyclohexane, octane, citralva, ethanol, xylene, toluene, cyclohexanone, isopropanol, ethyl ether, propylene oxide, methyl butanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, ethylenediamine.

[0033] In some embodiments, the pre-drying temperature is -200°C to 200°C, preferably 20°C to 100°C, and the pre-drying time is 1 hour to 48 hours, preferably 2 to 8 hours.

[0034] In some embodiments, the filler in step 1 contains nanometal particles, and the mass ratio of the nanometal particles, organic binder, other fillers, crosslinking agent and solvent is (0.01-20 parts):(4-15 parts):(10-30 parts):(0.01-20 parts):(20-400 parts).

[0035] In some embodiments, the porous framework obtained in step 3 is a lithium-affinity carbon framework.

[0036] In some embodiments, the heating in step 3 is carried out for 2 to 24 hours, preferably 2 to 10 hours.

[0037] In some embodiments, the mass ratio of the porous framework to metallic lithium in the lithium-carbon composite material obtained in step 4 is 1:0.1 to 1:6.

[0038] In some embodiments, the obtained lithium-carbon composite material can be processed by, for example, turning, slicing, mechanical roll pressing, laser cutting, extrusion, etc.

[0039] According to another aspect of the present invention, a metallic lithium anode is provided which includes the composite described above or a composite manufactured by the method described above.

[0040] According to another aspect of the present invention, a metallic lithium battery is provided that includes the metallic lithium anode described above.

[0041] The present invention has at least one of the following advantages.

[0042] 1. Industrial production of composites of a mesh-like skeletal material having a strong lithium affinity modification layer and metallic lithium can be realized, and the manufactured composite is completely impregnated, with no layering or voids inside the material.

[0043] 2. The conductive three-dimensional carbon framework structure within the composite can mitigate volume expansion when used as a metallic lithium anode by providing a reserve space for the deposition of metallic lithium.

[0044] 3. The conductive properties of the carbon skeleton structure reduce the current density on the electrode surface, thereby minimizing the growth of lithium dendrites.

[0045] 4. Electrodes manufactured using this composite material have a stable structure and are advantageous for manufacturing electrodes with a long cycle life. [Brief explanation of the drawing]

[0046] [Figure 1] Figure 1 is a schematic diagram of a composite material of a mesh-like skeletal material having a lithium affinity modified layer according to the present invention and metallic lithium. [Figure 2] Figure 2 is a scanning electron microscope image of a cross-section of the composite fabricated in Example 1. [Figure 3] Figure 3 is a graph showing the measurement of the specific volume of the composite in Example 1. [Figure 4] Figure 4 is an optical photograph of the composite from Example 1 after lithium removal. [Figure 5] Figure 5 is a scanning electron microscope image of the composite prepared in Comparative Example 1. [Figure 6] Figure 6 shows the button battery cycle diagrams of the composite in Example 1 and Comparative Example 1. [Modes for carrying out the invention]

[0047] The present invention will be described below with reference to examples.

[0048] Example 1 Polyvinyl alcohol (Alading Reagents (Shanghai) Co., Ltd.), polystyrene microspheres (Suzhou Weimai New Materials Co., Ltd.), carbon nanotubes (Shandong Dazhan), diethylenetriamine (Shanghai Yantai Industrial Co., Ltd.), isothiazolinone (Alading Reagents (Shanghai) Co., Ltd.), and deionized water were uniformly mixed in a ratio of 6:9:9:5:5:75 (parts by mass).

[0049] The prepared mixture was pre-dried at 85°C for 5 hours.

[0050] The pre-dried material was placed in a crucible and subjected to high-temperature treatment under the protection of an inert gas atmosphere to obtain a carbon skeleton material. The high-temperature treatment was carried out at a temperature of 1000°C for 5 hours.

[0051] The carbon skeleton material prepared as described above was brought into contact with molten metallic lithium, and the metallic lithium was immersed in the carbon skeleton material (and its voids). After cooling, a composite was obtained consisting of a mesh-like skeleton material having a strong lithium affinity modification layer and metallic lithium.

[0052] To determine the bonding state between metallic lithium and carbon material, scanning electron microscopy measurements were performed on the composite obtained above, and the measurement results are shown in Figure 2. As can be seen from Figure 2, there are no layers or voids inside the composite, and the materials are completely infiltrated and bonded together as a single unit.

[0053] The resulting composite is blanked and assembled into a button cell, with a metallic lithium sheet serving as the counter electrode. A carbonate-based electrolyte and a polypropylene separator are used, and in particular, the carbonate-based electrolyte is a solution of 1 mol / L LiPF6 solute and EC and EMC solvent (volume ratio 1:1).

[0054] To determine the specific capacity of the composite, a lithium-free test was performed on the composite, and the graph of the measured specific capacity of the composite is shown in Figure 3. As can be seen from Figure 3, the specific capacity of the composite electrode was high at 2500 mAh / g.

[0055] To examine the condition of the remaining carbon skeleton, the button battery was disassembled after lithium removal, and an optical photograph of the disassembled button battery is shown in Figure 4. As can be seen from Figure 4, the carbon skeleton remaining after lithium removal is clearly visible, the arcs of the carbon skeleton's edges are well-formed, and the carbon skeleton still maintains a good shape even after the complete removal of metallic lithium.

[0056] Example 2 Polyurethane (Alading Reagents (Shanghai) Co., Ltd.), polystyrene microspheres (Suzhou Weimai New Materials Co., Ltd.), silver nanoparticles, carbon nanotubes (Shandong Dazhan), benzoyl peroxide (Alading), isothiazolinone (Alading Reagents (Shanghai) Co., Ltd.), and deionized water were uniformly mixed in a ratio of 10:8:1:9:5:5:80 (parts by mass).

[0057] The prepared mixture was pre-dried at 65°C for 10 hours.

[0058] The pre-dried material was placed in a crucible and subjected to high-temperature treatment under the protection of an inert gas atmosphere to obtain a carbon skeleton material containing silver nanoparticles. The high-temperature treatment was carried out at a temperature of 800°C for 3 hours.

[0059] The carbon skeleton material prepared as described above was brought into contact with molten metallic lithium, and the metallic lithium was immersed in the carbon skeleton material. After cooling, a composite was obtained formed of a mesh-like skeleton material having a strong lithium affinity modification layer and metallic lithium.

[0060] Example 3 Polyvinyl alcohol (Alading Reagents (Shanghai) Co., Ltd.), hydrated silica (Suzhou Weimai New Materials Co., Ltd.), carbon nanotubes (Shandong Dazhan), benzoyl peroxide (Alading), isothiazolinone (Alading Reagents (Shanghai) Co., Ltd.), and deionized water were uniformly mixed in a ratio of 10:12:9:5:1:55 (parts by mass).

[0061] The prepared mixture was pre-dried at 65°C for 10 hours.

[0062] The pre-dried material was placed in a crucible and subjected to high-temperature treatment under the protection of an inert gas atmosphere to obtain a carbon skeleton material. The high-temperature treatment was carried out at a temperature of 800°C for 6 hours.

[0063] The carbon skeleton material prepared as described above was brought into contact with molten metallic lithium, and the metallic lithium was immersed in the carbon skeleton material. After cooling, a composite was obtained formed of a mesh-like skeleton material having a strong lithium affinity modification layer and metallic lithium.

[0064] Example 4 Polyvinyl alcohol (Alading Reagents (Shanghai) Co., Ltd.), hydrated silica (Suzhou Weimai New Materials Co., Ltd.), carbon nanotubes (Shandong Dazhan), benzoyl peroxide (Alading), and p-xylene were uniformly mixed in a ratio of 10:12:9:5:55 (parts by mass).

[0065] The prepared mixture was pre-dried at 65°C for 10 hours.

[0066] The pre-dried material was placed in a crucible and subjected to high-temperature treatment under the protection of an inert gas atmosphere to obtain a carbon skeleton material. The high-temperature treatment was carried out at a temperature of 800°C for 6 hours.

[0067] The carbon skeleton material prepared as described above was brought into contact with molten metallic lithium, and the metallic lithium was immersed in the carbon skeleton material. After cooling, a composite was obtained formed of a mesh-like skeleton material having a strong lithium affinity modification layer and metallic lithium.

[0068] Comparative Example 1 A sandwich structure was employed, and a carbon cloth with a three-dimensional skeletal structure was placed between two layers of lithium strip material, each 50 microns thick. A composite material consisting of a 180-micron thick carbon material and metallic lithium strip material was then fabricated using a roll press. Scanning electron microscopy was performed on the fabricated composite to identify the bonding state between the three-dimensional carbon skeletal material and metallic lithium, and the measurement results are shown in Figure 5. As can be seen from Figure 5, the composite material produced by the roll press clearly shows layer separation, and metallic lithium is very difficult to penetrate into the carbon skeletal material.

[0069] Button batteries were assembled using the composites from Example 1 and Comparative Example 1 as working electrodes, with a commercially available lithium sheet used as the counter electrode. A carbonate-based electrolyte and a polypropylene separator were used, and the carbonate-based electrolyte was a solution of EC and EMC (volume ratio 1:1) with a solute of 1 mol / L LiPF6.

[0070] After assembling the battery, cycle performance was measured. The steps for measuring cycle performance were as follows: The assembled button battery was left for 12 hours and measured at 1 mA / cm². 2 The battery is charged with a constant current of 1 mA / cm² for 1 hour, and the current is 1 mA / cm². 2 The battery was discharged with a constant current for 1 hour, and the time and voltage changes during the cycle process were recorded. The cycle measurement results are shown in Figure 6. As can be seen from Figure 6, the battery assembled with the composite of Comparative Example 1 had a relatively large polarization voltage in the initial stage, and after approximately 450 hours of cycling, the battery voltage rapidly decreased, at which point the battery short-circuited and its lifespan ended. However, the battery assembled with the composite of Example 1 had a smaller polarization voltage in the initial stage than the battery assembled with the composite of Comparative Example 1, and as the cycle progressed, the voltage of the battery gradually stabilized. Even after more than 700 hours of cycling, the polarization voltage of the battery remained stable, no clear "sudden voltage drop" occurred, and the battery was still able to operate normally. Therefore, the electrodes of the composite of Example 1 have a more stable structure, and the cycle life of the manufactured electrodes is longer.

[0071] In the embodiments of the present invention, specific embodiments are combined to describe in detail the composite of a mesh-like skeletal material having a strong lithium affinity modification layer and metallic lithium, and the method for producing the same, according to the present invention. However, this is a description to satisfy legal requirements, and the present invention is not limited to the embodiments described above. Those skilled in the art can replicate the composite of a mesh-like skeletal material having a strong lithium affinity modification layer and metallic lithium, and the method for producing the same, by appropriate methods based on the disclosure and teachings of the specification.

[0072] Based on the disclosures and teachings of the specification described above, those skilled in the art can make appropriate changes and modifications to the embodiments described above. Accordingly, the present invention is not limited to the specific embodiments described and presented above, and several modifications and changes to the present invention should also be included within the scope of protection of the claims of the present invention. In this specification, several specific terms are used, but these terms are for convenience of explanation and do not limit the present invention in any way.

Claims

1. A metallic lithium-carbon nanotube composite, It comprises a carbon nanotube framework and metallic lithium filling the voids within the carbon nanotube framework. The carbon nanotube framework is a network-like framework having a lithium affinity modified layer formed by the entanglement of carbon nanotubes, and the surface of the carbon nanotubes is coated with a lithium affinity amorphous carbon coating layer. The composite material is in the form of a strip, and the strip has a thickness in the range of 1 micron to 1000 microns and a width in the range of 5 millimeters to 1 meter. The thickness of the amorphous carbon coating layer is in the range of 10 nm to 600 nm. The aforementioned amorphous carbon coating layer is further characterized by containing nanometal particles embedded inside or on its surface, thereby forming a metallic lithium-carbon nanotube composite.

2. The metallic lithium-carbon nanotube composite according to claim 1, characterized in that the amorphous carbon coating layer is a carbonization product of an organic material blended with carbon nanotubes, and the organic material is selected from the group consisting of organic binders, organic fillers, and crosslinking agents.

3. A method for producing a metallic lithium-carbon nanotube composite according to claim 1 or 2, characterized by comprising the following steps. Step 1: A uniform mixture of an organic binder, filler, crosslinking agent, and solvent is obtained, wherein the filler includes carbon nanotubes and any organic and inorganic fillers. Step 2: The mixture obtained in Step 1 is subjected to pre-drying to remove the solvent. Step 3: Under the protection of an inert gas atmosphere, the material obtained in Step 2 is heated to a temperature in the range of 300°C to 1200°C, and after cooling, a carbon nanotube skeleton is obtained. Step 4: The carbon nanotube skeleton obtained in Step 3 is immersed in molten lithium to obtain a metallic lithium-carbon nanotube composite. However, the organic binder is selected from the group consisting of polyvinyl alcohol, polyvinylidene fluoride, polybutene styrene, polystyrene, polycarboxylated cellulose, cyanoacrylate, polyacrylic acid, cyclodextrin, cyclic ether derivatives, polyurethane, methacrylate, epoxy resin, vinyl acetate polymer, polyimide, organofluoropolymer, organosiloxane, polyethylene glycol, polyethylene, polyvinyl chloride, polypropylene, glycerin, ethylparaben and its derivatives, monosaccharide or polysaccharide polymers. The aforementioned organic filler is selected from the group consisting of plastic microparticles, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, calcium propionate, and dehydroacetate. The inorganic filler is selected from the group consisting of metal nanoparticles, metal oxides, metal nitrides, calcium carbonate, hydrated magnesium silicate, mica, hydrated silica, and silica. The crosslinking agent is selected from the group consisting of a polymer obtained by bonding allyl curese or pentaerythritol allyl ether to acrylic acid, benzoyl peroxide, diethylenetriamine, sodium borate hydrate, and isothiazolinone. The solvent is selected from the group consisting of water, tetrachloroethylene, toluene, turpentine oil, acetone, methyl acetate, ethyl acetate, pentane, n-hexane, cyclohexane, octane, citralba, ethanol, xylene, toluene, cyclohexanone, isopropanol, ethyl ether, propylene oxide, methyl butanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, and ethylenediamine.

4. The mass ratio of the organic binder, filler, crosslinking agent and solvent is (4-15 parts):(10-30 parts):(0.01-20 parts):(20-400 parts), The method according to claim 3, characterized in that the mass percentage of the carbon nanotubes in the filler is 15% to 100%.

5. The method according to claim 3, characterized in that the mass ratio of the carbon nanotube skeleton to the metallic lithium in the metallic lithium-carbon nanotube composite obtained in step 4 is 1:0.1 to 1:

6.

6. The method according to claim 3, characterized in that the plastic fine particles include polypropylene microspheres, polyethylene terephthalate microspheres, polystyrene microspheres, or a combination thereof.

7. A metallic lithium anode comprising the composite according to claim 1.

8. A metallic lithium battery comprising a metallic lithium anode as described in claim 7.

Images