CN113488657B - 3D lithium-philic composite carbon fiber framework and preparation method and application thereof - Google Patents
3D lithium-philic composite carbon fiber framework and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of lithium metal battery cathode materials, and particularly discloses a 3D lithium-philic composite carbon fiber skeleton which comprises a 3D carbon fiber skeleton and Cu compounded on carbon fibers 3 A P layer and a phosphorus-containing functional group doped on the carbon fiber. The 3D lithium-philic composite carbon fiber framework material provided by the invention has rich specific surface area and pore structure, can effectively reduce local current density, promotes diffusion of lithium ions, and inhibits volume effect; phosphorus-containing functional groups and Cu on carbon fiber backbone 3 The P nanometer thin layers are mutually cooperated, the lithium nucleation overpotential is obviously reduced, lithium is induced to be uniformly deposited/dissolved, the constructed lithium metal negative electrode has excellent electrochemical performance, and the coulombic efficiency and the cycling stability are greatly improved. The invention also discloses a preparation method and application of the 3D lithium-philic composite carbon fiber skeleton.
Description
Technical Field
The invention belongs to the technical field of electrode materials of lithium metal batteries, and particularly relates to a composite carbon fiber framework applied to a lithium metal battery.
Background
Lithium metal has extremely high mass specific energy, and is a key for solving the problems of mileage anxiety of new energy automobiles and long endurance of mobile electronic equipment. However, the frameless nature of lithium metal leads to large volume changes during repeated cycling of the battery, and in addition, uneven lithium metal deposition leads to the growth and accumulation of large amounts of lithium dendrites, which leads to unavoidable reduction in coulombic efficiency, sharp reduction in cycling performance, and large potential safety hazards.
The specific surface area of the 3D current collector or the skeleton structure is large, so that the local current density of the electrode can be effectively reduced, and lithium dendrite is inhibited. In addition, the skeleton of the 3D structure can provide excellent support and bearing for lithium metal, and relieve the volume change of the lithium metal deposition/dissolution process. 3D framework structures are widely studied at present, for example, a Quan-Hong Yang et al [ Wu H, zhang Y, deng Y, et al. A light weight carbon nanofiber-based 3D structured matrix with high nitrogen-doping for lithium metals [ J ]. Scichina. Materials,62 (2019) 87-94 ] improves lithium affinity, homogenizes lithium nuclei and realizes lithium deposition without dendrites; effectively relieve the volume change and inhibit the growth of lithium dendrites. Yong-Ning Zhou et al [ Yue X, li X, wang W, et al, wettable carbon felt for high loading Li-metal composite anode [ J ]. Nano Energy,60 (2019) 257-266 ] use carbon foam felt as a structural skeleton, copper is electroplated on carbon fiber and in-situ oxidation is carried out, and the filling amount of molten lithium is further controlled to prepare the 3D structure lithium metal negative electrode. The 3D negative electrode with the structure can provide very beneficial electrolyte infiltration, and the depletion of lithium ion concentration is reduced; the second larger specific surface reduces the current density and effectively suppresses the volume effect. However, the lithium-philic layer is easily exfoliated during repeated cycling, and the generated lithium oxide causes deterioration of electrode conductivity, thereby restricting the key of the lithium metal negative electrode in maintaining high coulombic efficiency and long cycle performance. Based on the above, it is difficult for the electrochemical performance of the lithium metal negative electrode to be effectively improved and to be stable.
Disclosure of Invention
Aiming at the problems of large volume effect and incapability of dendrite generation in the circulation process of the conventional lithium metal negative electrodeThe invention provides a 3D lithium-philic composite carbon fiber framework material (also called lithium-philic composite carbon fiber or composite carbon fiber for short) aiming at solving the problems that the structure of a lithium-philic layer is unstable and a lithium product after reaction is not conductive 3 The P-doped carbon fiber framework coated by the P thin layer selectively induces lithium to be uniformly deposited in the carbon framework, so that the deposition nonuniformity of the lithium under large current is improved, the volume effect is reduced, and the cycle performance of the lithium metal cathode is improved.
A3D lithium-philic composite carbon fiber skeleton comprises a 3D carbon fiber skeleton and Cu compounded on carbon fibers 3 A P layer and a phosphorus-containing functional group doped on the carbon fiber; the 3D carbon fiber skeleton is formed by mutually interweaving carbon fibers and contains a large number of pores; the Cu 3 The P layer is a lithium-philic thin layer coated on the carbon fiber; the phosphorus-containing functional groups are uniformly distributed on the surface of the carbon fiber.
Preferably, the 3D carbon fiber skeleton is at least one of carbon paper, carbon cloth, and carbon felt.
Preferably, the phosphorus-containing functional groups uniformly distributed on the surface of the carbon fiber have a phosphorus content of 3 to 20at.%.
Preferably, the specific surface area of the 3D carbon fiber skeleton is 50-1100 m 2 (ii)/g; more preferably 80 to 950m 2 /g。
The carbon fibers preferably have a diameter of 0.1 to 50 μm, more preferably 0.2 to 30 μm.
The thickness of the 3D carbon fiber skeleton is preferably 10 to 500. Mu.m, more preferably 15 to 300. Mu.m, and still more preferably 40 to 160. Mu.m.
The 3D carbon fiber skeleton preferably has a pore pitch of 0.5 to 400 μm, more preferably 2 to 300 μm, and still more preferably 70 to 150 μm.
The porosity of the 3D carbon fiber skeleton is preferably 15 to 90%, more preferably 40 to 75%, and still more preferably 40 to 60%.
Preferably, the Cu is 3 The thickness of the P layer is 5 to 100nm, preferably 6 to 80nm, and more preferably 8 to 50nm.
Preferably, in the 3D lithium-philic composite carbon fiber skeleton, cu is adopted 3 The content of the P layer is 10 to 95wt.%, more preferably 20 to 90wt.%, and still more preferably 30 to 85wt.%.
The research of the invention finds that the surface of the carbon fiber is uniformly coated with Cu 3 The P nano thin layer and the doped phosphorus-containing functional group have obvious affinity to lithium metal, and further research finds that the excellent conductivity of the carbon fiber effectively and uniformly distributes electrons and optimizes the lithium ion concentration; cu having phosphorus-containing functional group capable of uniform lithium deposition and more excellent lithium affinity 3 The P nano particles and the P functional groups are mutually cooperated to selectively induce lithium to be uniformly nucleated on the whole carbon fiber framework. The large number of pore structures of the carbon fiber skeleton can effectively buffer the volume change of lithium deposition/dissolution. Further research has found that Cu 3 The P nano thin layer can always maintain the composition with the carbon fiber, and Li with more excellent lithium affinity is generated in the lithium deposition process 3 P and provides excellent lithium-philic interface and lithium ion/electron conductivity, thereby securing Cu 3 Structural stability of the P nanolayer.
Based on the same inventive concept, the invention also provides a preparation method of the 3D lithium-philic composite carbon fiber skeleton, which comprises the following steps: firstly, preparing a copper-coated composite carbon fiber framework by using an electroplating method, then carrying out liquid phase reaction, converting the copper-coated layer into the copper hydroxide-coated carbon fiber framework in situ, and further carrying out phosphating to prepare the 3D lithium-philic composite carbon fiber framework.
Further, the preparation method of the 3D lithium-philic composite carbon fiber skeleton comprises the following steps:
step (1), electroplating:
the carbon fiber framework which is cleaned in a certain size is used as a working electrode, the copper foil is used as a counter electrode, the counter electrode is added into electrolyte at a certain distance, and direct current with a certain size is introduced for electrodeposition.
Step (2), liquid phase reaction:
and cleaning and drying the electroplated carbon fiber framework, adding the carbon fiber framework into a mixed solution of strong base and an oxidant for soaking, and cleaning and drying to obtain the carbon fiber framework coated with the copper hydroxide.
And (3) phosphating:
and (3) placing the carbon fiber skeleton coated with the copper hydroxide at the downwind position of argon flow in a tubular furnace, and carrying out phosphorus source pyrolysis and phosphorization to finally obtain the 3D lithium-philic composite carbon fiber skeleton.
Further, in step (1):
the distance between the working electrode and the counter electrode is 5-100 mm;
the electrolyte is an aqueous solution, and the solute is at least one of copper sulfate, sodium tartrate, sodium citrate and potassium nitrate; the concentration of the electrolyte is 0.5-200 g/L, and the electrolyte is adjusted according to different selected solutes;
preferably, the magnitude of the direct current is 10 to 500mAcm -2 More preferably 20 to 400mAcm -2 ；
The electrodeposition time is preferably 1 to 90min, more preferably 2 to 60min.
Further, in the step (2):
preferably, the surface of the copper hydroxide coating is at least one of nanowire, spike, plane and particle;
preferably, the oxidant is at least one of sodium dichromate, potassium permanganate, nitric acid, ammonium persulfate and hydrogen peroxide;
preferably, the concentration of the aqueous oxidizing agent solution is 0.01 to 50mmol/L, and more preferably 0.05 to 20mmol/L;
preferably, the concentration of the strong alkali solution is 0.1 to 6mol/L, and more preferably 0.5 to 5mol/L;
preferably, the liquid phase reaction time is 5 to 120min, more preferably 10 to 90min;
the liquid phase reaction temperature is preferably 5 to 80 ℃ and more preferably 20 to 50 ℃.
Further, in step (3):
preferably, the phosphorus source is at least one of metaphosphate and hypophosphite;
preferably, the mass ratio of the phosphorus source to the copper hydroxide-coated carbon fiber skeleton is from 0.6;
preferably, the temperature of the phosphating treatment is 280-600 ℃, and more preferably 300-500 ℃;
preferably, the temperature rise rate of the tubular furnace is 0.5-10 ℃/min, and more preferably 1-5 ℃/min;
preferably, the aeration rate of the argon flow is 100 to 400ml/min, more preferably 150 to 250ml/min;
preferably, the time for the phosphating treatment is 0.5 to 8 hours, preferably 1 to 5 hours.
Based on the same inventive concept, the invention also provides the application of the 3D lithium-philic composite carbon fiber framework in the lithium metal anode. Specifically, the 3D lithium-philic composite carbon fiber framework material is punched into a pole piece, and metal lithium is filled into the pole piece to serve as an active electrode, so that the high-performance 3D lithium-philic composite carbon fiber lithium metal anode is prepared.
Preferably, the thickness of the active electrode is 10 to 800 μm, preferably 30 to 100 μm;
preferably, the method for filling the metal lithium is electrodeposition and/or melting lithium filling, and preferably melting lithium;
preferably, the amount of the metal lithium to be filled is 3 to 200mAh/cm 2 More preferably 5 to 150mAh/cm 2 More preferably 8 to 100mAh/cm 2 。
The invention also provides application of the high-performance 3D lithium-philic composite carbon fiber metal anode, which is used as an electrode material and assembled into a metal lithium battery. The metal lithium battery can be a lithium-sulfur battery, a lithium-iodine battery, a lithium-selenium battery, a lithium-tellurium battery, a lithium-oxygen battery or a lithium-carbon dioxide battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the 3D lithium-philic composite carbon fiber framework material provided by the invention has rich specific surface area and pore structure, can effectively reduce local current density, promotes diffusion of lithium ions, and inhibits volume effect.
2. The 3D lithium-philic composite carbon fiber framework material provided by the invention has very excellent lithium-philic property, and phosphorus-containing functional groups and Cu on the carbon fiber framework 3 The P nanometer thin layers are mutually cooperated, the lithium nucleation overpotential is obviously reduced, lithium is induced to be uniformly deposited/dissolved, the constructed lithium metal negative electrode has excellent electrochemical performance, and the coulombic efficiency and the cycling stability are greatly improved.
3. The high-performance 3D lithium-philic composite carbon fiber lithium metal anode provided by the invention is used for a lithium sulfur battery, can be used as a sulfur carrier while stabilizing lithium metal, effectively inhibits shuttle of lithium polysulfide, and simultaneously Cu 3 The P nano thin layer is beneficial to accelerating the catalytic conversion of polysulfide and reducing the negative effect of polysulfide on a lithium metal negative electrode interface.
Drawings
FIG. 1 is a schematic diagram of the structure of a 3D lithium-philic composite carbon fiber skeleton material prepared in example 1.
Detailed Description
The following is a detailed description of the preferred embodiments of the invention and is not intended to limit the invention in any way, i.e., the invention is not intended to be limited to the embodiments described below, and modifications and alternative compounds that are conventional in the art are intended to be included within the scope of the invention as defined in the claims.
Example 1
A carbon felt (2 x 3 cm) with the carbon fiber diameter of 3 mu m, the porosity of 60% and the thickness of 60 mu m is used as a working electrode and is separated from a counter electrode copper foil by 2cm, and the working electrode and the counter electrode copper foil are added into electrolyte. The electrolyte is an aqueous solution of solutes including copper sulfate (25 g/L), sodium tartrate (5 g/L), sodium citrate (40 g/L) and potassium nitrate (4 g/L). At 20mA/cm 2 Electroplating for 10min, and cleaning to obtain the composite carbon fiber skeleton coated with the nano copper layer. Then adding a mixed solution composed of a 3M NaOH solution and a 0.5mmol/L ammonium persulfate solution into the reaction kettle, reacting for 30min at normal temperature, cleaning and drying, placing the reaction kettle in a tubular furnace downwind of argon flow, placing 3g of sodium hypophosphite in the upwind direction, heating the tubular furnace to 300 ℃ at the speed of 2 ℃/min, and phosphating for 2h under the argon flow of 150 ml/min.
Experimental results show that as shown in FIG. 1, the 3D lithium-philic composite carbon fiber framework material prepared by the method has the carbon fiber uniformly coated with a layer of Cu 3 The surface of the P nano layer is in a nano line shape, the length of the nano line is 10 mu m, and Cu is added 3 The thickness of the P nanolayer was 70nm 3 The content of the P nano layer is 45wt.%, and the P element is uniformly distributed on the carbon fiber and the content is 11at.%.
Example 2
Carbon paper (2X 3 cm) having a carbon fiber diameter of 5 μm, a porosity of 50% and a thickness of 80 μm as a working electrode was added to the electrolyte at a distance of 2cm from the counter electrode copper foil. The electrolyte is an aqueous solution containing solutes of copper sulfate (50 g/L), sodium tartrate (8 g/L), sodium citrate (30 g/L) and potassium nitrate (10 g/L) at 50mA/cm 2 And electroplating for 60min by using the current, and cleaning to obtain the composite carbon fiber skeleton coated by the nano copper layer. Then adding a mixed solution composed of a 3M NaOH solution and a 1mmol/L potassium permanganate solution into the mixture to react for 30min at normal temperature, cleaning and drying the mixture, placing the mixture in a tubular furnace downwind of argon flow, placing 3g of sodium metaphosphate in the upwind direction, heating the tubular furnace to 300 ℃ at the speed of 2 ℃/min, and phosphating the mixture for 2h under the argon flow of 150 ml/min.
Experimental results show that a layer of Cu is uniformly coated on the carbon fiber 3 P nano-layer with nanowire-like surface, cu 3 The thickness of the P nano layer is 90nm, the length of the nano line is 12 mu m, and Cu 3 The content of the P nano layer is 80wt.%, and the P element is uniformly distributed on the carbon fiber, and the content of P is 8.5at.%.
Example 3
Carbon fibers having a diameter of 10 μm, a porosity of 65% and a thickness of 60 μm (2X 3 cm) were used as a working electrode and a counter electrode copper foil at a distance of 2cm, and added to the electrolyte. The electrolyte is an aqueous solution of solutes including copper sulfate (100 g/L), sodium tartrate (20 g/L) and sodium citrate (60 g/L). At 200mA/cm 2 And electroplating for 60min by using the current, and cleaning to obtain the composite carbon fiber skeleton coated by the nano copper layer. Then adding a mixed solution consisting of 3M NaOH solution and 2mmol/L sodium dichromate solution to react for 30min at normal temperature, cleaning and drying, placing in a tubular furnace with argon airflow downwind, placing 5g sodium hypophosphite in the upwind direction, and placing in a tubeThe furnace is heated to 400 ℃ at the speed of 6 ℃/min, and phosphorization is carried out for 3h under the argon flow of 200 ml/min.
Experimental results show that a layer of Cu is uniformly coated on the carbon fiber 3 P nano-layer with nanowire-like surface, cu 3 The thickness of the P nano layer is 95nm, the length of the nanowire is 15 mu m, and the Cu is 3 The content of the P nano layer is 90wt.%, and P elements are uniformly distributed on the carbon fiber, wherein the content of P is 15at.%.
Comparative example 1
Compared with example 1, the difference is that no Cu is doped and no phosphorization is carried out, specifically:
adding a carbon felt (2 multiplied by 3 cm) with the carbon fiber diameter of 3 mu M, the porosity of 60 percent and the thickness of 60 mu M into a mixed solution of a NaOH solution of 3M and an ammonium persulfate solution of 0.5mmol/L for reaction at normal temperature for 30min, cleaning and drying, placing in a tubular furnace downwind of argon flow, heating to 300 ℃ at the temperature of 2 ℃/min, and roasting for 2h under the argon flow of 150 ml/min.
As a result of experiments, the carbon fiber of the prepared material does not contain any Cu and P elements.
Comparative example 2
Compared with example 1, the difference is only that no phosphating treatment is carried out, specifically:
a carbon felt (2 x 3 cm) with the carbon fiber diameter of 3 mu m, the porosity of 60 percent and the thickness of 60 mu m is taken as a working electrode and is separated from a counter electrode copper foil by 2cm, and the working electrode and the counter electrode copper foil are added into electrolyte. The electrolyte is an aqueous solution of solutes including copper sulfate (25 g/L), sodium tartrate (5 g/L), sodium citrate (40 g/L) and potassium nitrate (4 g/L). At 20mA/cm 2 Electroplating for 10min, and cleaning to obtain the composite carbon fiber skeleton coated with the nano copper layer. Then adding a mixed solution composed of a 3M NaOH solution and a 0.5mmol/L ammonium persulfate solution into the mixture to react for 30min at normal temperature, cleaning and drying the mixture, placing the mixture into a tubular furnace downwind of argon flow, heating the tubular furnace to 300 ℃ at the speed of 2 ℃/min, and phosphorizing the mixture for 2h under the argon flow of 150 ml/min.
Experimental results show that the surface of the carbon fiber of the prepared material is rough, the thickness of the CuO nano layer is 80nm, and the content of the CuO nano layer is 40 wt%.
Comparative example 3
Compared with the embodiment 1, the difference is only that the cladding-free copper is only phosphorized, and specifically comprises the following steps:
placing a carbon felt (2 multiplied by 3 cm) with the carbon fiber diameter of 3 mu m, the porosity of 60 percent and the thickness of 60 mu m in a tubular furnace downwind of argon flow, placing 3g of sodium hypophosphite in the downwind direction, heating the tubular furnace to 300 ℃ at the speed of 2 ℃/min, and phosphorizing for 2 hours under the argon flow of 150 ml/min.
Experimental results show that the carbon fiber of the prepared material is Cu-free 3 P nanolayer, P content 18at.%.
The materials prepared in example 1 and comparative examples 1, 2 and 3 were used as working electrodes, metallic lithium sheets as counter electrodes, and 1MLiTFSI/DOL: DME (volume ratio =1 3 And (4) carrying out button cell assembly and charge-discharge cycle test on the electrolyte. At 2mA/cm 2 The current density of the current sensor was selected for charge-discharge cycle testing, and the test results are shown in table 1 below:
table 1 charge-discharge cycle test results
The result shows that the 3D lithium-philic composite carbon fiber skeleton electrode has optimal electrochemical performance, and Cu 3 The P nano thin layer and the P doping have positive influence on the uniform deposition/dissolution of lithium, and are beneficial to the improvement of the coulomb efficiency of the battery and the improvement of the cycling stability of the battery.
The materials prepared in example 1 and comparative examples 1 and 3 were used as working electrodes, a metal lithium sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio = 1) 3 Assembling the button half cell for the electrolyte, and depositing 3mAh/cm 2 And (4) disassembling the battery, washing the battery by using DME, and reassembling the lithium-sulfur full battery. The charge-discharge cycle test was performed at 1C, and the test results are shown in table 2 below:
TABLE 2 Charge-discharge cycling test results
The results show that Cu 3 The 3D lithium-philic composite carbon fiber skeleton material coated by the P nano thin layer has the optimal electrode electrochemical performance. In one aspect, cu 3 The P nano thin layer and the P element can cooperatively induce lithium metal to be uniformly deposited to inhibit lithium dendrite, and on the other hand, cu 3 The P nano thin layer and the P element doped 3D lithium-philic composite carbon fiber framework material can play a catalytic conversion function on polysulfide to inhibit the shuttle effect of the lithium polysulfide, so that the stability and the improvement of the cycle performance of the lithium-sulfur full battery are facilitated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A3D lithium-philic composite carbon fiber skeleton is characterized by comprising a 3D carbon fiber skeleton and Cu compounded on carbon fibers 3 A P layer and a phosphorus-containing functional group doped on the carbon fiber; the 3D carbon fiber skeleton is formed by mutually interweaving carbon fibers and contains a large number of pores; the Cu 3 The P layer is a lithium-philic thin layer coated on the carbon fiber; the phosphorus-containing functional groups are uniformly distributed on the surface of the carbon fiber; the preparation method of the 3D lithium-philic composite carbon fiber skeleton comprises the following steps:
step (1), electroplating:
taking a carbon fiber framework which is cleaned in a certain size as a working electrode, taking a copper foil as a counter electrode, adding the carbon fiber framework into electrolyte at a certain distance, and electrifying direct current with a certain size for electrodeposition;
step (2), liquid phase reaction:
cleaning and drying the electroplated carbon fiber framework, adding the carbon fiber framework into a mixed solution of strong base and an oxidant for soaking, and cleaning and drying to obtain a copper hydroxide coated carbon fiber framework;
and (3) phosphating:
and (3) placing the carbon fiber skeleton coated with the copper hydroxide at the downwind position of argon flow in a tubular furnace, and carrying out phosphorus source pyrolysis and phosphorization to finally obtain the 3D lithium-philic composite carbon fiber skeleton.
2. The 3D lithium-philic composite carbon fiber framework as claimed in claim 1, wherein the 3D carbon fiber framework is at least one of carbon paper, carbon cloth and carbon felt, and the specific surface area is 50-1100 m 2 The carbon fiber has a diameter of 0.1 to 50 μm, a thickness of 10 to 500 μm, a hole pitch of 0.5 to 400 μm, and a porosity of 15 to 90%.
3. The 3D lithium-philic composite carbon fiber skeleton as claimed in claim 1, wherein the phosphorus-containing functional group has a phosphorus content of 3 to 20at.%.
4. The 3D lithium-philic composite carbon fiber scaffold of claim 1, wherein the Cu is present in the form of a Cu 3 The thickness of the P layer is 5 to 100nm 3 The content of the P layer is 10 to 95wt.%.
5. The 3D lithium-philic composite carbon fiber scaffold as claimed in claim 1,
in the step (1):
the distance between the working electrode and the counter electrode is 5 to 100mm;
the electrolyte is an aqueous solution, and the solute is at least one of copper sulfate, sodium tartrate, sodium citrate and potassium nitrate;
the current of the direct current is 10 to 500mA cm −2 ；
The electrodeposition time is 1 to 90min;
in the step (2):
the surface of the copper hydroxide cladding layer is at least one of nanowire, spike, plane and particle;
the oxidant is at least one of sodium dichromate, potassium permanganate, nitric acid, ammonium persulfate and hydrogen peroxide;
the concentration of the oxidant water solution is 0.01 to 50 mmol/L;
the concentration of the strong alkali solution is 0.1 to 6 mol/L;
the liquid phase reaction time is 5 to 120min, and the reaction temperature is 5 to 80 ℃;
in the step (3):
the phosphorus source is at least one of metaphosphate and hypophosphite;
the mass ratio of the phosphorus source to the copper hydroxide-coated carbon fiber skeleton is (0.6) - (1);
the temperature of the phosphating treatment is 280-600 ℃, and the temperature rise rate of the tube furnace is 0.5-10 ℃/min; the time of the phosphating treatment is 0.5 to 8h;
the ventilation rate of the argon flow is 100 to 400ml/min.
6. Use of the 3D lithium-philic composite carbon fiber scaffold according to any one of claims 1 to 5 for a lithium metal anode.
7. A preparation method of a lithium metal anode is characterized in that the 3D lithium-philic composite carbon fiber framework material as described in any one of claims 1 to 5 is punched into a pole piece, and metal lithium is filled into the pole piece to be used as an active electrode.
8. A lithium metal battery, characterized in that a lithium metal anode prepared by using the 3D lithium-philic composite carbon fiber skeleton as claimed in any one of claims 1 to 5 is used as an electrode material.
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