CN113488657A - 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 PDF

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CN113488657A
CN113488657A CN202010901141.6A CN202010901141A CN113488657A CN 113488657 A CN113488657 A CN 113488657A CN 202010901141 A CN202010901141 A CN 202010901141A CN 113488657 A CN113488657 A CN 113488657A
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carbon fiber
lithium
philic
skeleton
composite carbon
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CN113488657B (en
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洪波
赖延清
姜怀
邢孝娟
张治安
张凯
方静
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Central South University
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M2004/027—Negative electrodes
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    • Y02E60/10—Energy storage using batteries

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 fibers3A 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 backbone3The P nanometer thin layers are mutually cooperated, the lithium nucleation overpotential is obviously reduced, and the lithium is induced to be uniformly distributedAnd deposition/dissolution, 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

3D lithium-philic composite carbon fiber framework and preparation method and application thereof
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 results in large volume changes during repeated cycling of the battery, and in addition, uneven lithium metal deposition results in the growth and accumulation of large amounts of lithium dendrites, resulting in unavoidable reduction of coulombic efficiency, sharp reduction of cycling performance and large potential safety hazards.
The specific surface area of the 3D current collector or the skeleton structure is large, 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. The 3D framework structure is widely studied at present, for example, Quan-Hong Yang et al [ Wu H, Zhang Y, Deng Y, et al. A light weight carbon n nonfiber-based 3D structured matrix with high nitrogen-doping level for lithium metals [ J ]. Science China materials,62(2019)87-94 ] improves the lithium affinity, homogenizes the lithium nucleation and realizes the lithium deposition without dendrite; 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 and 266 ] using carbon foam felt as a structural skeleton, electroplating copper on carbon fiber and carrying out in-situ oxidation, and further controlling the filling amount of molten lithium 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, uncontrollable dendritic crystal, unstable structure of a lithium-philic layer and non-conductivity of a lithium product after reaction in the circulation process of the conventional lithium metal negative electrode, the 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 passing through stable Cu3The 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 fibers3A 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 Cu3The 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 20 at.%.
Preferably, the specific surface area of the 3D carbon fiber skeleton is 50-1100 m2(ii)/g; further preferably 80 to 950m2/g。
Preferably, the carbon fiber has a diameter of 0.1 to 50 μm, and more preferably 0.2 to 30 μm.
Preferably, the thickness of the 3D carbon fiber skeleton is 10 to 500 μm, more preferably 15 to 300 μm, and still more preferably 40 to 160 μm.
Preferably, the 3D carbon fiber skeleton has a pore pitch of 0.5 to 400 μm, more preferably 2 to 300 μm, and still more preferably 70 to 150 μm.
Preferably, the porosity of the 3D carbon fiber skeleton is 15 to 90%, more preferably 40 to 75%, and still more preferably 40 to 60%.
Preferably, the Cu is3The thickness of the P layer is 5 to 100nm, preferably 6 to 80nm, and more preferably 8 to 50 nm.
Preferably, in the 3D lithium-philic composite carbon fiber skeleton, Cu is adopted3The content of the P layer is 10-95 wt.%, preferably 20-90 wt.%, and more preferably 30-85 wt.%.
The research of the invention finds that the surface of the carbon fiber is uniformly coated with Cu3The 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 affinity3The 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 Cu3The 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 process3P and provides excellent lithium-philic interface and lithium ion/electron conductivity, thereby securing Cu3Structural 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 performing 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 current of the direct current is 10-500 mAcm-2More preferably 20 to 400mAcm-2；
Preferably, the electrodeposition time is 1 to 90min, and more preferably 2 to 60 min.
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 oxidant aqueous solution is 0.01-50 mmol/L, and more preferably 0.05-20 mmol/L;
preferably, the concentration of the strong alkali solution is 0.1-6 mol/L, and more preferably 0.5-5 mol/L;
preferably, the liquid phase reaction time is 5-120 min, and more preferably 10-90 min;
preferably, the liquid phase reaction temperature is 5-80 ℃, and more preferably 20-50 ℃.
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 0.6: 1-30: 1, and more preferably 0.9: 1-15: 1;
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 100-400 ml/min, and more preferably 150-250 ml/min;
preferably, the time of the phosphating treatment is 0.5-8 hours, preferably 1-5 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 10-800 μm, preferably 30-100 μm;
preferably, the method for filling metallic lithium is electrodeposition and/or molten lithium filling, preferably molten lithium;
preferably, the amount of the filled lithium metal is 3 to 200mAh/cm2More preferably 5 to 150mAh/cm2More preferably 8 to 100mAh/cm2。
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, and can effectively reduce local current density, promote diffusion of lithium ions and inhibit 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 framework3The 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 Cu3The 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 3cm) 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 (25g/L), sodium tartrate (5g/L), sodium citrate (40g/L) and potassium nitrate (4 g/L). At 20mA/cm2Electroplating for 10min, and cleaning to obtain the composite carbon fiber skeleton coated with the nano copper layer. Then adding a mixed solution consisting 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 in a tubular furnace in an argon airflow downwind direction, placing 3g of sodium hypophosphite in the downwind direction, 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 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 Cu3The 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 added3The thickness of the P nano layer is 70nm, and Cu3The content of the P nano layer is 45 wt.%, and the P element is uniformly distributed on the carbon fiber and has the content of 11 at.%.
Example 2
Carbon paper (2X 3cm) 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 (50g/L), sodium tartrate (8g/L), sodium citrate (30g/L) and potassium nitrate (10g/L) at 50mA/cm2And electroplating for 60min by using the current, and cleaning to obtain the composite carbon fiber framework coated by the nano copper layer. Then adding a mixed solution consisting 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 in an argon airflow downwind direction, placing 3g of sodium metaphosphate in an upwind direction, 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 a layer of Cu is uniformly coated on the carbon fiber3P nano-layer with nanowire-like surface, Cu3The thickness of the P nanolayer is90nm, nanowire length of 12 μm, Cu3The content of the P nano layer is 80 wt.%, and the P element is uniformly distributed on the carbon fiber, and the content of P is 8.5 at.%.
Example 3
Carbon fibers having a diameter of 10 μm, a porosity of 65% and a thickness of 60 μm (2X 3cm) were introduced into the electrolyte as a working electrode at a distance of 2cm from the counter electrode copper foil. The electrolyte is an aqueous solution of solutes including copper sulfate (100g/L), sodium tartrate (20g/L) and sodium citrate (60 g/L). At 200mA/cm2And electroplating for 60min by using the current, and cleaning to obtain the composite carbon fiber framework 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 the mixture in a tubular furnace downwind of argon flow, placing 5g of sodium hypophosphite in the upwind direction, heating the tubular furnace to 400 ℃ at the speed of 6 ℃/min, and carrying out phosphorization for 3h under the argon flow of 200 ml/min.
Experimental results show that a layer of Cu is uniformly coated on the carbon fiber3P nano-layer with nanowire-like surface, Cu3The thickness of the P nano layer is 95nm, the length of the nano line is 15 mu m, and Cu is added3The content of the P nano layer is 90 wt.%, and P elements are uniformly distributed on the carbon fiber, wherein the content of P is 15 at.%.
Comparative example 1
Compared with example 1, the difference is that no doping with Cu nor phosphating is present, specifically:
adding a carbon felt (2 multiplied by 3cm) 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 (2X 3cm) having a carbon fiber diameter of 3 μm, a porosity of 60% and a thickness of 60 μm was used as a toolThe copper foil of the working electrode and the counter electrode are separated by 2cm and added into the electrolyte. The electrolyte is an aqueous solution of solutes including copper sulfate (25g/L), sodium tartrate (5g/L), sodium citrate (40g/L) and potassium nitrate (4 g/L). At 20mA/cm2Electroplating for 10min, and cleaning to obtain the composite carbon fiber skeleton coated with the nano copper layer. Then adding a mixed solution consisting 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 carbon fiber of the prepared material is uniformly coated with a layer of CuO nano-layer, the surface of the layer of CuO nano-layer 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 3cm) 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 gas flow, placing 3g of sodium hypophosphite in the upwind direction, heating the tubular furnace to 300 ℃ at the speed of 2 ℃/min, and phosphorizing for 2 hours under the argon gas flow of 150 ml/min.
Experimental results show that the carbon fiber of the prepared material is Cu-free3P nanolayer, P content 18 at.%.
The materials prepared in example 1 and comparative examples 1, 2 and 3 were used as working electrodes, a metallic lithium sheet was used as a counter electrode, and 1MLiTFSI/DOL: DME (volume ratio 1:1) contained 2 wt.% of LiNO3And (4) carrying out button cell assembly and charge-discharge cycle test on the electrolyte. At 2mA/cm2The 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
Figure BDA0002657930770000081
The result shows that the 3D lithium-philic composite carbon fiber skeleton electrode has the best electrochemical performancePreferably, Cu3The 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 metallic lithium sheet was used as a counter electrode, and 1M LiTFSI/DOL DME (volume ratio 1:1) containing 1% wtLiNO3Assembling the button half cell for the electrolyte, and depositing 3mAh/cm2And (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
Figure BDA0002657930770000091
The results show that Cu3The 3D lithium-philic composite carbon fiber framework material coated by the P nano thin layer has the optimal electrode electrochemical performance. In one aspect, Cu3The 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, Cu3The P nano thin layer and the P element doped 3D lithium-philic composite carbon fiber framework material can play a role in catalytic conversion of polysulfide, and inhibit the shuttle effect of lithium polysulfide, so that the stability and the promotion 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 decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A3D lithium-philic composite carbon fiber skeleton comprises a 3D carbon fiber skeleton and Cu compounded on carbon fibers3A 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 Cu3The P layer is a lithium-philic thin layer coated on the carbon fiber; said is composed ofThe phosphorus functional groups are uniformly distributed on the surface of the carbon fiber.
2. The 3D lithium-philic composite carbon fiber skeleton according to claim 1, wherein the 3D carbon fiber skeleton is at least one of carbon paper, carbon cloth and carbon felt, and the specific surface area is 50-1100 m2The carbon fiber has a diameter of 0.1 to 50 μm, a thickness of 10 to 500 μm, a pore spacing of 0.5 to 400 μm, and a porosity of 15 to 90%.
3. The 3D lithium-philic composite carbon fiber skeleton according to claim 1, wherein the phosphorus-containing functional group has a phosphorus content of 3 to 20 at.%.
4. The 3D lithium-philic composite carbon fiber scaffold of claim 1, wherein the Cu is present in the form of a Cu3The thickness of the P layer is 5-100 nm, and Cu3The content of the P layer is 10-95 wt.%.
5. A method for preparing the 3D lithium-philic composite carbon fiber skeleton as claimed in any one of claims 1 to 4, characterized in that the copper-coated composite carbon fiber skeleton is prepared by electroplating, then liquid phase reaction is carried out to convert the copper-coated layer into the copper hydroxide-coated carbon fiber skeleton in situ, and the 3D lithium-philic composite carbon fiber skeleton is prepared after further phosphorization.
6. The method according to claim 5, comprising in particular the steps of:
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 counter electrode 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 performing phosphorus source pyrolysis and phosphorization to finally obtain the 3D lithium-philic composite carbon fiber skeleton.
7. The method of claim 6,
in the 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 current of the direct current is 10-500 mA cm−2；
The electrodeposition time is 1-90 min;
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 aqueous solution is 0.01-50 mmol/L;
the concentration of the strong alkali solution is 0.1-6 mol/L;
the liquid phase reaction time is 5-120 min, and the reaction temperature is 5-80 ℃;
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: 1-30: 1;
the temperature of the phosphating treatment is 280-600 ℃, and the temperature rising rate of the tubular furnace is 0.5-10 ℃/min; the time of the phosphating treatment is 0.5-8 h;
the aeration rate of the argon gas flow is 100-400 ml/min.
8. Use of the 3D lithium-philic composite carbon fiber scaffold according to any one of claims 1 to 4 as a lithium metal anode.
9. A preparation method of a lithium metal anode is characterized in that the 3D lithium-philic composite carbon fiber framework material as defined in any one of claims 1 to 4 is punched into a pole piece, and metal lithium is filled into the pole piece to be used as an active electrode.
10. 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 4 is used as an electrode material.
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