CN109052359A - Three-dimensional carbon material and preparation method thereof, lithium metal combination electrode and preparation method thereof - Google Patents

Three-dimensional carbon material and preparation method thereof, lithium metal combination electrode and preparation method thereof Download PDF

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CN109052359A
CN109052359A CN201810883958.8A CN201810883958A CN109052359A CN 109052359 A CN109052359 A CN 109052359A CN 201810883958 A CN201810883958 A CN 201810883958A CN 109052359 A CN109052359 A CN 109052359A
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sponge
carbon material
preparation
dimensional carbon
lithium metal
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CN109052359B (en
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朱彦武
谢兼
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of preparation methods of three-dimensional carbon material, comprising: S1) sponge is immersed in soluble catalyst precursor water solution, the sponge after drying, after being impregnated；The soluble catalyst is the salt compounds of iron series element；S2) sponge after the immersion is heated and kept the temperature in protective atmosphere, obtains three-dimensional carbon material.Compared with prior art, the present invention is using sponge as solid carbon source, pass through adsorption catalyst presoma early period, the pyrolysis and carbonization of sponge are realized in protective atmosphere later, catalyst in-situ preparation, the synchronous of carbon nano tube growth carries out, it is prepared for the three-dimensional carbon material that carbon nanotube is wrapped on carbonization sponge skeleton, method is simple, without post-processing, and three-dimensional carbon material maintains the elasticity and three dimensional skeletal structure of sponge, with certain electric conductivity, also there is biggish specific surface area and gap structure abundant simultaneously, high current density and high face amount can be reached after deposited metal lithium, and the not formation of dendrite.

Description

Three-dimensional carbon material and preparation method thereof, lithium metal combination electrode and preparation method thereof
Technical field
The invention belongs to technical field of nano material more particularly to a kind of three-dimensional carbon material and preparation method thereof, lithium metal Combination electrode and preparation method thereof.
Background technique
Carbon nanotube is the one-dimensional carbon nano material with unique tubular structure.Compared with traditional carbon material, carbon nanometer Pipe has the performances such as excellent mechanics, electricity, has a wide range of applications in terms of energy storage.
There are many scholars to study solid-state carbon source preparation carbon nanotube, in Publication No. CN107032326A State's patent discloses a kind of method for preparing spiral carbon nano pipe using solid catalysis, and this method is with urea or melamine Powder is solid-state carbon source, carbon nanotube is prepared under the atmosphere of protection gas, but the material that this method obtains is powder；Sponge is A kind of solid material of three-dimensional network skeleton structure, the pore-size distribution containing certain size are moulded by wood cellulose fibers or foaming Material polymer is made, and can be carbonized, and keeps original sponge skeleton structure, and the China of Publication No. CN105217603A is specially Benefit discloses a kind of preparation method of carbon nanotube foamed material, and this method uses chemical vapour deposition technique, macromolecule sponge, Melamine sponge or polyurethane sponge surface grown carbon nanotube, but this method needs to be passed through the gas such as methane, ethylene, acetylene State carbon source.
Lithium metal is due to its high theoretical capacity (3860mAh/g), low electrochemical potential (- 3.04V), low-density (0.534g/cm3) the features such as and be more concerned by people in lithium secondary battery field.But the cathode as lithium battery Material, lithium metal always exist Li dendrite problem: Li dendrite during the growth process, is easy to pierce through diaphragm, leads to battery short circuit, Generate security risk；Meanwhile Li dendrite is constantly generated and is crushed during being precipitated and lithium deposition, generation is some to be free on lithium The lithium (dead lithium) of metal surface and lithium metal surface need constantly to regenerate solid electrolyte interface film (SEI), to make The cyclical stability and coulombic efficiency for obtaining lithium metal battery are greatly affected.
It constructs three-dimensional carbon material and has the advantage that (1) compared to metal material, density is lower；(2) three-dimensional framework itself machine Tool intensity is high, can hinder growing for Li dendrite；(3) surface area is big, reduces local current densities, is conducive to the life of dendrite inhibition It is long；(4) porosity is high, is conducive to alleviate internal pressure brought by volume change.
There are many researchs to be dedicated to three-dimensional carbon material being applied to lithium an- ode at present, but concentrates on low current density It is recycled under facet capacity, it is close in electric current if the Chinese patent of Publication No. CN105609783 discloses a kind of three-dimensional carbon material Spend 0.25mA/cm2With face amount 0.625mAh/cm2Lower circulation also has tried to follow under high current density and facet capacity Ring, if the Chinese patent of Publication No. CN106784635 discloses a kind of three-dimensional carbon material, in current density 5mA/cm2The face and Capacity 1mAh/cm2Lower circulation, but can seldom reach high current density and high face amount.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of preparation method simple and can reach high current Three-dimensional carbon material of density and high face amount and preparation method thereof, lithium metal combination electrode and preparation method thereof.
The present invention provides a kind of preparation methods of three-dimensional carbon material, comprising:
S1) sponge is immersed in soluble catalyst precursor water solution, the sponge after drying, after being impregnated；It is described Soluble catalyst is the salt compounds of iron series element；
S2) sponge after the immersion is heated and kept the temperature in protective atmosphere, obtains three-dimensional carbon material.
Preferably, the soluble catalyst presoma be selected from ferric nitrate, iron chloride, ferric acetate, cobalt nitrate, cobalt chloride, One of nickel nitrate, nickel chloride and nickel acetate are a variety of.
Preferably, in the soluble catalyst precursor water solution soluble catalyst presoma concentration be 0.1~ 1g/L。
Preferably, the sponge is selected from polyethers sponge, polyvinylalcohol sponge, melamine sponge, polyurethane sponge, cotton One of fiber sponge, bamboo fibre sponge and lignose sponge are a variety of.
Preferably, the step S1) in be additionally added soluble carbon source.
Preferably, the protective atmosphere is selected from one of nitrogen, argon gas and helium or a variety of.
Preferably, the rate of the heating is 1~10 DEG C/min；The temperature of the heat preservation is 700 DEG C~900 DEG C；It is described The time of heat preservation is 2~4h.
The present invention also provides a kind of three-dimensional carbon materials, including carbonization sponge skeleton and are wrapped on carbonization sponge skeleton Carbon nanotube.
The present invention also provides a kind of lithium metal combination electrodes, including three-dimensional carbon material and lithium metal；The three-dimensional carbon materials Material includes carbonization sponge skeleton and the carbon nanotube being wrapped on carbonization sponge skeleton；The lithium metal is deposited on carbonization spongy bone The surface of frame and carbon nanotube.
The present invention also provides a kind of preparation methods of lithium metal combination electrode, comprising:
S1) sponge is immersed in soluble catalyst precursor water solution, the sponge after drying, after being impregnated；It is described Soluble catalyst is the salt compounds of iron series element；
S2) sponge after the immersion is heated and kept the temperature in protective atmosphere, obtains three-dimensional carbon material；
S3) in the three-dimensional carbon deposited on materials lithium metal, lithium metal combination electrode is obtained.
The present invention provides a kind of preparation methods of three-dimensional carbon material, comprising: S1) it will be before sponge immersion soluble catalyst It drives in body aqueous solution, the sponge after drying, after being impregnated；The soluble catalyst is the salt compounds of iron series element； S2) sponge after the immersion is heated and kept the temperature in protective atmosphere, obtains three-dimensional carbon material.Compared with prior art, originally Invention is using sponge as solid carbon source, by adsorption catalyst presoma early period, realizes the pyrolysis of sponge in protective atmosphere later With carbonization, the synchronous progress of catalyst in-situ preparation, carbon nano tube growth, it is prepared for carbon nanotube and is wrapped in carbonization sponge skeleton On three-dimensional carbon material, the preparation method is simple, is not necessarily to post-processing, and obtained three-dimensional carbon material maintains the elasticity of sponge And three dimensional skeletal structure, there is certain electric conductivity, while also there is biggish specific surface area and gap structure abundant, deposition High current density and high face amount can be reached after lithium metal, and the not formation of dendrite.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the melamine sponge after carbonization；
Fig. 2 is the scanning electron microscope (SEM) photograph of three-dimensional carbon material obtained in the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope picture of three-dimensional carbon material obtained in the embodiment of the present invention 1；
Fig. 4 is the optical picture of three-dimensional carbon material obtained in the embodiment of the present invention 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of three-dimensional carbon material obtained in the embodiment of the present invention 2；
Fig. 6 is the scanning electron microscope (SEM) photograph of three-dimensional carbon material obtained in the embodiment of the present invention 3；
Fig. 7 is the scanning electron microscope (SEM) photograph of three-dimensional carbon material obtained in the embodiment of the present invention 4；
Fig. 8 is the scanning electron microscope (SEM) photograph of three-dimensional carbon material obtained in the embodiment of the present invention 5；
Fig. 9 is the circulation figure of half-cell obtained in the embodiment of the present invention 3, and wherein surface current is 5mA/cm2, face amount is 10mA h/cm2；
Figure 10 is the circulation figure of half-cell obtained in the embodiment of the present invention 3, and wherein surface current is 10mA/cm2, face amount For 5mA h/cm2。
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described, Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.
The present invention provides a kind of three-dimensional carbon materials, including carbonization sponge skeleton and the carbon being wrapped on carbonization sponge skeleton Nanotube.
The present invention also provides a kind of preparation methods of above-mentioned three-dimensional carbon material, comprising: S1) sponge immersion solubility is urged Sponge in agent precursor water solution, after drying, after being impregnated；The soluble catalyst is the salt of iron series element Close object；S2) sponge after the immersion is heated and kept the temperature in protective atmosphere, obtains three-dimensional carbon material.
Wherein, the present invention is not particularly limited the source of all raw materials, is commercially available.
The sponge is sponge well known to those skilled in the art, has no special limitation, is preferably in the present invention Polyethers sponge, polyvinylalcohol sponge, melamine sponge, polyurethane sponge, cotton fiber sponge, bamboo fibre sponge and wood-fibred One of plain sponge is a variety of, and when using melamine sponge, polyurethane sponge, obtained three-dimensional carbon material also contains rich Rich nitrogen.
The sponge is immersed in soluble catalyst precursor solution；The soluble catalyst presoma is this field The salt compounds of iron series element known to technical staff have no special limitation, are preferably ferric nitrate, chlorine in the present invention Change one of iron, ferric acetate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride and nickel acetate or a variety of；The soluble catalyst The concentration of soluble catalyst presoma is preferably 0.1~1g/L in agent precursor solution, more preferably 0.5~1g/L, then excellent It is selected as 0.75~1g/L；The soluble catalyst precursor solution preferably uses ultrapure water to prepare；In order to make complex catalyst precursor Body is equably adsorbed on sponge, is preferably additionally added soluble carbon source in the soluble catalyst precursor solution；It is described can Dissolubility carbon source is soluble carbon source well known to those skilled in the art, has no special limitation, preferably urinates in the present invention Element and/or starch；The amount that the solubility carbon source is added is preferably 2.5~5g/L；The time of immersion preferably inhales sponge sufficiently Receive soluble catalyst precursor solution.
Then it dries, the sponge after being impregnated；The temperature of the drying is preferably 50 DEG C~80 DEG C, more preferably 60 DEG C ~70 DEG C.
Sponge after the immersion is heated and kept the temperature in protective atmosphere, three-dimensional carbon material is obtained；The protective atmosphere For protective atmosphere well known to those skilled in the art, special limitation is had no, is preferably nitrogen, argon gas and helium in the present invention One of gas is a variety of；The rate of the heating is preferably 1~10 DEG C/min, more preferably 1~8 DEG C/min, is further preferably 1 ~6 DEG C/min, be further preferably 1~4 DEG C/min, most preferably 1~2 DEG C/min；The temperature of the heat preservation is preferably 700 DEG C~ 900 DEG C, more preferably 750 DEG C~850 DEG C, be further preferably 800 DEG C；The time of the heat preservation is preferably 2~4h, and more preferably 2 ~3h.
The present invention, by adsorption catalyst presoma early period, realizes in protective atmosphere later using sponge as solid carbon source The pyrolysis of sponge is carried out with carbonization, catalyst in-situ preparation, the synchronous of carbon nano tube growth, is prepared for carbon nanotube and is wrapped in carbon Change the three-dimensional carbon material on sponge skeleton, the preparation method is simple, is not necessarily to post-processing, and obtained three-dimensional carbon material maintains The elasticity and three dimensional skeletal structure of sponge have certain electric conductivity, while also having biggish specific surface area and sky abundant Gap structure can reach high current density and high face amount after deposited metal lithium, and the not formation of dendrite.
The present invention also provides a kind of lithium metal combination electrodes, including three-dimensional carbon material and lithium metal；The three-dimensional carbon materials Material includes carbonization sponge skeleton and the carbon nanotube being wrapped on carbonization sponge skeleton；The lithium metal is deposited on carbonization spongy bone The surface of frame and carbon nanotube；Wherein, the three-dimensional carbon material is same as above, and details are not described herein.
The present invention also provides a kind of preparation methods of above-mentioned lithium metal combination electrode, comprising: S1) sponge is immersed it is solvable In property catalyst precursor aqueous solution, the sponge after drying, after being impregnated；The soluble catalyst is the salt of iron series element Class compound；S2) sponge after the immersion is heated and kept the temperature in protective atmosphere, obtains three-dimensional carbon material；S3) described Three-dimensional carbon deposited on materials lithium metal, obtains lithium metal combination electrode.
Wherein, the step S1) it is same as above with step S2), details are not described herein.
In the three-dimensional carbon deposited on materials lithium metal；The method of the deposition is method well known to those skilled in the art , special limitation is had no, preferably uses electro-deposition in the present invention；The mass ratio of the three-dimensional carbon material and lithium metal is preferred For 1:(0.37~0.74).
In order to further illustrate the present invention, with reference to embodiments to three-dimensional carbon material provided by the invention and its preparation side Method, lithium metal combination electrode and preparation method thereof are described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
1) 0.15g nickel nitrate is dissolved in 200ml ultrapure water.
2) 1g urea is dissolved in above-mentioned solution.
3) melamine sponge is totally immersed in above-mentioned solution, 60 DEG C of drying after 12h is sufficiently adsorbed, after obtaining immersion Sponge.
4) sponge is put into quartz boat, under protection of argon gas, is raised to 800 from room temperature with 1 DEG C of heating rate per minute DEG C, 2 hours are kept the temperature, three-dimensional carbon material is obtained.
Melamine sponge after melamine sponge is directly carbonized in argon gas according to step 4), after being carbonized. The melamine sponge after carbonization is analyzed using scanning electron microscope, obtains its scanning electron microscope (SEM) photograph, as shown in Figure 1.
Three-dimensional carbon material obtained in embodiment 1 is analyzed using scanning electron microscope, obtains its scanning electron microscope (SEM) photograph, is such as schemed Shown in 2.Figure it is seen that the carbon material of preparation still keeps the three dimensional skeletal structure of sponge, carbon nanotube is wrapped in three-dimensional On skeleton.
Three-dimensional carbon material obtained in embodiment 1 is analyzed using transmission electron microscope, obtains its transmission electron microscope picture, is such as schemed Shown in 3.
Fig. 4 is the optical picture of three-dimensional carbon material obtained in embodiment 1.
Embodiment 2
1) 0.15g nickel nitrate is dissolved in 200ml ultrapure water.
2) 0.5g urea is dissolved in above-mentioned solution.
3) melamine sponge is totally immersed in above-mentioned solution, 60 DEG C of drying after 12h is sufficiently adsorbed, after obtaining immersion Sponge.
4) sponge is put into quartz boat, under protection of argon gas, is raised to 800 from room temperature with 1 DEG C of heating rate per minute DEG C, 2 hours are kept the temperature, three-dimensional carbon material is obtained.
Three-dimensional carbon material obtained in embodiment 2 is analyzed using scanning electron microscope, obtains its scanning electron microscope (SEM) photograph, is such as schemed Shown in 5.
Embodiment 3
1) 0.2g nickel nitrate is dissolved in 200ml ultrapure water.
2) 0.5g urea is dissolved in above-mentioned solution.
3) melamine sponge is totally immersed in above-mentioned solution, 60 DEG C of drying after 12h is sufficiently adsorbed, after obtaining immersion Sponge.
4) sponge is put into quartz boat, under protection of argon gas, is raised to 800 from room temperature with 1 DEG C of heating rate per minute DEG C, 2 hours are kept the temperature, three-dimensional carbon material is obtained.
Three-dimensional carbon material obtained in embodiment 3 is analyzed using scanning electron microscope, obtains its scanning electron microscope (SEM) photograph, such as 6 It is shown.
Embodiment 4
1) 0.2g cobalt nitrate is dissolved in 200ml ultrapure water.
2) 0.5g urea is dissolved in above-mentioned solution.
3) melamine sponge is totally immersed in above-mentioned solution, 60 DEG C of drying after 12h is sufficiently adsorbed, after obtaining immersion Sponge.
4) sponge is put into quartz boat, under protection of argon gas, is raised to 800 from room temperature with 1 DEG C of heating rate per minute DEG C, 2 hours are kept the temperature, three-dimensional carbon material is obtained.
Three-dimensional carbon material obtained in embodiment 4 is analyzed using scanning electron microscope, obtains its scanning electron microscope (SEM) photograph, such as 7 It is shown.
Embodiment 5
1) 0.15g nickel nitrate is dissolved in 200ml ultrapure water.
2) polyurethane sponge is totally immersed in above-mentioned solution, 60 DEG C of drying after 12h is sufficiently adsorbed, after being impregnated Sponge.
3) sponge is put into quartz boat, under protection of argon gas, is raised to 800 from room temperature with 1 DEG C of heating rate per minute DEG C, 2 hours are kept the temperature, three-dimensional carbon material is obtained.
Three-dimensional carbon material obtained in embodiment 5 is analyzed using scanning electron microscope, obtains its scanning electron microscope (SEM) photograph, is such as schemed Shown in 8.
In examples detailed above, according to the growth distribution of carbon nanotube is uniform and intensive situation, it will preferably be prepared in embodiment 3 Three-dimensional carbon material electrodeposit metals lithium obtains lithium metal combination electrode (being denoted as CNTs-MC).Lithium metal combination electrode and lithium assemble At half-cell, by negative electrode casing, lithium piece, electrolyte, diaphragm, electrolyte, lithium metal combination electrode, steel disc, elastic slice and anode cover Sequence assembles, then envelope pressure.Diaphragm uses polypropylene (PP) diaphragm, and electrolyte uses 1MLiTFSI (DOL:DME= 1:1vol%)+2vol%LiNO3, the operation carries out in argon gas glove box, and wherein water oxygen content is respectively less than 0.5ppm. The above-mentioned coin shape lithium metal half-cell being prepared first is stood into 12h, then first with 5mA/cm in blue electrical testing channel2Electricity Current density electric discharge 2h, then charged 2h (the mass ratio 1:0.74 of three-dimensional carbon material and lithium metal) with identical current density, not The process of disconnected reignition charging, until the overpotential fluctuating of battery significantly increases and stops battery, test result such as Fig. 9 institute Show, which has recycled the overpotential value that 600h still keeps stable, about 60mV.And comparative experiments, business copper is replaced CNTs-MC, under the same testing conditions, the cycle life of copper only have 70h, and big fluctuation occurs in potential.If by above-mentioned system Standby obtained coin shape lithium metal half-cell first stands 12h, then first with 10mA/cm in blue electrical testing channel2Current density Discharge 0.5h, then is charged 0.5h (the mass ratio 1:0.37 of three-dimensional carbon material and lithium metal) with identical current density, and constantly The process of reignition charging, until the overpotential fluctuating of battery significantly increases and stops battery, and test result as indicated by 10, should Half-cell has recycled the overpotential value that 500h still keeps stable.And comparative experiments, business copper is replaced into CNTs-MC, same Test condition under, there is big fluctuation in the potential of copper.

Claims (10)

1. a kind of preparation method of three-dimensional carbon material characterized by comprising
S1) sponge is immersed in soluble catalyst precursor water solution, the sponge after drying, after being impregnated；It is described solvable Property catalyst be iron series element salt compounds；
S2) sponge after the immersion is heated and kept the temperature in protective atmosphere, obtains three-dimensional carbon material.
2. preparation method according to claim 1, which is characterized in that the soluble catalyst presoma is selected from nitric acid One of iron, iron chloride, ferric acetate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride and nickel acetate are a variety of.
3. preparation method according to claim 1, which is characterized in that can in the soluble catalyst precursor water solution The concentration of soluble catalytic agent presoma is 0.1~1g/L.
4. preparation method according to claim 1, which is characterized in that the sponge is selected from polyethers sponge, polyvinyl alcohol sea One of silk floss, melamine sponge, polyurethane sponge, cotton fiber sponge, bamboo fibre sponge and lignose sponge are more Kind.
5. preparation method according to claim 1, which is characterized in that the step S1) in be additionally added soluble carbon source.
6. preparation method according to claim 1, which is characterized in that the protective atmosphere is selected from nitrogen, argon gas and helium One of or it is a variety of.
7. preparation method according to claim 1, which is characterized in that the rate of the heating is 1~10 DEG C/min；It is described The temperature of heat preservation is 700 DEG C~900 DEG C；The time of the heat preservation is 2~4h.
8. a kind of three-dimensional carbon material, which is characterized in that received including carbonization sponge skeleton with the carbon being wrapped on carbonization sponge skeleton Mitron.
9. a kind of lithium metal combination electrode, which is characterized in that including three-dimensional carbon material and lithium metal；It is described three-dimensional carbon material include Carbonization sponge skeleton and the carbon nanotube being wrapped on carbonization sponge skeleton；The lithium metal is deposited on carbonization sponge skeleton and carbon The surface of nanotube.
10. a kind of preparation method of lithium metal combination electrode characterized by comprising
S1) sponge is immersed in soluble catalyst precursor water solution, the sponge after drying, after being impregnated；It is described solvable Property catalyst be iron series element salt compounds；
S2) sponge after the immersion is heated and kept the temperature in protective atmosphere, obtains three-dimensional carbon material；
S3) in the three-dimensional carbon deposited on materials lithium metal, lithium metal combination electrode is obtained.
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