CN109052359B - Three-dimensional carbon material and preparation method thereof, and metal lithium composite electrode and preparation method thereof - Google Patents
Three-dimensional carbon material and preparation method thereof, and metal lithium composite electrode and preparation method thereof Download PDFInfo
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a preparation method of a three-dimensional carbon material, which comprises the following steps: s1) soaking the sponge into a soluble catalyst precursor aqueous solution, and drying to obtain the soaked sponge; the soluble catalyst is a salt compound of an iron element; s2) heating the soaked sponge in a protective atmosphere and preserving heat to obtain the three-dimensional carbon material. Compared with the prior art, the sponge is used as a solid carbon source, the catalyst precursor is adsorbed at the early stage, and then pyrolysis and carbonization of the sponge, in-situ generation of the catalyst and synchronous growth of the carbon nano tubes are realized in a protective atmosphere, so that the three-dimensional carbon material with the carbon nano tubes wound on the carbonized sponge framework is prepared.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a three-dimensional carbon material and a preparation method thereof, and a metal lithium composite electrode and a preparation method thereof.
Background
Carbon nanotubes are one-dimensional carbon nanomaterials with unique tubular structures. Compared with the traditional carbon material, the carbon nano tube has excellent mechanical and electrical properties and the like, and has wide application prospect in the aspect of energy storage.
Many researchers have studied the preparation of carbon nanotubes from solid carbon sources, for example, chinese patent publication No. CN107032326A discloses a method for preparing helical carbon nanotubes by solid phase catalysis, which uses urea or melamine powder as a solid carbon source to prepare carbon nanotubes in a protective gas atmosphere, but the material obtained by the method is powder; the sponge is a solid material with a three-dimensional network skeleton structure, contains certain-sized pore size distribution, is made of wood cellulose fibers or foamed plastic polymers, can be carbonized, and keeps the original sponge skeleton structure, and Chinese patent with publication number CN105217603A discloses a preparation method of a carbon nanotube foam material.
Lithium metal has high theoretical capacity (3860 mA.h/g), low electrochemical potential (-3.04V) and low density (0.534 g/cm)3) And the like, and has been receiving more attention in the field of lithium secondary batteries. However, lithium metal has a problem of lithium dendrites as a negative electrode material for lithium batteries: during the growth process of the lithium dendrite, the lithium dendrite is easy to pierce through a diaphragm, so that the battery is short-circuited, and potential safety hazards are generated; meanwhile, lithium dendrites are continuously generated and broken in the process of precipitating and depositing lithium, some lithium (dead lithium) dissociated on the surface of lithium metal is generated, and a solid electrolyte interface film (SEI) needs to be continuously regenerated on the surface of the lithium metal, so that the cycle stability and the coulombic efficiency of the lithium metal battery are greatly influenced.
The three-dimensional carbon material has the following advantages: (1) lower density compared to metallic materials; (2) the three-dimensional framework has high mechanical strength and can prevent the growth of lithium dendrites; (3) the surface area is large, the local current density is reduced, and the growth of dendritic crystals is favorably inhibited; (4) the porosity is high, and the internal pressure caused by volume change can be relieved.
At present, many researches are devoted to applying the three-dimensional carbon material to the lithium metal negative electrode, but all the researches focus on the circulation under the condition of small current density and small surface capacity, for example, Chinese patent with publication number CN105609783 discloses a three-dimensional carbon material with the current density of 0.25mA/cm2The dough mixing capacity is 0.625 mA.h/cm2For the lower circulation, there has been an attempt to circulate at a large current density and a small surface capacity, for example, Chinese patent publication No. CN106784635 discloses a three-dimensional carbon material at a current density of 5mA/cm2The mixing surface capacity is 1 mA.h/cm2Lower cycle, but high current density and high area capacity are rarely achieved.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a three-dimensional carbon material with a simple preparation method and capable of achieving high current density and high area capacity, a preparation method thereof, a lithium metal composite electrode, and a preparation method thereof.
The invention provides a preparation method of a three-dimensional carbon material, which comprises the following steps:
s1) soaking the sponge into a soluble catalyst precursor aqueous solution, and drying to obtain the soaked sponge; the soluble catalyst is a salt compound of an iron element;
s2) heating the soaked sponge in a protective atmosphere and preserving heat to obtain the three-dimensional carbon material.
Preferably, the soluble catalyst precursor is selected from one or more of ferric nitrate, ferric chloride, ferric acetate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride and nickel acetate.
Preferably, the concentration of the soluble catalyst precursor in the soluble catalyst precursor aqueous solution is 0.1-1 g/L.
Preferably, the sponge is selected from one or more of polyether sponge, polyvinyl alcohol sponge, melamine sponge, polyurethane sponge, cotton fiber sponge, bamboo fiber sponge and wood cellulose sponge.
Preferably, a soluble carbon source is also added in the step S1).
Preferably, the protective atmosphere is selected from one or more of nitrogen, argon and helium.
Preferably, the heating rate is 1-10 ℃/min; the temperature of the heat preservation is 700-900 ℃; the heat preservation time is 2-4 h.
The invention also provides a three-dimensional carbon material which comprises a carbonized sponge framework and carbon nano tubes wound on the carbonized sponge framework.
The invention also provides a metal lithium composite electrode, which comprises a three-dimensional carbon material and metal lithium; the three-dimensional carbon material comprises a carbonized sponge framework and carbon nano tubes wound on the carbonized sponge framework; and the metal lithium is deposited on the surfaces of the carbonized sponge framework and the carbon nano tube.
The invention also provides a preparation method of the metal lithium composite electrode, which comprises the following steps:
s1) soaking the sponge into a soluble catalyst precursor aqueous solution, and drying to obtain the soaked sponge; the soluble catalyst is a salt compound of an iron element;
s2) heating the soaked sponge in a protective atmosphere and preserving heat to obtain a three-dimensional carbon material;
s3) depositing metal lithium on the three-dimensional carbon material to obtain the metal lithium composite electrode.
The invention provides a preparation method of a three-dimensional carbon material, which comprises the following steps: s1) soaking the sponge into a soluble catalyst precursor aqueous solution, and drying to obtain the soaked sponge; the soluble catalyst is a salt compound of an iron element; s2) heating the soaked sponge in a protective atmosphere and preserving heat to obtain the three-dimensional carbon material. Compared with the prior art, the preparation method is simple, does not need post treatment, and the obtained three-dimensional carbon material keeps the elasticity and the three-dimensional skeleton structure of the sponge, has certain conductivity, also has larger specific surface area and abundant void structure, can reach high current density and high surface volume after depositing the metal lithium, and does not form dendrite.
Drawings
FIG. 1 is a scanning electron micrograph of a carbonized melamine sponge;
FIG. 2 is a scanning electron micrograph of a three-dimensional carbon material obtained in example 1 of the present invention;
FIG. 3 is a transmission electron micrograph of a three-dimensional carbon material obtained in example 1 of the present invention;
FIG. 4 is an optical diagram of a three-dimensional carbon material obtained in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of a three-dimensional carbon material obtained in example 2 of the present invention;
FIG. 6 is a scanning electron micrograph of a three-dimensional carbon material obtained in example 3 of the present invention;
FIG. 7 is a scanning electron micrograph of a three-dimensional carbon material obtained in example 4 of the present invention;
FIG. 8 is a scanning electron micrograph of a three-dimensional carbon material obtained in example 5 of the present invention;
FIG. 9 is a cycle diagram of a half cell obtained in example 3 of the present invention, in which the area current is 5mA/cm2Surface capacity of 10mA h/cm2；
FIG. 10 is a cycle diagram of a half cell obtained in example 3 of the present invention, in which the area current is 10mA/cm2The surface capacity is 5mA h/cm2。
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a three-dimensional carbon material which comprises a carbonized sponge framework and carbon nano tubes wound on the carbonized sponge framework.
The invention also provides a preparation method of the three-dimensional carbon material, which comprises the following steps: s1) soaking the sponge into a soluble catalyst precursor aqueous solution, and drying to obtain the soaked sponge; the soluble catalyst is a salt compound of an iron element; s2) heating the soaked sponge in a protective atmosphere and preserving heat to obtain the three-dimensional carbon material.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The sponge is a sponge well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of a polyether sponge, a polyvinyl alcohol sponge, a melamine sponge, a polyurethane sponge, a cotton fiber sponge, a bamboo fiber sponge, and a wood cellulose sponge is preferred, and when the melamine sponge and the polyurethane sponge are used, the obtained three-dimensional carbon material further contains abundant nitrogen elements.
Immersing the sponge in a soluble catalyst precursor solution; the soluble catalyst precursor is not particularly limited as long as it is a salt compound of an iron-based element well known to those skilled in the art, and in the present invention, one or more of ferric nitrate, ferric chloride, ferric acetate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride and nickel acetate are preferred; the concentration of the soluble catalyst precursor in the soluble catalyst precursor solution is preferably 0.1-1 g/L, more preferably 0.5-1 g/L, and still more preferably 0.75-1 g/L; the soluble catalyst precursor solution is preferably prepared by adopting ultrapure water; in order to make the catalyst precursor uniformly adsorbed on the sponge, a soluble carbon source is preferably added into the soluble catalyst precursor solution; the soluble carbon source is not particularly limited as long as it is well known to those skilled in the art, and urea and/or starch are preferred in the present invention; the adding amount of the soluble carbon source is preferably 2.5-5 g/L; the immersion time is preferably sufficient for the sponge to absorb the soluble catalyst precursor solution.
Then drying to obtain soaked sponge; the drying temperature is preferably 50-80 ℃, and more preferably 60-70 ℃.
Heating the soaked sponge in a protective atmosphere and preserving heat to obtain a three-dimensional carbon material; the protective atmosphere is not particularly limited, but is preferably one or more of nitrogen, argon and helium; the heating rate is preferably 1-10 ℃/min, more preferably 1-8 ℃/min, still more preferably 1-6 ℃/min, still more preferably 1-4 ℃/min, and most preferably 1-2 ℃/min; the temperature of the heat preservation is preferably 700-900 ℃, more preferably 750-850 ℃, and further preferably 800 ℃; the heat preservation time is preferably 2-4 h, and more preferably 2-3 h.
The preparation method is simple, no post-treatment is needed, the elasticity and the three-dimensional framework structure of the sponge are maintained, the sponge has certain conductivity, and simultaneously has a large specific surface area and a rich void structure, and the high current density and the high surface capacity can be achieved after the metal lithium is deposited, and no dendritic crystal is formed.
The invention also provides a metal lithium composite electrode, which comprises a three-dimensional carbon material and metal lithium; the three-dimensional carbon material comprises a carbonized sponge framework and carbon nano tubes wound on the carbonized sponge framework; the metal lithium is deposited on the surfaces of the carbonized sponge framework and the carbon nano tube; the three-dimensional carbon material is the same as the above, and is not repeated herein.
The invention also provides a preparation method of the metal lithium composite electrode, which comprises the following steps: s1) soaking the sponge into a soluble catalyst precursor aqueous solution, and drying to obtain the soaked sponge; the soluble catalyst is a salt compound of an iron element; s2) heating the soaked sponge in a protective atmosphere and preserving heat to obtain a three-dimensional carbon material; s3) depositing metal lithium on the three-dimensional carbon material to obtain the metal lithium composite electrode.
Wherein, the steps S1) and S2) are the same as above, and are not repeated herein.
Depositing lithium metal on the three-dimensional carbon material; the deposition method is not particularly limited as long as it is well known to those skilled in the art, and electrodeposition is preferably employed in the present invention; the mass ratio of the three-dimensional carbon material to the metal lithium is preferably 1: (0.37-0.74).
In order to further illustrate the present invention, the following will describe the three-dimensional carbon material and the preparation method thereof, the lithium metal composite electrode and the preparation method thereof in detail with reference to the examples.
The reagents used in the following examples are all commercially available.
Example 1
1) 0.15g of nickel nitrate was dissolved in 200ml of ultrapure water.
2) 1g of urea was dissolved in the above solution.
3) And completely soaking the melamine sponge into the solution, fully adsorbing for 12h, and drying at 60 ℃ to obtain the soaked sponge.
4) And (3) putting the sponge into a quartz boat, heating the sponge from room temperature to 800 ℃ at the heating rate of 1 ℃ per minute under the protection of argon, and preserving the heat for 2 hours to obtain the three-dimensional carbon material.
And (3) carbonizing the melamine sponge in argon directly according to the step 4) to obtain the carbonized melamine sponge. The carbonized melamine sponge was analyzed by scanning electron microscopy to obtain a scanning electron micrograph, as shown in fig. 1.
The three-dimensional carbon material obtained in example 1 was analyzed by scanning electron microscopy to obtain a scanning electron micrograph, which is shown in fig. 2. As can be seen from FIG. 2, the prepared carbon material still maintains the three-dimensional skeleton structure of the sponge, and the carbon nanotubes are wound on the three-dimensional skeleton.
The three-dimensional carbon material obtained in example 1 was analyzed by transmission electron microscopy to obtain a transmission electron microscopy image, which is shown in fig. 3.
FIG. 4 is an optical diagram of the three-dimensional carbon material obtained in example 1.
Example 2
1) 0.15g of nickel nitrate was dissolved in 200ml of ultrapure water.
2) 0.5g of urea was dissolved in the above solution.
3) And completely soaking the melamine sponge into the solution, fully adsorbing for 12h, and drying at 60 ℃ to obtain the soaked sponge.
4) And (3) putting the sponge into a quartz boat, heating the sponge from room temperature to 800 ℃ at the heating rate of 1 ℃ per minute under the protection of argon, and preserving the heat for 2 hours to obtain the three-dimensional carbon material.
The three-dimensional carbon material obtained in example 2 was analyzed by scanning electron microscopy to obtain a scanning electron micrograph, which is shown in fig. 5.
Example 3
1) 0.2g of nickel nitrate was dissolved in 200ml of ultrapure water.
2) 0.5g of urea was dissolved in the above solution.
3) And completely soaking the melamine sponge into the solution, fully adsorbing for 12h, and drying at 60 ℃ to obtain the soaked sponge.
4) And (3) putting the sponge into a quartz boat, heating the sponge from room temperature to 800 ℃ at the heating rate of 1 ℃ per minute under the protection of argon, and preserving the heat for 2 hours to obtain the three-dimensional carbon material.
The three-dimensional carbon material obtained in example 3 was analyzed by scanning electron microscopy to obtain a scanning electron micrograph, which is shown in fig. 6.
Example 4
1) 0.2g of cobalt nitrate was dissolved in 200ml of ultrapure water.
2) 0.5g of urea was dissolved in the above solution.
3) And completely soaking the melamine sponge into the solution, fully adsorbing for 12h, and drying at 60 ℃ to obtain the soaked sponge.
4) And (3) putting the sponge into a quartz boat, heating the sponge from room temperature to 800 ℃ at the heating rate of 1 ℃ per minute under the protection of argon, and preserving the heat for 2 hours to obtain the three-dimensional carbon material.
The three-dimensional carbon material obtained in example 4 was analyzed by scanning electron microscopy to obtain a scanning electron micrograph, which is shown in fig. 7.
Example 5
1) 0.15g of nickel nitrate was dissolved in 200ml of ultrapure water.
2) And completely soaking the polyurethane sponge into the solution, fully adsorbing for 12h, and drying at 60 ℃ to obtain the soaked sponge.
3) And (3) putting the sponge into a quartz boat, heating the sponge from room temperature to 800 ℃ at the heating rate of 1 ℃ per minute under the protection of argon, and preserving the heat for 2 hours to obtain the three-dimensional carbon material.
The three-dimensional carbon material obtained in example 5 was analyzed by scanning electron microscopy to obtain a scanning electron micrograph, which is shown in fig. 8.
In the above example, the three-dimensional carbon material prepared in example 3 is preferably electrodeposited with metallic lithium according to the uniform and dense growth distribution of carbon nanotubes, to obtain a metallic lithium composite electrode (referred to as CNTs-MC). The lithium metal composite electrode and lithium are assembled into a half battery, and the half battery is assembled according to the sequence of a negative electrode shell, a lithium sheet, electrolyte, a diaphragm, the electrolyte, the lithium metal composite electrode, a steel sheet, an elastic sheet and a positive electrode shell, and then is sealed and pressed. The separator used was a polypropylene (PP) separator, and the electrolyte used was 1MLiTFSI (DOL: DME ═ 1:1 vol%) +2 vol% LiNO3All the operations were carried out in an argon glove box, wherein the water oxygen content was less than 0.5 ppm. Standing the button-type lithium metal half-cell prepared by the method for 12 hours, and then firstly placing the button-type lithium metal half-cell in a blue test channel at a rate of 5mA/cm2Discharging for 2h at a current density, charging for 2h at the same current density (the mass ratio of the three-dimensional carbon material to the metal lithium is 1: 0.74), continuously repeating the discharging and charging process until the overpotential fluctuation of the battery is obviously increased and the battery is stopped, and testing results show that the half-cell still maintains a stable overpotential value of about 60mV after 600h cycles as shown in FIG. 9. In contrast, in the comparative experiment, in which commercial copper was used instead of CNTs-MC, the cycle life of copper was only 70h and large fluctuations in potential occurred under the same test conditions. If the button-type lithium metal half-cell prepared by the method is stood for 12 hours, then 10mA/cm is firstly put in a blue test channel2Discharging at the current density for 0.5h, charging at the same current density for 0.5h (the mass ratio of the three-dimensional carbon material to the metal lithium is 1: 0.37), continuously repeating the discharging and charging process until the overpotential fluctuation of the battery is obviously increased and the battery is stopped, and testing results show that the half-cell still maintains a stable overpotential value after 500h circulation as shown in 10. In contrast, in a comparative experiment, commercial copper was used in place of CNTs-MC under the same test conditionsThe potential of copper fluctuates greatly.
Claims (5)
1. A lithium metal composite electrode is characterized by comprising a three-dimensional carbon material and lithium metal; the three-dimensional carbon material comprises a carbonized sponge framework and carbon nano tubes wound on the carbonized sponge framework; the metal lithium is deposited on the surfaces of the carbonized sponge framework and the carbon nano tube;
the three-dimensional carbon material is prepared according to the following method:
s1) soaking the sponge into a soluble catalyst precursor aqueous solution, and drying to obtain the soaked sponge; the soluble catalyst is a salt compound of an iron element;
s2) heating the soaked sponge in a protective atmosphere and preserving heat to obtain a three-dimensional carbon material;
the soluble catalyst precursor is selected from one of ferric nitrate, ferric chloride, ferric acetate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride and nickel acetate;
the concentration of the soluble catalyst precursor in the soluble catalyst precursor water solution is 0.1-1 g/L;
a soluble carbon source is also added in the step S1);
the soluble carbon source is selected from urea; the adding amount of the soluble carbon source is 2.5-5 g/L.
2. The lithium metal composite electrode according to claim 1, wherein the sponge is selected from one or more of polyether sponge, polyvinyl alcohol sponge, melamine sponge, polyurethane sponge, cotton fiber sponge, bamboo fiber sponge, and wood cellulose sponge.
3. The lithium metal composite electrode according to claim 1, wherein the protective atmosphere is selected from one or more of nitrogen, argon and helium.
4. The lithium metal composite electrode according to claim 1, wherein the heating rate is 1 to 10 ℃/min; the temperature of the heat preservation is 700-900 ℃; the heat preservation time is 2-4 h.
5. A method for preparing a lithium metal composite electrode, comprising:
s1) soaking the sponge into a soluble catalyst precursor aqueous solution, and drying to obtain the soaked sponge; the soluble catalyst is a salt compound of an iron element;
s2) heating the soaked sponge in a protective atmosphere and preserving heat to obtain a three-dimensional carbon material;
s3) depositing metal lithium on the three-dimensional carbon material to obtain a metal lithium composite electrode;
the soluble catalyst precursor is selected from one of ferric nitrate, ferric chloride, ferric acetate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel chloride and nickel acetate;
the concentration of the soluble catalyst precursor in the soluble catalyst precursor water solution is 0.1-1 g/L;
a soluble carbon source is also added in the step S1);
the soluble carbon source is selected from urea; the adding amount of the soluble carbon source is 2.5-5 g/L.
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