CN110323431B - Preparation of porous carbon microspheres and application of porous carbon microspheres in lithium-sulfur battery - Google Patents
Preparation of porous carbon microspheres and application of porous carbon microspheres in lithium-sulfur battery Download PDFInfo
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- CN110323431B CN110323431B CN201910618463.7A CN201910618463A CN110323431B CN 110323431 B CN110323431 B CN 110323431B CN 201910618463 A CN201910618463 A CN 201910618463A CN 110323431 B CN110323431 B CN 110323431B
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Abstract
The invention discloses a preparation method of a porous carbon microsphere and application of the porous carbon microsphere in a lithium-sulfur battery, wherein the porous carbon microsphere is of a micro-nano hierarchical porous structure and is assembled by carbon nanofibers, the diameter of each carbon nanofiber is 10-50 nm, and the diameter of each porous carbon microsphere is 1-10 mu m; the preparation method of the porous carbon microsphere comprises the following steps: preparing a precursor solution, forming a hydroxide template and a fibrous polymer, carbonizing at high temperature and removing the template. The preparation method of the porous carbon microsphere provided by the invention is simple and convenient, the effect is good, the prepared porous carbon microsphere has good conductivity, simultaneously has rich micro-nano hierarchical porous structures, can contain more sulfur and improve the electrochemical performance of a sulfur anode, can be used for preparing a high-capacity sulfur anode when being applied to a lithium-sulfur battery anode, obviously improves the energy density of the lithium-sulfur battery, and has wide application prospects on the lithium-sulfur battery.
Description
Technical Field
The invention relates to the technical field of micro-nano carbon materials and preparation thereof, in particular to preparation of porous carbon microspheres and application of the porous carbon microspheres in lithium-sulfur batteries.
Background
The commercialized nano carbon particles such as carbon black, superconducting carbon SP, acetylene black and the like have excellent conductivity and larger specific surface area, are often used as conductive agents of anode and cathode materials of batteries, and can also be used as sulfur carriers in lithium-sulfur batteries. However, the commercial nano carbon particles are nano-sized, so that the tap density is low, the nano sulfur positive electrode obtained by compounding the particles with sulfur has the defects of poor manufacturability, easiness in cracking and powder falling of thick coating of a pole piece and the like in the preparation process of a battery pole piece, more binders are needed, and the content of sulfur in the pole piece is reduced. The thickness of the pole piece and the content of sulfur have great influence on the specific energy of the lithium-sulfur positive pole, and in order to improve the tap density of the nano-sulfur positive pole and the thickness of the pole piece, the construction of the porous carbon microsphere with the micro-nano structure is an effective and feasible strategy. The micro-nano structure takes nano materials as structural elements, and a micron-scale mixed network structure is gradually formed under the aggregation effect. The sulfur-carbon anode with the micro-nano structure can keep the advantages of large specific surface area of nano-structure elements, rich pores and the like on one hand, and improve the electrochemical performance of the sulfur anode; on the other hand, the micron-sized particles can improve the tap density of the material, and are beneficial to preparing a sulfur anode with high sulfur surface density in the traditional slurry coating process, and the sulfur-carbon anode with the micro-nano structure can obtain a thick pole piece and is not easy to crack, so that the sulfur loading capacity in the pole piece is improved.
Disclosure of Invention
The invention provides a preparation method of a porous carbon microsphere and an application of the porous carbon microsphere in a lithium-sulfur battery, which are used for overcoming the defects in the prior art.
In order to achieve the purpose, the invention provides a porous carbon microsphere which is of a micro-nano hierarchical porous structure and is formed by assembling carbon nanofibers, wherein the diameters of the carbon nanofibers are 10-50 nm, and the diameters of the porous carbon microspheres are 1-10 microns.
In order to achieve the above object, the present invention further provides a preparation method of the porous carbon microsphere, comprising the following steps:
(1) adding nitrate and urea into a mixed solution of water and ethylene glycol for dissolving, then sequentially adding resorcinol and formaldehyde solution, and uniformly stirring to obtain a precursor solution;
(2) putting the precursor solution into a closed container for closed reaction, cooling, filtering, washing and drying to obtain precursor powder;
(3) placing the precursor powder in an inert reducing atmosphere for heat treatment to obtain black sintering powder;
(4) and (3) placing the black sintered powder in an acidic aqueous solution for washing, filtering and drying to obtain porous carbon microsphere powder.
In order to achieve the purpose, the invention also provides an application of the porous carbon microsphere or the porous carbon microsphere prepared by the preparation method in a lithium-sulfur battery, and the porous carbon microsphere is used for preparing a porous carbon microsphere/sulfur composite material; the mass fraction of sulfur in the composite material is 60-90 wt%.
Compared with the prior art, the invention has the beneficial effects that:
1. the porous carbon microsphere provided by the invention is of a micro-nano hierarchical porous structure, and is formed by assembling carbon nanofibers, wherein the diameter of each carbon nanofiber is 10-50 nm, and the diameter of each porous carbon microsphere is 1-10 mu m. The porous carbon microsphere has a micro-nano hierarchical structure and excellent conductivity, wherein the nano carbon fiber is beneficial to improving the conductivity, and the micro-nano hierarchical porous structure is beneficial to improving the sulfur carrying capacity; the porous carbon microspheres can be compounded with sulfur to obtain a composite material with excellent performance, and the composite material can effectively improve the sulfur capacity and the electrochemical performance of the lithium-sulfur battery.
2. According to the preparation method of the porous carbon microsphere, resorcinol, formaldehyde, nitrate, urea and the like are used as raw materials to prepare a precursor solution, and the raw materials are cheap and easy to obtain; then putting the precursor solution into a closed container for closed reaction, wherein resorcinol and formaldehyde are polymerized under a hydrothermal condition to form a three-dimensional reticular fiber polymer, nitrate forms a hydroxide template under the hydrothermal condition, and urea is used for adjusting the pH value of the precursor solution so as to regulate and control the formation of the hydroxide template; cooling, filtering, washing and drying a product obtained by the hydrothermal reaction to obtain precursor powder; then placing the precursor powder in an inert reducing atmosphere for heat treatment, carbonizing the three-dimensional reticular fiber polymer precursor, and reducing the metal hydroxide nano template into nano metal to obtain black sintered powder; and finally, removing the nano metal in the black sintered powder by acid washing to obtain the porous carbon microsphere. The preparation method provided by the invention has the advantages of cheap and easily available raw materials, simple preparation process and capability of realizing mass preparation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a porous carbon microsphere in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a porous carbon microsphere in example 1 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a porous carbon microsphere in example 2 of the present invention;
FIG. 4 is a low-temperature nitrogen desorption isotherm diagram of porous carbon microspheres in example 1 of the present invention;
FIG. 5 is a graph showing cycle performance of the lithium sulfur battery of example 1;
fig. 6 is a charge-discharge graph of the lithium sulfur battery in example 1.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 drugs/reagents used are all commercially available without specific mention.
The invention provides a porous carbon microsphere which is of a micro-nano hierarchical porous structure and is formed by assembling carbon nanofibers, wherein the diameters of the carbon nanofibers are 10-50 nm, and the diameters of the porous carbon microspheres are 1-10 microns.
The micro-nano structure takes nano materials as structural elements, and a micron-scale mixed network structure is gradually formed under the aggregation effect. The porous carbon microsphere takes the carbon nanofibers as structural elements, and finally, micron-sized porous carbon microspheres are formed.
The invention also provides a preparation method of the porous carbon microsphere, which comprises the following steps:
(1) preparing a precursor solution: adding nitrate and urea into a mixed solution of water and ethylene glycol for dissolving, then sequentially adding resorcinol and formaldehyde solution, and uniformly stirring to obtain a precursor solution.
Preferably, the molar ratio of the nitrate to the urea is (0.5-5): 1, and the proper proportion relationship ensures that the formed template has better appearance and is beneficial to the formation of a micro-nano structure; the volume ratio of the water to the glycol is 1 (2-10), so that the nitrate and the urea are fully dissolved; the molar ratio of the resorcinol to the formaldehyde is 1 (1-2), so that polymerization reaction is facilitated to generate a nanoscale three-dimensional reticular fiber polymer, and the appearance of a product generated by the polymerization reaction of the resorcinol and the formaldehyde is different along with the difference of the appearance of the template; the stirring time is 0.5-2.0 h, so that the precursor solution is uniformly mixed.
Preferably, the nitrate is at least one of nickel nitrate, cobalt nitrate, iron nitrate and manganese nitrate. The common transition metal nitrate is selected, so that the reaction is facilitated, and the raw materials are easy to obtain.
Preferably, the concentration of the nitrate in the precursor solution is 0.02-0.06 mol/L, and the concentration of the resorcinol is 0.01-0.05 mol/L. The size of the finally formed porous carbon microspheres is controlled by controlling the concentration of nitrate and resorcinol in the precursor solution.
(2) Formation of hydroxide templates and three-dimensional network fiber polymers: and (3) placing the precursor solution into a closed container for closed reaction, cooling, filtering, washing and drying to obtain precursor powder. Resorcinol and formaldehyde can be subjected to polymerization reaction under a hydrothermal condition to form a three-dimensional reticular fiber polymer, and nitrate is subjected to hydrolysis reaction under the hydrothermal condition to generate a hydroxide template.
Preferably, the temperature of the sealing reaction is 120-200 ℃, the time is 6-24 h, and proper reaction temperature and time are selected to promote the polymerization reaction and curing between resorcinol and formaldehyde and promote the formation of a hydroxide template; the drying temperature is 100-120 ℃, the drying time is 4-7 h, and the drying is accelerated without damaging the original structure of the material.
(3) High-temperature carbonization: placing the precursor powder in an inert reducing atmosphere for heat treatment to obtain black sintering powder; carbonizing the three-dimensional reticular fiber polymer precursor at high temperature, and reducing the metal hydroxide nano template into nano metal.
Preferably, the inert reducing atmosphere is Ar and H2Mixed gas of Ar and H2The volume percentage of (70-95): (5-30) reducing the metal hydroxide nano template into nano metal in a reducing atmosphere; the temperature of the heat treatment is 500-1200 ℃, the time is 1-24 hours, so that the three-dimensional reticular fiber polymer is completely carbonized, and the reduction of the metal hydroxide template into the nano metal is promoted.
(4) And removing the template, placing the black sintered powder in an acidic aqueous solution for washing, filtering and drying to obtain the porous carbon microsphere. And removing the reduced metal by acid washing to enable the prepared material to form a porous structure.
Preferably, the acid in the acidic aqueous solution is at least one of hydrochloric acid, sulfuric acid and nitric acid. Common acid reagents are selected, so that the method is easy to obtain and reduces the cost.
Preferably, the mass fraction of the acid in the acidic aqueous solution is 10-30 wt%. The metal can be effectively removed and the cost is saved by selecting proper acid content.
The invention also provides an application of the porous carbon microsphere or the porous carbon microsphere prepared by the preparation method in a lithium-sulfur battery, and the porous carbon microsphere is used for preparing a porous carbon microsphere/sulfur composite material; the mass fraction of sulfur in the composite material is 60-90 wt%.
Example 1
The embodiment provides a porous carbon microsphere which is of a micro-nano hierarchical porous structure and is formed by assembling carbon nanofibers, wherein the diameters of the carbon nanofibers are 10-50 nm, and the diameters of the porous carbon microspheres are 2-6 microns.
The embodiment also provides a preparation method of the porous carbon microsphere, which comprises the following steps:
(1) adding 2.1g of nickel nitrate and 0.2g of urea into a mixed solution of 20ml of water and 140ml of ethylene glycol for dissolving, then sequentially adding 0.4g of resorcinol and 0.6g of formaldehyde solution, and stirring for 1.5h to obtain a precursor solution;
(2) carrying out closed reaction on the precursor solution in a hydrothermal kettle at 160 ℃ for 12h, cooling, filtering, washing, and drying at 100 ℃ for 7h to obtain precursor powder;
(3) precursor powder is added in Ar/20% H2Heating to 800 ℃ in the atmosphere, preserving the heat for 2h, and naturally cooling to obtain black sintered powder;
(4) and (3) washing the black sintered powder in 20g of 30% hydrochloric acid aqueous solution, filtering and drying to obtain the porous carbon microspheres.
As shown in fig. 1 and fig. 2, both are SEM images of the porous carbon microspheres prepared in this embodiment, and it can be seen from the SEM images that the porous carbon microspheres prepared in this embodiment are of a micro-nano hierarchical porous structure, and the porous carbon microspheres are assembled from carbon nanofibers; the diameter of the carbon nanofiber is 10-50 nm, and the diameter of the porous carbon microsphere is 2-6 microns.
FIG. 4 is a low-temperature nitrogen desorption isotherm diagram of the porous carbon microsphere of the present example, and it can be found from FIG. 4 that the porous carbon microsphere has certain micropores (the pore diameter is less than 2 nm)) The specific surface area of the structure and the abundant mesoporous (the aperture is between 2 and 50 nm) structure is 122m2Per g, pore volume 0.75cm3/g。
The porous carbon microsphere prepared in the embodiment can be used for preparing a porous carbon microsphere/sulfur composite material, and has good electrochemical performance when being applied to a lithium-sulfur battery.
The preparation method of the porous carbon microsphere/sulfur composite material comprises the following steps: 0.1g of the porous carbon microsphere prepared in the example 1 and 0.46g of elemental sulfur powder are mixed and ground uniformly, and then the mixture is placed in N2Heating the porous carbon microsphere/sulfur composite material in a protected tube furnace to 155 ℃, preserving the heat for 12h, and naturally cooling to obtain the porous carbon microsphere/sulfur composite material.
The sulfur content of the composite was 82.3%.
The prepared porous carbon microsphere/sulfur composite material is used for preparing a positive pole piece of a lithium-sulfur battery, and the sulfur capacity of the pole piece is 2.5mg/cm2The positive pole piece is assembled into a lithium-sulfur battery (the specific preparation method is shown in doctor's scientific paper ' research on electrochemical properties of hollow carbon spheres and graphene nanostructures in a lithium-sulfur battery positive pole material, university of national defense science and technology, 2016 '), and the lithium-sulfur battery is subjected to cycle performance test and charge-discharge test.
Fig. 5 is a cycle performance graph of the lithium-sulfur battery prepared in this example, the first discharge capacity of the lithium-sulfur battery is 1084mAh/g, and the capacity retention rate after 120 cycles is 70.7%, which indicates that the lithium-sulfur battery has good electrochemical stability under high sulfur loading.
Fig. 6 is a charge-discharge curve diagram of the lithium-sulfur battery prepared in this example, and it can be seen from the graph that under the condition of high sulfur loading, the battery has two charge-discharge plateaus, and the 2 nd discharge plateau is 2.1V, which indicates that the lithium-sulfur battery has good conductivity and the polarization of the battery is small.
Example 2
The embodiment provides a porous carbon microsphere which is of a micro-nano hierarchical porous structure and is formed by assembling carbon nanofibers; the diameter of the carbon nanofiber is 10-20 nm, and the diameter of the porous carbon microsphere is 1-2 microns.
The embodiment also provides a preparation method of the porous carbon microsphere, which comprises the following steps:
(1) adding 1.05g of cobalt nitrate and 0.1g of urea into a mixed solution of 20ml of water and 140ml of ethylene glycol for dissolving, then sequentially adding 0.2g of resorcinol and 0.3g of formaldehyde solution, and stirring for 0.5h to obtain a precursor solution;
(2) carrying out closed reaction on the precursor solution in a hydrothermal kettle at 200 ℃ for 6h, cooling, filtering, washing, and drying at 120 ℃ for 4h to obtain precursor powder;
(3) precursor powder is added in Ar/30% H2Preserving heat for 1h at 1000 ℃ in the atmosphere, and naturally cooling to obtain black sintered powder;
(4) and (3) placing the black sintered powder in 15g of 20% sulfuric acid aqueous solution for washing, filtering and drying to obtain the porous carbon microspheres.
Fig. 3 is an SEM image of the porous carbon microsphere prepared in this embodiment, and it can be seen from the SEM image that the porous carbon microsphere prepared in this embodiment is a micro-nano hierarchical porous structure, and the porous carbon microsphere is assembled by carbon nanofibers; the diameter of the carbon nanofiber is 10-20 nm, and the diameter of the porous carbon microsphere is 1-2 microns.
Example 3
The embodiment provides a porous carbon microsphere which is of a micro-nano hierarchical porous structure and is formed by assembling carbon nanofibers; the diameter of the carbon nanofiber is 10-50 nm, and the diameter of the porous carbon microsphere is 1-10 mu m.
The embodiment also provides a preparation method of the porous carbon microsphere, which comprises the following steps:
(1) adding 2.1g of nickel nitrate and 0.2g of urea into a mixed solution of 20ml of water and 140ml of ethylene glycol for dissolving, then sequentially adding 0.4g of resorcinol and 0.6g of formaldehyde solution, and stirring for 2 hours to obtain a precursor solution;
(2) carrying out closed reaction on the precursor solution in a hydrothermal kettle at 120 ℃ for 24h, cooling, filtering, washing, and drying at 110 ℃ for 6h to obtain porous microsphere precursor powder;
(3) precursor powder is added in Ar/5% H2Keeping the temperature at 600 ℃ for 24h under the atmosphere, and naturally cooling to obtainTo black sintered powder;
(4) and (3) placing the black sintered powder into 20g of 10% hydrochloric acid aqueous solution, washing away the nano metal particles, and filtering and drying to obtain the porous carbon microspheres.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The preparation method of the porous carbon microsphere is characterized by comprising the following steps:
(1) adding nitrate and urea into a mixed solution of water and ethylene glycol for dissolving, then sequentially adding resorcinol and formaldehyde solution, and uniformly stirring to obtain a precursor solution;
(2) putting the precursor solution into a closed container for closed reaction, cooling, filtering, washing and drying to obtain precursor powder; in the closed reaction process, resorcinol and formaldehyde are polymerized under a hydrothermal condition to form a three-dimensional reticular fiber polymer, nitrate forms a metal hydroxide template under the hydrothermal condition, and urea regulates and controls the formation of the metal hydroxide template by regulating the pH value of a precursor solution;
the temperature of the closed reaction is 120-200 ℃, and the time is 6-24 hours;
(3) placing the precursor powder in an inert reducing atmosphere for heat treatment to obtain sintered powder;
in the heat treatment process, the three-dimensional reticular fiber polymer is carbonized, and meanwhile, the metal hydroxide template is reduced into nano metal;
the temperature of the heat treatment is 500-1200 ℃, and the time is 1-24 h;
(4) and (3) placing the sintered powder into an acidic aqueous solution for washing to remove the nano metal in the sintered powder, and filtering and drying to obtain the porous carbon microsphere powder.
2. The method for preparing a porous carbon microsphere as claimed in claim 1, wherein in the step (1), the molar ratio of the nitrate to the urea is (0.5-5): 1; the volume ratio of the water to the glycol is 1 (2-10); the molar ratio of the resorcinol to the formaldehyde is 1 (1-2); the stirring time is 0.5-2.0 h.
3. The method for preparing a porous carbon microsphere according to claim 2, wherein the nitrate is at least one of nickel nitrate, cobalt nitrate, iron nitrate and manganese nitrate.
4. The method for preparing porous carbon microspheres according to claim 1, wherein the concentration of nitrate in the precursor solution is 0.02-0.06 mol/L, and the concentration of resorcinol is 0.01-0.05 mol/L.
5. The method for preparing porous carbon microspheres according to claim 1, wherein in the step (2), the drying temperature is 100-120 ℃ and the drying time is 4-7 hours.
6. The method for preparing a porous carbon microsphere as claimed in claim 1, wherein in the step (3), the inert reducing atmosphere is Ar and H2Mixed gas of Ar and H2The volume percentage of (70-95): (5-30).
7. The method for preparing a porous carbon microsphere according to claim 1, wherein in the step (4), the acid in the acidic aqueous solution is at least one of hydrochloric acid, sulfuric acid and nitric acid.
8. The method for preparing porous carbon microspheres according to claim 7, wherein the mass fraction of the acid in the acidic aqueous solution is 10-30 wt%.
9. A porous carbon microsphere is characterized by being of a micro-nano hierarchical porous structure and assembled by carbon nanofibers, wherein the diameter of the carbon nanofibers is 10-50 nm, and the diameter of the porous carbon microsphere is 1-10 microns; the porous carbon microsphere is prepared by the preparation method of any one of claims 1-8.
10. The application of the porous carbon microsphere according to claim 9 or the porous carbon microsphere prepared by the preparation method according to any one of claims 1 to 8 in a lithium-sulfur battery, which is characterized in that the porous carbon microsphere is used for preparing a porous carbon microsphere/sulfur composite material; the mass fraction of sulfur in the composite material is 60-90 wt%.
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