CN114956035B - Ultra-microporous carbon material, sulfur positive electrode material and application research of ultra-microporous carbon material and sulfur positive electrode material in lithium sulfur battery - Google Patents

Ultra-microporous carbon material, sulfur positive electrode material and application research of ultra-microporous carbon material and sulfur positive electrode material in lithium sulfur battery Download PDF

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CN114956035B
CN114956035B CN202210465404.2A CN202210465404A CN114956035B CN 114956035 B CN114956035 B CN 114956035B CN 202210465404 A CN202210465404 A CN 202210465404A CN 114956035 B CN114956035 B CN 114956035B
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carbon material
solution
sulfur
microporous carbon
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CN114956035A (en
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周成冈
孙睿敏
王静
夏开胜
韩波
高强
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China University of Geosciences
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    • 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
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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 invention provides a super-microporous carbon material, a sulfur positive electrode material and application research thereof in lithium-sulfur batteries. The preparation method of the ultra-microporous carbon material comprises the following steps: s1, dispersing a high molecular compound containing carboxylate radicals in water to obtain a solution A; s2, cuCl 2 ·2H 2 O is dissolved in water to obtain solution B; s3, slowly adding the solution A into the solution B, and after the addition is completed, sequentially carrying out standing and first drying treatment; s4, in a first inert atmosphere, performing first calcination on the first dried product to obtain the ultra-microporous carbon material; the high polymer compound containing carboxylate radical includes sodium alginate and/or sodium carboxymethyl cellulose. By using a polymer compound containing a carboxylate group and Cu 2+ The gel with a three-dimensional cross-linked structure is prepared through electrostatic interaction, and the ultra-microporous carbon material is obtained after calcination; and the preparation process of the ultra-microporous carbon material is simple, and is beneficial to large-scale production.

Description

Ultra-microporous carbon material, sulfur positive electrode material and application research of ultra-microporous carbon material and sulfur positive electrode material in lithium sulfur battery
Technical Field
The invention relates to the technical field of material preparation, in particular to a super-microporous carbon material, a sulfur positive electrode material and application thereof in lithium-sulfur batteries.
Background
Among battery systems, lithium sulfur batteries are receiving a great deal of attention due to their ultra-high theoretical energy density and specific discharge capacity, and are considered as one of the next generation of rechargeable battery systems with development prospects. However, both active sulfur and the discharge end product are electron/ion insulators, and the transition between the two has a serious volume expansion process, which seriously affects the structure of the positive electrode. In addition, the shuttle effect caused by dissolution of the discharge intermediate polysulfide in the electrolyte severely affects the cycling stability of the sulfur anode.
The current common strategy is to load active sulfur into the nano pore canal of porous carbon, and the preparation method comprises a physical activation method, a chemical activation method, a template method and the like. Physical activation processes generally require the external introduction of an activator, such as steam, CO 2 And the like, the method can enhance the porosity of the biomass carbon material to a certain extent, so that the electrochemical performance of the material is improved, but the method has higher requirements on instruments and equipment, has higher energy consumption, and the pore diameter of the prepared carbon material is difficult to control. The activating agent adopted by the chemical activation method is KOH, K 2 CO 3 、ZnCl 2 、H 3 PO 4 And the like, the precursor is uniformly mixed with the activating agent in a grinding or dipping mode, and the carbon material is obtained after the activation is carried out at different temperatures. The chemical activation method has high efficiency in improving the pores, but the use of a large amount of corrosive reagents and the removal of chemical substances in the activated products lead to limited preparation yield of the carbon material and are not beneficial to mass production. The template method introduces a certain template into the system, assembles the template and the precursor, removes the template after carbonization, and the porous carbon with uniform pore size can be obtained by adopting the carbon material prepared by the method, but the current obtained carbon material cannot meet the requirements.
In view of this, the present invention has been made.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a method for producing a microporous carbon material using a polymer compound having-COOH groups and Cu 2+ The gel with a three-dimensional cross-linked structure is prepared through electrostatic interaction, and the ultra-microporous carbon material is obtained after calcination, wherein the aperture of the ultra-microporous carbon material can be as small as 0.6nm, the aperture is uniform and easy to control, the pore structure has excellent physical confinement effect on small molecular sulfur, and the sulfur anode material obtained after the pore structure is compounded with sulfur has excellent electrochemical performance; and the preparation process of the ultra-microporous carbon material is simple, the regulation and control are easy, the pore-forming agent is easy to elute, the ultra-microporous carbon material can be recycled, and the mass production is facilitated.
In one aspect of the present invention, there is provided a method for preparing a super microporous carbon material, the method comprising:
s1, dispersing a high molecular compound containing carboxylate radicals in water to obtain a solution A;
s2, cuCl 2 ·2H 2 O is dissolved in water to obtain solution B;
s3, slowly adding the solution A into the solution B, and after the addition is completed, sequentially carrying out standing and first drying treatment;
s4, in a first inert atmosphere, performing first calcination on the first dried product to obtain the ultra-microporous carbon material;
the high polymer compound containing carboxylate radical includes sodium alginate and/or sodium carboxymethyl cellulose.
Further, the concentration of the solution A is 0.2 to 0.4mol L -1 ；
The concentration of the solution B is 0.1 to 0.2mol L -1 。
Further, the means for slowly adding the solution a to the solution B includes:
injecting the solution A into the solution B using a syringe pump, the injectingThe injection speed of the jet pump is 50-100 mL h -1 。
Further, in the argon atmosphere, the temperature is 5-10 ℃ for min -1 Heating to 700-900 ℃ at a heating rate to perform the first calcination, wherein the time of the first calcination is 2h;
and/or, the first drying mode comprises: and (3) placing the product after standing into a vacuum drying oven at 60-80 ℃ for drying.
Further, in step S4, the product obtained by the first calcination is soaked in HCl solution for 12 hours, and then washed and dried for the second time to obtain the microporous carbon material;
and/or the concentration of the HCl solution is 5-10 mol L -1 。
In another aspect of the present invention, there is provided a supermicroporous carbon material prepared using the preparation method described above,
and/or the pore size of the ultra-microporous carbon material is 0.6nm, and the specific surface area is 1048.8m 2 g -1 。
In another aspect of the present invention, the present invention provides a method for preparing a sulfur cathode material, comprising: a mixture of second calcined elemental sulfur and the previously described ultra microporous carbon material in a second inert atmosphere, the second calcining conditions comprising: at 1 ℃ for min -1 Heating to 155 ℃ at a heating rate, and preserving heat for 20h;
third calcining the product of the second calcination in a third inert atmosphere to obtain the sulfur cathode material, wherein the third calcining conditions comprise: preserving heat for 2-4 h at 200 ℃.
Further, the content of the elemental sulfur is 30 to 50wt% based on the total mass of the elemental sulfur and the ultra microporous carbon material;
and/or placing the mixture of elemental sulfur and the ultra-microporous carbon material in a closed container for the second calcination.
In another aspect of the present invention, there is provided a sulfur cathode material prepared using the preparation method described above.
In another aspect of the invention, there is provided a lithium sulfur battery comprising the sulfur cathode material described above.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention utilizes a high molecular compound containing carboxylate (-COOH) groups and Cu 2+ The gel with a three-dimensional cross-linked network structure is prepared by controlling the cross-linking concentration and the cross-linking time through electrostatic interaction, and then the gel is subjected to carbonization pyrolysis treatment at high temperature, and after metal oxide particles in the carbon material are removed, the ultra-microporous carbon material with the pore diameter as small as 0.6nm is obtained, and the pore diameter is uniform and easy to control. The ultra-microporous carbon material has excellent physical confinement effect on small molecular sulfur, and the prepared sulfur anode material can be widely applied to different battery systems. In addition, the synthesis steps of the ultra-microporous carbon material are simple and convenient, the regulation and control are easy, the pore-forming agent is easy to elute, the ultra-microporous carbon material can be recycled, and the mass production is facilitated.
The carbon material prepared by the invention is a super-microporous carbon material, and the nitrogen adsorption and desorption curve of the carbon material shows typical I-type adsorption and desorption curve characteristics through a nitrogen adsorption and desorption test, so that the carbon material is proved to be the super-microporous carbon material. At the same time, XRD test results prove that the material has a diffraction peak of graphitized carbon, and the material has good conductivity, and can be widely applied to battery systems.
The ultra-microporous carbon material is compounded with sulfur to obtain a sulfur positive electrode material, the lithium-sulfur battery is assembled, and the capacity of the lithium-sulfur battery still maintains 980mAh g after the lithium-sulfur battery is cycled for 100 circles at 0.1 ℃ through constant current charge-discharge test -1 Cycling for 200 circles at 1C, the specific discharge capacity of the battery is kept at 760.5mAh g -1 The ultra-microporous carbon material plays a certain role in limiting the small molecular sulfur, inhibits the shuttle effect, and improves the electrochemical performance of the lithium-sulfur battery.
Drawings
FIG. 1 is an SEM image of a microporous carbon material of example 1;
FIG. 2 is an XRD pattern for the supermicroporous carbon material of example 1;
FIG. 3 is a graph of nitrogen adsorption and desorption for the microporous carbon material of example 1;
FIG. 4 is a pore size distribution curve of the ultra microporous carbon material of example 1;
fig. 5 is a cycle chart at 0.1C for the lithium sulfur battery of example 1;
fig. 6 is a cycle chart at 1C for the lithium sulfur battery of example 1.
Detailed Description
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In one aspect of the present invention, there is provided a method for preparing a super microporous carbon material, the method comprising:
s1, dispersing a high molecular compound containing carboxylate radicals in water to obtain a solution A.
The high polymer compound containing carboxylate radicals comprises Sodium Alginate (SA) and/or sodium carboxymethyl cellulose.
In some embodiments of the invention, the concentration of the solution A is 0.2 to 0.4mol L -1 。
S2, cuCl 2 ·2H 2 O was dissolved in water to give solution B.
In some embodiments of the invention, the concentration of the solution B is 0.1 to 0.2mol L -1 。
It will be appreciated that the steps S1 and S2 may be interchanged, and the sequence thereof is not limited.
S3, slowly adding the solution A into the solution B, and after the addition is completed, sequentially carrying out standing and first drying treatment.
In some embodiments of the invention, the means for slowly adding the solution a to the solution B comprises: using a syringe pump to pump saidInjecting the solution A into the solution B, wherein the injection speed of the injection pump is 50-100 mL h -1 . Thereby, copper ions (Cu 2+ ) And carboxylate radical are crosslinked to prepare the three-dimensional gel network structure with copper ions uniformly dispersed in SA.
In some embodiments of the invention, the first drying means comprises: and (3) placing the product after standing into a vacuum drying oven at 60-80 ℃ for drying.
And S4, in a first inert atmosphere, performing first calcination on the first dried product to obtain the ultra-microporous carbon material.
In some embodiments of the present invention, the first inert atmosphere is an argon atmosphere, and the first inert atmosphere is an argon atmosphere at 5 to 10 ℃ for a minute -1 The temperature rising rate is increased to 700-900 ℃ to perform the first calcination (namely, the temperature of the first calcination is 700-900 ℃), and the time of the first calcination is 2h. Thus, a microporous carbon material having a suitable pore size can be obtained.
In some embodiments of the present invention, in step S4, the product obtained by the first calcination is soaked in HCl solution for 12 hours, and then washed and dried for the second time to obtain the microporous carbon material; the concentration of the HCl solution is 5-10 mol L -1 . Therefore, impurities in the ultra-microporous carbon material can be removed, and the ultra-microporous carbon material with higher purity can be obtained.
In some embodiments of the invention, the second drying means comprises drying using a forced air drying oven.
The inventor of the invention discovers that the active substance sulfur is loaded in the nano pore canal of the porous carbon, so that not only can the conductivity of the sulfur positive electrode be improved, but also a limited space is provided for volume expansion in the process of charging and discharging the sulfur positive electrode, and the dissolution of polysulfide is inhibited, thus being one of effective ways for improving the electrochemical performance of the sulfur positive electrode. If the pore size of the porous carbon can be controlled within the ultra-microporous range (the pore size is less than 0.7 nm), the limited space can effectively limit the conversion of active substance sulfur to soluble long-chain polysulfide, thereby relieving the problem that the polysulfide is dissolved in electrolyte, reducing the possibility of shuttle effect, and remarkably improving the circulation stability of the sulfur anode.
The invention utilizes a high molecular compound containing carboxylate (-COOH) groups and Cu 2+ The gel with a three-dimensional cross-linked network structure is prepared by controlling the cross-linking concentration and the cross-linking time through electrostatic interaction, and then the gel is subjected to carbonization pyrolysis treatment at high temperature, and after metal oxide particles in the carbon material are removed, the ultra-microporous carbon material with the pore diameter as small as 0.6nm is obtained, and the pore diameter is uniform and easy to control. The ultra-microporous carbon material has excellent physical confinement effect on small molecular sulfur, and the prepared sulfur anode material can be widely applied to different battery systems. In addition, the synthesis steps of the ultra-microporous carbon material are simple and convenient, the regulation and control are easy, the pore-forming agent is easy to elute, the ultra-microporous carbon material can be recycled, and the mass production is facilitated.
The carbon material prepared by the invention is a super-microporous carbon material, and the nitrogen adsorption and desorption curve of the carbon material shows typical I-type adsorption and desorption curve characteristics through a nitrogen adsorption and desorption test, so that the carbon material is proved to be the super-microporous carbon material. At the same time, XRD test results prove that the material has a diffraction peak of graphitized carbon, and the material has good conductivity, and can be widely applied to battery systems.
In some embodiments of the present invention, a method of preparing a microporous carbon material includes the steps of:
1) Weighing a certain amount of Sodium Alginate (SA) powder, dispersing the Sodium Alginate (SA) powder in deionized water, and magnetically stirring to form a uniform mixed solution A;
2) Weighing a certain amount of CuCl 2 ·2H 2 O is dissolved in deionized water and fully dispersed to form uniform mixed solution B;
3) Injecting the mixed solution A into the solution B at a certain speed by using an injection pump, standing for several hours after injection is completed, and drying in a vacuum drying oven at 60-80 ℃;
4) Calcining the dried product obtained in the step 3) in a tube furnace at 5-10 ℃ for min in an inert atmosphere -1 Heating at a heating rate, wherein the calcining temperature is 700-900 ℃ and calcining is carried out for 2h;
5) Soaking the carbon material obtained in the step 4) in HCl solution with a certain concentration, stirring for a certain time, washing, filtering to obtain the carbon material, and finally drying in a blast drying oven to obtain the ultramicropore carbon material.
In another aspect of the present invention, there is provided a supermicroporous carbon material prepared by the above-described preparation method, the supermicroporous carbon material having an amorphous bulk structure, a pore size of 0.6nm, and a specific surface area of 1048.8m 2 g -1 . Therefore, the ultra-microporous carbon material has excellent physical confinement effect on small molecular sulfur, and the sulfur anode material prepared by compounding the ultra-microporous carbon material with elemental sulfur has excellent electrochemical performance, so that the ultra-microporous carbon material can be applied to a battery system.
In another aspect of the present invention, the present invention provides a method for preparing a sulfur cathode material, comprising: in a second inert atmosphere (which may be, for example, an argon atmosphere or the like), a mixture of second calcined elemental sulfur with the previously described microporous carbon material, the second calcining conditions comprising: at 1 ℃ for min -1 Heating to 155 ℃ at a heating rate, and preserving heat for 20h;
third calcining the product of the second calcining in a third inert atmosphere (which may be, for example, an argon atmosphere or the like) to obtain the sulfur cathode material, the conditions of the third calcining including: preserving heat for 2-4 h at 200 ℃. Therefore, the method is simple and convenient to operate and easy to realize, the ultra-microporous carbon material plays a certain role in limiting the small molecular sulfur, the shuttle effect is restrained, and the electrochemical performance of the lithium-sulfur battery is improved; the ultra-microporous carbon material is compounded with sulfur to obtain a sulfur positive electrode material, the lithium-sulfur battery is assembled, and the capacity of the lithium-sulfur battery still maintains 980mAh g after the lithium-sulfur battery is cycled for 100 circles at 0.1 ℃ through constant current charge-discharge test -1 Cycling for 200 circles at 1C, the specific discharge capacity of the battery is kept at 760.5mAh g -1 。
In some embodiments of the present invention, the content of elemental sulfur is 30 to 50wt% based on the total mass of the elemental sulfur and the ultra microporous carbon material.
In some embodiments of the invention, the second calcination is performed by placing the mixture of elemental sulfur and the ultra-microporous carbon material in a closed vessel.
In some embodiments of the present invention, a method for preparing a sulfur cathode material includes the steps of: grinding and mixing the microporous carbon material with elemental sulfur according to a certain mass, placing the mixture into a glass bottle, heating in a muffle furnace for 1 ℃ for min -1 Heating to 155 ℃ at a heating rate, and preserving heat for 20h; the material was then transferred to a tube furnace and incubated for 4h in an inert atmosphere at a temperature of 200 ℃.
In another aspect of the present invention, there is provided a sulfur cathode material prepared using the preparation method described above.
In another aspect of the invention, there is provided a lithium sulfur battery comprising the sulfur cathode material described above.
It is understood that the lithium-sulfur battery may include a structure that a conventional lithium-sulfur battery such as a sulfur positive electrode, a negative electrode, an electrolyte, a separator, etc., should have, wherein the sulfur positive electrode is prepared using a sulfur positive electrode material.
In some embodiments of the invention, the lithium sulfur battery may be a button cell battery.
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Examples
Example 1
The preparation method of the lithium-sulfur battery comprises the following steps:
1) Preparation of a super-microporous carbon material: 2g Sodium Alginate (SA) solution was dissolved in 125mL deionized water to form solution A, 3.4421g CuCl 2 ·2H 2 O was dissolved in 100mL of solution to form solution B at 50mL h using a syringe pump -1 Solution a was slowly added dropwise to solution B to form a uniform gel, and then the gel was transferred to a vacuum oven and dried at 60 ℃ for 12 hours. Drying the sample at 5deg.C in argon (Ar) atmosphere for min -1 Slowly heating to 800 ℃, and preserving heat for 2 hours, wherein the obtained carbon material uses 3MSoaking for 24 hours, and drying and washing to neutrality to obtain the Cu-SA (ultra microporous carbon material);
2) Preparation of a sulfur positive electrode material: uniformly mixing the obtained microporous carbon material and sulfur powder in a mass ratio of 6:4, sealing in a glass bottle, filling Ar atmosphere for protection, and then carrying out a reaction at 1 ℃ for min -1 After the temperature rising rate is increased to 155 ℃, preserving heat for 20 hours, transferring the mixture to a tube furnace, continuing to heat to 200 ℃, and preserving heat for 2 hours to obtain a sulfur anode material Cu-SA/S;
3) And (3) slurry preparation: uniformly mixing a sulfur anode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), weighing 0.21g of Cu-SA/S according to the mass ratio of Cu-SA/S to Super P to PVDF=8:1:1, respectively weighing 0.06g of the conductive agent Super P and 0.03g of PVDF, grinding the weighed Cu-SA/S and Super P for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of PVDF N-methylpyrrolidone (NMP) solution for a small amount for many times after grinding, sealing a small beaker at room temperature, and stirring for 12h under the condition that the rotating speed of a magnetic stirrer is maximum;
4) And (3) battery assembly: assembled using CR2025 button electric die with 1M LiPF as electrolyte 6 The solvent was EC: dec=1:1 (v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium sheet, and corresponding electrochemical tests were performed.
The SEM image (scanning electron microscope image) of fig. 1 demonstrates that the ultra-microporous carbon material of the present example is an amorphous bulk material, and the XRD image (X-ray diffraction image) sheet of fig. 2 demonstrates that the ultra-microporous carbon material is a graphitized carbon material structure, and that the conductivity is good. FIGS. 3 and 4 demonstrate that the material is a microporous carbon material with a specific surface area of 1048.8m 2 g -1 Wherein the micropore volume is 0.56cm 3 g -1 . As can be seen from fig. 5, the charge and discharge capacity of the lithium sulfur battery of this example at the first cycle of the 0.1C battery is: 1670mAh g -1 After 100 circles of circulation, the battery capacity still remains to be 997.2mAh g -1 . As can be seen from fig. 6, at 1C, the battery first-cycle charge-discharge capacity is: 2000.8mAh g -1 After 200 cycles, the battery capacity is kept at 720.1mAh g -1 。
Example 2
The preparation method of the lithium-sulfur battery comprises the following steps:
1) Preparation of a super-microporous carbon material: 2g Sodium Alginate (SA) solution was dissolved in 250mL deionized water to form solution A, 3.4421g CuCl 2 ·2H 2 O was dissolved in 200mL of solution to form solution B at 50mL h using a syringe pump -1 Solution a was slowly added dropwise to solution B to form a uniform gel, and then the gel was transferred to a vacuum oven and dried at 60 ℃ for 12 hours. Drying the sample at 5deg.C in Ar atmosphere for min -1 Slowly heating to 800 ℃, preserving heat for 2 hours, soaking the obtained carbon material in 3M HCl for 24 hours, and drying and washing to neutrality to obtain the ultra-microporous carbon material Cu-SA;
2) Preparation of a sulfur positive electrode material: uniformly mixing the obtained microporous carbon material and sulfur powder in a mass ratio of 6:4, sealing in a glass bottle, filling Ar atmosphere for protection, and then carrying out a reaction at 1 ℃ for min -1 After the temperature rising rate is increased to 155 ℃, preserving heat for 20 hours, transferring the mixture to a tube furnace, continuing to heat to 200 ℃, and preserving heat for 2 hours to obtain a sulfur anode material Cu-SA/S;
3) And (3) slurry preparation: uniformly mixing a sulfur anode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), weighing 0.21g of Cu-SA/S according to the mass ratio of Cu-SA/S to Super P to PVDF=8:1:1, respectively weighing 0.06g of the conductive agent Super P and 0.03g of PVDF, grinding the weighed Cu-SA/S and Super P for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of PVDF N-methylpyrrolidone (NMP) solution for a small amount for many times after grinding, sealing a small beaker at room temperature, and stirring for 12h under the condition that the rotating speed of a magnetic stirrer is maximum;
4) And (3) battery assembly: assembled using CR2025 button electric die with 1M LiPF as electrolyte 6 The solvent was EC: dec=1:1 (v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium sheet, and corresponding electrochemical tests were performed.
After dilution, the size of the ultra-microporous carbon material block is reduced, and the charge and discharge capacity of the lithium sulfur battery in the embodiment at the first cycle of the 0.1C battery is as follows: 2100mAh g -1 After 100 circles of circulation, the battery capacity still remains to be 873.8mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1C batteryThe first charge and discharge capacity is: 1800.8mAh g -1 After 200 circles of circulation, the battery capacity still remains to be 623.2mAh g -1 。
Example 3
The preparation method of the lithium-sulfur battery comprises the following steps:
1) Preparation of a super-microporous carbon material: 2g Sodium Alginate (SA) solution was dissolved in 125mL deionized water to form solution A, 1.7211g CuCl 2 ·2H 2 O was dissolved in 100mL of solution to form solution B at 50mL h using a syringe pump -1 Solution a was slowly added dropwise to solution B to form a uniform gel, and then the gel was transferred to a vacuum oven and dried at 60 ℃ for 12 hours. Drying the sample at 5deg.C in Ar atmosphere for min -1 Slowly heating to 800 ℃, preserving heat for 2 hours, soaking the obtained carbon material in 3M HCl for 24 hours, and drying and washing to neutrality to obtain the ultra-microporous carbon material Cu-SA;
2) Preparation of a sulfur positive electrode material: uniformly mixing the obtained microporous carbon material and sulfur powder in a mass ratio of 6:4, sealing in a glass bottle, filling Ar atmosphere for protection, and then carrying out a reaction at 1 ℃ for min -1 After the temperature rising rate is increased to 155 ℃, preserving heat for 20 hours, transferring the mixture to a tube furnace, continuing to heat to 200 ℃, and preserving heat for 2 hours to obtain a sulfur anode material Cu-SA/S;
3) And (3) slurry preparation: uniformly mixing a sulfur anode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), weighing 0.21g of Cu-SA/S according to the mass ratio of Cu-SA/S to Super P to PVDF=8:1:1, respectively weighing 0.06g of the conductive agent Super P and 0.03g of PVDF, grinding the weighed Cu-SA/S and Super P for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of PVDF N-methylpyrrolidone (NMP) solution for a small amount for many times after grinding, sealing a small beaker at room temperature, and stirring for 12h under the condition that the rotating speed of a magnetic stirrer is maximum;
4) And (3) battery assembly: assembled using CR2025 button electric die with 1M LiPF as electrolyte 6 The solvent was EC: dec=1:1 (v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium sheet, and corresponding electrochemical tests were performed.
The implementation isThe lithium sulfur battery of the example has the following charge and discharge capacities at the first cycle of the 0.1C battery: 1600mAh g -1 After 100 cycles, the battery capacity still remains at 634.8mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the The first charge and discharge capacity of the 1C battery is as follows: 1400.5mAh g -1 After 200 circles of circulation, the capacity of the battery is kept to be 508.8mAh g -1 。
Example 4
The preparation method of the lithium-sulfur battery comprises the following steps:
1) Preparation of a super-microporous carbon material: 2g Sodium Alginate (SA) solution was dissolved in 125mL deionized water to form solution A, 5.163g CuCl 2 ·2H 2 O was dissolved in 100mL of solution to form solution B at 50mL h using a syringe pump -1 Solution a was slowly added dropwise to solution B to form a uniform gel, and then the gel was transferred to a vacuum oven and dried at 60 ℃ for 12 hours. Drying the sample at 5deg.C in Ar atmosphere for min -1 Slowly heating to 800 ℃, preserving heat for 2 hours, soaking the obtained carbon material in 3M HCl for 24 hours, and drying and washing to neutrality to obtain the ultra-microporous carbon material Cu-SA;
2) Preparation of a sulfur positive electrode material: uniformly mixing the obtained microporous carbon material and sulfur powder in a mass ratio of 6:4, sealing in a glass bottle, filling Ar atmosphere for protection, and then carrying out a reaction at 1 ℃ for min -1 After the temperature rising rate is increased to 155 ℃, preserving heat for 20 hours, transferring the mixture to a tube furnace, continuing to heat to 200 ℃, and preserving heat for 2 hours to obtain a sulfur anode material Cu-SA/S;
3) And (3) slurry preparation: uniformly mixing a sulfur anode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), weighing 0.21g of Cu-SA/S according to the mass ratio of Cu-SA/S to Super P to PVDF=8:1:1, respectively weighing 0.06g of the conductive agent Super P and 0.03g of PVDF, grinding the weighed Cu-SA/S and Super P for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of PVDF N-methylpyrrolidone (NMP) solution for a small amount for many times after grinding, sealing a small beaker at room temperature, and stirring for 12h under the condition that the rotating speed of a magnetic stirrer is maximum;
4) And (3) battery assembly: assembled using CR2025 button electric die with 1M LiPF as electrolyte 6 SolventsFor EC: dec=1:1 (v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium sheet, and corresponding electrochemical tests were performed.
The lithium sulfur battery of this embodiment has a first charge and discharge capacity at 0.1C battery of: 1500.4mAh g -1 After 100 circles of circulation, the battery capacity is gradually attenuated to 500.8mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1C, the battery first-turn charge-discharge capacity is: 1600.5mAh g -1 After 200 cycles, the capacity of the battery is kept to be 308.8mAh g -1 The peak area of the small molecular sulfur discharge peak is reduced, and the large molecular sulfur appears, which is related to the damage to the pore diameter structure of the ultra-microporous carbon material.
Example 5
The preparation method of the lithium-sulfur battery comprises the following steps:
1) Preparation of a super-microporous carbon material: 2g Sodium Alginate (SA) solution was dissolved in 125mL deionized water to form solution A, 3.4421g CuCl 2 ·2H 2 O was dissolved in 100mL of solution to form solution B at 50mL h using a syringe pump -1 Slowly drop-wise adding solution A to solution B to form a uniform gel. The gel was then transferred to a vacuum oven and dried at 60 ℃ for 12h. Drying the sample at 5deg.C in Ar atmosphere for min -1 Slowly heating to 800 ℃, preserving heat for 2 hours, soaking the obtained carbon material in 3M HCl for 24 hours, and drying and washing to neutrality to obtain the ultra-microporous carbon material Cu-SA;
2) Preparation of a sulfur positive electrode material: uniformly mixing the obtained microporous carbon material and sulfur powder in a mass ratio of 7:3, sealing in a glass bottle, filling Ar atmosphere for protection, and then carrying out a reaction at 1 ℃ for min -1 After the temperature rising rate is increased to 155 ℃, preserving heat for 20 hours, transferring the mixture to a tube furnace, continuing to heat to 200 ℃, and preserving heat for 2 hours to obtain a sulfur anode material Cu-SA/S;
3) And (3) slurry preparation: uniformly mixing a sulfur anode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), weighing 0.21g of Cu-SA/S according to the mass ratio of Cu-SA/S to Super P to PVDF=8:1:1, respectively weighing 0.06g of the conductive agent Super P and 0.03g of PVDF, grinding the weighed Cu-SA/S and Super P for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of PVDF N-methylpyrrolidone (NMP) solution for a small amount for many times after grinding, sealing a small beaker at room temperature, and stirring for 12h under the condition that the rotating speed of a magnetic stirrer is maximum;
4) And (3) battery assembly: assembled using CR2025 button electric die with 1M LiPF as electrolyte 6 The solvent was EC: dec=1:1 (v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium sheet, and corresponding electrochemical tests were performed.
The lithium sulfur battery of this embodiment has a first charge and discharge capacity at 0.1C battery of: 1800.4mAh g -1 After 100 circles of circulation, the battery capacity is kept to be 1000.5mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1C, the battery first-turn charge-discharge capacity is: 2100.5mAh g -1 After 200 circles of circulation, the capacity of the battery is kept to be 800.9mAh g -1 The cycle performance is obviously improved compared with the performance of the traditional lithium sulfur battery.
Example 6
The preparation method of the lithium-sulfur battery comprises the following steps:
1) Preparation of a super-microporous carbon material: 2g Sodium Alginate (SA) solution was dissolved in 125mL deionized water to form solution A, 3.4421g CuCl 2 ·2H 2 O was dissolved in 100mL of solution to form solution B at 50mL h using a syringe pump -1 Solution a was slowly added dropwise to solution B to form a uniform gel, and then the gel was transferred to a vacuum oven and dried at 60 ℃ for 12 hours. Drying the sample at 5deg.C in Ar atmosphere for min -1 Slowly heating to 800 ℃, preserving heat for 2 hours, soaking the obtained carbon material in 3M HCl for 24 hours, and drying and washing to neutrality to obtain the ultra-microporous carbon material Cu-SA;
2) Preparation of a sulfur positive electrode material: uniformly mixing the obtained microporous carbon material and sulfur powder in a mass ratio of 1:1, sealing in a glass bottle, filling Ar atmosphere for protection, and then carrying out a reaction at 1 ℃ for min -1 After the temperature rising rate is increased to 155 ℃, preserving heat for 20 hours, transferring the mixture to a tube furnace, continuing to heat to 200 ℃, and preserving heat for 2 hours to obtain a sulfur anode material Cu-SA/S;
3) And (3) slurry preparation: uniformly mixing a sulfur anode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), weighing 0.21g of Cu-SA/S according to the mass ratio of Cu-SA/S to Super P to PVDF=8:1:1, respectively weighing 0.06g of the conductive agent Super P and 0.03g of PVDF, grinding the weighed Cu-SA/S and Super P for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of PVDF N-methylpyrrolidone (NMP) solution for a small amount for many times after grinding, sealing a small beaker at room temperature, and stirring for 12h under the condition that the rotating speed of a magnetic stirrer is maximum;
4) And (3) battery assembly: assembled using CR2025 button electric die with 1M LiPF as electrolyte 6 The solvent was EC: dec=1:1 (v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium sheet, and corresponding electrochemical tests were performed.
The lithium sulfur battery of this embodiment has a first charge and discharge capacity at 0.1C battery of: 1200.5mAh g -1 After 100 circles of circulation, the battery capacity is kept to be 400.8mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1C, the battery first-turn charge-discharge capacity is: 1600.4mAh g -1 After 200 cycles, the capacity of the battery decays to 300.2mAh g -1 This is because the sulfur loading content is too high, and the sulfur volume expands during the charge and discharge process, so that the structure of the ultra-microporous carbon material is destroyed, and the active material sulfur falls off from the electrode plate, thereby irreversibly attenuating the battery capacity.
The specific capacities of the lithium sulfur batteries of examples 1 to 6 after 100 cycles at 0.1C and 200 cycles at 1C are shown in table 1 below:
TABLE 1
As can be seen from Table 1, the electrochemical performance of the sulfur cathode material prepared by using the ultra-microporous carbon material of example 5 is best, but the sulfur loading content is too low, but compared with the conventional sulfur cathode material, the cycle performance of the sulfur cathode material of the invention is remarkably improved.
The above is not relevant and is applicable to the prior art.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While certain specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the foregoing examples are provided for the purpose of illustration only and are not intended to limit the scope of the invention, and that various modifications or additions and substitutions to the described specific embodiments may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modification, equivalent substitution, improvement, etc. made to the above embodiments according to the technical substance of the present invention should be included in the scope of protection of the present invention.

Claims (10)

1. A method for preparing a microporous carbon material, comprising:
s1, dispersing sodium alginate or sodium carboxymethyl cellulose powder in water to obtain a solution A; the concentration of the solution A is 0.2-0.4 mol/L;
s2, cuCl 2 ·2H 2 O is dissolved in water to obtain solution B; the concentration of the solution B is 0.1-0.2 mol/L;
s3, injecting the mixed solution A into the solution B at a certain speed by using an injection pump, standing for several hours after injection is completed, and drying in a vacuum drying oven at 60-80 ℃;
s4, calcining the dried product obtained in the step S3 in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in an inert atmosphere, and preserving heat for 2h;
and S5, soaking and stirring the carbon material obtained in the step S4 with an HCl solution with the concentration of 3-10 mol/L for a certain time, washing and filtering to obtain the carbon material, and finally drying the carbon material with a blast drying oven to obtain the ultra-microporous carbon material.
2. The method of claim 1, wherein the slow addition of the solution a to the solution B comprises:
and injecting the solution A into the solution B by using an injection pump, wherein the injection speed of the injection pump is 50-100 mL/h.
3. The preparation method of claim 1, wherein the concentration of the HCl solution is 3-10 mol/L.
4. A microporous carbon material, characterized in that the microporous carbon material is prepared by the preparation method of any one of claims 1 to 3.
5. The material according to claim 4, wherein the pore size of the material is 0.6-nm and the specific surface area is 1048.8m 2 / g。
6. A method for preparing a sulfur cathode material, comprising: a mixture of a second calcined elemental sulfur and the ultra-microporous carbon material of claim 5 in a second inert atmosphere, said second calcining conditions comprising: heating to 155 ℃ at a heating rate of 1 ℃/min, and preserving heat for 20h;
third calcining the product of the second calcination in a third inert atmosphere to obtain the sulfur cathode material, wherein the third calcining conditions comprise: and preserving heat for 2-4 hours at the temperature of 200 ℃.
7. The method according to claim 6, wherein the content of elemental sulfur is 30 to 50wt% based on the total mass of the elemental sulfur and the microporous carbon material.
8. The method according to claim 7, wherein the second calcination is performed by placing the mixture of elemental sulfur and a microporous carbon material in a closed container.
9. A sulfur cathode material, characterized in that the sulfur cathode material is prepared by the preparation method according to any one of claims 6 to 8.
10. A lithium sulfur battery comprising the sulfur cathode material of claim 9.
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