CN114956035A - Ultramicropore carbon material, sulfur positive electrode material and application research thereof in lithium-sulfur battery - Google Patents
Ultramicropore carbon material, sulfur positive electrode material and application research thereof in lithium-sulfur battery Download PDFInfo
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Abstract
The invention provides an ultra-microporous carbon material, a sulfur positive electrode material and application research thereof in a lithium-sulfur battery. The preparation method of the ultramicropore carbon material comprises the following steps: s1, dispersing a macromolecular compound containing carboxylate radicals in water to obtain a solution A; s2, mixing CuCl 2 ·2H 2 Dissolving O in water to obtain a solution B; s3, slowly adding the solution A into the solution B, and after the solution A is added, sequentially carrying out standing and first drying treatment; s4, carrying out first calcination on the first dried product in a first inert atmosphere to obtain the ultramicropore carbon material; the above-mentionedThe carboxylate-containing polymer compound comprises sodium alginate and/or sodium carboxymethylcellulose. Using macromolecular compounds containing carboxylate groups and Cu 2+ Preparing gel with a three-dimensional cross-linking structure through electrostatic interaction, and calcining to obtain the ultramicropore carbon material; and the preparation process of the ultramicropore carbon material is simple and is beneficial to large-scale production.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to an ultra-microporous carbon material, a sulfur positive electrode material and application thereof in a lithium-sulfur battery.
Background
Among battery systems, lithium-sulfur batteries are receiving wide attention due to their ultra-high theoretical energy density and specific discharge capacity, and are considered to be one of the next generation rechargeable battery systems with promising prospects. However, the active sulfur and the final discharge product are electron/ion insulators, and the conversion between the active sulfur and the final discharge product has a serious volume expansion process, so that the structure of the positive electrode is seriously influenced. In addition, the shuttle effect caused by the polysulfide of the discharge intermediate product dissolved in the electrolyte seriously influences the cycle stability of the sulfur anode.
The current common strategy is to load active substance sulfur in the nanometer 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 methods generally require the external introduction of an activating agent, such as steam, CO 2 The method can enhance the porosity of the biomass carbon material to a certain extent, so as to improve the electrochemical performance of the material, but the method has high requirements on instruments and equipment and high 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 or K 2 CO 3 、ZnCl 2 、H 3 PO 4 And the precursor is uniformly mixed with an activating agent by grinding or soaking, and the mixture is activated at different temperatures to obtain the carbon material. The chemical activation method is efficient in improving pores, but the use of a large amount of corrosive reagents and the removal of chemical substances in activated products limit the preparation yield of carbon materials, which is not favorable for large-scale production. DieThe plate method is characterized in that a certain template is introduced into a system, the template and a precursor are assembled, the template is removed after carbonization, and the carbon material prepared by the method can obtain porous carbon with uniform pore size, but the carbon material obtained at present cannot meet the requirements.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Accordingly, an object of the present invention is to provide a method for producing an ultra-microporous carbon material using a high molecular compound having a-COOH group and Cu 2+ The pore structure has excellent physical confinement effect on micromolecular sulfur, and the sulfur cathode material obtained by compounding the pore structure with sulfur has excellent electrochemical performance; and the preparation process of the ultramicropore carbon material is simple, easy to regulate and control, the pore-forming agent is easy to elute and can be recycled, and the method is favorable for large-scale production.
In one aspect of the present invention, there is provided a method for producing an ultra-microporous carbon material, the method comprising:
s1, dispersing a macromolecular compound containing carboxylate radicals in water to obtain a solution A;
s2, mixing CuCl 2 ·2H 2 Dissolving O in water to obtain a solution B;
s3, slowly adding the solution A into the solution B, and after the solution A is added, sequentially carrying out standing and first drying treatment;
s4, carrying out first calcination on the first dried product in a first inert atmosphere to obtain the ultramicropore carbon material;
the carboxylate-containing macromolecular compound comprises sodium alginate and/or sodium carboxymethyl cellulose.
Further, the concentration of the solution A is 0.2-0.4 mol L -1 ；
Concentration of the solution B0.1 to 0.2mol L -1 。
Further, the manner of slowly adding the solution a to the solution B includes:
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 -1 。
Further, in an argon atmosphere, at 5-10 ℃ for min -1 Raising the temperature to 700-900 ℃ at a heating rate to carry out the first calcination, wherein the time of the first calcination is 2 hours;
and/or, the first drying mode comprises the following steps: and (3) putting the product after standing into a vacuum drying oven at the temperature of 60-80 ℃ for drying.
Further, in step S4, soaking the product obtained by the first calcination in an HCl solution for 12 hours, and then washing and second drying the product to obtain the ultra-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 microporous carbon material prepared by the above-described method,
and/or the ultra-microporous carbon material has a pore size of 0.6nm and a specific surface area of 1048.8m 2 g -1 。
In another aspect of the present invention, the present invention provides a method for preparing a sulfur positive electrode material, comprising: second calcining the mixture of elemental sulfur and the previously described nanoporous carbon material in a second inert atmosphere under conditions comprising: at 1 ℃ for min -1 The temperature is raised to 155 ℃ at the temperature raising rate, and the temperature is kept for 20 hours;
third calcining the product obtained by the second calcining in a third inert atmosphere to obtain the sulfur cathode material, wherein the conditions of the third calcining comprise: and preserving the heat for 2-4 hours at the temperature of 200 ℃.
Further, the content of the elemental sulfur is 30 to 50 wt% based on the total mass of the elemental sulfur and the ultra-microporous carbon material;
and/or placing the mixture of the elemental sulfur and the ultramicropore carbon material in a closed container for secondary calcination.
In another aspect of the present invention, the present invention provides a sulfur positive electrode material prepared by the above-described preparation method.
In another aspect of the present invention, the present invention provides a lithium sulfur battery comprising the foregoing sulfur positive electrode material.
Compared with the prior art, the invention can at least obtain the following beneficial effects:
the present invention utilizes a high molecular compound having a carboxylate (-COOH) group 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, 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 micromolecular sulfur, and the prepared sulfur cathode material can be widely applied to different battery systems. Moreover, the synthesis steps of the ultramicropore carbon material are simple and convenient, the regulation and control are easy, the pore-forming agent is easy to elute and can be recycled, and the method is favorable for large-scale production.
The carbon material prepared by the method is an ultramicropore carbon material, and a nitrogen adsorption and desorption curve of the ultramicropore carbon material shows the characteristic of a typical I-type adsorption and desorption curve through a nitrogen adsorption and desorption test, so that the material is proved to be the ultramicropore carbon material. And the XRD test result proves that the material has a diffraction peak of graphitized carbon, so that the material is proved to have good conductivity and can be widely applied to a battery system.
The ultra-microporous carbon material is compounded with sulfur to obtain a sulfur positive electrode material, a lithium-sulfur battery is assembled, and through constant current charge and discharge tests, after 100 cycles of circulation at 0.1 ℃, the capacity of the lithium-sulfur battery still maintains 980mAh g -1 Cycling for 200 circles under 1C, the specific discharge capacity of the material is kept 760.5mAh g -1 The ultramicropore carbon material plays a certain confinement role on micromolecular sulfur, inhibits the generation of shuttle effect, and improves the electrochemistry of the lithium-sulfur batteryAnd (4) performance.
Drawings
FIG. 1 is an SEM photograph of an ultra-microporous carbon material of example 1;
FIG. 2 is an XRD pattern of an ultra-microporous carbon material of example 1;
FIG. 3 is a nitrogen adsorption/desorption curve of the nanoporous 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
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the present invention, there is provided a method for producing an ultra-microporous carbon material, the method comprising:
s1, dispersing the polymer compound containing a carboxylate group in water to obtain a solution a.
The carboxylate-containing polymer compound includes Sodium Alginate (SA) and/or sodium carboxymethylcellulose.
In some embodiments of the invention, the concentration of the solution A is 0.2-0.4 mol L -1 。
S2, mixing 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 0.1-0.2 mol L -1 。
It should be understood that, the steps S1 and S2 may be interchanged, and the sequence is not limited.
And S3, slowly adding the solution A into the solution B, and after the solution A is added, sequentially carrying out standing and first drying treatment.
In some embodiments of the invention, the slow addition of solution a to solution B comprises: 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 -1 . Thereby, copper ions (Cu) 2+ ) And the three-dimensional gel network structure with copper ions uniformly dispersed in SA can be prepared by crosslinking with carboxylate radicals.
In some embodiments of the invention, the first drying comprises: and (3) putting the product after standing into a vacuum drying oven at the temperature of 60-80 ℃ for drying.
S4, first calcining the first dried product in a first inert atmosphere to obtain the ultra-microporous carbon material.
In some embodiments of the present invention, the first inert atmosphere is an argon atmosphere, and the temperature is 5 to 10 ℃ for min in the argon atmosphere -1 And raising the temperature to 700-900 ℃ at the temperature raising rate for carrying out the first calcination (namely the temperature of the first calcination is 700-900 ℃), wherein the time of the first calcination is 2 hours. Thus, an ultra-microporous carbon material having an appropriate pore diameter 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 to obtain the ultra-microporous carbon material; the concentration of the HCl solution is 5-10 mol L -1 . Thus, impurities in the microporous carbon material can be removed, and a highly pure microporous carbon material can be obtained.
In some embodiments of the invention, the second drying mode comprises drying using a forced air drying oven.
The inventor of the invention finds that the active substance sulfur is loaded in the nanometer pore canal of the porous carbon, which not only can improve the conductivity of the sulfur anode, but also can provide a limited space for the volume expansion of the sulfur anode in the charging and discharging process, and inhibit the dissolution of polysulfide, and is one of effective ways for improving the electrochemical performance of the sulfur anode. If the pore size of the porous carbon can be controlled within an ultramicropore range (the pore size is less than 0.7nm), the limited space can effectively limit the conversion of active substance sulfur to soluble long-chain polysulfide, the problem that polysulfide is dissolved in electrolyte is relieved, the possibility of occurrence of shuttle effect is reduced, and the cycle stability of the sulfur anode is remarkably improved.
The present invention utilizes a high molecular compound having a carboxylate (-COOH) group 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, 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 micromolecular sulfur, and the prepared sulfur cathode material can be widely applied to different battery systems. Moreover, the synthesis steps of the ultramicropore carbon material are simple and convenient, the regulation and control are easy, the pore-forming agent is easy to elute and can be recycled, and the method is favorable for large-scale production.
The carbon material prepared by the method is an ultramicropore carbon material, and a nitrogen adsorption and desorption curve of the ultramicropore carbon material shows the characteristic of a typical I-type adsorption and desorption curve through a nitrogen adsorption and desorption test, so that the material is proved to be the ultramicropore carbon material. And the XRD test result proves that the material has the diffraction peak of graphitized carbon, so that the material is proved to have good conductivity and can be widely applied to a battery system.
In some embodiments of the present invention, a method of preparing an ultra-microporous carbon material comprises 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 Dissolving O in deionized water, and fully dispersing to form a 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 finished, and drying in a vacuum drying oven at the temperature of 60-80 ℃;
4) will step withCalcining the dried product obtained in the step 3) in a tubular 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 for 2 h;
5) soaking and stirring the carbon material obtained in the step 4) by using HCl solution with a certain concentration for a certain time, washing and filtering to obtain the carbon material, and finally drying by using an air-blast drying oven to obtain the ultramicropore carbon material.
In another aspect of the present invention, there is provided an ultra-microporous carbon material prepared by the above-mentioned method, wherein the ultra-microporous carbon material has an amorphous bulk structure, a pore size of 0.6nm, and a specific surface area of 1048.8m 2 g -1 . Therefore, the ultramicropore carbon material has an excellent physical confinement effect on micromolecular sulfur, and the sulfur cathode material prepared by compounding the ultramicropore carbon material with elemental sulfur has excellent electrochemical performance and can be applied to a battery system.
In another aspect of the present invention, the present invention provides a method for preparing a sulfur positive electrode material, comprising: the mixture of elemental sulfur and the aforementioned nanoporous carbon material is subjected to a second calcination in a second inert atmosphere (e.g., argon atmosphere, etc.), under conditions comprising: at 1 ℃ for min -1 The temperature is raised to 155 ℃ at the temperature raising rate, and the temperature is kept for 20 hours;
and thirdly calcining the product obtained by the second calcination in a third inert atmosphere (such as argon atmosphere) to obtain the sulfur cathode material, wherein the conditions of the third calcination comprise: and preserving the heat for 2-4 hours at the temperature of 200 ℃. Therefore, the method is simple and convenient to operate and easy to realize, the ultramicropore carbon material plays a certain confinement role on the micromolecule sulfur, the shuttle effect is inhibited, 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, a lithium-sulfur battery is assembled, and through constant current charge and discharge tests, after 100 cycles of circulation at 0.1 ℃, the capacity of the lithium-sulfur battery still maintains 980mAh g -1 Cycling for 200 circles under 1C, the specific discharge capacity of the material is kept 760.5mAh g -1 。
In some embodiments of the present invention, the content of the elemental sulfur is 30 to 50 wt% based on the total mass of the elemental sulfur and the ultra microporous carbon material.
In some embodiments of the present invention, the second calcination is performed by placing the mixture of elemental sulfur and nanoporous carbon material in a closed vessel.
In some embodiments of the present invention, a method of preparing a sulfur positive electrode material includes the steps of: grinding and mixing the ultramicropore carbon material with elemental sulfur according to a certain mass, then placing the mixture in a glass bottle, heating in a muffle furnace for 1 min -1 The temperature is raised to 155 ℃ at the temperature raising rate, and the temperature is kept for 20 hours; the material was then transferred to a tube furnace and allowed to warm to 200 ℃ for 4h under an inert atmosphere.
In another aspect of the present invention, the present invention provides a sulfur positive electrode material prepared by the above-described preparation method.
In another aspect of the invention, the invention provides a lithium sulfur battery comprising the foregoing sulfur positive electrode material.
It is understood that the lithium sulfur battery may include a sulfur positive electrode, a negative electrode, an electrolyte, a separator, and the like, which should be provided in a conventional lithium sulfur battery, 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.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Examples
Example 1
The preparation method of the lithium-sulfur battery comprises the following steps:
1) preparing an ultra-microporous carbon material: a solution A was prepared by dissolving 2g of Sodium Alginate (SA) solution in 125mL of deionized water, and 3.4421g of CuCl 2 ·2H 2 O was dissolved in 100mL of the solution to form solution B, which was pumped using a syringe pump at 50mL h -1 Slowly dropwise adding the solution ATo solution B, after a homogeneous gel was formed, the gel was then transferred to a vacuum oven and dried at 60 ℃ for 12 h. Drying the sample at 5 deg.C for min in argon (Ar) atmosphere -1 Slowly heating to 800 ℃ at the heating rate, preserving heat for 2h, soaking the obtained carbon material in 3M HCl for 24h, and drying and washing to be neutral to obtain the ultramicropore carbon material Cu-SA;
2) preparation of the sulfur positive electrode material: uniformly mixing the obtained ultramicropore carbon material and sulfur powder at a mass ratio of 6:4, sealing in a glass bottle, charging Ar atmosphere for protection, and heating at 1 deg.C for min -1 After the temperature is raised to 155 ℃ at the heating rate, preserving the heat for 20 hours, transferring the material to a tube furnace, continuously raising the temperature to 200 ℃, and preserving the heat for 2 hours to obtain a sulfur anode material Cu-SA/S;
3) preparing slurry: uniformly mixing a sulfur positive electrode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), respectively weighing 0.21g of Cu-SA/S, 0.06g of conductive agent SuperP and 0.03g of PVDF according to the mass ratio of Cu-SA/S to SuperP to PVDF being 8:1:1, grinding the weighed Cu-SA/S and SuperP for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of N-methylpyrrolidone (NMP) solution of PVDF in small amount for multiple times after grinding is finished, 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) assembling the battery: assembling was carried out using a CR2025 type tab die using 1M LiPF as an electrolyte 6 The corresponding electrochemical test was carried out with EC: DEC ═ 1:1(v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium plate.
The SEM image (scanning electron micrograph) of fig. 1 shows that the ultra-microporous carbon material of the present example is an amorphous bulk material, and the XRD pattern (X-ray diffraction pattern) of fig. 2 shows that the ultra-microporous carbon material has a graphitized carbon material structure and is excellent in electrical conductivity. FIGS. 3 and 4 demonstrate that the material is an ultra-microporous carbon material having a specific surface area of 1048.8m 2 g -1 Wherein the pore volume of the micropores is 0.56cm 3 g -1 . As can be seen from fig. 5, the charge/discharge capacity of the lithium-sulfur battery of the present example at the first cycle of the 0.1C battery is: 1670mAh g -1 After circulating for 100 circles, the battery capacity is still maintained to be 997.2mAh g -1 . From the figure6, at 1C, the charge-discharge capacity of the first circle of the battery is as follows: 2000.8mAh g -1 After 200 cycles, the battery capacity was maintained at 720.1mAh g -1 。
Example 2
The preparation method of the lithium-sulfur battery comprises the following steps:
1) preparing an ultra-microporous carbon material: a solution A was prepared by dissolving 2g of Sodium Alginate (SA) solution in 250mL of deionized water, and 3.4421g of CuCl 2 ·2H 2 O was dissolved in 200mL of the solution to form solution B, which was pumped using a syringe pump at 50mL h -1 After the solution A was slowly added dropwise to the solution B to form a uniform gel, the gel was then transferred to a vacuum drying oven and dried at 60 ℃ for 12 hours. Drying the sample at 5 deg.C for min in Ar atmosphere -1 Slowly heating to 800 ℃ at the heating rate, preserving heat for 2h, soaking the obtained carbon material in 3M HCl for 24h, and drying and washing to be neutral to obtain the ultramicropore carbon material Cu-SA;
2) preparation of the sulfur positive electrode material: uniformly mixing the obtained ultramicropore carbon material and sulfur powder at a mass ratio of 6:4, sealing in a glass bottle, filling Ar atmosphere for protection, and then keeping the temperature at 1 ℃ for min -1 After the temperature is raised to 155 ℃ at the heating rate, transferring the material to a tube furnace after heat preservation for 20h, continuously raising the temperature to 200 ℃, and preserving the heat for 2h to obtain a sulfur anode material Cu-SA/S;
3) preparing slurry: uniformly mixing a sulfur positive electrode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), respectively weighing 0.21g of Cu-SA/S, 0.06g of conductive agent SuperP and 0.03g of PVDF according to the mass ratio of Cu-SA/S to SuperP to PVDF being 8:1:1, grinding the weighed Cu-SA/S and SuperP for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of N-methylpyrrolidone (NMP) solution of PVDF in small amount for multiple times after grinding is finished, 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) assembling the battery: assembling was carried out using a CR2025 type tab die using 1M LiPF as an electrolyte 6 The corresponding electrochemical test was carried out with EC: DEC ═ 1:1(v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium plate.
After dilution, the size of the ultra-microporous carbon material block in this example is reduced, and the first cycle charge-discharge capacity of the lithium-sulfur battery in this example at 0.1C is: 2100mAh g -1 After 100 cycles, the battery capacity is still maintained to be 873.8mAh g -1 (ii) a The charge-discharge capacity of the first circle of the 1C battery is as follows: 1800.8mAh g -1 After 200 cycles, the battery capacity is still maintained to be 623.2mAh g -1 。
Example 3
The preparation method of the lithium-sulfur battery comprises the following steps:
1) preparing an ultra-microporous carbon material: dissolve 2g Sodium Alginate (SA) solution in 125mL deionized water to form solution A, and add 1.7211g CuCl 2 ·2H 2 O was dissolved in 100mL of the solution to form solution B, which was pumped using a syringe pump at 50mL h -1 After forming a homogeneous gel by slowly dropping the solution A into the solution B, the gel was then transferred to a vacuum drying oven and dried at 60 ℃ for 12 hours. Drying the sample at 5 deg.C for min in Ar atmosphere -1 Slowly heating to 800 ℃ at the heating rate, preserving heat for 2h, soaking the obtained carbon material in 3M HCl for 24h, and drying and washing to be neutral to obtain the ultramicropore carbon material Cu-SA;
2) preparation of the sulfur positive electrode material: uniformly mixing the obtained ultramicropore carbon material and sulfur powder at a mass ratio of 6:4, sealing in a glass bottle, filling Ar atmosphere for protection, and then keeping the temperature at 1 ℃ for min -1 After the temperature is raised to 155 ℃ at the heating rate, transferring the material to a tube furnace after heat preservation for 20h, continuously raising the temperature to 200 ℃, and preserving the heat for 2h to obtain a sulfur anode material Cu-SA/S;
3) preparing slurry: uniformly mixing a sulfur positive electrode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), respectively weighing 0.21g of Cu-SA/S, 0.06g of conductive agent SuperP and 0.03g of PVDF according to the mass ratio of Cu-SA/S to SuperP to PVDF being 8:1:1, grinding the weighed Cu-SA/S and SuperP for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of N-methylpyrrolidone (NMP) solution of PVDF in small amount for multiple times after grinding is finished, 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) battery with a battery cellAssembling: assembling was carried out using a CR2025 type tab die using 1M LiPF as an electrolyte 6 The corresponding electrochemical test was carried out with EC: DEC ═ 1:1(v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium plate.
The first cycle charge-discharge capacity of the lithium-sulfur battery of this example at 0.1C was: 1600mAh g -1 After 100 cycles, the battery capacity is still maintained at 634.8mAh g -1 (ii) a The charge-discharge capacity of the first circle of the 1C battery is as follows: 1400.5mAh g -1 After 200 cycles, the capacity of the battery is kept at 508.8mAh g -1 。
Example 4
The preparation method of the lithium-sulfur battery comprises the following steps:
1) preparing an ultra-microporous carbon material: 2g of Sodium Alginate (SA) solution was dissolved in 125mL of deionized water to form solution A, and 5.163g of CuCl was added 2 ·2H 2 O was dissolved in 100mL of the solution to form solution B, which was pumped using a syringe pump at 50mL h -1 After forming a homogeneous gel by slowly dropping the solution A into the solution B, the gel was then transferred to a vacuum drying oven and dried at 60 ℃ for 12 hours. Drying the sample at 5 deg.C for min in Ar atmosphere -1 Slowly heating to 800 ℃, preserving the temperature for 2 hours, soaking the obtained carbon material in 3M HCl for 24 hours, drying and washing to be neutral to obtain the ultramicropore carbon material Cu-SA;
2) preparation of the sulfur positive electrode material: uniformly mixing the obtained ultramicropore carbon material and sulfur powder at a mass ratio of 6:4, sealing in a glass bottle, filling Ar atmosphere for protection, and then keeping the temperature at 1 ℃ for min -1 After the temperature is raised to 155 ℃ at the heating rate, transferring the material to a tube furnace after heat preservation for 20h, continuously raising the temperature to 200 ℃, and preserving the heat for 2h to obtain a sulfur anode material Cu-SA/S;
3) preparing slurry: uniformly mixing a sulfur positive electrode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), respectively weighing 0.21g of Cu-SA/S, 0.06g of conductive agent SuperP and 0.03g of PVDF according to the mass ratio of Cu-SA/S to SuperP to PVDF being 8:1:1, grinding the weighed Cu-SA/S and SuperP for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of N-methylpyrrolidone (NMP) solution of PVDF in small amount for multiple times after grinding is finished, 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) assembling the battery: assembling was carried out using a CR2025 type tab die using 1M LiPF as an electrolyte 6 The corresponding electrochemical test was carried out with EC: DEC ═ 1:1(v: v), the separator was a polypropylene separator with a diameter of 19mm, and the negative electrode was a lithium plate.
The charge and discharge capacity of the lithium-sulfur battery of the embodiment in the first circle of the 0.1C battery is as follows: 1500.4mAh g -1 After 100 cycles of circulation, the battery capacity gradually decays to 500.8mAh g -1 (ii) a At 1C, the charge-discharge capacity of the first circle of the battery is as follows: 1600.5mAh g -1 After 200 cycles, the capacity of the battery is maintained at 308.8mAh g -1 The discharge peak area of the small molecular sulfur is reduced, and the appearance of the large molecular sulfur is related to the damage of 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) preparing an ultra-microporous carbon material: dissolve 2g Sodium Alginate (SA) solution in 125mL deionized water to form solution A, and add 3.4421g CuCl 2 ·2H 2 O was dissolved in 100mL of the solution to form solution B, which was pumped using a syringe pump at 50mL h -1 Solution a was slowly added dropwise to solution B at a rate to form a uniform gel. The gel was then transferred to a vacuum oven and dried at 60 ℃ for 12 h. Drying the sample at 5 deg.C for min in Ar atmosphere -1 Slowly heating to 800 ℃ at the heating rate, preserving heat for 2h, soaking the obtained carbon material in 3M HCl for 24h, and drying and washing to be neutral to obtain the ultramicropore carbon material Cu-SA;
2) preparation of the sulfur positive electrode material: mixing the obtained ultramicropore carbon material and sulfur powder at a mass ratio of 7:3, sealing in a glass bottle, charging Ar atmosphere for protection, and heating at 1 deg.C for min -1 After the temperature is raised to 155 ℃ at the heating rate, transferring the material to a tube furnace after heat preservation for 20h, continuously raising the temperature to 200 ℃, and preserving the heat for 2h to obtain a sulfur anode material Cu-SA/S;
3) preparing slurry: uniformly mixing a sulfur positive electrode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), respectively weighing 0.21g of Cu-SA/S, 0.06g of conductive agent Super P and 0.03g of PVDF according to the mass ratio of Cu-SA/S to Super P to PVDF of 8:1:1, grinding the weighed Cu-SA/S and Super P for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of N-methylpyrrolidone (NMP) solution of PVDF in a small amount for multiple times after grinding is finished, 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) assembling the battery: assembling was carried out using a CR2025 type tab die using 1M LiPF as an electrolyte 6 The corresponding electrochemical tests were carried out with EC: DEC ═ 1:1(v: v), separator polypropylene separator 19mm in diameter, negative electrode lithium sheet.
The charge and discharge capacity of the lithium-sulfur battery of the embodiment in the first circle of the 0.1C battery is as follows: 1800.4mAh g -1 After 100 cycles, the battery capacity was maintained at 1000.5mAh g -1 (ii) a At 1C, the charge-discharge capacity of the first circle of the battery is as follows: 2100.5mAh g -1 After 200 cycles, the capacity of the battery was maintained at 800.9mAh g -1 And compared with the traditional lithium-sulfur battery, the cycle performance is obviously improved.
Example 6
The preparation method of the lithium-sulfur battery comprises the following steps:
1) preparing an ultra-microporous carbon material: dissolve 2g Sodium Alginate (SA) solution in 125mL deionized water to form solution A, and add 3.4421g CuCl 2 ·2H 2 O was dissolved in 100mL of the solution to form solution B, which was pumped using a syringe pump at 50mL h -1 After forming a homogeneous gel by slowly dropping the solution A into the solution B, the gel was then transferred to a vacuum drying oven and dried at 60 ℃ for 12 hours. Drying the sample at 5 deg.C for min in Ar atmosphere -1 Slowly heating to 800 ℃ at the heating rate, preserving heat for 2h, soaking the obtained carbon material in 3M HCl for 24h, and drying and washing to be neutral to obtain the ultramicropore carbon material Cu-SA;
2) preparation of the sulfur positive electrode material: uniformly mixing the obtained ultramicropore carbon material and sulfur powder at a mass ratio of 1:1, sealing in a glass bottle, charging Ar atmosphere for protection, and then keeping the temperature at 1 ℃ for min -1 Rate of temperature riseAfter the temperature is raised to 155 ℃, the mixture is transferred into a tube furnace to be continuously raised to 200 ℃ after heat preservation is carried out for 20 hours, and heat preservation is carried out for 2 hours, so that the sulfur anode material Cu-SA/S is obtained;
3) preparing slurry: uniformly mixing a sulfur positive electrode material, a conductive agent and a binder polyvinylidene fluoride (PVDF), respectively weighing 0.21g of Cu-SA/S, 0.06g of conductive agent SuperP and 0.03g of PVDF according to the mass ratio of Cu-SA/S to SuperP to PVDF being 8:1:1, grinding the weighed Cu-SA/S and SuperP for 30min under the irradiation of an infrared lamp, adding the mixture into 800uL of N-methylpyrrolidone (NMP) solution of PVDF in small amount for multiple times after grinding is finished, 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) assembling the battery: assembling was carried out using a CR2025 type tab die using 1M LiPF as an electrolyte 6 The corresponding electrochemical tests were carried out with EC: DEC ═ 1:1(v: v), separator polypropylene separator 19mm in diameter, negative electrode lithium sheet.
The first cycle charge-discharge capacity of the lithium-sulfur battery of this example at 0.1C was: 1200.5mAh g -1 After 100 cycles, the battery capacity was maintained at 400.8mAh g -1 (ii) a At 1C, the charge-discharge capacity of the first circle of the battery is as follows: 1600.4mAh g -1 After 200 cycles, the capacity of the battery is attenuated to 300.2mAh g -1 This is because the volume of sulfur expands during charge and discharge to destroy the structure of the microporous carbon material, and the active material sulfur falls off from the electrode sheet, thereby causing irreversible degradation of 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 sulfur cathode material prepared from the ultra-microporous carbon material of example 5 has the best electrochemical performance, but the sulfur loading content is too low, so that the cycle performance of the sulfur cathode material of the present invention is significantly improved compared to the conventional sulfur cathode material.
The above is not relevant and is applicable to the prior art.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer 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, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A method for producing an ultra-microporous carbon material, comprising:
s1, dispersing a macromolecular compound containing carboxylate radicals in water to obtain a solution A;
s2, mixing CuCl 2 ·2H 2 Dissolving O in water to obtain a solution B;
s3, slowly adding the solution A into the solution B, and after the solution A is added, sequentially carrying out standing and first drying treatment;
s4, carrying out first calcination on the first dried product in a first inert atmosphere to obtain the ultramicropore carbon material;
the carboxylate-containing macromolecular compound comprises sodium alginate and/or sodium carboxymethyl cellulose.
2. The method according to claim 1, wherein the concentration of the solution A is 0.2 to 0.4mol L -1 ；
The concentration of the solution B is 0.1-0.2 mol L -1 。
3. The method of claim 1, wherein the slow addition of the solution a to the solution B comprises:
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 -1 。
4. The method according to claim 1, wherein the temperature is controlled at 5 to 10 ℃ for min in an argon atmosphere -1 Raising the temperature to 700-900 ℃ at a heating rate to carry out the first calcination, wherein the time of the first calcination is 2 hours;
and/or, the first drying mode comprises the following steps: and (3) placing the product after standing in a vacuum drying oven at the temperature of 60-80 ℃ for drying.
5. The method according to any one of claims 1 to 4, wherein in step S4, the product obtained by the first calcination is immersed in an HCl solution for 12 hours, and then washed and second dried to obtain the ultra-microporous carbon material;
and/or the concentration of the HCl solution is 3-10 mol L -1 。
6. A microporous carbon material produced by the production method according to any one of claims 1 to 5,
and/or the ultra-microporous carbon material has a pore size of 0.6nm and a specific surface area of 1048.8m 2 g -1 。
7. A method for producing a sulfur positive electrode material, comprising: second calcining a mixture of elemental sulfur and the nanoporous carbon material of claim 6 in a second inert atmosphere under conditions comprising: at 1 ℃ for min -1 The temperature is raised to 155 ℃ at the temperature raising rate, and the temperature is kept for 20 hours;
third calcining the product obtained by the second calcining in a third inert atmosphere to obtain the sulfur cathode material, wherein the conditions of the third calcining comprise: and preserving the heat for 2-4 hours at the temperature of 200 ℃.
8. The production method according to claim 7, wherein the elemental sulfur is contained in an amount of 30 to 50 wt% based on the total mass of the elemental sulfur and the ultra-microporous carbon material;
and/or placing the mixture of the elemental sulfur and the ultramicropore carbon material in a closed container for secondary calcination.
9. A sulfur positive electrode material, characterized in that it is produced by the production method according to claim 7 or 8.
10. A lithium-sulfur battery comprising the sulfur positive electrode material according to claim 9.
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