CN109830674B - Tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material and preparation method and application thereof - Google Patents
Tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material as well as a preparation method and application thereof, belonging to the technical field of lithium-sulfur battery electrode materials. In order to improve the conductivity of a sulfur electrode and solve the problem of poor cycle stability of a lithium-sulfur battery, the shell layer of the electrode material provided by the invention is tin oxide, the core layer is a gas-carbide gel microsphere, monomer sulfur is uniformly dispersed in the gas-carbide gel microsphere, and the mass of the sulfur accounts for 60-80% of the total mass of the core-shell structure composite sulfur electrode material. The invention improves the conductivity of the sulfur electrode, inhibits the volume expansion of sulfur in the reaction process, and limits the sulfur in the gas carbide gel core layer by the tin oxide shell layer to inhibit the seepage of the sulfur, thereby ensuring that the composite sulfur electrode material keeps good cycle stability in the charging and discharging processes. The tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material provided by the invention is applied to a lithium sulfur battery, and can prolong the service life and improve the capacity retention rate of the battery.
Description
Technical Field
The invention belongs to the technical field of electrode materials of lithium-sulfur batteries, and particularly relates to a tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material as well as a preparation method and application thereof.
Background
The widespread use of large energy storage devices and electric vehicles requires further improvement in the technology in the field of rechargeable batteries to achieve higher energy densities. However, the lithium battery using graphite as a negative electrode material, which is widely used commercially, has almost approached its theoretical energy density of 372mAh g-1The requirements of lithium ion batteries for higher energy density and power density cannot be met.
Lithium-sulfur batteries are drawing more and more attention due to their higher theoretical specific energy density, which is 1675mAh g theoretical capacity-1And 3-5 times higher than that of the lithium ion battery. In a lithium sulfur battery, each sulfur atom can react with two lithium ions to form Li2S and therefore has a higher energy storage capacity than a lithium ion battery.
However, the lithium-sulfur battery has limitations as a secondary battery system, and there are some problems to be solved, including: the lithium-sulfur battery has poor cycle stability due to the loss of electrode active substances in the cycle process; the sulfur electrode has poor conductivity; the chemical reaction cycle at the sulfur electrode is the conversion between monomer sulfur and lithium sulfide, and the inherent volume difference of the two molecules can cause the positive electrode to generate larger volume change in the charge and discharge processes in the cycle process and cause the structural damage of the electrode material; polysulfide ions generated in charge-discharge reactions can generate shuttle effect, so that the loss of effective active substances at the lithium negative electrode end is caused, and the coulombic efficiency of the battery is reduced. These drawbacks limit the service life and capacity retention of lithium-sulfur batteries, which in turn affects the commercial application of lithium-sulfur batteries, making them less competitive as high-end applications.
Disclosure of Invention
In order to improve the conductivity of a sulfur electrode and solve the problem of poor cycle stability of a lithium-sulfur battery, the invention provides a tin oxide/carbon aerogel core-shell structure composite sulfur electrode material and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the shell layer of the electrode material is tin oxide, the core layer is a carbonized aerogel microsphere, monomer sulfur is uniformly dispersed in the carbonized aerogel microsphere, and the mass of the monomer sulfur accounts for 60-80% of the total mass of the core-shell structure composite sulfur electrode material.
Further, the thickness of the tin oxide shell layer is 5-15 nm, and the sphere diameter of the carbonized aerogel micro-sphere is 1-2 microns.
The invention provides a preparation method of a tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material, which comprises the following steps:
step one, synthesizing the carbonized aerogel micro-spheres
Mixing resorcinol, formaldehyde and water according to a certain molar volume ratio, adding a certain mass of catalyst into the mixed system, and uniformly mixing to obtain a suspension; aging the suspension at a certain temperature for a certain time, collecting precipitates in the suspension, washing the precipitates with absolute ethyl alcohol and drying the precipitates; placing the dried precipitate in an inert gas atmosphere, and calcining at a certain temperature for a certain time to obtain the carbonized aerogel microspheres with a certain sphere diameter;
step two, preparing tin oxide/carbon aerogel core-shell structure microspheres
Putting the carbonized aerogel microspheres prepared in the step one into acid liquor for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2Pretreating the O pretreatment mixed solution at a certain temperature; collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2Stirring the mixed solution for a certain time in O pressure maintaining treatment, and maintaining the pressure of the obtained suspension at a certain temperature for a certain time to generate a tin oxide shell layer with a certain thickness on the surface of the carbon aerogel microspheres; collecting the precipitate in the mixed solution after pressure maintaining, washing the precipitate with absolute ethyl alcohol and drying the precipitate; placing the dried precipitate in an inert gas atmosphere, and calcining at a certain temperature for a certain time to obtain tin oxide/carbon aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material
Fully mixing the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two with sulfur powder according to a certain mass ratio; and (3) carrying out sulfur steaming treatment at a certain temperature in an inert gas atmosphere to prepare the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material.
Further, in the first step, the molar volume ratio of the resorcinol, the formaldehyde and the water is 1mol:2mol:15 mL; said catalysisThe agent is Na2CO3Said Na2CO3The mass ratio of the resorcinol to the resorcinol is 1: 250; the ageing temperature of the suspension is 80 ℃, and the ageing time is 5 d.
Further, the drying temperature of the precipitate in the first step is 60-90 ℃; the inert gas is nitrogen or argon, the calcining temperature is 800 ℃, and the calcining time is 1-3 h; the diameter of the carbonized aerogel microspheres is 1-2 μm.
Further, the acid solution in the second step is prepared from nitric acid with the mass concentration of 70% and sulfuric acid with the mass concentration of 37% according to the volume ratio of 1: 3; the NaOH and SnCl2·2H2The molar concentration of NaOH in the O pretreatment mixed solution is 0.106mol/L, and SnCl2·2H2The molar concentration of O is 0.1 mol/L; the pretreatment temperature is 70 ℃, and the pretreatment time is 10-16 h.
Further, step two is NaOH and SnCl2·2H2The molar concentration of NaOH in the O pressure maintaining treatment mixed solution is 0.075mol/L, and SnCl2·2H2The molar concentration of O is 0.2 mol/L; the stirring time is 15-30 min.
Further, the pressure maintaining pressure in the second step is 1-3 MPa, the pressure maintaining temperature is 200 ℃, and the pressure maintaining time is 40-50 h; the thickness of the tin oxide shell layer is 5-15 nm; the drying temperature of the precipitate is 60-90 ℃; the inert gas is nitrogen or argon, the calcining temperature is 300 ℃, and the calcining time is 2-3 h.
Further, the mass ratio of the tin oxide/carbon aerogel core-shell structure microspheres to the sulfur powder in the third step is 2: 8-4: 6; the inert gas is argon; the temperature is 145-160 ℃, and the time of sulfur steaming treatment is 12-20 h.
The tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material provided by the invention is applied to a lithium-sulfur battery.
The invention has the beneficial effects that:
according to the tin oxide/carbide aerogel core-shell structure composite sulfur electrode material, the conductivity of a sulfur electrode is improved through the compounding of monomer sulfur and carbide aerogel, the carbide aerogel can also inhibit the volume expansion of sulfur in the reaction process, and the structure of the electrode material is prevented from being damaged; the tin oxide shell layer limits sulfur in the gas carbide gel core layer, so that the seepage of sulfur in the charging and discharging process can be inhibited, and the shuttle effect of polysulfide ions can be inhibited; the composite sulfur electrode material keeps good cycling stability in the charging and discharging process.
Secondly, the preparation method of the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material obtains the carbonized aerogel microspheres with more uniform sphere diameters through reasonable raw material proportion and aging conditions, the thickness of tin oxide shells coated outside the carbonized aerogel microspheres is more uniform through pretreatment and high-temperature pressure maintaining treatment, and monomer sulfur can be uniformly distributed in the carbonized aerogel microspheres through sulfur steaming treatment, so that the micrometer spherical composite sulfur electrode material with stable structure, regular appearance and uniform particle diameter is obtained. When the micron spherical composite sulfur electrode material with regular appearance and uniform particle size is used for preparing the lithium sulfur battery, the electrode material can be tightly stacked to form a smooth and uniform electrode structure, so that effective transmission of ions and electrons is better realized.
The tin oxide/carbon aerogel core-shell structure composite sulfur electrode material provided by the invention has good cycling stability, and can be applied to a lithium sulfur battery, so that the service life and the capacity retention rate of the battery can be improved, and the application value and the commercial value of the lithium sulfur battery can be improved.
Drawings
FIG. 1 is an SEM image of 5000 times as large as the carbon aerogel micro-spheres prepared in example 7;
FIG. 2 is an SEM image of the carbonized aerogel micro-spheres prepared in example 7 at 10000 times magnification;
FIG. 3 is an SEM image of the carbonized aerogel micro-spheres of example 7 after pretreatment at 16000 magnification;
FIG. 4 is an SEM image of core-shell structured microspheres of tin oxide/aerogel carbide prepared in example 7 at 10000 times magnification;
FIG. 5 is an SEM image of 10000 times magnification of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
FIG. 6 is a TEM image of 2 ten thousand times magnification of core-shell structured microspheres of tin oxide/carbon aerogel prepared in example 7;
FIG. 7 is a TEM image of 10 ten thousand times magnification of core-shell structured microspheres of tin oxide/carbon aerogel prepared in example 7;
FIG. 8 is a HRTEM image at 50 ten thousand times magnification of core-shell structured microspheres of tin oxide/carbon aerogel prepared in example 7;
FIG. 9 is a TEM image of the total elemental analysis of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
FIG. 10 is a TEM image of elemental analysis of C performed on the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
FIG. 11 is a TEM image of Sn elemental analysis of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
FIG. 12 is a TEM image of O elemental analysis of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
FIG. 13 is a TEM image of S element analysis of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
FIG. 14 is an XRD diffraction pattern of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
FIG. 15 is a Raman spectrum of a tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
fig. 16 is a thermogravimetric analysis chart of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7;
fig. 17 is a cycle curve of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The shell layer of the electrode material is tin oxide, the core layer is a carbonized aerogel microsphere, monomer sulfur is uniformly dispersed in the carbonized aerogel microsphere, and the mass of the monomer sulfur accounts for 60-80% of the total mass of the core-shell structure composite sulfur electrode material.
In the embodiment, the monomer sulfur is uniformly dispersed in the carbonized aerogel microspheres, the conductivity of the sulfur electrode is improved by compounding the monomer sulfur and the carbonized aerogel, and meanwhile, the carbonized aerogel can also inhibit the volume expansion of the sulfur in the electrochemical reaction process and prevent the structure of an electrode material from being damaged; the tin oxide shell layer limits sulfur in the gas carbide gel core layer, so that the seepage of sulfur in the charging and discharging process can be inhibited, and the shuttle effect of polysulfide ions can be inhibited; the composite sulfur electrode material keeps good cycling stability in the charging and discharging process.
Example 2
A tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material is characterized in that a shell layer of the electrode material is tin oxide, a core layer is carbonized aerogel microspheres, monomer sulfur is uniformly dispersed in the carbonized aerogel microspheres, and the mass of the monomer sulfur accounts for 65% of the total mass of the core-shell structure composite sulfur electrode material.
The thickness of the tin oxide shell layer in this embodiment is 5-15 nm, and the sphere diameter of the carbonized aerogel micro-sphere is 1-2 μm.
Example 3
The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material provided by the embodiment comprises the following steps:
step one, synthesizing the carbonized aerogel micro-spheres
Mixing resorcinol, formaldehyde and water according to a certain molar volume ratio, adding a certain mass of catalyst into the mixed system, and uniformly mixing to obtain a suspension; aging the suspension at a certain temperature for a certain time, collecting precipitates in the suspension, washing the precipitates with absolute ethyl alcohol and drying the precipitates; placing the dried precipitate in an inert gas atmosphere, and calcining at a certain temperature for a certain time to obtain the carbonized aerogel microspheres with a certain sphere diameter;
step two, preparing tin oxide/carbon aerogel core-shell structure microspheres
Putting the carbonized aerogel microspheres prepared in the step one into acid liquor for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2Pretreating the O pretreatment mixed solution at a certain temperature; collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2Stirring the mixed solution for a certain time in O pressure maintaining treatment, and maintaining the pressure of the obtained suspension at a certain temperature for a certain time to generate a tin oxide shell layer with a certain thickness on the surface of the carbon aerogel microspheres; collecting the precipitate in the mixed solution after pressure maintaining, washing the precipitate with absolute ethyl alcohol and drying the precipitate; placing the dried precipitate in an inert gas atmosphere, and calcining at a certain temperature for a certain time to obtain tin oxide/carbon aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material
Fully mixing the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two with sulfur powder according to a certain mass ratio; and (3) carrying out sulfur steaming treatment at a certain temperature in an inert gas atmosphere to prepare the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material.
Example 4
The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material provided by the embodiment comprises the following steps:
step one, synthesizing the carbonized aerogel micro-spheres
According to the mol volume ratio of resorcinol, formaldehyde and water of 1mol:2mol: mixing resorcinol, formaldehyde and water by 15mL, and adding catalyst Na into the mixed system2CO3，Na2CO3Uniformly mixing the resorcinol and the organic solvent according to the mass ratio of 1:250 to obtain a suspension; placing the suspension in a sealed bottleAging at 80 ℃ for 5 days, collecting the precipitate in the suspension, washing the precipitate with absolute ethyl alcohol, and drying at 60-90 ℃; calcining the dried precipitate in nitrogen or argon atmosphere at 800 ℃ for 1-3 h to obtain carbonized aerogel microspheres with the sphere diameter of 1-2 microns;
step two, preparing tin oxide/carbon aerogel core-shell structure microspheres
Putting the carbonized aerogel microspheres prepared in the step one into acid liquor for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2Pretreating the O pretreatment mixed solution at a certain temperature; collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2Stirring the mixed solution for a certain time in O pressure maintaining treatment, and maintaining the pressure of the obtained suspension at a certain temperature for a certain time to generate a tin oxide shell layer with a certain thickness on the surface of the carbon aerogel microspheres; collecting the precipitate in the mixed solution after pressure maintaining, washing the precipitate with absolute ethyl alcohol and drying the precipitate; placing the dried precipitate in an inert gas atmosphere, and calcining at a certain temperature for a certain time to obtain tin oxide/carbon aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material
Fully mixing the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two with sulfur powder according to a certain mass ratio; and (3) carrying out sulfur steaming treatment at a certain temperature in an inert gas atmosphere to prepare the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material.
The carbonized aerogel microspheres with the sphere diameter of 1-2 microns, which are obtained through reasonable raw material proportion and aging conditions, are a novel light, porous and amorphous micron material, have a large specific surface area and are conductive; the porosity of the electrode material is up to 80-98% through measurement, so that the loading capacity of the sulfur monomer can be greatly improved, and meanwhile, the carbonized aerogel can inhibit the volume expansion of sulfur in the electrochemical reaction process and prevent the structure of the electrode material from being damaged.
Example 5
The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material provided by the embodiment comprises the following steps:
step one, synthesizing the carbonized aerogel micro-spheres
According to the mol volume ratio of resorcinol, formaldehyde and water of 1mol:2mol: mixing resorcinol, formaldehyde and water by 15mL, and adding catalyst Na into the mixed system2CO3，Na2CO3Uniformly mixing the resorcinol and the organic solvent according to the mass ratio of 1:250 to obtain a suspension; placing the suspension in a sealed bottle, aging at 80 ℃ for 5d, collecting precipitates in the suspension, washing the precipitates with absolute ethyl alcohol, and drying at 60-90 ℃; calcining the dried precipitate in nitrogen or argon atmosphere at 800 ℃ for 1-3 h to obtain carbonized aerogel microspheres with the sphere diameter of 1-2 microns;
step two, preparing tin oxide/carbon aerogel core-shell structure microspheres
Putting the carbonized aerogel microspheres prepared in the step one into acid liquor prepared by nitric acid with the mass concentration of 70% and sulfuric acid with the mass concentration of 37% according to the volume ratio of 1:3 for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pretreatment mixed solution, the molar concentration of NaOH in the solution is 0.106mol/L, and SnCl2·2H2The molar concentration of O is 0.1mol/L, and the pretreatment is carried out for 10-16 h at 70 ℃;
collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pressure maintaining treatment mixed solution, the molar concentration of NaOH in the solution is 0.075mol/L, and SnCl2·2H2The molar concentration of O is 0.2mol/L, stirring is carried out for 15-30 min, 60mL of turbid liquid is placed in a 100mL polytetrafluoroethylene inner container, the inner container is placed in a stainless steel autoclave, the pressure is kept at 1-3 MPa at 200 ℃, the pressure keeping time is 40-50 h, and a tin oxide shell layer with the thickness of 5-15 nm is generated on the surface of the carbonized aerogel microspheres; after pressure maintaining is finished, collecting precipitates in the mixed solution, washing the precipitates with absolute ethyl alcohol, and drying at 60-90 ℃; after dryingCalcining the precipitate in nitrogen or argon atmosphere at 300 ℃ for 2-3 h to obtain the tin oxide/carbonized aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material
Fully mixing the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two with sulfur powder according to a certain mass ratio; and (3) carrying out sulfur steaming treatment at a certain temperature in an inert gas atmosphere to prepare the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material.
In the step of this embodiment, the surface of the carbonized aerogel microspheres is activated by using an acid solution, so that the surface of the microspheres is easier to be anchored by Sn; the pretreatment step enables rough anchoring Sn-based active sites to grow on the surface of the carbonized aerogel microspheres so as to facilitate the continuous growth of SnO on the anchoring sites2Granules, SnCl after calcination at 300 ℃2The thickness of the tin oxide shell is 5 to 15 nm. The tin oxide shell layer limits sulfur in the gas carbide gel core layer, so that the seepage of sulfur in the charging and discharging process can be inhibited, and the shuttle effect of polysulfide ions can be inhibited.
Example 6
The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material provided by the embodiment comprises the following steps:
step one, synthesizing the carbonized aerogel micro-spheres
According to the mol volume ratio of resorcinol, formaldehyde and water of 1mol:2mol: mixing resorcinol, formaldehyde and water by 15mL, and adding catalyst Na into the mixed system2CO3，Na2CO3Uniformly mixing the resorcinol and the organic solvent according to the mass ratio of 1:250 to obtain a suspension; placing the suspension in a sealed bottle, aging at 80 ℃ for 5d, collecting precipitates in the suspension, washing the precipitates with absolute ethyl alcohol, and drying at 60-90 ℃; calcining the dried precipitate in nitrogen or argon atmosphere at 800 ℃ for 1-3 h to obtain carbonized aerogel microspheres with the sphere diameter of 1-2 microns;
step two, preparing tin oxide/carbon aerogel core-shell structure microspheres
Putting the carbonized aerogel microspheres prepared in the step one into acid liquor prepared by nitric acid with the mass concentration of 70% and sulfuric acid with the mass concentration of 37% according to the volume ratio of 1:3 for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pretreatment mixed solution, the molar concentration of NaOH in the solution is 0.106mol/L, and SnCl2·2H2The molar concentration of O is 0.1mol/L, and the pretreatment is carried out for 10-16 h at 70 ℃;
collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pressure maintaining treatment mixed solution, the molar concentration of NaOH in the solution is 0.075mol/L, and SnCl2·2H2The molar concentration of O is 0.2mol/L, stirring is carried out for 15-30 min, 60mL of turbid liquid is placed in a 100mL polytetrafluoroethylene inner container, the inner container is placed in a stainless steel autoclave, the pressure is kept at 1-3 MPa at 200 ℃, the pressure keeping time is 40-50 h, and a tin oxide shell layer with the thickness of 5-15 nm is generated on the surface of the carbonized aerogel microspheres; after pressure maintaining is finished, collecting precipitates in the mixed solution, washing the precipitates with absolute ethyl alcohol, and drying at 60-90 ℃; calcining the dried precipitate in nitrogen or argon atmosphere at 300 ℃ for 2-3 h to obtain the tin oxide/carbon aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material
Mixing and grinding the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two and sulfur powder according to the mass ratio of the tin oxide/carbon aerogel core-shell structure microspheres to the sulfur powder of 2: 8-4: 6, and uniformly mixing the tin oxide/carbon aerogel core-shell structure microspheres and the sulfur powder together; and (3) putting the mixed powder into a reaction kettle with a polytetrafluoroethylene lining in an argon atmosphere, and carrying out sulfur steaming treatment at 145-160 ℃ for 12-20 h to obtain the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material, wherein the mass of the monomer sulfur accounts for 60-80% of the total mass of the core-shell structure composite sulfur electrode material.
In the embodiment, the monomer sulfur can permeate into the tin oxide/carbonized aerogel microspheres through sulfur steaming treatment and is uniformly dispersed in the nuclear layer carbonized aerogel microspheres, so that the microspherical composite sulfur electrode material with stable structure, regular appearance and uniform particle size is obtained. When the micron spherical composite sulfur electrode material with regular appearance and uniform particle size is used for preparing the lithium sulfur battery, the electrode material can be tightly stacked to form a smooth and uniform electrode structure, so that effective transmission of ions and electrons is better realized.
Example 7
The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material provided by the embodiment comprises the following steps:
step one, synthesizing the carbonized aerogel micro-spheres
According to the mol volume ratio of resorcinol, formaldehyde and water of 1mol:2mol: mixing resorcinol, formaldehyde and water by 15mL, and adding catalyst Na into the mixed system2CO3，Na2CO3Uniformly mixing the resorcinol and the organic solvent according to the mass ratio of 1:250 to obtain a suspension; aging the suspension at 80 deg.C for 5d in a sealed bottle, collecting precipitate, washing the precipitate with anhydrous ethanol, and drying at 70 deg.C; calcining the dried precipitate in a nitrogen atmosphere at 800 ℃ for 2h to obtain carbonized aerogel microspheres with the sphere diameter of 1-2 microns;
step two, preparing tin oxide/carbon aerogel core-shell structure microspheres
Putting the carbonized aerogel microspheres prepared in the step one into acid liquor prepared by nitric acid with the mass concentration of 70% and sulfuric acid with the mass concentration of 37% according to the volume ratio of 1:3 for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pretreatment mixed solution, the molar concentration of NaOH in the solution is 0.106mol/L, and SnCl2·2H2The molar concentration of O is 0.1mol/L, and the pretreatment is carried out for 12 hours at 70 ℃;
collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pressure maintaining treatment mixed solution, the molar concentration of NaOH in the solution is 0.075mol/L, and SnCl2·2H2The molar concentration of O is 0.2mol/L, stirring is carried out for 15min, 60mL of suspension is placed in a 100mL polytetrafluoroethylene liner,placing the inner container in a stainless steel autoclave, keeping the pressure of 2MPa at 200 ℃, and keeping the pressure for 48 hours to generate a tin oxide shell layer with the thickness of 5-15 nm on the surface of the carbonized aerogel microspheres; collecting precipitate in the mixed solution after maintaining pressure, washing the precipitate with anhydrous ethanol, and drying at 70 deg.C; calcining the dried precipitate in nitrogen atmosphere at 300 ℃ for 2h to obtain the tin oxide/carbon aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material
Mixing and grinding the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two and sulfur powder according to the mass ratio of the tin oxide/carbon aerogel core-shell structure microspheres to the sulfur powder of 4:6, so that the tin oxide/carbon aerogel core-shell structure microspheres and the sulfur powder are uniformly mixed together; and (3) putting the mixed powder into a reaction kettle with a polytetrafluoroethylene lining in an argon atmosphere, and carrying out sulfur steaming treatment at 145 ℃ for 12h to prepare the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material, wherein the mass of the monomer sulfur accounts for 60% of the total mass of the core-shell structure composite sulfur electrode material.
Fig. 1 and 2 are SEM images of carbonized aerogel micro beads prepared in example 7 at 5000 and 10000 times magnification, respectively; as can be seen from the figure 1-2, the surface of the carbon aerogel micron sphere is smooth, and the diameter of the carbon aerogel micron sphere is 1-2 microns;
FIG. 3 is an SEM image of the carbonized aerogel micro-spheres of example 7 after pretreatment at 16000 magnification; as can be seen from FIG. 3, rough anchoring SnO grows on the surface of the pretreated carbon aerogel microspheres2A site.
FIG. 4 is an SEM image of core-shell structured microspheres of tin oxide/aerogel carbide prepared in example 7 at 10000 times magnification; as can be seen from FIG. 4, the surface of the carbon aerogel micro-spheres is coated with SnO2The structure of the micro-spheres is complete and the surface becomes rough when the particles are covered.
FIG. 5 is an SEM image of 10000 times magnification of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7; as can be seen from FIG. 5, the basic structure of the tin oxide/aerogel carbide core-shell structure microspheres after sulfur evaporation treatment is not changed, which indicates that the monomer sulfur has penetrated into the microspheres.
FIGS. 6 and 7 are TEM images of core-shell structured microspheres of tin oxide/carbon aerogel prepared in example 7 at 2 ten thousand and 10 ten thousand magnifications; as can be seen from FIGS. 6 and 7, the tin oxide/aerogel carbide core-shell structure microspheres are circular structures having a core layer of aerogel carbide microspheres with a sphere diameter of about 1 μm and SnO with a thickness of about 10nm2A shell layer formed by the particles.
FIG. 8 is a HRTEM image at 50 ten thousand times magnification of core-shell structured microspheres of tin oxide/carbon aerogel prepared in example 7; as can be seen from FIG. 8, the lattice analysis interplanar spacings 0.33nm, 0.37nm, 0.38nm and 0.41nm correspond to SnO of the (101), (200), (111) and (021) planes2The structure of the nanoparticle crystal chain is SnO according to the standard crystal card2(JCPDS No. 21-1250).
Fig. 9 to 13 are TEM images of total element, C element, Sn element, O element and S element analyses performed on the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7; comparison of fig. 9-13 confirms the presence of tin oxide, carbon aerogel micro-spheres and sulfur in the samples. The element analysis of C, Sn, O and S elements shows that the elements are uniformly distributed in the structure of the tin oxide/carbon aerogel/sulfur microspheres. Wherein C, S element is present in the core of the aerogel carbon microspheres and Sn, O elements are present in the shell of the tin oxide nanoparticles, it is clear from these elemental analyses that the presence of tin oxide, aerogel carbon microspheres and sulfur, comprising the core of aerogel carbon microspheres and the shell of tin oxide nanoparticles, and sulfur is present inside aerogel carbon microspheres, can be demonstrated.
FIG. 14 is an XRD diffraction pattern of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7; as can be seen from fig. 14, the tin oxide/carbon aerogel/sulfur core-shell structure microspheres all have a tin oxide diffraction peak with a very high peak intensity in the spectrum, which can prove the existence of tin oxide. However, the diffraction peak of the carbon aerogel microspheres cannot be seen in the diffraction pattern, and the raman pattern is measured in the detection of the carbon material because the 26.6-degree peak in the tin oxide is very close to the 26.4-degree carbon peak.
FIG. 15 is a drawing showingThe raman spectrum of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7; the presence of carbon material can be seen in FIG. 15, and it can also be seen that a typical 634cm sample is present-1，486cm-1And 706cm-1The peak position of (1) is the Raman peak of the tin oxide nanoparticles, and the two strong peaks are positioned at 1348cm-1D peak and 1568cm-1Typical of carbon aerogel micro-spheres.
Comparing the raman spectrum in fig. 15 with the XRD diffraction pattern in fig. 14 shows that a core layer containing aerogel carbon microspheres and a shell layer of tin oxide nanoparticles are present in the tin oxide/aerogel carbon core-shell structure composite sulfur electrode material.
Fig. 16 is a thermogravimetric analysis chart of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7; as can be seen from the thermogravimetric curve of the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material shown in fig. 16, the mass of sulfur accounts for 60% of the total mass of the core-shell structure composite sulfur electrode material.
Fig. 17 is a cycle curve of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material prepared in example 7, and it can be seen from fig. 17 that, under the current density of 0.1C, the capacity retention performance of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material is very good after charging and discharging for 100 cycles.
Meanwhile, under the current density of 0.1C, the charging capacity of the stabilized tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material is up to 1393Ah g-1And the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material still keeps more than 970mAh g after 100 cycle periods-1Showing good cycling performance, maintaining a capacity of more than 70.2% indicates that the electrode material is able to maintain its structure relatively stable after a large current surge.
Example 8
The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material provided by the embodiment comprises the following steps:
step one, synthesizing the carbonized aerogel micro-spheres
According to the mol volume ratio of resorcinol, formaldehyde and water of 1mol:2mol: mixing resorcinol, formaldehyde and water by 15mL, and adding catalyst Na into the mixed system2CO3，Na2CO3Uniformly mixing the resorcinol and the organic solvent according to the mass ratio of 1:250 to obtain a suspension; aging the suspension in a sealed bottle at 80 deg.C for 5d, collecting precipitate, washing the precipitate with anhydrous ethanol, and drying at 80 deg.C; placing the dried precipitate in an argon atmosphere, and calcining at 800 ℃ for 3h to obtain carbonized aerogel microspheres with the sphere diameter of 1-2 microns;
step two, preparing tin oxide/carbon aerogel core-shell structure microspheres
Putting the carbonized aerogel microspheres prepared in the step one into acid liquor prepared by nitric acid with the mass concentration of 70% and sulfuric acid with the mass concentration of 37% according to the volume ratio of 1:3 for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pretreatment mixed solution, the molar concentration of NaOH in the solution is 0.106mol/L, and SnCl2·2H2The molar concentration of O is 0.1mol/L, and the pretreatment is carried out for 14h at 70 ℃;
collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pressure maintaining treatment mixed solution, the molar concentration of NaOH in the solution is 0.075mol/L, and SnCl2·2H2The molar concentration of O is 0.2mol/L, stirring is carried out for 20min, 60mL of turbid liquid is placed in a 100mL polytetrafluoroethylene inner container, the inner container is placed in a stainless steel autoclave, the pressure of 3MPa is kept at 200 ℃, the pressure maintaining time is 45h, and a tin oxide shell layer with the thickness of 5-15 nm is generated on the surface of the carbonized aerogel microsphere; collecting precipitate in the mixed solution after maintaining pressure, washing the precipitate with anhydrous ethanol, and drying at 80 deg.C; placing the dried precipitate in an argon atmosphere, and calcining for 3h at 300 ℃ to obtain the tin oxide/carbon aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material
Mixing and grinding the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two and sulfur powder according to the mass ratio of the tin oxide/carbon aerogel core-shell structure microspheres to the sulfur powder of 3:7 to uniformly mix the tin oxide/carbon aerogel core-shell structure microspheres and the sulfur powder together; and (3) in an argon atmosphere, putting the mixed powder into a reaction kettle with a polytetrafluoroethylene lining, and carrying out sulfur steaming treatment at 155 ℃ for 18h to prepare the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material, wherein the mass of the monomer sulfur accounts for 70% of the total mass of the core-shell structure composite sulfur electrode material.
Example 9
The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material provided by the embodiment comprises the following steps:
step one, synthesizing the carbonized aerogel micro-spheres
According to the mol volume ratio of resorcinol, formaldehyde and water of 1mol:2mol: mixing resorcinol, formaldehyde and water by 15mL, and adding catalyst Na into the mixed system2CO3，Na2CO3Uniformly mixing the resorcinol and the organic solvent according to the mass ratio of 1:250 to obtain a suspension; aging the suspension at 80 deg.C for 5d in a sealed bottle, collecting precipitate, washing the precipitate with anhydrous ethanol, and drying at 70 deg.C; calcining the dried precipitate in a nitrogen atmosphere at 800 ℃ for 2h to obtain carbonized aerogel microspheres with the sphere diameter of 1-2 microns;
step two, preparing tin oxide/carbon aerogel core-shell structure microspheres
Putting the carbonized aerogel microspheres prepared in the step one into acid liquor prepared by nitric acid with the mass concentration of 70% and sulfuric acid with the mass concentration of 37% according to the volume ratio of 1:3 for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pretreatment mixed solution, the molar concentration of NaOH in the solution is 0.106mol/L, and SnCl2·2H2The molar concentration of O is 0.1mol/L, and the pretreatment is carried out for 12 hours at 70 ℃;
collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2In the O pressure maintaining treatment mixed solution, the molar concentration of NaOH in the solution is 0.075mol/L, and SnCl2·2H2The molar concentration of O is 0.2mol/L, stirring is carried out for 15min, 60mL of turbid liquid is placed in a 100mL polytetrafluoroethylene inner container, the inner container is placed in a stainless steel autoclave, the pressure of 1MPa is kept at 200 ℃, the pressure maintaining time is 48h, and a tin oxide shell layer with the thickness of 5-15 nm is generated on the surface of the carbonized aerogel microsphere; collecting precipitate in the mixed solution after maintaining pressure, washing the precipitate with anhydrous ethanol, and drying at 70 deg.C; calcining the dried precipitate in nitrogen atmosphere at 300 ℃ for 2h to obtain the tin oxide/carbon aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material
Mixing and grinding the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two and sulfur powder according to the mass ratio of the tin oxide/carbon aerogel core-shell structure microspheres to the sulfur powder of 2:8, and uniformly mixing the tin oxide/carbon aerogel core-shell structure microspheres and the sulfur powder together; and (3) putting the mixed powder into a reaction kettle with a polytetrafluoroethylene lining in an argon atmosphere, and carrying out sulfur steaming treatment at 145 ℃ for 12h to prepare the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material, wherein the mass of the monomer sulfur accounts for 80% of the total mass of the core-shell structure composite sulfur electrode material.
Claims (7)
1. A preparation method of a tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material is characterized by comprising the following steps:
step one, synthesizing a carbonized aerogel micro-sphere:
mixing resorcinol, formaldehyde and water according to a certain molar volume ratio, adding a certain mass of catalyst into the mixed system, and uniformly mixing to obtain a suspension; aging the suspension at a certain temperature for a certain time, collecting precipitates in the suspension, washing the precipitates with absolute ethyl alcohol and drying the precipitates; placing the dried precipitate in an inert gas atmosphere, and calcining at a certain temperature for a certain time to obtain the carbonized aerogel microspheres with a certain sphere diameter;
step two, preparing the tin oxide/carbon aerogel core-shell structure microspheres:
will be described in detailFirstly, putting the prepared carbonized aerogel micro-spheres into acid liquor for surface activation; collecting surface activated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2Pretreating the O pretreatment mixed solution at a certain temperature; collecting the pretreated carbon aerogel micro-spheres and placing the micro-spheres in NaOH and SnCl2·2H2Stirring the mixed solution for a certain time in O pressure maintaining treatment, and maintaining the pressure of the obtained suspension at a certain temperature for a certain time to generate a tin oxide shell layer with a certain thickness on the surface of the carbon aerogel microspheres; collecting the precipitate in the mixed solution after pressure maintaining, washing the precipitate with absolute ethyl alcohol and drying the precipitate; placing the dried precipitate in an inert gas atmosphere, and calcining at a certain temperature for a certain time to obtain tin oxide/carbon aerogel core-shell structure microspheres;
step three, preparing the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material:
fully mixing the tin oxide/carbon aerogel core-shell structure microspheres prepared in the step two with sulfur powder according to a certain mass ratio; and (3) carrying out sulfur steaming treatment at a certain temperature in an inert gas atmosphere to prepare the tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material.
2. The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material according to claim 1, wherein the molar volume ratio of the resorcinol, the formaldehyde and the water in the step one is 1mol:2mol:15 mL; the catalyst is Na2CO3Said Na2CO3The mass ratio of the resorcinol to the resorcinol is 1: 250; the ageing temperature of the suspension is 80 ℃, and the ageing time is 5 d.
3. The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material according to claim 1 or 2, wherein the drying temperature of the precipitate in the first step is 60-90 ℃; the inert gas is nitrogen or argon, the calcining temperature is 800 ℃, and the calcining time is 1-3 h; the diameter of the carbonized aerogel microspheres is 1-2 μm.
4. The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material according to claim 3, wherein the acid solution in the second step is prepared from nitric acid with a mass concentration of 70% and sulfuric acid with a mass concentration of 37% according to a volume ratio of 1: 3; the NaOH and SnCl2·2H2The molar concentration of NaOH in the O pretreatment mixed solution is 0.106mol/L, and SnCl2·2H2The molar concentration of O is 0.1 mol/L; the pretreatment temperature is 70 ℃, and the pretreatment time is 10-16 h.
5. The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material according to claim 4, wherein NaOH and SnCl are added in the second step2·2H2The molar concentration of NaOH in the O pressure maintaining treatment mixed solution is 0.075mol/L, and SnCl2·2H2The molar concentration of O is 0.2 mol/L; the stirring time is 15-30 min.
6. The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material according to claim 5, wherein the pressure maintaining pressure in the second step is 1-3 MPa, the pressure maintaining temperature is 200 ℃, and the pressure maintaining time is 40-50 h; the thickness of the tin oxide shell layer is 5-15 nm; the drying temperature of the precipitate is 60-90 ℃; the inert gas is nitrogen or argon, the calcining temperature is 300 ℃, and the calcining time is 2-3 h.
7. The preparation method of the tin oxide/carbon aerogel core-shell structure composite sulfur electrode material according to claim 6, wherein the mass ratio of the tin oxide/carbon aerogel core-shell structure microspheres to the sulfur powder in the third step is 2: 8-4: 6; the inert gas is argon; the temperature is 145-160 ℃, and the time of sulfur steaming treatment is 12-20 h.
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