CN114604892A - Preparation method of double-doped hollow sphere material and application of double-doped hollow sphere material in lithium-sulfur battery - Google Patents
Preparation method of double-doped hollow sphere material and application of double-doped hollow sphere material in lithium-sulfur battery Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 78
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- -1 metal oxide sulfate Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 10
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229930182817 methionine Natural products 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 239000005077 polysulfide Substances 0.000 abstract description 4
- 229920001021 polysulfide Polymers 0.000 abstract description 4
- 150000008117 polysulfides Polymers 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
- 210000003739 neck Anatomy 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- C01F11/00—Compounds of calcium, strontium, or barium
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Abstract
The invention discloses a preparation method of a double-doped hollow sphere material and application of the double-doped hollow sphere material in a lithium-sulfur battery, belonging to the technical field of lithium-sulfur batteries, and the preparation method of the double-doped hollow sphere material comprises the following steps: s1: the metal oxide sulfate, the acid solvent, the commercial aluminum powder and the deionized water are mixed according to a molar ratio of 1: 2-10: 2-5: 5-50, uniformly mixing; s2: stirring, filtering and cleaning the solution; s3: placing the cleaned sample in a drying box for drying, and then placing the dried sample in a tubular furnace, wherein organic matters containing nitrogen and sulfur are placed at the upper end of the tubular furnace; s4: introducing gas, heating, preserving heat and cooling to obtain the double-doped hollow ball material; the double-doped hollow sphere material prepared by the invention is used as an additive material of a sulfur electrode of a lithium sulfur battery, so that the cycling stability and the electrode multiplying power characteristic of the lithium sulfur battery are obviously improved; solves the problem of shuttle effect of the prior lithium polysulfide.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a preparation method of a double-doped hollow sphere material and application of the double-doped hollow sphere material in a lithium-sulfur battery.
Background
The lithium-sulfur battery has a theoretical specific capacity of 1672mAh/g and a theoretical mass specific energy density of 2600wh/kg, is far higher than the ternary material battery widely applied commercially, and is a lithium battery with very promising prospect. In recent years, the increasing demand for energy density of batteries by new electronic products and new energy automobiles has greatly stimulated the development and research enthusiasm of lithium-sulfur batteries. However, some key problems of the lithium-sulfur battery also exist, and the lithium-sulfur battery needs to be solved urgently, and in the aspect of a sulfur positive electrode, the lower electrochemical performance is caused by the following main points: (i) elemental sulfur and polysulfides are electrical insulators (conductivity 5X 10)-30S/cm) such that a portion of the elemental sulfur carried by the electrode during discharge is unable to follow the reaction S +2Li++2e-→Li2S proceeds, resulting in low utilization of sulfur; (ii) during the reaction, polysulfide (i.e. Li) is formed2S8，Li2S6，Li2S4) The lithium ion battery is very easy to dissolve in common ether electrolyte and shuttles back and forth between a positive electrode and a negative electrode in the charging and discharging process to form a shuttle effect; (iii) byThe density of the reactant and the product in the positive electrode of the battery is different, and the volume of the positive electrode expands (maximum 80%) after discharge, and the volume of the electrode repeatedly changes during a long-term charge-discharge cycle, so that the active material is easily separated from the current collector, and the cycle performance is reduced.
Therefore, a proper sulfur acceptor material needs to be prepared, so that the whole electrical conductivity of the electrode can be improved, the shuttle effect of lithium polysulfide can be effectively prevented, and the volume expansion of the sulfur electrode can be fully adapted.
Disclosure of Invention
The invention aims to provide a preparation method of a double-doped hollow sphere material and application of the double-doped hollow sphere material in a lithium-sulfur battery, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a double-doped hollow sphere material comprises the following steps:
s1: the metal oxide sulfate, the acid solvent, the commercial aluminum powder and the deionized water are mixed according to a molar ratio of 1: 2-10: 2-5: 5-50, uniformly mixing under the stirring action;
s2: after stirring for 8-20 hours, filtering or centrifuging the solution, and then cleaning for 2-5 times;
s3: placing the cleaned sample in a drying oven at 30-200 ℃ for drying for 2-10 hours, and then placing the dried sample in a tubular furnace, wherein organic matters containing nitrogen and sulfur with the mass 1-5 times that of the front-end dried sample are placed at the upper end of the tubular furnace;
s4: after the material is placed in a tube furnace, heating to 300-500 ℃ for heat preservation for 1-6 hours under the condition of introducing gas flow of 10-30 ml/s, and cooling to obtain the double-doped hollow ball material.
As a further scheme of the invention: the metal oxide sulfate, the acid solvent, the commercial aluminum powder and the deionized water are mixed according to a molar ratio of 1: 4: 4: 10 stirring and mixing.
As a further scheme of the invention: in step S2, the solution is filtered or centrifuged for 8 to 18 hours, and then washed with deionized water 1 time, then with alcohol 1 time, and then with deionized water 1 time.
As a further scheme of the invention: in step S2, the solution is filtered or centrifuged for 12 hours, and then washed with deionized water 1 time, then with alcohol 1 time, and then with deionized water 1 time
As a further scheme of the invention: in the step S3, the cleaned sample is placed in a drying oven at 60-180 ℃ for drying for 8-10 hours, and then the dried sample is placed in a tube furnace, wherein the upper end of the tube furnace is provided with organic matters containing nitrogen and sulfur, the mass of which is 2 times of that of the front-end dried sample.
As a further scheme of the invention: in the step S3, the cleaned sample is placed in a drying oven at 60 ℃ for drying for 8 hours, and then the dried sample is placed in a tube furnace, wherein the upper end of the tube furnace is placed with organic matters containing nitrogen and sulfur with the mass 2 times of that of the front-end dried sample
As a further scheme of the invention: the organic matter containing nitrogen and sulfur is one of thiourea and methionine.
As a further scheme of the invention: the organic matter containing nitrogen and sulfur is preferably thiourea.
As a further scheme of the invention: in the step S4, after the material is placed in a tube furnace, the material is heated to 400-450 ℃ and is kept for 2-6 hours under the condition that the gas flow is 15 ml/S, and the double-doped hollow sphere material can be obtained after cooling.
As a further scheme of the invention: in the step S4, after the material is placed in a tube furnace, the material is heated to 400 ℃ for heat preservation for 3 hours under the condition of introducing gas flow of 15 ml/S, and the double-doped hollow sphere material can be obtained after cooling.
As a further scheme of the invention: the metal oxide sulfate is one of titanyl sulfate, vanadyl sulfate and calcium oxysulfate.
The application of the double-doped hollow sphere material prepared by the preparation method of the double-doped hollow sphere in the lithium-sulfur battery comprises the following steps of:
(1) the double-doped hollow sphere material and elemental sulfur are mixed according to the mass ratio of 1: 2-5, heating the mixture of the two to 150-180 ℃ in a closed environment with variable volume, preserving heat for 10-30 minutes, and cooling to obtain the sulfur-loaded double-doped hollow sphere material;
(2) the sulfur-loaded double-doped hollow sphere material is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard 2400 is used as a diaphragm, 1 mol/L lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) is dissolved in 1, 3-dioxysilane and 1, 2-dimethoxyethane (v/v ═ 1:1) to be used as electrolyte, and the soft-package lithium-sulfur battery is assembled in a glove box.
As a further scheme of the invention: the double-doped hollow sphere material and elemental sulfur are mixed according to the mass ratio of 1: 4, uniformly mixing, heating the mixture of the two to 165 ℃ in a closed environment with variable volume, preserving heat for 20 minutes, and cooling to obtain the sulfur-loaded double-doped hollow sphere material.
Compared with the prior art, the invention has the beneficial effects that: the double-doped hollow sphere material prepared by the invention is used as an additive material of a sulfur electrode of a lithium sulfur battery, and is used for obviously improving the cycling stability and the electrode multiplying power characteristic of the lithium sulfur battery; the mass ratio in the preparation process of the sulfur electrode material is optimized, and an industrial technical support is provided for preparing the anode and cathode coating slurry with high dispersion, high viscosity and high electrochemical performance; the invention solves the problems of clamping necks existing in the commercial use of the sulfur electrode of the lithium-sulfur battery, provides experimental basis for designing an electrode material with good electrocatalytic activity, and has wide application space in the fields of electrochemical catalysis and energy storage of the additive.
Drawings
FIG. 1 is a scanning electron microscope curve of the double-doped hollow sphere material prepared in example 1.
Fig. 2 is a high-magnification scanning electron microscope curve of the double-doped hollow sphere material prepared in example 2.
FIG. 3 is a scanning electron microscope plot of sulfur loading of the dual-doped hollow sphere material prepared in example 3.
FIG. 4 is a high-magnification scanning electron microscope curve of sulfur-loaded double-doped hollow sphere material prepared in example 2.
FIG. 5 is an X-ray photoelectron spectrum of the double-doped hollow sphere material prepared in example 3.
FIG. 6 is an X-ray photoelectron spectrum of sulfur-loaded double-doped hollow sphere material prepared in example 2.
Fig. 7 is a sulfur-loading cycle profile for the dual-doped hollow sphere material prepared in example 1.
Fig. 8 is a charge and discharge curve of the sulfur-loaded dual-doped hollow sphere material prepared in example 2.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
Example 1
The method comprises the following steps: synthesis of double-doped hollow sphere material
(1) Titanyl sulfate and 0.1 mol/l sulfuric acid solvent, commercial aluminum powder and deionized water in a molar ratio of 1: 3: 3: 10 evenly mixing under the stirring action;
(2) after stirring for 12 hours, filtering the solution, washing the solution for 2 times by using deionized water, and washing the solution for 1 time by using alcohol in the middle;
(3) after drying the obtained sample in a drying oven at 80 ℃ for 8 hours, putting the dried sample in a tube furnace, wherein thiourea is placed at the upper end of the tube furnace, and the mass of the thiourea is 3 times that of the front-end dried sample.
(4) After the material is placed in a tubular furnace, the material is heated to 450 ℃ for 2 hours under the condition of introducing 15 ml/s of gas flow, and the temperature is kept for 2 hours, and the double-doped hollow sphere material can be obtained after cooling.
Step two: application of double-doped hollow sphere material in field of lithium-sulfur battery
(1) The mass ratio of the double-doped hollow spheres to the elemental sulfur is 1: 4, uniformly mixing, heating the mixture of the two to 165 ℃ in a closed environment with variable volume, preserving heat for 20 minutes, and cooling to obtain the sulfur-loaded double-doped hollow sphere material.
(2) The sulfur-loaded double-doped hollow sphere material is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard 2400 is used as a diaphragm, 1 mol/L lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) is dissolved in 1, 3-dioxysilane and 1, 2-dimethoxyethane (v/v ═ 1:1) to be used as electrolyte, and the soft-package lithium-sulfur battery is assembled in a glove box.
Example 2
The method comprises the following steps: synthesis of double-doped hollow sphere material
(1) Vanadyl sulfate and 0.1 mol/l hydrochloric acid solvent, commercial aluminum powder and deionized water in a molar ratio of 1: 2: 2: 10 evenly mixing under the stirring action;
(2) after stirring for 8 hours, centrifuging the solution, and washing with deionized water for 4 times;
(3) after drying the obtained sample in a drying oven at 60 ℃ for 10 hours, the dried sample was placed in a tube furnace, wherein methionine was placed at the upper end of the tube furnace in a mass 2 times that of the front end dried sample.
(4) After the material is placed in a tube furnace, the material is heated to 400 ℃ for heat preservation for 6 hours under the condition of introducing gas flow of 10 ml/s, and the double-doped hollow sphere material can be obtained after cooling.
Step two: application of double-doped hollow sphere material in field of lithium-sulfur battery
(1) The mass ratio of the double-doped hollow spheres to the elemental sulfur is 1: 2, uniformly mixing, heating the mixture of the two to 150 ℃ in a closed environment with variable volume, preserving heat for 30 minutes, and cooling to obtain the sulfur-loaded double-doped hollow sphere material.
(2) The sulfur-loaded double-doped hollow sphere material is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard 2400 is used as a diaphragm, 1 mol/L lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) is dissolved in 1, 3-dioxysilane and 1, 2-dimethoxyethane (v/v ═ 1:1) to be used as electrolyte, and the soft-package lithium-sulfur battery is assembled in a glove box.
Example 3
The method comprises the following steps: synthesis of double-doped hollow sphere material
(1) Calcium oxysulfate and 0.1 mol/l sulfuric acid solvent, commercial aluminum powder and deionized water in a molar ratio of 1: 8: 2: 50 are evenly mixed under the stirring action;
(2) after stirring for 18 hours, the solution was filtered and washed with alcohol 2 times;
(3) after drying the obtained sample in a drying oven at 180 ℃ for 2 hours, putting the dried sample in a tube furnace, wherein thiourea with the mass 2 times that of the front-end dried sample is placed at the upper end of the tube furnace.
(4) After the material is placed in a tube furnace, the material is heated to 450 ℃ for 1 hour under the condition of introducing gas flow of 30 ml/s, and the temperature is kept for 1 hour, and the double-doped hollow sphere material can be obtained after cooling.
Step two: application of double-doped hollow sphere material in field of lithium-sulfur battery
(1) The mass ratio of the double-doped hollow spheres to the elemental sulfur is 1: 3.5, uniformly mixing, heating the mixture of the two to 180 ℃ in a closed environment with variable volume, preserving the heat for 10 minutes, and cooling to obtain the sulfur-loaded double-doped hollow sphere material.
(2) The sulfur-loaded double-doped hollow sphere material is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard 2400 is used as a diaphragm, 1 mol/L lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) is dissolved in 1, 3-dioxysilane and 1, 2-dimethoxyethane (v/v ═ 1:1) to be used as electrolyte, and the electrolyte is assembled into the soft-package lithium-sulfur battery in a glove box.
The above examples material characterization and electrochemical performance test equipment:
and (3) morphology testing: a field emission scanning electron microscope and a high-resolution transmission electron microscope are used, the equipment names of which are FEI (scanning electron microscope) and G2F 20FEI Tecnai (high-resolution transmission electron microscope).
And (3) testing the structural performance of the material: use of the Raney-Stokes thermo K-Alpha X-ray photoelectron spectroscopy instrument
And (3) electrochemical performance testing: the cell was tested for cyclic voltammetry and ac impedance using the CHI6600E electrochemical workstation manufactured by shanghai chenhua corporation.
And (3) charge and discharge test: the maximum range of current and voltage is 20mA and 5V respectively using the Wuhan blue electricity battery test system.
In summary, the following steps: the double-doped hollow sphere material prepared by the invention is used as an additive material of a sulfur electrode of a lithium sulfur battery, and can obviously improve the cycle stability and the electrode multiplying power characteristic of the lithium sulfur battery; the mass ratio in the preparation process of the sulfur electrode material is optimized, and an industrial technical support is provided for preparing the anode and cathode coating slurry with high dispersion, high viscosity and high electrochemical performance; the invention solves the problems of clamping necks existing in the commercial use of the sulfur electrode of the lithium-sulfur battery, provides experimental basis for designing an electrode material with good electrocatalytic activity, and has wide application space in the fields of electrochemical catalysis and energy storage of the additive.
The present invention is not limited to the above-described embodiments, and various changes and modifications of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.
Claims (7)
1. A preparation method of a double-doped hollow sphere material is characterized by comprising the following steps:
s1: the metal oxide sulfate, the acid solvent, the commercial aluminum powder and the deionized water are mixed according to a molar ratio of 1: 2-10: 2-5: 5-50, uniformly mixing under the stirring action;
s2: after stirring for 8-20 hours, filtering or centrifuging the solution, and then cleaning for 2-5 times;
s3: placing the cleaned sample in a drying oven at 30-200 ℃ for drying for 2-10 hours, and then placing the dried sample in a tubular furnace, wherein organic matters containing nitrogen and sulfur with the mass 1-5 times that of the front-end dried sample are placed at the upper end of the tubular furnace;
s4: after the material is placed in a tube furnace, heating to 300-500 ℃ for heat preservation for 1-6 hours under the condition of introducing gas flow of 10-30 ml/s, and cooling to obtain the double-doped hollow sphere material.
2. The method of claim 1, wherein the stirring time is 8-18 hours in the step of S2, the solution is filtered or centrifuged, and then washed with deionized water for 1 time, then washed with alcohol for 1 time, and then washed with deionized water for 1 time.
3. The method of claim 1, wherein in the step S3, the cleaned sample is dried in a drying oven at 60-180 ℃ for 8-10 hours, and then the dried sample is placed in a tube furnace, wherein the upper end of the tube furnace is placed with organic substances containing nitrogen and sulfur, the mass of which is 2 times of the mass of the front-end dried sample.
4. The method for preparing the double-doped hollow sphere material according to claim 3, wherein the organic matter containing nitrogen and sulfur is one of thiourea and methionine.
5. The method as claimed in claim 1, wherein in step S4, the material is placed in a tube furnace, heated to 400-450 ℃ under the condition of 15 ml/S of gas flow, and kept for 2-6 hours, and then cooled to obtain the double-doped hollow sphere material.
6. The method as claimed in claim 1, wherein the metal oxide sulfate is one of titanyl sulfate, vanadyl sulfate, and calcium oxysulfate.
7. The application of the double-doped hollow sphere material prepared by the preparation method of the double-doped hollow sphere material in the lithium-sulfur battery is characterized in that the preparation method of the lithium-sulfur battery by using the double-doped hollow sphere material comprises the following steps:
(1) the double-doped hollow sphere material and elemental sulfur are mixed according to the mass ratio of 1: 2-5, heating the mixture of the two to 150-180 ℃ in a closed environment with variable volume, preserving heat for 10-30 minutes, and cooling to obtain the sulfur-loaded double-doped hollow sphere material;
(2) the sulfur-loaded double-doped hollow sphere material is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard 2400 is used as a diaphragm, 1 mol/L lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) is dissolved in 1, 3-dioxysilane and 1, 2-dimethoxyethane (v/v ═ 1:1) to be used as electrolyte, and the soft-package lithium-sulfur battery is assembled in a glove box.
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| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN103746095A (en) * | 2013-12-18 | 2014-04-23 | 广西科技大学 | Carbon-sulfur composite positive pole material and preparation method thereof |
| CN109599535A (en) * | 2017-09-30 | 2019-04-09 | 天津大学 | Carbon fluoride nano-tube/carbon nanotube sponge composite material and preparation method for lithium-sulphur cell positive electrode |
| CN113972381A (en) * | 2021-10-22 | 2022-01-25 | 广东技术师范大学 | Sulfur electrode electrochemical reaction dual-function catalyst and preparation method thereof |
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| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN103746095A (en) * | 2013-12-18 | 2014-04-23 | 广西科技大学 | Carbon-sulfur composite positive pole material and preparation method thereof |
| CN109599535A (en) * | 2017-09-30 | 2019-04-09 | 天津大学 | Carbon fluoride nano-tube/carbon nanotube sponge composite material and preparation method for lithium-sulphur cell positive electrode |
| CN113972381A (en) * | 2021-10-22 | 2022-01-25 | 广东技术师范大学 | Sulfur electrode electrochemical reaction dual-function catalyst and preparation method thereof |
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