CN109616647B - Three-dimensional ordered porous hydrogel-loaded sulfur particle composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery - Google Patents
Three-dimensional ordered porous hydrogel-loaded sulfur particle composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000000017 hydrogel Substances 0.000 title claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 56
- 239000002245 particle Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000767 polyaniline Polymers 0.000 claims abstract description 42
- 239000004793 Polystyrene Substances 0.000 claims description 48
- 229920002223 polystyrene Polymers 0.000 claims description 48
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 9
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229940068041 phytic acid Drugs 0.000 claims description 9
- 235000002949 phytic acid Nutrition 0.000 claims description 9
- 239000000467 phytic acid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000003958 fumigation Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 abstract description 7
- 239000005077 polysulfide Substances 0.000 abstract description 7
- 150000008117 polysulfides Polymers 0.000 abstract description 7
- 239000010406 cathode material Substances 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000005457 ice water Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 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 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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Abstract
The invention provides a three-dimensional ordered porous structure hydrogel loaded sulfur particle composite material and a preparation method thereof, a lithium sulfur battery anode and a lithium sulfur battery. The prepared polyaniline sulfur-loaded three-dimensional ordered porous structure composite material has a good three-dimensional structure and a large comparative area, is beneficial to loading more sulfur particles and has good conductivity; moreover, polysulfide can be combined, and the shuttle effect of the polysulfide is relieved; the lithium-sulfur battery cathode material has high capacity and good cycle performance.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a three-dimensional ordered porous hydrogel sulfur particle-loaded composite material, a preparation method thereof, a lithium-sulfur battery positive electrode and a lithium-sulfur battery.
Background
With the increasing prominence of resource problems, lithium batteries are widely used due to their advantages of cleanliness, high specific capacity, stable electrochemical performance, long service life, and the like. However, as the quality of life of people is further improved, especially in the field of power automobiles and the like, higher requirements are put on lithium batteries with high energy density.
Among them, the lithium-sulfur battery has 1675mAh g-1Has attracted a wide range of attention. The lithium-sulfur battery mainly comprises a sulfur-containing positive electrode, a lithium negative electrode and electrolyte. Meanwhile, the anode sulfur has the advantages of low price, environmental friendliness and the like, and has exploration significance as a next-generation energy material with great potential. However, problems of low conductivity, volume expansion, "polysulfide shuttling phenomenon", etc. in the lithium sulfur battery seriously hinder the practical application of the lithium sulfur battery.
Disclosure of Invention
In view of the defects of the existing sulfur cathode material, the invention aims to provide a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure, which has a three-dimensional structure and good electrical conductivity.
The invention also aims to provide a preparation method of the three-dimensional ordered porous hydrogel sulfur-loaded particle composite material, which is characterized in that a polyaniline solution is prepared by using low-cost raw materials, and then the polyaniline solution is dripped on a template and dissolved to remove the template, so that the three-dimensional ordered porous conductive hydrogel polyaniline material is obtained; then carrying sulfur to obtain the lithium-sulfur battery cathode material.
The invention also aims to provide a lithium-sulfur battery positive electrode which is prepared from the three-dimensional ordered porous hydrogel-loaded sulfur particle composite material.
Still another object of the present invention is to provide a lithium-sulfur battery fabricated using the above-mentioned positive electrode.
The specific technical scheme of the invention is as follows:
a preparation method of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure comprises the following steps:
A. placing aniline and phytic acid into deionized water, uniformly mixing, adding an ammonium persulfate solution, and fully stirring for carrying out polymerization reaction to obtain conductive hydrogel polyaniline sol;
B. dripping the polystyrene solution on a substrate, and drying at constant temperature to obtain a polystyrene template with a three-dimensional ordered structure;
C. dropwise adding the conductive hydrogel polyaniline sol prepared in the step A onto the polystyrene template with the three-dimensional ordered structure prepared in the step B, curing in an oven, removing the template, and washing to obtain polyaniline with the three-dimensional ordered porous structure;
D. and D, uniformly mixing the polyaniline with the three-dimensional ordered porous structure prepared in the step C with sulfur powder, and carrying out sulfur fumigation to obtain the hydrogel-loaded sulfur particle composite material with the three-dimensional ordered porous structure.
Further, in the step A, the molar ratio of the aniline to the phytic acid is 1: 1-10: 1, preferably 3: 1-6: 1;
in the step A, the molar ratio of aniline to ammonium persulfate in the ammonium persulfate solution is 1: 1-1: 10, preferably 1: 1-1: 3;
the concentration of the ammonium persulfate solution in step A is 0.05-0.5g/mL, preferably 0.1-0.3 g/mL.
Step A is carried out at a temperature of 0-5 ℃, preferably 2-4 ℃; stirring for 5-90 minutes, preferably 10-20 minutes;
and the volume ratio of the aniline to the deionized water in the step A is 1-4: 10.
And step B, diluting the purchased polystyrene solution with the mass concentration of 2.5% for use, wherein the concentration of the diluted polystyrene solution is 0.05% -0.3%, and preferably 0.08% -0.15%. Wherein the polystyrene particle diameter is 300nm-1000nm, preferably 300nm-600 nm;
and in the step B, the substrate is a titanium sheet substrate, a tungsten sheet substrate or an adhesive tape substrate.
Drying at constant temperature of 40-100 deg.C, preferably 60-90 deg.C in step B; the drying time is 6 to 20 hours, preferably 8 to 12 hours;
the dosage of the conductive hydrogel polyaniline sol in the step C is 1-3 ml;
in the step C, the curing temperature is 40-80 ℃, and preferably 55-65 ℃; the curing time is 4 to 20 hours, preferably 6 to 12 hours;
removing the template in the step C, namely soaking the cured template in toluene or xylene to remove the template; the dipping time is 10-200 seconds;
in the step D, the mass ratio of the polyaniline with the three-dimensional ordered porous structure to the sulfur powder is 1: 1-1: 4;
in step D, the sulfuration is carried out in N2The reaction is carried out under the atmosphere;
further, the temperature of the sulfuring in the step D is 100-200 ℃, preferably 140-165 ℃; the time of the sulfuring is 10-36 h, preferably 15-18 h.
The sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure, which is provided by the invention, is prepared by the method, has the diameter of 500 nanometers and has the three-dimensional ordered porous structure.
A lithium-sulfur battery positive electrode is prepared by using the prepared three-dimensional ordered porous hydrogel-loaded sulfur particle composite material;
a lithium-sulfur battery is manufactured by using a positive electrode made of a three-dimensional ordered porous structure hydrogel-loaded sulfur particle composite material;
the mechanism of the invention is as follows: synthesizing a template with a three-dimensional ordered structure by a template method, and removing the template by similarity and intermiscibility to obtain the three-dimensional ordered porous hydrogel polyaniline; and then the hydrogel is immersed into the holes by utilizing a sulfur melting method to form the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure. The invention provides a three-dimensional ordered porous conductive hydrogel polyaniline loaded sulfur as a lithium-sulfur battery positive electrode material. The conductive hydrogel material has good conductivity, solves the problem of too low conductivity of the sulfur anode, and improves the electron transmission capability; the three-dimensional ordered pore structure provides a sulfur loading space, and reduces the damage of volume expansion; meanwhile, the three-dimensional structure has a large specific surface area and a short lithium ion transmission path, which is beneficial to capture polysulfide and promote the transmission of lithium ions.
Compared with the existing common sulfur anode, the method utilizes a template method to synthesize the three-dimensional ordered porous conductive hydrogel polyaniline, and then loads sulfur particles in a sulfur smoking mode. The three-dimensional template structure in regular arrangement is prepared from commercial polystyrene solution with particles with uniform diameters, polyaniline sol is synthesized by a simple stirring method, the template is removed by utilizing substance similarity and intermiscibility, the three-dimensional ordered structure hydrogel is obtained, the experiment does not need high temperature and high pressure, and the method is simple and convenient. Then the polyaniline is compounded with sulfur to obtain a three-dimensional ordered porous structure composite material, wherein the porous structure is favorable for sulfur loading, and the polyaniline can well overcome the defects of poor conductivity of a sulfur positive electrode, shuttle of polysulfide and the like, so that the aim of improving the battery performance is fulfilled. The prepared polyaniline sulfur-loaded three-dimensional ordered porous structure composite material has a good three-dimensional structure and a large comparative area, is beneficial to loading more sulfur particles and has good conductivity; moreover, polysulfide can be combined, and the shuttle effect of the polysulfide is relieved; the lithium-sulfur battery cathode material has high capacity and good cycle performance.
Drawings
FIG. 1 is an SEM image of a polystyrene template having a three-dimensional ordered structure prepared in example 1;
FIG. 2 is an SEM image of a three-dimensional ordered porous hydrogel prepared in example 1;
FIG. 3 is an SEM image of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure prepared in example 1;
FIG. 4 is an SEM image of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure prepared in example 2;
FIG. 5 is an SEM image of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure prepared in example 3;
FIG. 6 is an SEM image of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure prepared in example 4;
FIG. 7 is an SEM image of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure prepared in example 5;
FIG. 8 is an XRD pattern of the sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure prepared in example 3;
FIG. 9 is a cycle stability test chart of the three-dimensional ordered porous hydrogel loaded sulfur particle composite material prepared in example 3 as a lithium sulfur battery cathode material at a current density of 100 mA/g.
Detailed Description
Example 1
A preparation method of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure comprises the following steps:
A. 1 ml of aniline and 1 ml of phytic acid are dissolved in 10 ml of water, after stirring for 10 minutes in an ice-water bath, 20 ml of ammonium persulfate solution containing 3g of ammonium persulfate is added, and stirring is continued for 10 minutes in the ice-water bath at 0 ℃ to obtain the uniformly mixed conductive hydrogel polyaniline sol.
B. 2 ml of a 500-nanometer-diameter commercial 2.5-percent-concentration polystyrene solution is placed in 30ml of water, ultrasonic treatment is carried out for 30 minutes, the obtained polystyrene solution is dripped on a tungsten sheet substrate, and constant-temperature drying is carried out for 12 hours at 50 ℃ to obtain the polystyrene template with the three-dimensional ordered structure.
C. And (3) dropwise adding 1 ml of the conductive hydrogel polyaniline sol obtained in the step (A) onto the polystyrene template with the three-dimensional ordered structure prepared in the step (B), putting the polystyrene template into a 60-DEG C oven for curing for 8 hours, then immersing the polystyrene template into toluene for 15 seconds to remove the polystyrene template, and washing to obtain the polyaniline with the three-dimensional ordered porous structure.
D. And C, uniformly mixing 0.5g of polyaniline with the three-dimensional ordered porous structure prepared in the step C and 0.5g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling nitrogen into the bottle, keeping the temperature at 110 ℃ for 12 hours, and naturally cooling to obtain the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure.
Example 2
A preparation method of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure comprises the following steps:
A. 1 ml of aniline and 2 ml of phytic acid are dissolved in 10 ml of water, after stirring for 10 minutes in an ice-water bath, 20 ml of ammonium persulfate solution dissolved with 7 g of ammonium persulfate is added, and stirring is continued for 10 minutes in the ice-water bath at 1 ℃ to obtain the uniformly mixed conductive hydrogel polyaniline sol.
B. 1 ml of a 500-nanometer-diameter commercial 2.5-percent-concentration polystyrene solution is placed in 30ml of water, ultrasonic treatment is carried out for 30 minutes, the polystyrene solution is dropwise added onto a tungsten plate substrate, and constant-temperature drying is carried out for 10 hours at 60 ℃ to obtain the polystyrene template with the three-dimensional ordered structure.
C. And (3) dropwise adding 1 ml of the conductive hydrogel polyaniline sol obtained in the step (A) onto the polystyrene template with the three-dimensional ordered structure prepared in the step (B), putting the polystyrene template into a 60-DEG C oven for curing for 10 hours, then immersing the polystyrene template into toluene for 30 seconds to remove the polystyrene template, and washing to obtain the polyaniline with the three-dimensional ordered porous structure.
D. And C, uniformly mixing 0.5g of polyaniline with the three-dimensional ordered porous structure prepared in the step C and 1 g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling nitrogen into the bottle, keeping the temperature at 130 ℃ for 12 hours, and naturally cooling to obtain the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure.
Example 3
A preparation method of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure comprises the following steps:
A. dissolving 2 ml of aniline and 4.3 ml of phytic acid in 10 ml of water, stirring for 10 minutes in an ice-water bath, adding 30ml of ammonium persulfate solution dissolved with 10 g of ammonium persulfate, and continuously stirring for 10 minutes at 3 ℃ in the ice-water bath to obtain the uniformly mixed conductive hydrogel polyaniline sol.
B. 2 ml of a 500-nanometer-diameter commercial 2.5-percent-concentration polystyrene solution is placed in 30ml of water, ultrasonic treatment is carried out for 30 minutes, the obtained polystyrene solution is dropwise added onto a tungsten plate substrate, and constant-temperature drying is carried out for 10 hours at 65 ℃, so as to obtain the polystyrene template with the three-dimensional ordered structure.
C. And (3) dropwise adding 1 ml of the conductive hydrogel polyaniline sol obtained in the step (A) onto the polystyrene template with the three-dimensional ordered structure prepared in the step (B), putting the polystyrene template into a 60-DEG C oven for curing for 12 hours, then immersing the polystyrene template into toluene for 60 seconds to remove the polystyrene template, and washing to obtain the polyaniline with the three-dimensional ordered porous structure.
D. And D, uniformly mixing 1 g of polyaniline with the three-dimensional ordered porous structure prepared in the step C and 1 g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling nitrogen into the bottle, keeping the temperature at 160 ℃ for 24 hours, and naturally cooling to obtain the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure.
Example 3The obtained final product of the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure is used as the positive active material of the lithium-sulfur battery, the electrode plate of the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure loaded on the substrate is cut by a mechanical cutting machine, the lithium plate is used as a counter electrode, the electrolyte is a commercially available 1mol/L LiTFSI/DME + DOL solution, a battery tester is used for testing the charge and discharge performance, and the obtained product is used as the positive material of the lithium-sulfur battery and is subjected to a charge and discharge performance test at 200mA g-1The results of the cycling stability test at current density are shown in figure 7. As can be seen from the attached figure 7, the cycling stability of the battery is good, and the battery capacity is still stabilized at 810mAh g after 100 cycles-1。
Example 4
A preparation method of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure comprises the following steps:
A. 3 ml of aniline and 4.3 ml of phytic acid are dissolved in 10 ml of water, after stirring for 10 minutes in an ice-water bath, 30ml of ammonium persulfate solution dissolved with 10 g of ammonium persulfate is added, and stirring is continued for 10 minutes at 4 ℃ in the ice-water bath, so that the uniformly mixed conductive hydrogel polyaniline sol is obtained.
B. 2 ml of a 500-nanometer-diameter commercial 2.5-percent-concentration polystyrene solution is placed in 30ml of water, ultrasonic treatment is carried out for 30 minutes, the obtained polystyrene solution is dropwise added onto a tungsten plate substrate, and constant-temperature drying is carried out for 8 hours at 70 ℃ to obtain the polystyrene template with the three-dimensional ordered structure.
C. And (3) dropwise adding 1 ml of the conductive hydrogel polyaniline sol obtained in the step (A) onto the polystyrene template with the three-dimensional ordered structure prepared in the step (B), putting the polystyrene template into a 60-DEG C oven for curing for 17 hours, then immersing the polystyrene template into toluene for 100 seconds to remove the polystyrene template, and washing to obtain the polyaniline with the three-dimensional ordered porous structure.
D. And C, uniformly mixing 0.5g of polyaniline with the three-dimensional ordered porous structure prepared in the step C and 1.5 g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling nitrogen into the bottle, keeping the temperature at 180 ℃ for 12 hours, and naturally cooling to obtain the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure.
Example 5
A preparation method of a sulfur particle-loaded hydrogel composite material with a three-dimensional ordered porous structure comprises the following steps:
A. dissolving 4 ml of aniline and 6 ml of phytic acid in 10 ml of water, stirring for 10 minutes in an ice-water bath, adding 30ml of ammonium persulfate solution dissolved with 15 g of ammonium persulfate, and continuously stirring for 10 minutes at 0 ℃ in the ice-water bath to obtain the uniformly mixed conductive hydrogel polyaniline sol.
B. 2 ml of a 500-nanometer-diameter commercial 2.5-percent-concentration polystyrene solution is placed in 30ml of water, ultrasonic treatment is carried out for 30 minutes, the obtained polystyrene solution is dropwise added onto a tungsten plate substrate, and constant-temperature drying is carried out for 6 hours at 80 ℃ to obtain the polystyrene template with the three-dimensional ordered structure.
C. And (3) dropwise adding 1 ml of the conductive hydrogel polyaniline sol obtained in the step (A) onto the polystyrene template with the three-dimensional ordered structure prepared in the step (B), putting the polystyrene template into a 60-DEG C oven for curing for 20 hours, then immersing the polystyrene template into toluene for 150 seconds to remove the polystyrene template, and washing to obtain the polyaniline with the three-dimensional ordered porous structure.
D. And C, uniformly mixing 0.5g of polyaniline with the three-dimensional ordered porous structure prepared in the step C and 2 g of sulfur powder, putting the mixture into a polytetrafluoroethylene plastic bottle, filling nitrogen into the bottle, keeping the temperature at 180 ℃ for 36 hours, and naturally cooling to obtain the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure.
Claims (8)
1. The preparation method of the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure is characterized by comprising the following steps of:
A. placing aniline and phytic acid into deionized water, uniformly mixing, adding an ammonium persulfate solution, and fully stirring for carrying out polymerization reaction to obtain conductive hydrogel polyaniline sol;
B. dripping the polystyrene solution on a substrate, and drying at constant temperature to obtain a polystyrene template with a three-dimensional ordered structure;
C. dropwise adding the conductive hydrogel polyaniline sol prepared in the step A onto the polystyrene template with the three-dimensional ordered structure prepared in the step B, curing in an oven, removing the template, and washing to obtain polyaniline with the three-dimensional ordered porous structure;
D. c, uniformly mixing the polyaniline with the three-dimensional ordered porous structure prepared in the step C with sulfur powder, and carrying out sulfur fumigation to obtain the sulfur particle-loaded hydrogel composite material with the three-dimensional ordered porous structure;
in the step A, the molar ratio of aniline to ammonium persulfate in the ammonium persulfate solution is 1: 1-1: 10;
and C, curing at 40-80 ℃ for 4-20 hours.
2. The preparation method according to claim 1, wherein the ratio of aniline to phytic acid in step a is 1: 1-10: 1.
3. the method according to claim 1 or 2, wherein the polystyrene solution in step B has polystyrene particles with a diameter of 300nm to 1000 nm.
4. The method according to claim 1 or 2, wherein the removing of the template in step C is dipping in toluene or xylene after curing to remove the template; the dipping time is 10-200 seconds.
5. The preparation method according to claim 1 or 2, wherein the mass ratio of the polyaniline with the three-dimensional ordered porous structure to the sulfur powder in the step D is 1: 1-1: 4.
6. a sulfur particle-loaded hydrogel composite material having a three-dimensional ordered porous structure, which is prepared by the method according to any one of claims 1 to 5.
7. A lithium-sulfur battery positive electrode, characterized in that it is made of a sulfur particle-loaded hydrogel composite material having a three-dimensional ordered porous structure prepared by the method of any one of claims 1 to 5.
8. A lithium-sulfur battery, characterized by being produced using the positive electrode for a lithium-sulfur battery according to claim 7.
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