CN111193017B - Self-repairing hydrogel microcapsule composite material, preparation method thereof, self-repairing lithium-sulfur battery anode and self-repairing lithium-sulfur battery - Google Patents
Self-repairing hydrogel microcapsule composite material, preparation method thereof, self-repairing lithium-sulfur battery anode and self-repairing lithium-sulfur battery Download PDFInfo
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 58
- 239000000017 hydrogel Substances 0.000 title claims abstract description 55
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 27
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 26
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 22
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 abstract description 12
- 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 abstract description 12
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 12
- 229940068041 phytic acid Drugs 0.000 claims abstract description 12
- 239000000467 phytic acid Substances 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000013543 active substance Substances 0.000 claims abstract description 6
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- 239000012071 phase Substances 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000008385 outer phase Substances 0.000 claims description 5
- 239000008384 inner phase Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
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- 238000007605 air drying Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
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- 238000005286 illumination Methods 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 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 2
- 238000011056 performance test Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- MTPIZGPBYCHTGQ-UHFFFAOYSA-N 2-[2,2-bis(2-prop-2-enoyloxyethoxymethyl)butoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCC(CC)(COCCOC(=O)C=C)COCCOC(=O)C=C MTPIZGPBYCHTGQ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a self-repairing hydrogel microcapsule composite material, a preparation method thereof, a self-repairing lithium-sulfur battery anode and a self-repairing lithium-sulfur battery.A mixed solution A obtained by dissolving pyrrole and phytic acid in isopropanol is mixed with an ammonium sulfate aqueous solution and deionized water to obtain a precursor solution B; dispersing 2-hydroxy-2-methyl propiophenone and trimethylolpropane ethoxy triacrylate in absolute ethyl alcohol, heating and volatilizing to remove the absolute ethyl alcohol to obtain a mixed solution C; the method comprises the steps of taking a precursor solution B, a mixed solution C and a polyvinyl alcohol aqueous solution as an internal phase, an external phase and a driving phase, preparing microcapsules by using a liquid-driving coaxial flow focusing technology, standing for 2-3 days after washing, drying to obtain a self-repairing hydrogel microcapsule composite material, preparing a lithium-sulfur battery anode by using the self-repairing hydrogel microcapsule composite material doped in sulfur powder as an active substance, and releasing hydrogel in the microcapsules to accurately repair cracks of an anode plate of the lithium-sulfur battery when cracks occur in an electrode plate, so that good performance of the lithium-sulfur battery can be maintained.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a self-repairing hydrogel microcapsule composite material, a preparation method thereof, a self-repairing lithium-sulfur battery positive electrode and a self-repairing lithium-sulfur battery.
Background
Due to environmental pollution and exhaustion of fossil fuels, the storage amount of non-renewable energy resources is reduced day by day, the climate environment is severe day by day, ecosystems are fragile and more, and the requirements of clean and renewable energy resources such as solar energy, wind energy and the like become more and more urgent, so that the development of secondary batteries with high energy density, long cycle life, high safety, environmental protection and low cost has great significance in the field of new energy resources.
The lithium-sulfur battery is a lithium battery with sulfur element as the positive electrode and metal lithium as the negative electrode, and the theoretical specific energy is high (2600Wh Kg)-1) Its higher theoretical specific capacity (1675mAh g)-1) Far higher than the current commercial lithium ion battery. The lithium-sulfur battery can have certain volume expansion in the charging and discharging process, the electrode plate of the lithium-sulfur battery can have cracks while the volume expansion is carried out, the cracks can be continuously enlarged due to long-term repeated charging and discharging, and then the active substances can fall off from the current collector to influence the performance of the battery, so that the utilization rate of sulfur in the battery is low, the cycle performance is poor, the capacity attenuation is fast, and the rate performance is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a self-repairing hydrogel microcapsule composite material, a preparation method thereof, a self-repairing lithium-sulfur battery positive electrode and a self-repairing lithium-sulfur battery. The self-repairing hydrogel microcapsule composite material is formed by wrapping hydrogel with a trimethylolpropane ethoxytriacrylate shell, the hydrogel is doped with sulfur powder and then serves as a positive active substance of a lithium-sulfur battery positive electrode, when a positive plate of the lithium-sulfur battery cracks, the hydrogel-wrapping microcapsule shell can crack to release hydrogel, and the crack of the positive plate of the lithium-sulfur battery can be accurately repaired after the hydrogel with a self-healing function is released.
The technical scheme adopted by the invention is as follows:
a preparation method of a self-repairing hydrogel microcapsule composite material comprises the following steps:
(1) dissolving pyrrole and phytic acid in isopropanol, and performing ultrasonic treatment to obtain a uniform mixed solution A;
(2) mixing the mixed solution A with an ammonium sulfate aqueous solution and deionized water to obtain a colorless viscous precursor solution B; the mixed solution A and the ammonium sulfate aqueous solution are directly mixed to generate a layering phenomenon, and the mixed solution A and the ammonium sulfate aqueous solution can be fully mixed to form a viscous and uniform liquid by adding the deionized water;
(3) dispersing 2-hydroxy-2-methyl propiophenone and trimethylolpropane ethoxy triacrylate in absolute ethyl alcohol, uniformly mixing, and then heating to volatilize and remove the absolute ethyl alcohol to obtain a mixed solution C;
(4) and (3) respectively taking the precursor solution B, the mixed solution C and the polyvinyl alcohol aqueous solution in the step (2) as an internal phase, an external phase and a driving phase, obtaining microcapsules under the shearing action of the driving phase by utilizing a liquid-driven coaxial flow focusing technology, washing, standing for 2-3 days, and drying to obtain the self-repairing hydrogel microcapsules.
In the step (1), the volume ratio of the isopropanol to the phytic acid to the pyrrole is (10-100): (10-30): (5-15).
In the step (2), the concentration of the ammonium sulfate aqueous solution is 0.05-0.3 g/mL, preferably 0.09-0.2 g/mL.
In the step (2), the volume ratio of the mixed solution A, the ammonium sulfate aqueous solution and the deionized water is (1-2): (0.8-2): (1-3), preferably (1-1.2): (0.8-1): (1-2).
In the step (3), the volume ratio of 2-hydroxy-2-methyl propiophenone, trimethylolpropane ethoxy triacrylate and absolute ethyl alcohol is (0.1-1): (2-20): (2-20), preferably (0.2-0.4): 20: 20.
and (3) heating in a forced air drying oven, and standing overnight in the forced air drying oven at the temperature of 60-80 ℃ to completely volatilize the absolute ethyl alcohol.
In the step (4), the concentration of the polyvinyl alcohol aqueous solution is 0.01-0.1 g/mL, preferably 0.02-0.04 g/mL.
In the step (4), the flow rate of the inner phase pump is 1-10 mL/h, the flow rate of the outer phase pump is 1-10 mL/h, and the flow rate of the outermost layer driving phase pump is 500-1000 mL/h, so that the microcapsules with the particle size of 20-80 μm can be formed at the flow rates.
The invention also provides a self-repairing hydrogel microcapsule composite material prepared by the preparation method, which is a microcapsule with the particle size of 20-80 mu m and formed by coating hydrogel with a 2-hydroxy-2-methyl propiophenone and trimethylolpropane ethoxylate triacrylate shell.
The invention also provides application of the self-repairing hydrogel microcapsule composite material in a lithium-sulfur battery.
The invention also provides a self-repairing lithium-sulfur battery anode, which is prepared by using the self-repairing hydrogel microcapsule composite material doped with sulfur powder as an anode active substance.
The invention also provides a self-repairing lithium-sulfur battery which is assembled by taking the positive electrode of the self-repairing lithium-sulfur battery as the positive electrode.
According to the technical scheme provided by the invention, pyrrole and phytic acid are dissolved in isopropanol, a uniformly mixed liquid A is obtained after ultrasonic treatment, the uniformly mixed liquid A is mixed with an ammonium sulfate aqueous solution, deionized water is added, and a uniform mixed viscous precursor solution B is obtained under the dissolving assisting action of ammonium sulfate, wherein the solution is still in a liquid state and has good fluidity.
When the outer phase is prepared, 2-hydroxy-2-methyl propiophenone and trimethylolpropane ethoxy triacrylate are dispersed in absolute ethyl alcohol, and after the materials are uniformly mixed, the obtained solution is placed in an oven to be dried until the absolute ethyl alcohol is completely evaporated, so that the photocuring material trimethylolpropane ethoxy triacrylate and the initiator 2-hydroxy-2-methyl propiophenone in the obtained mixed liquid C can be completely and uniformly mixed, and a uniform shell for wrapping a hydrogel precursor can be formed subsequently.
And finally, respectively taking the precursor solution B, the mixed solution C and the polyvinyl alcohol solution as an internal phase, an external phase and a driving phase, wrapping the internal phase by the external phase under the shearing action of the polyvinyl alcohol solution by using a liquid-driven coaxial flow focusing technology to form microcapsules, standing for two to three days under the illumination, gradually oxidizing and polymerizing the precursor solution wrapped in the microcapsules to form hydrogel, and drying to obtain the self-repairing hydrogel microcapsules.
The self-repairing hydrogel microcapsule composite material provided by the invention is prepared by wrapping a hydrogel precursor in a mixture of a light-cured material trimethylolpropane ethoxy triacrylate and 2-hydroxy-2-methyl propiophenone to form the microcapsule composite material, and taking doped sulfur powder as a positive active substance to prepare a lithium-sulfur battery positive electrode.
Drawings
FIG. 1 is an SEM image of the self-repairing hydrogel microcapsule composite prepared in example 3 after standing and drying;
FIG. 2 is an optical microscope photograph of the self-healing hydrogel microcapsule composite prepared in example 3 before being left to stand and dried;
FIG. 3 is an optical microscope photograph of the self-healing hydrogel microcapsule composite prepared in example 3 after standing and drying;
FIG. 4 is an SEM image of the breakage of a self-repairing hydrogel microcapsule composite material after the electrode plate of a lithium-sulfur battery cracks;
fig. 5 is an SEM image of the electrode tab of a lithium sulfur battery being repaired under the action of the self-healing hydrogel microcapsule composite after a crack occurs.
FIG. 6 is a graph showing the cycling stability of the self-repairing hydrogel microcapsule composite material prepared in example 3 applied to a positive electrode of a lithium-sulfur battery at a current density of 0.1C;
FIG. 7 is a charge-discharge curve diagram of the self-repairing hydrogel microcapsule composite material prepared in example 3 applied to a lithium-sulfur battery anode at a current density of 0.1C;
FIG. 8 is a graph showing the cycle stability test at a current density of 0.1C, which is the active material of pure sulfur powder in comparative example 1.
Detailed Description
The construction of the liquid-driven coaxial flow focusing technical device is carried out by referring to the content in Chinese patent CN 206935332U: utilize welding technique to obtain coaxial syringe needle, interior syringe needle inlays inside the outer syringe needle, constitutes the shell with transparent organic glass pipe, and coaxial syringe needle passes through the cork and fixes in the organic glass shell to align with the aperture (its diameter is 0.3mm) on the glass board of bottom, adjust the distance between the aperture bottom the glass board bottom and the bottom of interior syringe needle to 0.8 mm. And three injection pumps are used for controlling the flow of the inner phase, the outer phase and the driving phase respectively. The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a self-repairing hydrogel microcapsule composite material comprises the following steps:
1) dispersing 184 mu L of phytic acid and 84 mu L of pyrrole in 1mL of isopropanol, and performing ultrasonic treatment to obtain a mixed solution A; dissolving 0.184g of ammonium sulfate in 2mL of deionized water in another beaker to obtain an ammonium sulfate aqueous solution; and (3) mixing the obtained mixed solution A, an ammonium sulfate aqueous solution and deionized water according to the ratio of (1-1.2): (0.8-1): (1-2) mixing to obtain a viscous colorless precursor solution B;
2) dispersing 0.2mL of 2-hydroxy-2-methyl propiophenone and 20mL of trimethylolpropane ethoxy triacrylate in 20mL of absolute ethanol, uniformly mixing, placing the obtained solution in an oven at the temperature of 60-80 ℃ for 12 hours to completely evaporate the absolute ethanol to obtain a mixed solution C;
3) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
4) and respectively placing the precursor solution B, the mixed solution C and the polyvinyl alcohol aqueous solution in a needle tube to be used as an internal phase, an external phase and a driving phase, respectively, utilizing a liquid-driven coaxial flow focusing technology, wherein the flow rate of an internal phase pump is 6mL/h, the flow rate of an external phase pump is 4mL/h, and the flow rate of an outermost layer driving phase pump is 700mL/h, collecting a product, repeatedly washing the product with deionized water, standing the product in the deionized water for 2-3 days, filtering the product, and placing the product in a 60 ℃ oven for overnight drying to obtain the self-repairing hydrogel microcapsule composite material.
Example 2
A preparation method of a self-repairing hydrogel microcapsule composite material comprises the following steps:
1) dispersing 184 mu L of phytic acid and 84 mu L of pyrrole in 1mL of isopropanol, and performing ultrasonic treatment to obtain a mixed solution A; dissolving 0.184g of ammonium sulfate in 2mL of deionized water in another beaker to obtain an ammonium sulfate aqueous solution; and (3) mixing the obtained mixed solution A, an ammonium sulfate aqueous solution and deionized water according to the ratio of (1-1.2): (0.8-1): (1-2) mixing to obtain a viscous colorless precursor solution B;
2) dispersing 0.2mL of 2-hydroxy-2-methyl propiophenone and 20mL of trimethylolpropane ethoxy triacrylate in 20mL of absolute ethyl alcohol, uniformly mixing, placing the obtained solution in an oven at the temperature of 60-80 ℃ for 12 hours, and completely evaporating the absolute ethyl alcohol to obtain a mixed solution C;
3) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
4) and respectively placing the precursor solution B, the mixed solution C and the polyvinyl alcohol aqueous solution in a needle tube to be used as an internal phase, an external phase and a driving phase, respectively, utilizing a liquid-driven coaxial flow focusing technology, wherein the flow rate of an internal phase pump is 3mL/h, the flow rate of an external phase pump is 8mL/h, and the flow rate of an outermost layer driving phase pump is 700mL/h, collecting a product, repeatedly washing the product with deionized water, standing the product in the deionized water for 2-3 days, filtering the product, and placing the product in a 60 ℃ oven for overnight drying to obtain the self-repairing hydrogel microcapsule composite material.
Example 3
A preparation method of a self-repairing hydrogel microcapsule composite material comprises the following steps:
1) dispersing 184 mu L of phytic acid and 84 mu L of pyrrole in 1mL of isopropanol, and performing ultrasonic treatment to obtain a mixed solution A; dissolving 0.184g of ammonium sulfate in 2mL of deionized water in another beaker to obtain an ammonium sulfate aqueous solution; and (3) mixing the obtained mixed solution A, an ammonium sulfate aqueous solution and deionized water according to the ratio of (1-1.2): (0.8-1): (1-2) mixing to obtain a viscous colorless precursor solution B;
2) dispersing 0.4mL of 2-hydroxy-2-methyl propiophenone and 20mL of trimethylolpropane ethoxy triacrylate in 20mL of absolute ethyl alcohol, uniformly mixing, placing the obtained solution in an oven at 60-80 ℃ for 12 hours, and drying until the absolute ethyl alcohol is completely evaporated to obtain a mixed solution C;
3) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
4) respectively placing the precursor solution B, the mixed solution C and the polyvinyl alcohol aqueous solution obtained in the step 1) into a needle tube to be used as an internal phase, an external phase and a driving phase, respectively, utilizing a liquid-driven coaxial flow focusing technology, wherein the flow rate of an internal phase pump is 3mL/h, the flow rate of an external phase pump is 4mL/h, the flow rate of an outermost layer driving phase pump is 700mL/h, collecting a product, repeatedly washing the product with deionized water, standing the product in the deionized water for 2-3 days, filtering the product, and placing the product in a 60 ℃ oven for overnight drying to obtain the self-repairing hydrogel microcapsule composite material. An optical microscope photograph of the product before standing and drying is shown in fig. 2, and microcapsules with uniform size are obtained from fig. 2, and the wrappage in the capsules is colorless.
SEM and optical microscope pictures of the product after standing and drying are respectively shown in figures 1 and 3, and as can be seen from figure 1, the self-repairing hydrogel microcapsule composite material prepared by the invention is a small ball with the uniform particle size of 30-50 microns; as can be seen from fig. 3, the self-repairing hydrogel microcapsule composite material obtained after standing and drying is a microcapsule with uniform size, and the content of the inclusion is black, which indicates that the precursor solution wrapped in the microcapsule is gradually oxidized and polymerized into the polypyrrole hydrogel crosslinked with phytic acid by standing for 2-3 days under illumination.
The colorless precursor solution B obtained in step 1) of this example was placed in an oven at 60 ℃ for overnight drying, and was ground for 30 minutes to obtain a black solid gel. The black gel is cut from the middle, and after the black gel is contacted, two separated gels can be seen to be quickly and automatically healed, which shows that the black gel has strong self-repairing effect.
Example 4
A preparation method of a self-repairing hydrogel microcapsule composite material comprises the following steps:
1) dispersing 184 mu L of phytic acid and 84 mu L of pyrrole in 1mL of isopropanol, and performing ultrasonic treatment to obtain a mixed solution A; dissolving 0.184g of ammonium sulfate in 2mL of deionized water in another beaker to obtain an ammonium sulfate aqueous solution; and (3) mixing the obtained mixed solution A, an ammonium sulfate aqueous solution and deionized water according to the ratio of (1-1.2): (0.8-1): (1-2) mixing to obtain a viscous colorless precursor solution B;
2) dispersing 0.4mL of 2-hydroxy-2-methyl propiophenone and 20mL of trimethylolpropane ethoxy triacrylate in 20mL of absolute ethyl alcohol, uniformly mixing, placing the obtained solution in an oven at 60-80 ℃ for 12 hours, and drying until the absolute ethyl alcohol is completely evaporated to obtain a mixed solution C;
3) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
4) respectively placing the precursor solution B, the mixed solution C and the polyvinyl alcohol aqueous solution obtained in the step 1) into a needle tube to be used as an internal phase, an external phase and a driving phase, and utilizing a liquid-driven coaxial flow focusing technology, wherein the flow rate of an internal phase pump is 6 mL/h. And (3) collecting the product, repeatedly washing the product with deionized water, standing the product in the deionized water for 2-3 days, filtering, and placing the product in a 60 ℃ oven for overnight drying to obtain the self-repairing hydrogel microcapsule composite material, wherein the flow rate of the outer phase pump is 4mL/h, and the flow rate of the outermost layer driving phase pump is 700 mL/h.
Example 5
A preparation method of a self-repairing hydrogel microcapsule composite material comprises the following steps:
1) dispersing 184 mu L of phytic acid and 84 mu L of pyrrole in 1mL of isopropanol, and performing ultrasonic treatment to obtain a mixed solution A; dissolving 0.184g of ammonium sulfate in 2mL of deionized water in another beaker to obtain an ammonium sulfate aqueous solution; and (3) mixing the obtained mixed solution A, an ammonium sulfate aqueous solution and deionized water according to the ratio of (1-1.2): (0.8-1): (1-2) mixing to obtain a viscous colorless precursor solution B;
2) dispersing 0.4mL of 2-hydroxy-2-methyl propiophenone and 20mL of trimethylolpropane ethoxy triacrylate in 20mL of absolute ethanol, uniformly mixing, placing the obtained solution in an oven at 60-80 ℃ for 12 hours, and drying until the absolute ethanol is completely evaporated to obtain a mixed solution C;
3) dispersing 20g of polyvinyl alcohol into 1000mL of deionized water, placing the deionized water in a water bath kettle, and stirring at constant temperature until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution;
4) respectively placing the precursor solution B, the mixed solution C and the polyvinyl alcohol aqueous solution obtained in the step 1) into a needle tube to be used as an internal phase, an external phase and a driving phase, respectively, utilizing a liquid-driven coaxial flow focusing technology, wherein the flow rate of an internal phase pump is 3mL/h, the flow rate of an external phase pump is 8mL/h, the flow rate of an outermost layer driving phase pump is 700mL/h, collecting a product, repeatedly washing the product with deionized water, standing the product in the deionized water for 2-3 days, filtering the product, and placing the product in a 60 ℃ oven for overnight drying to obtain the self-repairing hydrogel microcapsule composite material.
Example 6
The self-repairing hydrogel microcapsule composite material is applied to a lithium-sulfur battery.
The self-repairing hydrogel microcapsule composite material obtained in example 3 and sulfur powder were mixed in a ratio of 3: 1 proportion, mixing the active material with superconductive carbon black and PVDF in a ratio of 7: 2: 1, preparing uniform slurry by using an N-methyl pyrrolidone (NMP) solvent, coating the uniform slurry on an aluminum foil, putting the prepared coating in a drying oven, and drying for 4 hours at 60 ℃; after drying, moving the mixture into a vacuum drying oven, and carrying out vacuum drying for 12 hours at the temperature of 60 ℃; and tabletting and cutting the dried composite material coating by a tablet press and the like to obtain the lithium-sulfur battery anode.
A lithium sheet is used as a counter electrode, a polypropylene film is used as a diaphragm, the battery is assembled in an argon atmosphere, and the electrolyte consists of 1M LiTFSI/DME + DOL solution. And finally, performing charge and discharge performance test by using a battery tester, wherein the obtained product is used as the lithium-sulfur battery anode material, and the cycle stability test result under the current density of 0.1C is shown in the attached figures 6 and 7. As can be seen from the figure, the battery has better cycle stability.
FIGS. 4 and 5 are SEM images of the positive plate of the lithium-sulfur battery after cracks appear, and the self-repairing hydrogel microcapsule composite material is broken in the state as can be seen from the SEM image in FIG. 4; from fig. 5, it can be seen that the ruptured self-healing hydrogel microcapsule composite is repairing the positive plate of the lithium sulfur battery which has a crack.
Comparative example 1
Mixing pure sulfur powder, superconducting carbon black and PVDF in a proportion of 7: 2: 1, preparing uniform slurry by using an N-methyl pyrrolidone (NMP) solvent, coating the uniform slurry on an aluminum foil, putting the prepared coating in a drying oven, and drying for 4 hours at 60 ℃; after drying, moving the mixture into a vacuum drying oven, and carrying out vacuum drying for 12 hours at the temperature of 60 ℃; and tabletting and cutting the dried composite material coating by a tablet press and the like to obtain the lithium-sulfur battery anode.
A lithium sheet is used as a counter electrode, a polypropylene film is used as a diaphragm, the battery is assembled in an argon atmosphere, and the electrolyte consists of 1M LiTFSI/DME + DOL (1: 1) solution as the electrolyte. And finally, performing charge and discharge performance test by using a battery tester, wherein the result of the cycle stability test at the current density of 0.1C is shown in the attached figure 8. As can be seen from the figure, the cell performance was much inferior to the lithium sulfur cell doped with the self-healing hydrogel microcapsule composite of example 3.
The above detailed descriptions of the self-repairing hydrogel microcapsule composite material, the preparation method thereof, the self-repairing lithium-sulfur battery positive electrode and the self-repairing lithium-sulfur battery with reference to the embodiments are illustrative and not restrictive, and several embodiments can be enumerated within the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a self-repairing hydrogel microcapsule composite material for a lithium-sulfur battery positive electrode is characterized by comprising the following steps of:
(1) dissolving pyrrole and phytic acid in isopropanol, and performing ultrasonic treatment to obtain a uniform mixed solution A;
(2) mixing the mixed solution A with an ammonium sulfate aqueous solution and deionized water to obtain a precursor solution B;
(3) dispersing 2-hydroxy-2-methyl propiophenone and trimethylolpropane ethoxy triacrylate in absolute ethyl alcohol, uniformly mixing, and then heating to volatilize and remove the absolute ethyl alcohol to obtain a mixed solution C;
(4) and (3) respectively taking the precursor solution B, the mixed solution C and the polyvinyl alcohol aqueous solution in the step (2) as an internal phase, an external phase and a driving phase, preparing microcapsules by using a liquid-driven coaxial flow focusing technology, collecting products, washing, standing in deionized water for 2-3 days, and drying to obtain the self-repairing hydrogel microcapsule composite material.
2. The preparation method according to claim 1, wherein in the step (1), the volume ratio of the isopropanol to the phytic acid to the pyrrole is (10-100): (10-30): (5-15).
3. The method according to claim 1, wherein in the step (2), the concentration of the aqueous solution of ammonium sulfate is 0.05 to 0.3 g/mL; the volume ratio of the mixed solution A to the ammonium sulfate aqueous solution to the deionized water is (1-2): (0.8-2): (1-3).
4. The method according to claim 1, wherein in step (3), the volume ratio of 2-hydroxy-2-methyl propiophenone to trimethylolpropane ethoxytriacrylate to absolute ethanol is (0.1-1): (2-20): (2-20).
5. The method according to claim 1, wherein in the step (4), the concentration of the aqueous solution of polyvinyl alcohol is 0.01 to 0.1 g/mL.
6. The process according to claim 1, wherein in the step (4), the flow rate of the inner phase pump is 1 to 10mL/h, the flow rate of the outer phase pump is 1 to 10mL/h, and the flow rate of the outermost layer driving phase pump is 500 to 1000 mL/h.
7. The self-repairing hydrogel microcapsule composite material for the positive electrode of the lithium-sulfur battery, which is prepared by the preparation method of any one of claims 1 to 6.
8. The use of the self-healing hydrogel microcapsule composite for a lithium sulfur battery positive electrode of claim 7 in a lithium sulfur battery.
9. The self-repairing lithium-sulfur battery positive electrode is characterized in that the self-repairing lithium-sulfur battery positive electrode is prepared by taking the self-repairing hydrogel microcapsule composite material doped with sulfur powder for the lithium-sulfur battery positive electrode as a positive electrode active substance according to claim 8.
10. A self-repairing lithium-sulfur battery, which is assembled by using the positive electrode of the self-repairing lithium-sulfur battery according to claim 9 as a positive electrode.
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| CN112271278B (en) * | 2020-09-30 | 2021-09-24 | 中科南京绿色制造产业创新研究院 | Self-healing branched polyethylene diamine hydrogel microcapsule composite material, and preparation method and application thereof |
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