CN114678492A - Micron flower material with flower-shaped cobalt disulfide surface loaded with nickel disulfide and preparation method thereof - Google Patents
Micron flower material with flower-shaped cobalt disulfide surface loaded with nickel disulfide and preparation method thereof Download PDFInfo
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- CN114678492A CN114678492A CN202210227435.4A CN202210227435A CN114678492A CN 114678492 A CN114678492 A CN 114678492A CN 202210227435 A CN202210227435 A CN 202210227435A CN 114678492 A CN114678492 A CN 114678492A
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- 239000000463 material Substances 0.000 title claims abstract description 90
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 title claims abstract description 65
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000007790 solid phase Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims abstract description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 19
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- 238000004073 vulcanization Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 56
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000012300 argon atmosphere Substances 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007810 chemical reaction solvent Substances 0.000 description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 8
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000007600 charging Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- -1 cobalt disulfide compound Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- HNDMNBUITRNJKK-UHFFFAOYSA-N [Ni](=S)=S Chemical group [Ni](=S)=S HNDMNBUITRNJKK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion 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
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of electrochemistry and new energy, and relates to a flower-shaped cobalt disulfide surface nickel disulfide micron flower material and a preparation method thereof. The method comprises the following steps: in an inert atmosphere, adding disodium ethylene diamine tetraacetate, urotropine, nickel salt and cobalt salt into carbon-free water for dissolving, and adding alkali liquor to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution to obtain a solid-phase precursor; sublimating sulfur by using a chemical vapor deposition method, then contacting the sulfur with a solid phase precursor for a vulcanization reaction, and simultaneously calcining to obtain the sulfur-containing catalyst; wherein the carbohydrate-free water is obtained by heating ethanol and water under inert atmosphere to remove oxygen. The material prepared by the method is micrometer spherical flowers with uniform sizes, and the surfaces of the micrometer flower pieces are provided with micro holes. The material prepared by the invention is applied to the anode catalysis of the lithium oxygen battery, excellent cycle stability can be obtained, the preparation method is simple and convenient, the material can be obtained only by simple hydrothermal reaction and subsequent heat treatment, and the material has good industrial production value and practical application value.
Description
Technical Field
The invention belongs to the field of electrochemistry and new energy, and relates to a nickel disulfide micron flower material loaded on the surface of flower-shaped cobalt disulfide and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Lithium oxygen batteries exhibit an ultra-high theoretical energy density, almost ten times that of lithium ion batteries, even approaching the combustion value of gasoline. But the practical application of lithium oxygen batteries is currently hampered by their limited practical energy density, rate capability and cycle life. The cobalt sulfide has excellent electrochemical activity, but the performance of the lithium-oxygen battery is not obviously improved by singly adopting the cobalt sulfide as the anode catalyst of the lithium-oxygen battery. While the prior art has attempted to combine cobalt sulfide with a second phase to improve the cycle life and first charge-discharge capacity of lithium-oxygen batteries, the results have not been entirely satisfactory.
The inventor researches and discovers that the existing cobalt sulfide catalyst material simply combines cobalt sulfide and a second phase (carbon material), the process is complex, the obtained electrochemical performance effect is not ideal, and the practical large-scale industrial production and application are not facilitated, so that the cobalt sulfide electrode material which is cheap in raw materials, simple and convenient to prepare and high in yield is required to be solved urgently in the field.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a flower-shaped cobalt disulfide surface-loaded nickel disulfide micro flower material and a preparation method thereof. And the micro rice flakes are provided with more holes, so that gas transmission and electrolyte infiltration are facilitated in the charging and discharging process, the cycle performance and the rate performance can be improved, and the problem of easy agglomeration in the charging and discharging process is solved. Meanwhile, the raw materials are cheap and easy to obtain, the preparation method is simple and convenient, the yield is high, and the lithium-oxygen battery can be obtained by combining a hydrothermal method and a chemical vapor deposition method, so that the lithium-oxygen battery provides effective benefits for large-scale industrial production and practical application of the lithium-oxygen battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the preparation method of the flower-shaped cobalt disulfide surface loaded nickel disulfide micro flower material comprises the following steps:
adding disodium ethylene diamine tetraacetate, urotropine, nickel salt and cobalt salt into carbon-free water to be dissolved in inert atmosphere, and adding alkali liquor to obtain mixed liquor;
Carrying out hydrothermal reaction on the mixed solution to obtain a solid-phase precursor;
sublimating sulfur by using a chemical vapor deposition method, then contacting the sulfur with a solid phase precursor for a vulcanization reaction, and simultaneously calcining to obtain the sulfur-containing catalyst;
wherein the carbohydrate-free water is obtained by heating ethanol and water under an inert atmosphere to remove oxygen.
According to the invention, the reaction of disodium ethylene diamine tetraacetate and urotropine in the hydrothermal reaction process is utilized to make the solid-phase precursor into a flower shape, and then the flower-shaped cobalt disulfide surface nickel disulfide micron flower material can be obtained by further processing by using a chemical vapor deposition method.
EDTA-2Na as complexing agent and Ni2+In combination, [ NiEDTA ]]2-. NH released by reaction of urotropine and water at high temperature and high pressure3。NH3Is a complexing agent with Co2+Combined to form [ Co (NH)3)4]2+. Simultaneous NH3Hydrolysis to generate OH-to form alkaline environment and Co2+Formation of Co (OH)2。
The slow hydrolysis of urotropine in the reaction process controls [ Co (NH)3)4]2+To thereby control Co2+The release rate of the crystal is reduced, the growth rate of the crystal is reduced, and the Gibbs free energy on the surface of the system is controlled so as to influence and control the formation of a flower-shaped structure. Wherein and as urotropine is hydrolyzed, with increasing pH [ NiEDTA]2-The more stable the complexation, the less easy the release, thus keeping stable and adhering to the surface of the generated flower-shaped nickel disulfide structure in the hydrothermal process.
In hydrothermal high-temperature high-pressure sealing, urotropine and deionized water react as follows:
(CH2)6N4+6H2O→HCHO+4NH3
NH released by HMTA in solution3Is a complexing agent.
Co2++2OH-→Co(OH)2
Researches show that the preparation environment of a solvent in a hydrothermal reaction system and a mixed solution before hydrothermal reaction has great influence on the appearance of a solid-phase precursor. Firstly, the mixed solution is prepared in inert atmosphere, so that the oxidation of materials can be avoided, and the final material is ensured to present the flower-shaped target morphology. Secondly, when deoxygenated water is used as a solvent in the present invention, it is difficult to make the solid phase precursor take on a flower shape. According to the invention, ethanol and water are heated to deoxidize in an inert atmosphere to obtain carbohydrate-free water as a solvent, and the mixed solution is prepared in the inert atmosphere to enable the solid-phase precursor to be flower-shaped, so that the final material is in a target shape.
On the other hand, the flower-shaped cobalt disulfide micron flower material with the nickel disulfide loaded on the surface is obtained by the preparation method.
In a third aspect, the application of the flower-shaped cobalt disulfide material with nickel disulfide micro flowers loaded on the surface thereof in the preparation of a lithium oxygen battery or a lithium oxygen battery anode catalyst is provided.
In a fourth aspect, a lithium oxygen battery positive electrode includes an active material, a conductive agent, a binder, and a current collector, where the active material is a micrometer flower material of nickel disulfide supported on the surface of the flower-shaped cobalt disulfide.
In a fifth aspect, a lithium oxygen battery includes the above lithium oxygen battery positive electrode, negative electrode, separator, and electrolyte.
The invention has the beneficial effects that:
(1) according to the invention, disodium ethylene diamine tetraacetate and urotropine are used as morphology regulators in the hydrothermal reaction process, so that a solid phase precursor is in a flower shape, and then further sulfuration and calcination are carried out to obtain a nickel disulfide micrometer flower material loaded on the surface of flower-shaped cobalt disulfide.
(2) The surface of the flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers prepared by the method has micro holes, and the nano sheets with the micro hole structures facilitate oxygen transmission and electrolyte infiltration, and the material has good conductivity, facilitates electron and ion transportation, and has excellent electrochemical performance.
(3) The electrode anode catalyst prepared by the invention has good repeatability in morphology and electrochemical performance, excellent cycle stability, and test verification shows that the catalyst has a current density of 1000mA g-1Fixed specific capacity 500mAh g-1And the charging and discharging are carried out, so that 209 circles can be stably circulated, and the practical application value is good.
(4) According to the invention, the crystal structure and morphology of the solid-phase precursor are influenced by the temperature and time of the hydrothermal reaction, the temperature (including the heating rate) and the time of the sulfuration reaction greatly influence the secondary recrystallization of the crystal, and the formation rate of the morphology and the particle size uniformity of the material can be adjusted by adjusting the parameters, so that the performance of the lithium-oxygen battery as a catalytic material is influenced.
(5) The flower-like cobalt disulfide prepared by adopting optimized parameters has the surface loaded with nickel disulfide micrometer flower materials with the average particle size of 5 micrometers, and compared with a nanometer structure, the aggregation phenomenon is difficult to occur in the charging and discharging processes.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an XRD pattern of the flower-like cobalt disulfide micrometer flower material loaded with nickel disulfide on the surface prepared in example 1.
Fig. 2 is an FESEM image of the flower-like cobalt disulfide supported nickel disulfide micro flower material on the surface prepared in example 1, and its magnification is 5000.
Fig. 3 is an FESEM image of the flower-like cobalt disulfide micron flower material loaded on the surface, which is prepared in example 1, and the magnification is 20000.
Fig. 4 is an HRTEM of the flower-shaped cobalt disulfide supported nickel disulfide micro flower material on the surface prepared in example 1, wherein the magnification is 50000.
Fig. 5 is a graph of cycle performance of the flower-like cobalt disulfide material loaded with nickel disulfide micro flowers on the surface, prepared in example 1, when the flower-like cobalt disulfide material is used in a lithium oxygen battery test.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The invention provides a nickel disulfide micrometer flower material loaded on the surface of flower-shaped cobalt disulfide and a preparation method thereof, and solves the problems that the electrochemical performance effect of a cobalt sulfide electrode material is not ideal, the preparation process is complex and the like in the prior art.
The invention provides a preparation method of a nickel disulfide micron flower material loaded on the surface of flower-shaped cobalt disulfide, which comprises the following steps:
In an inert atmosphere, adding disodium ethylene diamine tetraacetate, urotropine, nickel salt and cobalt salt into carbon-free water for dissolving, and adding alkali liquor to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution to obtain a solid-phase precursor;
sublimating sulfur by using a chemical vapor deposition method, contacting the sublimed sulfur with a solid-phase precursor to perform a vulcanization reaction, and calcining the sulfur simultaneously to obtain the sulfur-containing catalyst;
wherein the carbohydrate-free water is obtained by heating ethanol and water under an inert atmosphere to remove oxygen.
According to the invention, the shape of the solid-phase precursor is adjusted through the reaction of disodium ethylene diamine tetraacetate and urotropine in the hydrothermal reaction, so that the final material is ensured to be in a flower shape, and the electrochemical performance of the material is favorably improved.
The method is prepared in an inert atmosphere in the process of preparing the mixed solution before the hydrothermal reaction, and carbon-free water obtained by heating ethanol and water in the inert atmosphere for deoxidation is used as a solvent, so that the material oxidation is avoided, and the morphology of a solid phase precursor is ensured to be flower-shaped, thereby ensuring that the final material is flower-shaped.
The nickel salt of the present invention is a compound in which the cation is a nickel ion, such as nickel nitrate, nickel chloride, nickel sulfate, and the like.
The cobalt salt of the present invention is a compound in which the cation is nickel ion, such as cobalt nitrate, cobalt chloride, cobalt sulfate, and the like.
In some examples of this embodiment, the process of preparing the mixed liquor is: adding disodium ethylene diamine tetraacetate and nickel salt into carbon-free water for dissolving, and adding alkali liquor to obtain solution A;
adding urotropine and cobalt salt into carbon-free water for dissolving to obtain a solution B;
and mixing the solution A and the solution B to obtain a mixed solution.
In one or more embodiments, the pH of solution A is 4-6. Research shows that the pH value of a solution obtained by adding disodium ethylene diamine tetraacetate and nickel salt into carbonless water for dissolution is about 2-3, and at the moment, if the disodium ethylene diamine tetraacetate and the nickel salt are directly mixed with the solution B, hydrothermal reaction is carried out again, so that the target morphology is difficult to obtain, and the pH value is increased by adding alkali liquor. When the pH value of the solution A is 4-6, the material can be in a flower shape and is relatively uniform in appearance.
The inert atmosphere in the present invention is to prevent oxygen from entering the system, and may be formed of nitrogen, or may be formed of an inert gas such as helium, argon, or xenon.
In some examples of this embodiment, the molar ratio of disodium edetate to nickel salt is 1-2: 1. Preferably 1-1.1: 1.
In some examples of this embodiment, the molar ratio of urotropin to cobalt salt is 1 to 2: 1. Preferably 1-1.1: 1.
In some examples of this embodiment, the molar ratio of nickel salt to cobalt salt is 1:2.0 to 5.0.
The hydrothermal reaction in the present invention is a reaction carried out under a condition of heating to a high temperature and a high pressure in a closed condition using water as a solvent. In some examples of this embodiment, the hydrothermal reaction is carried out at a temperature of 120 to 150 ℃ for 12 to 36 hours. Under the condition, the formation rate of the target flower-shaped material can be ensured to be higher. When the temperature of the hydrothermal reaction is 120-125 ℃ and the reaction time is 19-21 h, the formation rate of the target flower-shaped material is higher.
In some examples of this embodiment, the temperature of the sulfidation reaction and calcination treatment is 400-600 ℃ for 2-5 hours. Under the condition, the formation rate of the target flower-shaped material can be ensured to be higher. In the process, when the temperature is 400-500 ℃ and the time is 2-2.1 h, the formation rate of the target flower-shaped material is higher. Meanwhile, the rate of temperature rise in the process also influences the formation rate of the target flower-shaped material, and when the rate of temperature rise is 2-10 ℃ for min-1In this case, the formation rate of the target flower-like material is high.
In some examples of this embodiment, the ethanol and water may be mixed in any ratio in the carbon-free water, and when the volume ratio of the ethanol to the water is 1: 4.5-5.5, the formation rate of the target flower-like material is high.
In some examples of this embodiment, the carbohydrate-free process is heated to boiling. The oxygen in the solvent can be better removed.
The preferred scheme of the invention comprises the following steps:
s1, preparing a reaction solvent, namely, carbohydrate-free water: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1: 4.5-5.5, heating and boiling under the argon atmosphere, and naturally cooling to room temperature;
s2, preparing a reaction solution: dissolving disodium ethylene diamine tetraacetate and nickel nitrate hexahydrate in a molar ratio of 1-2: 1 into the carbon-free aqueous solution prepared in S1, and then adjusting the pH value of the solution to 4.0-6.0 by using a sodium hydroxide solution; and simultaneously dissolving urotropine and cobalt nitrate hexahydrate in a molar ratio of 1-2: 1 into the carbon-free aqueous solution prepared in S1, and then uniformly mixing the two solutions in an argon atmosphere.
S3, preparing a solid-phase precursor: reacting the reaction solution prepared by S2 at 120-180 ℃ for 12-36 h, and purifying to obtain a solid phase precursor after the reaction is finished;
s4, preparing a flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers on the surface: s3, respectively placing the prepared solid-phase precursor and sublimed sulfur at the lower end and the upper end of a tube furnace, calcining for 2-5 hours at 400-500 ℃ under the argon atmosphere, and raising the temperature for 2 min -1And obtaining the flower-shaped cobalt disulfide micron flower material loaded with nickel disulfide on the surface after the reaction is finished.
In another embodiment of the invention, a flower-shaped cobalt disulfide micron flower material with nickel disulfide loaded on the surface is provided, and the flower-shaped cobalt disulfide micron flower material is obtained by the preparation method.
The micron-sized flower material loaded with nickel disulfide on the surface of the flower-shaped cobalt disulfide is micron-sized, the micron-sized flower material is uniform, the particle size is 3-10 microns, the average particle size is 4-6 microns, the appearance is in a flower-shaped three-dimensional structure, and the surface of a micron-sized flower piece is provided with micro holes.
According to a third embodiment of the invention, the application of the flower-shaped cobalt disulfide material with nickel disulfide micro flowers supported on the surface in the preparation of a lithium oxygen battery or a lithium oxygen battery cathode catalyst is provided.
In a fourth embodiment of the invention, a lithium oxygen battery positive electrode is provided, which comprises an active material, a conductive agent, a binder and a current collector, wherein the active material is the flower-shaped cobalt disulfide with a nickel disulfide micrometer flower material loaded on the surface.
In a fifth embodiment of the present invention, a lithium oxygen battery is provided, which includes the above-mentioned positive electrode, negative electrode, separator and electrolyte.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
The method is characterized in that a micron-sized flower material of nickel disulfide is loaded on the surface of flower-shaped cobalt disulfide and is prepared by the following steps:
s1, preparing a reaction solvent, namely, carbohydrate-free water: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:5, heating and boiling under the argon atmosphere, and naturally cooling to room temperature.
S2, preparing a reaction solution: 0.7g of disodium ethylenediaminetetraacetate and 0.7g of nickel nitrate hexahydrate were dissolved in 60mL of a carbon-free aqueous solution prepared in S1 and stirred at room temperature for 30 min. The pH of the solution was then adjusted to 5.0 using sodium hydroxide solution. 2g of urotropin and 2g of cobalt nitrate hexahydrate are simultaneously dissolved in 100mL of a carbonless aqueous solution prepared in S1 and stirred at room temperature for 30 min. Then, the two solutions were mixed uniformly under argon atmosphere and stirred for 10 min.
S3, preparing a solid-phase precursor: and (3) reacting the reaction solution prepared by the step S2 at 120 ℃ for 20h, and purifying after the reaction is finished to obtain a solid-phase precursor.
S4, preparing a flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers on the surface: s3, respectively placing the prepared solid-phase precursor and sublimed sulfur at the lower end and the upper end of a tube furnace, calcining for 2 hours at 500 ℃ under the argon atmosphere, and raising the temperature for 2 min-1After the reaction is finished, obtaining the flower-shaped cobalt disulfide micron flower material with nickel disulfide loaded on the surface;
FIG. 1 is an XRD (X-ray diffraction) pattern, diffraction data and CoS (cobalt disulfide) data of a flower-shaped cobalt disulfide surface-loaded nickel disulfide micro-flower material2Standard card (JCPDS No.89-3056) and NiS2Standard card (JCPDS No.80-0377) was identical, and no other impurity phases appeared, indicating that the product was a high purity nickel disulfide and cobalt disulfide compound. FIGS. 2 to 3 are FESEM pictures of a sample of a flower-shaped cobalt disulfide material with nickel disulfide micro-flowers loaded on the surface, and the pictures show that the material synthesized by the method is microspherical, the particle size is about 5 mu m, and the appearance is in a flower-shaped three-dimensional structure; fig. 4 is an HRTEM picture of a flower-shaped cobalt disulfide surface-supported nickel disulfide micro flower material, and it can be seen that the surface has tiny pores of about 2 nm.
The flower-like cobalt disulfide material loaded with nickel disulfide micro flower on the surface obtained in example 1 was used to prepare an electrode by the following method:
weighing a flower-shaped cobalt disulfide micron flower material loaded with nickel disulfide on the surface, carbon black and polytetrafluoroethylene respectively according to a mass ratio of 4:4:2, adding a certain volume of isopropanol, uniformly dispersing by ultrasonic, uniformly coating on carbon paper to prepare an electrode, adopting a metal lithium sheet as a negative electrode and 1mol L of electrolyte-1The 2032 type half cell is assembled by selecting a glass fiber diaphragm as the diaphragm of the lithium bistrifluoromethanesulfonimide/tetraglyme. All constant current charging and discharging tests were performed by a blue test system (LAND CT 2001A) in a test chamber filled with oxygen. The electrode material has a fixed specific capacity of 1000mAh g -1After charging and discharging, and 209 cycles, the higher discharge terminal voltage and the lower charge terminal voltage are still maintainedAs shown in fig. 5.
Example 2
The method is characterized in that a nickel disulfide micrometer flower material is loaded on the surface of flower-shaped cobalt disulfide, and the method is prepared by the following steps:
s1, preparing a reaction solvent, namely, carbohydrate-free water: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:5, heating and boiling the mixture in an argon atmosphere, and naturally cooling the mixture to room temperature.
S2, preparing a reaction solution: 0.7g of disodium ethylenediaminetetraacetate and 0.6g of nickel nitrate hexahydrate were dissolved in 60mL of a carbon-free aqueous solution prepared in S1 and stirred at room temperature for 30 min. The solution was then adjusted to pH 5.0 using sodium hydroxide solution. 2g of urotropin and 2g of cobalt nitrate hexahydrate were dissolved in 100mL of a carbonless aqueous solution prepared in S1 and the mixture was stirred at room temperature for 30 min. Then, the two solutions were mixed uniformly under argon atmosphere and stirred for 10 min.
S3, preparing a solid-phase precursor: and (3) reacting the reaction solution prepared by the step S2 at 120 ℃ for 20h, and purifying after the reaction is finished to obtain a solid-phase precursor.
S4, preparing a flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers on the surface: s3, respectively placing the prepared solid-phase precursor and sublimed sulfur at the lower end and the upper end of a tube furnace, calcining for 2 hours at 500 ℃ under the argon atmosphere, and raising the temperature for 2 min -1And obtaining the flower-shaped cobalt disulfide micron flower material loaded with nickel disulfide on the surface after the reaction is finished.
Example 3
The method is characterized in that a micron-sized flower material of nickel disulfide is loaded on the surface of flower-shaped cobalt disulfide and is prepared by the following steps:
s1, preparing a reaction solvent, namely, carbohydrate-free water: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:5, heating and boiling under the argon atmosphere, and naturally cooling to room temperature.
S2, preparing a reaction solution: 0.7g of disodium ethylenediaminetetraacetate and 0.5g of nickel nitrate hexahydrate were dissolved in 60mL of a carbon-free aqueous solution prepared in S1 and stirred at room temperature for 30 min. The pH of the solution was then adjusted to 5.0 using sodium hydroxide solution. 2g of urotropin and 2g of cobalt nitrate hexahydrate were dissolved in 100mL of a carbonless aqueous solution prepared in S1 and the mixture was stirred at room temperature for 30 min. Then, the two solutions were mixed uniformly under argon atmosphere and stirred for 10 min.
S3, preparing a solid-phase precursor: and (3) reacting the reaction solution prepared by the step S2 at 120 ℃ for 20h, and purifying after the reaction is finished to obtain a solid-phase precursor.
S4, preparing a flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers on the surface: s3, respectively placing the prepared solid-phase precursor and sublimed sulfur at the lower end and the upper end of a tube furnace, calcining for 2 hours at 500 ℃ under the argon atmosphere, and raising the temperature for 2 min -1And obtaining the flower-shaped cobalt disulfide micron flower material loaded with nickel disulfide on the surface after the reaction is finished.
Example 4
The method is characterized in that a micron-sized flower material of nickel disulfide is loaded on the surface of flower-shaped cobalt disulfide and is prepared by the following steps:
s1, preparing a reaction solvent, namely, carbohydrate-free water: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:5, heating and boiling the mixture in an argon atmosphere, and naturally cooling the mixture to room temperature.
S2, preparing a reaction solution: 0.7g of disodium ethylenediaminetetraacetate and 0.5g of nickel nitrate hexahydrate were dissolved in 60mL of a carbon-free aqueous solution prepared in S1 and stirred at room temperature for 30 min. The pH of the solution was then adjusted to 5.0 using sodium hydroxide solution. 2g of urotropin and 2g of cobalt nitrate hexahydrate were dissolved in 100mL of a carbonless aqueous solution prepared in S1 and the mixture was stirred at room temperature for 30 min. Then, the two solutions were mixed uniformly under argon atmosphere and stirred for 10 min.
S3, preparing a solid-phase precursor: and (3) reacting the reaction solution prepared by the step S2 at 130 ℃ for 20h, and purifying after the reaction is finished to obtain a solid-phase precursor.
S4, preparing a flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers on the surface: s3, respectively placing the prepared solid-phase precursor and sublimed sulfur at the lower end and the upper end of a tube furnace, calcining for 2 hours at 500 ℃ under the argon atmosphere, and raising the temperature for 2 min -1And after the reaction is finished, obtaining the micrometer flower material of the flower-shaped cobalt disulfide with the nickel disulfide loaded on the surface.
Example 5
The method is characterized in that a nickel disulfide micrometer flower material is loaded on the surface of flower-shaped cobalt disulfide, and the method is prepared by the following steps:
s1, preparing a reaction solvent, namely, carbohydrate-free water: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:5, heating and boiling the mixture in an argon atmosphere, and naturally cooling the mixture to room temperature.
S2, preparing a reaction solution: 0.7g of disodium ethylenediaminetetraacetate and 0.7g of nickel nitrate hexahydrate were dissolved in 60mL of a carbon-free aqueous solution prepared in S1 and stirred at room temperature for 30 min. The solution was then adjusted to pH 5.0 using sodium hydroxide solution. 2g of urotropin and 2g of cobalt nitrate hexahydrate were dissolved in 100mL of a carbonless aqueous solution prepared in S1 and the mixture was stirred at room temperature for 30 min. Then, the two solutions were mixed uniformly under argon atmosphere and stirred for 10 min.
S3, preparing a solid-phase precursor: and (3) reacting the reaction solution prepared by the step S2 at 120 ℃ for 20h, and purifying after the reaction is finished to obtain a solid-phase precursor.
S4, preparing a flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers on the surface: s3, respectively placing the prepared solid-phase precursor and sublimed sulfur at the lower end and the upper end of a tube furnace, calcining for 3 hours at 500 ℃ under the argon atmosphere, and raising the temperature for 2 min -1And obtaining the flower-shaped cobalt disulfide micron flower material loaded with nickel disulfide on the surface after the reaction is finished.
Example 6
The method is characterized in that a nickel disulfide micrometer flower material is loaded on the surface of flower-shaped cobalt disulfide, and the method is prepared by the following steps:
s1, preparing a reaction solvent, namely, carbohydrate-free water: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:5, heating and boiling the mixture in an argon atmosphere, and naturally cooling the mixture to room temperature.
S2, preparing a reaction solution: 0.7g of disodium ethylenediaminetetraacetate and 0.5g of nickel nitrate hexahydrate were dissolved in 60mL of a carbon-free aqueous solution prepared in S1 and stirred at room temperature for 30 min. The solution was then adjusted to pH 5.0 using sodium hydroxide solution. 2g of urotropin and 2g of cobalt nitrate hexahydrate were dissolved in 100mL of a carbonless aqueous solution prepared in S1 and the mixture was stirred at room temperature for 30 min. Then, the two solutions were mixed uniformly under argon atmosphere and stirred for 10 min.
S3, preparing a solid-phase precursor: and (3) reacting the reaction solution prepared by the step S2 at 130 ℃ for 24h, and purifying after the reaction is finished to obtain a solid-phase precursor.
S4, preparing a flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers on the surface: s3, respectively placing the prepared solid-phase precursor and sublimed sulfur at the lower end and the upper end of a tube furnace, calcining for 2 hours at 500 ℃ under the argon atmosphere, and raising the temperature for 2 min -1And obtaining the flower-shaped cobalt disulfide micron flower material loaded with nickel disulfide on the surface after the reaction is finished.
Example 7
The method is characterized in that a nickel disulfide micrometer flower material is loaded on the surface of flower-shaped cobalt disulfide, and the method is prepared by the following steps:
s1, preparing a reaction solvent, namely, carbohydrate-free water: mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:5, heating and boiling the mixture in an argon atmosphere, and naturally cooling the mixture to room temperature;
s2, preparing a reaction solution: 0.7g of disodium ethylenediaminetetraacetate and 0.5g of nickel nitrate hexahydrate were dissolved in 60mL of a carbon-free aqueous solution prepared in S1 and stirred at room temperature for 30 min. The solution was then adjusted to pH 5.0 using sodium hydroxide solution. 2g of urotropin and 2g of cobalt nitrate hexahydrate were dissolved in 100mL of a carbonless aqueous solution prepared in S1 and the mixture was stirred at room temperature for 30 min. Then, the two solutions were mixed uniformly under argon atmosphere and stirred for 10 min.
S3, preparing a solid-phase precursor: and (3) reacting the reaction solution prepared by the step S2 at 120 ℃ for 20h, and purifying after the reaction is finished to obtain a solid-phase precursor.
S4, preparing a flower-shaped cobalt disulfide material loaded with nickel disulfide micro flowers on the surface: s3, respectively placing the prepared solid-phase precursor and sublimed sulfur at the lower end and the upper end of a tube furnace, calcining for 3 hours at 500 ℃ under the argon atmosphere, and raising the temperature for 2 min -1And after the reaction is finished, obtaining the micrometer flower material of the flower-shaped cobalt disulfide with the nickel disulfide loaded on the surface.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a flower-shaped cobalt disulfide surface loaded nickel disulfide micrometer flower material is characterized by comprising the following steps:
adding disodium ethylene diamine tetraacetate, urotropine, nickel salt and cobalt salt into carbon-free water to be dissolved in inert atmosphere, and adding alkali liquor to obtain mixed liquor;
carrying out hydrothermal reaction on the mixed solution to obtain a solid-phase precursor;
sublimating sulfur by using a chemical vapor deposition method, contacting the sublimed sulfur with a solid-phase precursor to perform a vulcanization reaction, and calcining the sulfur simultaneously to obtain the sulfur-containing catalyst;
wherein the carbohydrate-free water is obtained by heating ethanol and water under an inert atmosphere to remove oxygen.
2. The method for preparing the micron flower material of nickel disulfide supported on the surface of the flower-shaped cobalt disulfide according to claim 1, wherein the process for preparing the mixed solution comprises the following steps: adding disodium ethylene diamine tetraacetate and nickel salt into carbon-free water for dissolving, and adding alkali liquor to obtain solution A;
Adding urotropine and cobalt salt into carbon-free water for dissolving to obtain a solution B;
mixing the solution A and the solution B to obtain a mixed solution;
preferably, the pH of the solution A is 4-6.
3. The preparation method of the flower-like cobalt disulfide surface-supported nickel disulfide micro flower material as claimed in claim 1, wherein the molar ratio of disodium ethylenediamine tetraacetic acid to nickel salt is 1-2: 1; preferably 1-1.1: 1;
or the mol ratio of the urotropine to the cobalt salt is 1-2: 1; preferably 1-1.1: 1;
or the molar ratio of the nickel salt to the cobalt salt is 1: 2.5-3.5.
4. The preparation method of the flower-shaped cobalt disulfide micron flower material with nickel disulfide loaded on the surface as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 120-150 ℃, and the reaction time is 12-36 h; preferably, the temperature of the hydrothermal reaction is 120-125 ℃, and the reaction time is 19-21 h.
5. The preparation method of the flower-shaped cobalt disulfide micron flower material with nickel disulfide loaded on the surface as claimed in claim 1, wherein the temperature of the sulfuration reaction and the calcination treatment is 400-600 ℃, and the time is 2-5 h; the temperature is preferably 400-500 ℃, and the time is preferably 2-2.1 h;
or the heating rate of the vulcanization reaction and the calcination treatment is 2-10 ℃ min -1。
6. The method for preparing the micron flower material of nickel disulfide supported on the surface of the flower-shaped cobalt disulfide as claimed in claim 1, wherein in the carbon-free water, the ethanol and the water can be mixed in any proportion; preferably, the volume ratio of the ethanol to the water is 1: 4.5-5.5.
7. A micro flower material with flower-shaped cobalt disulfide surface loaded with nickel disulfide is characterized by being obtained by the preparation method of any one of claims 1-6;
preferably, the micron-sized flower material loaded with nickel disulfide on the surface of the flower-shaped cobalt disulfide is micron-sized, the micron-sized flowers are uniform, the particle size is 3-10 mu m, the average particle size is 4-6 mu m, the appearance of the micron-sized flower material is in a flower-shaped three-dimensional structure, and the surface of the micron flower piece is provided with micro holes.
8. Use of the flower-like cobalt disulfide material with nickel disulfide micro flowers supported on the surface thereof according to claim 7 in preparation of lithium oxygen battery or lithium oxygen battery positive electrode catalyst.
9. A positive electrode of a lithium oxygen battery, which comprises an active material, a conductive agent, a binder and a current collector, and is characterized in that the active material is the flower-shaped cobalt disulfide with nickel disulfide micro flower material loaded on the surface.
10. A lithium oxygen cell comprising the positive electrode, the negative electrode, the separator and the electrolyte according to claim 9.
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