CN113548699A - Cobalt oxide/carbon nanotube composite material, preparation method thereof and application thereof in lithium air battery - Google Patents
Cobalt oxide/carbon nanotube composite material, preparation method thereof and application thereof in lithium air battery Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 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 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical group CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims 1
- 229910001641 magnesium iodide Inorganic materials 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000005844 autocatalytic reaction Methods 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002070 nanowire Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910003004 Li-O2 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- ZQBVUULQVWCGDQ-UHFFFAOYSA-N propan-1-ol;propan-2-ol Chemical compound CCCO.CC(C)O ZQBVUULQVWCGDQ-UHFFFAOYSA-N 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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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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- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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Abstract
The invention discloses a cobalt oxide/carbon nanotube composite material, a preparation method thereof and application thereof in a lithium air battery, wherein the composite material takes a rhombic dodecahedron ZIF-8@ ZIF-67 double MOF material as a substrate, and mSiO is coated on the surface of the dodecahedron2Balls, and then deriving CNTs from Co by autocatalysis. The composite material has larger specific surface area, provides more catalytic active sites, and has excellent catalytic performances of low overvoltage, high discharge specific capacity, good cycle performance and the like when being used as a lithium air battery anode catalyst.
Description
Technical Field
The invention relates to the field of battery material preparation, in particular to Co3O4a/CNTs composite material, a preparation method thereof and application in a lithium air battery.
Background
With the continuous development of society, environmental problems become more severe, and the development of sustainable green new energy is not slow. Compared with a lithium ion battery, the lithium air battery has ultrahigh discharge specific energy which can reach 11400Wh kg at most-1Is considered to be one of the most promising high-performance secondary batteries[1]. A plurality of scholars have conducted extensive research on the high-performance ionic liquid, but still face the challenges of low actual specific capacity, high overpotential, poor cycling stability and the like[2]. The development of the high-efficiency bifunctional catalyst can improve the reaction kinetics of the lithium-air battery, reduce the overpotential and improve the rate capability and the cycle performance of the battery. The catalyst used in common use mainly comprises noble metal and its oxide, carbon material, transition metal oxide, etc. Noble metals and their oxides have good catalytic properties, but their high price limits their large-scale use. The carbon material has good conductivity and large specific surface area, but the single carbon material pore structure cannot well support the material transmission and the storage of reaction products in the reaction process. Transition metal oxides are sought after by researchers for their low cost and high catalytic activity.
Lu et al synthesized alpha-MnO of different lengths by hydrothermal method2Nano wire, high specific discharge capacity and high cyclic stability[3]. CeO is prepared from poplar and the like2@NiCo2O4The nano-wire has excellent ORR and OER dual-functional catalytic activity, and when the nano-wire is used as a catalyst for a lithium air battery, the rate performance of the battery is greatly improved[4]。
Although the method is beneficial to improving the performance of the lithium-air battery, the preparation method is complicated, the morphology regulation and control difficulty is high, and the large-scale application is difficult. The method develops a novel catalyst material with high efficiency and simple preparation process so as to improve the performance of the lithium-air battery, and has important research value.
Reference documents:
[1] li Red, Yanglin Li-O2(Air) batteries research progress [ J ] Ship electric technology, 2018,38(007):21-27.
[2] Zhang, Tanggong, Zengyu, et al. soluble oxidation-reduction media promote the performance of lithium-oxygen batteries with hierarchical carbon nanocages [ J ]. reports of chemistry 2020,78: 572-.
[3]Lou Chang Jian, Zhu Fa, Yin Ji Guang, et al2 Nanowires via Facile Hydrothermal Method and Their Application in Li-O2 Battery[J]The journal of inorganic materials, 2018,33(9): 1029-.
[4] Yang Z D, Chang Z W, Xu J, et al, CeO2@ NiCo2O4 nanowire arrays on carbon tissues as high, performance category for Li-O2 batteries [ J ] Chinese science, 2017,000(012) P.1540-1545.
Disclosure of Invention
Aiming at the defects of the existing lithium-air battery anode catalyst material, the invention aims to provide Co which can be prepared by a simple process method and has good conductivity and catalytic activity3O4A/CNTs composite material is used for a lithium air battery to improve the performance thereof.
In order to solve the technical problem, the invention adopts the following technical scheme:
the invention firstly discloses Co3O4The preparation method of the/CNTs composite material is characterized by comprising the following steps: mixing 2-methylimidazole with methanol solution of cobalt salt and zinc salt, uniformly stirring, standing, centrifuging and drying to obtain ZIF-8@ ZIF-67 precipitate; dissolving the ZIF-8@ ZIF-67 precipitate in deionized water, adding hexadecyl trimethyl ammonium bromide, sodium hydroxide, a silicon source and methanol to form mSiO on the surface of the ZIF-8@ ZIF-672A protective shell; after calcination in an inert atmosphere, the surface of the mSiO is washed away with hydrofluoric acid2Protective shell, finally annealing in oxygen atmosphere to obtain Co3O4a/CNTs composite material. The method specifically comprises the following steps:
(1) dissolving 4-8 g of 2-methylimidazole in 20mL of methanol, dissolving 1-2 g of zinc salt in 20mL of methanol, and dissolving 1-2 g of cobalt salt in 20mL of methanol; then quickly adding the methanol solution of 2-methylimidazole into the methanol solution of zinc salt, uniformly stirring, then adding the methanol solution of cobalt salt, uniformly stirring, standing for 12-24 hours, centrifuging, and drying to obtain a ZIF-8@ ZIF-67 precipitate;
(2) dissolving 1g of ZIF-8@ ZIF-67 precipitate in 200mL of solution to removeAdding 0.5-1 g of hexadecyl trimethyl ammonium bromide, 0.02-0.1 g of sodium hydroxide, 1-5 mL of silicon source and 5-10 mL of methanol into water, stirring for 0.5-1 h, performing suction filtration and drying to form mSiO on the surface of ZIF-8@ ZIF-672Protective shell, marked as ZIF-8@ ZIF-67@ mSiO2；
(3) ZIF-8@ ZIF-67@ mSiO2Calcining at 900-1000 ℃ for 3-4 h under inert atmosphere, washing with 5-10 wt% hydrofluoric acid, and annealing at 300-350 ℃ for 4-5 h in a muffle furnace under oxygen atmosphere to obtain Co3O4a/CNTs composite material.
Further, the cobalt salt is cobalt chloride, cobalt bromide, cobalt carbonate, cobalt acetate or cobalt nitrate hexahydrate, preferably cobalt nitrate hexahydrate.
Further, the zinc salt is zinc chloride, zinc acetate, zinc sulfate or zinc nitrate hexahydrate, and zinc nitrate hexahydrate is preferred.
Further, the silicon source is tetrabutyl silicate or tetraethyl silicate, preferably tetrabutyl silicate.
Further, the inert atmosphere is argon or nitrogen, preferably argon.
The invention also discloses Co prepared by the preparation method3O4CNTs composite material, which is rhombic dodecahedral Co3O4The surface of the carbon nano tube is wrapped, and the carbon nano tube can be used as a lithium-air battery anode catalyst material.
Compared with the prior art, the invention has the beneficial effects that:
1. co provided by the invention3O4the/CNTs composite material takes a rhombic dodecahedron ZIF-8@ ZIF-67 double MOF material as a substrate, and mSiO is coated on the surface of the dodecahedron2Balls, and then CNTs derived by autocatalysis of Co. The composite material has a large specific surface area, provides more catalytic active sites, and has excellent catalytic performances such as low overvoltage, high discharge specific capacity and good cycle performance when being used as a lithium-air battery anode catalyst.
2. Co of the invention3O4In the/CNTs composite material, CNTs are generated by Co autocatalysis, and the processSimply, the CNTs improve the specific surface area and porosity of the material, can promote the diffusion of metal ions and oxygen in the catalytic reaction process, and meanwhile, the Co-N-C improves the catalytic activity of the material.
3. Co of the invention3O4CNTs composite material, using mSiO2The high temperature resistance of the material avoids the evaporation of a large amount of carbon at high temperature, and the optimal catalytic activity of the material is exerted.
4. The composite material provided by the invention is used for a lithium-air battery, and the result shows that the deep battery performance test (2.0-4.5V) is carried out under the condition of high-purity oxygen, the first discharge specific capacity is 10866mAh/g, the composite material can stably run for 187 cycles under the current density of 500mA/g, the overvoltage is maintained at about 1.02V, and the performance is excellent.
5. The preparation process is simple and low in cost.
Drawings
FIG. 1 shows Co3O4A structural schematic diagram of/CNTs;
FIG. 2 shows Co obtained in example 13O4X-ray photoelectron spectroscopy (XPS) of the/CNTs composite;
FIG. 3 shows Co obtained in example 13O4Scanning Electron Micrographs (SEM) of/CNTs composite;
FIG. 4 shows Co obtained in example 13O4Transmission Electron Microscopy (TEM) of the/CNTs composite;
FIG. 5 shows Co obtained in example 13O4A first charge-discharge performance diagram of a lithium air battery assembled by the/CNTs composite material;
FIG. 6 shows Co obtained in example 13O4A cycle performance diagram of a lithium air battery assembled by the/CNTs composite material;
FIG. 7 shows Co obtained in example 13O4Overvoltage diagram of lithium air battery assembled by/CNTs composite material;
FIG. 8 shows Co obtained in comparative example 13O4SEM images of the material;
FIG. 9 is a graph showing ORR performance test results of the materials obtained in examples 1 to 3 and comparative example 1, and a to d represent the materials obtained in examples 1 to 3 and comparative example 1 in this order.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
(1) 4.5g of 2-methylimidazole are dissolved in 20mL of methanol, 1.5g of zinc nitrate hexahydrate is dissolved in 20mL of methanol, and 1.5g of cobalt nitrate hexahydrate is dissolved in 20mL of methanol; then quickly adding the methanol solution of 2-methylimidazole into the methanol solution of zinc nitrate hexahydrate, stirring for 30min, then adding the methanol solution of cobalt nitrate hexahydrate, stirring for 30min, standing for 24h, then centrifuging, and drying at 60 ℃ for 24h to obtain the ZIF-8@ ZIF-67 precipitate.
(2) Dissolving 1g ZIF-8@ ZIF-67 precipitate in 200mL deionized water, adding 0.8g hexadecyltrimethylammonium bromide, 0.1g sodium hydroxide, 1.5mL tetrabutyl silicate and 8mL methanol, stirring for 30min, filtering, and drying at 60 ℃ for 24h to form mSiO on the surface of ZIF-8@ ZIF-672Protective shell, marked as ZIF-8@ ZIF-67@ mSiO2。
(3) ZIF-8@ ZIF-67@ mSiO2Placing the powder in a quartz boat, heating to 900 ℃ by a tube furnace at the heating rate of 2 ℃/min under the Ar gas atmosphere, carrying out heat preservation and calcination for 3h, evaporating Zn at the high temperature of 900 ℃ to leave vacant sites, and obtaining Co/CNTs-mSiO2And (3) powder.
(4) Dripping 5 wt% of hydrofluoric acid into Co/CNTs-mSiO2In the powder, the surface of the mSiO is washed off2Protecting the shell, drying at 60 ℃ for 24h, and then putting the shell into a muffle furnace to anneal at 350 ℃ for 4h in an oxygen atmosphere to obtain Co3O4a/CNTs composite material.
FIG. 2 shows the Co obtained in this example3O4X-ray photoelectron spectroscopy (XPS) of the/CNTs composite material shows that the obtained material is Co3O4/CNTs。
FIG. 3 shows Co obtained in this example3O4Scanning Electron Microscopy (SEM) of the/CNTs composite material shows that the composite materialIs made of tubular carbon material wrapping rhombic dodecahedron Co3O4。
FIG. 4 shows the Co obtained in this example3O4Transmission Electron Microscopy (TEM) of/CNTs material, it can be seen that CNTs are wrapped in rhombic dodecahedron Co3O4Of (2) is provided.
Co obtained in this example3O4the/CNTs composite material is used as a lithium air battery anode catalyst material and is assembled with a lithium sheet into a button lithium air battery, and the assembling method is as follows: the homogenate containing 60% KB, 30% catalyst material and 10% PVDF was loaded onto a carbon paper collector and then dried in a vacuum oven at 60 ℃ for 12 h. The net mass of the dried catalyst on the carbon paper is about 0.3-0.5 mg. And (3) taking a lithium foil as an anode, spreading a glass fiber separator, dripping 110 mu L of electrolyte, adding carbon paper with a catalyst, covering a cathode instrument with foamed nickel as a filler, and completing battery assembly in a glove box filled with argon.
FIG. 5 shows Co of this example3O4First charge and discharge performance diagram of lithium air battery assembled by/CNTs composite material, and it can be seen that the first charge and discharge performance diagram is 100mA gcarbon -1Under the constant current discharge density, the first discharge specific capacity reaches 10866mA h gcarbon -1。
FIG. 6 shows Co of this example3O4The cycle performance of the lithium-air battery assembled by the/CNTs composite material can be seen in a graph of 500mA gcarbon -1The discharge density of the electrode can be 187 circles under the constant current discharge density, and the excellent cycling stability is shown.
FIG. 7 shows Co of this example3O4Overvoltage diagram of lithium air battery assembled by/CNTs composite material, which can be seen at 100mA gcarbon -1The overvoltage is about 1.02V at the constant current discharge density of (2).
Example 2
This example was carried out in the same manner as in example 1 to prepare Co3O4a/CNTs composite material, based on which a lithium-air battery was assembled, except that the mass of 2-methylimidazole in step (1) was 8 g.
Tested, based on the Co of the embodiment3O4The lithium air battery assembled by the/CNTs composite material is at 500mA g-1The capacity decayed after 81 cycles at constant current discharge density of (1).
Example 3
This example was carried out in the same manner as in example 1 to prepare Co3O4a/CNTs composite material, and a lithium air battery assembled based thereon, with the only difference that the calcination temperature in step (2) is 1000 ℃.
Tested, based on the Co of the embodiment3O4The lithium air battery assembled by the/CNTs composite material is 500mAg-1The capacity decays after 43 cycles at constant current discharge density of (1).
Comparative example 1
This example was carried out in the same manner as in example 1 to prepare Co3O4Materials, except without encapsulation of mSiO2The method comprises the following specific steps:
4.5g of 2-methylimidazole are dissolved in 20mL of methanol, 1.5g of zinc nitrate hexahydrate is dissolved in 20mL of methanol, and 1.5g of cobalt nitrate hexahydrate is dissolved in 20mL of methanol; then quickly adding the methanol solution of 2-methylimidazole into the methanol solution of zinc nitrate hexahydrate, stirring for 30min, then adding the methanol solution of cobalt nitrate hexahydrate, stirring for 30min, standing for 24h, then centrifuging, and drying at 60 ℃ for 24h to obtain the ZIF-8@ ZIF-67 precipitate.
Putting ZIF-8@ ZIF-67 powder into a quartz boat, heating to 900 ℃ at a heating rate of 2 ℃/min in a tube furnace under Ar gas atmosphere, carrying out heat preservation and calcination for 3h, and then putting the quartz boat into a muffle furnace to anneal for 4h at 350 ℃ under oxygen atmosphere to obtain Co3O4A material.
FIG. 8 is a comparative example without packaging of mSiO2In the case of (2) obtained Co3O4SEM images of the material, from which it can be seen that there are no CNTs present on the surface of the material.
Co obtained in this example was reacted in the same manner as in example 13O4Material Assembly into Co3O4The materials are assembled into a lithium air battery.
Tested based onCo of the present example3O4The material is assembled by adopting a lithium air battery and is arranged at 500mA g-1The capacity decayed after 37 cycles at constant current discharge density of (1).
FIG. 9 is a graph showing ORR performance test results of the materials obtained in examples 1 to 3 and comparative example 1, and a to d represent the materials obtained in examples 1 to 3 and comparative example 1 in this order. The sample preparation and testing methods were as follows: 10mg of catalyst, 2mg KB and 40. mu.L naphthol were dissolved together in 2mL of an aqueous isopropanol solution (V)Isopropanol (I-propanol)：VWater (W)1:5), and performing ultrasonic treatment for 1 hour to obtain a uniform mixed solution. Dropping 3 mu L of solution on a glassy carbon electrode, and air-drying for 2h to form a catalyst layer. The LSV test was performed on a disk electrode. It can be seen from the figure that the catalyst prepared in example 1 can achieve the highest limiting current density and the best catalytic effect when tested.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A preparation method of a cobalt oxide/carbon nano tube composite material is characterized by comprising the following steps: mixing 2-methylimidazole with methanol solution of cobalt salt and zinc salt, uniformly stirring, standing, centrifuging and drying to obtain ZIF-8@ ZIF-67 precipitate; dissolving the ZIF-8@ ZIF-67 precipitate in deionized water, adding hexadecyl trimethyl ammonium bromide, sodium hydroxide, a silicon source and methanol to form mSiO on the surface of the ZIF-8@ ZIF-672A protective shell; after calcination in an inert atmosphere, the surface of the mSiO is washed away with hydrofluoric acid2Protective shell, finally annealing in oxygen atmosphere to obtain Co3O4a/CNTs composite material.
2. The method for preparing a cobalt oxide/carbon nanotube composite material according to claim 1, comprising the steps of:
(1) dissolving 4-8 g of 2-methylimidazole in 20mL of methanol, dissolving 1-2 g of zinc salt in 20mL of methanol, and dissolving 1-2 g of cobalt salt in 20mL of methanol; then quickly adding the methanol solution of 2-methylimidazole into the methanol solution of zinc salt, uniformly stirring, then adding the methanol solution of cobalt salt, uniformly stirring, standing for 12-24 hours, centrifuging, and drying to obtain a ZIF-8@ ZIF-67 precipitate;
(2) dissolving 1g of ZIF-8@ ZIF-67 precipitate in 200mL of deionized water, adding 0.5-1 g of hexadecyl trimethyl ammonium bromide, 0.02-0.1 g of sodium hydroxide, 1-5 mL of silicon source and 5-10 mL of methanol, stirring for 0.5-1 h, performing suction filtration and drying to form mSiO (magnesium iodide oxide) on the surface of the ZIF-8@ ZIF-672Protective shell, marked as ZIF-8@ ZIF-67@ mSiO2；
(3) ZIF-8@ ZIF-67@ mSiO2Calcining at 900-1000 ℃ for 3-4 h under inert atmosphere, washing with 5-10 wt% hydrofluoric acid, and annealing at 300-350 ℃ for 4-5 h in a muffle furnace under oxygen atmosphere to obtain Co3O4a/CNTs composite material.
3. The method for preparing a cobalt oxide/carbon nanotube composite material according to claim 1 or 2, wherein: the cobalt salt is cobalt chloride, cobalt bromide, cobalt carbonate, cobalt acetate or cobalt nitrate hexahydrate.
4. The method for preparing a cobalt oxide/carbon nanotube composite material according to claim 1 or 2, wherein: the zinc salt is zinc chloride, zinc acetate, zinc sulfate or zinc nitrate hexahydrate.
5. The method for preparing a cobalt oxide/carbon nanotube composite material according to claim 1 or 2, wherein: the silicon source is tetrabutyl silicate or tetraethyl silicate.
6. The method for preparing a cobalt oxide/carbon nanotube composite material according to claim 1 or 2, wherein: the inert atmosphere is argon atmosphere or nitrogen atmosphere.
7. Co prepared by the preparation method of any one of claims 1 to 63O4a/CNTs composite material.
8. Co according to claim 73O4the/CNTs composite material is characterized in that: the Co3O4the/CNTs composite material is Co with rhombic dodecahedron3O4The surface is wrapped with carbon nanotubes.
9. Co as claimed in claim 7 or 83O4The application of the/CNTs composite material is characterized in that: the catalyst is used as a lithium-air battery anode catalyst material.
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