CN108172782B - Preparation method and application of carbon-coated porous cobaltous oxide nano material with shell-core structure - Google Patents
Preparation method and application of carbon-coated porous cobaltous oxide nano material with shell-core structure Download PDFInfo
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- CN108172782B CN108172782B CN201711329542.3A CN201711329542A CN108172782B CN 108172782 B CN108172782 B CN 108172782B CN 201711329542 A CN201711329542 A CN 201711329542A CN 108172782 B CN108172782 B CN 108172782B
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 61
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002086 nanomaterial Substances 0.000 title abstract description 31
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 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 9
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- 238000003756 stirring Methods 0.000 claims description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
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- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 26
- 238000005530 etching Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
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- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000003917 TEM image Methods 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 5
- 229920001690 polydopamine Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Abstract
The invention provides a simple method for preparing a carbon-coated porous cobaltous oxide nano material with a shell-core structure and electrochemical performance of the carbon-coated porous cobaltous oxide nano material as an anode of a lithium ion battery, and the specific preparation steps comprise: preparing a solid cobaltosic oxide nanocube by a hydrothermal method; after the surface of the prepared nanocube is coated with PDA, the carbon-coated porous cobaltous oxide shell-core nanomaterial is obtained by medium-high temperature calcination, and finally the carbon-coated porous cobaltous oxide nanomaterial with the shell-core structure is formed by hydrochloric acid etching. The method does not add any directing agent and surfactant, has mild conditions, environmental protection, cheap raw materials and low requirement on equipment in the whole synthesis process, is convenient for industrial production, and has great application prospect in the preparation of the anode material of the lithium ion battery.
Description
Technical Field
The invention relates to a synthesis method for preparing a carbon-coated porous cobaltous oxide nano material with a shell-core structure and application of the carbon-coated porous cobaltous oxide nano material in a power lithium ion battery anode.
Background
With the continuous development of the technology and the gradual change of life style of people, the lithium ion battery has more and more prominent position in life, and the demand of people for electrode materials with high rate performance is more and more urgent. As a negative electrode material of a lithium ion battery, the theoretical specific capacity of cobaltous oxide is up to 715mAh g-1About 2 times as much as graphitized carbon. But the first coulombic efficiency and the cycle performance of cobaltous oxide are poor. To overcome these disadvantages, the structural design of cobaltous oxide is especially important, for example, Chinese patent document CN 103950994B adopts organic metal cobalt salt and two kinds of cobalt saltsThe protective agent finally synthesizes the double-layer cobaltous oxide hollow nano-particles through solvothermal reaction; K.J.an and N.Y.Lee et al adopt cobalt chloride hexahydrate as a raw material to synthesize cobaltous oleate, and then decompose the cobaltous oleate through high-temperature thermal decomposition to finally prepare a CoO nanorod (J.Am.chem.Soc.2006,128, 9753-9760); chinese patent document CN 101800302 a invented graphene nanosheet-cobaltous oxide composite negative electrode material synthesized by hydrothermal reaction. At present, few reports are made on carbon-coated porous cobaltous oxide nanocube three-dimensional materials with shell-core structures, so that the materials have practical significance and application value for research and development.
Disclosure of Invention
The invention aims to provide a synthesis method for synthesizing a carbon-coated porous cobaltous oxide nano material with a shell-core structure and application of the carbon-coated porous cobaltous oxide nano material to a lithium ion battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a carbon-coated porous cobaltous oxide nano material with a shell-core structure comprises the following steps:
firstly, preparing cobaltosic oxide nano material by using hydrothermal method
Dispersing cobalt nitrate hexahydrate in deionized water, magnetically stirring until the cobalt nitrate hexahydrate is transparent, adding sodium hydroxide into the solution, continuously stirring until the cobalt nitrate hexahydrate is transparent, transferring the obtained solution into a reaction kettle, reacting for 24 hours at 180 ℃, cooling to room temperature after the reaction is finished, centrifuging, centrifugally washing the obtained solid for a plurality of times by using an ethanol water solution, and drying the centrifuged solid to obtain a cobaltosic oxide nano material;
secondly, coating the surface of the cobaltosic oxide nano material prepared in the first step with PDA
Dissolving the cobaltosic oxide nano material prepared in the first step and dopamine hydrochloride in a tris (hydroxymethyl) aminomethane buffer solution, stirring for 3h at room temperature, centrifuging, centrifugally washing the obtained solid with an ethanol aqueous solution for several times, and drying the centrifuged solid to obtain the cobaltosic oxide nano material with the surface coated with PDA;
thirdly, calcining the material obtained in the second step to obtain the carbon-coated porous cobaltous oxide nano material with the shell-core structure
The calcining condition is that the cobaltosic oxide nano material with the surface wrapped by the PDA obtained in the second step is kept at the constant temperature of 450-500 ℃ for 2-4 h at the heating rate of 5 ℃/min.
Preferably, the method also comprises a fourth step of hydrochloric acid etching, wherein the carbon-coated porous cobaltous oxide nano material obtained in the third step is soaked in a hydrochloric acid solution for 12min or less, then washed with an ethanol water solution for a plurality of times, centrifuged, and then the solid is dried in vacuum to obtain the carbon-coated porous cobaltous oxide nano material with the shell-core structure.
Preferably, the mass ratio of the cobalt nitrate hexahydrate to the sodium hydroxide in the first step is 4: 1.
Preferably, the concentration of the tris (hydroxymethyl) aminomethane buffer in the second step is 10 mM.
Preferably, the concentration of cobaltosic oxide in the second step is 0.9g/ml, and the concentration of dopamine hydrochloride in the second step is 0.4 g/ml.
Preferably, the concentration of the hydrochloric acid solution in the fourth step is 0.1 mol/L.
The carbon-coated porous cobaltous oxide nano material prepared by the preparation method of the carbon-coated porous cobaltous oxide nano material with the shell-core structure is applied to a lithium ion battery as a negative electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1. the carbon-coated porous cobaltous oxide nanocube three-dimensional material prepared by the preparation method has a shell-core structure, the structure has a plurality of mesopores, and the transmission path of lithium ions and electrons can be effectively improved, so that the multiplying power performance of the material is improved; secondly, the carbon coated outside can effectively prevent the capacity from being attenuated due to the direct contact of the electrolyte and the active material.
2. The whole process of the invention is carried out in a water system, no guiding agent and surfactant are added, and the preparation process is simple, green, cheap and safe, and is easier to realize industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of the carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure prepared in example 1;
FIG. 2 is a scanning electron micrograph of the carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure prepared in example 1;
FIG. 3 is a transmission electron micrograph of the carbon-coated porous cobaltous oxide nanomaterial with the shell-core structure prepared in example 1;
FIG. 4 is a transmission electron micrograph of a carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure obtained by etching for 3 minutes in example 2;
FIG. 5 is a transmission electron micrograph of a carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure obtained by etching for 6 minutes in example 3;
FIG. 6 is a transmission electron micrograph of a carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure obtained by etching for 12 minutes in example 4;
FIG. 7 is a cyclic voltammogram of the carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure prepared in example 1;
fig. 8 is a cycle chart of the carbon-coated porous cobaltous oxide nanomaterial with a shell-core structure prepared in example 1 as an electrode material under different current densities.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The preparation method of the carbon-coated porous cobaltous oxide nano material with the shell-core structure comprises the following steps:
first, preparation of cobaltosic oxide nanocubes
Preparing cobaltosic oxide by a hydrothermal method (also called hydrothermal method), dispersing 0.04 mol of cobalt nitrate hexahydrate in 40 mL of deionized water, and stirring the mixture under magnetic stirring until the mixture is transparent; adding 0.01 mol of sodium hydroxide into the solution, and continuously stirring the solution until a clear solution is obtained; transferring the solution into a 50 mL polytetrafluoroethylene reaction kettle, and placing the reaction kettle in an oven to react for 24 hours at 180 ℃; after the reaction is finished, naturally cooling the reaction kettle to room temperature, centrifugally separating the obtained sample, centrifugally washing the sample for three times by using a water/ethanol mixed solution, and drying the sample for 12 hours at 65 ℃;
second, preparation of PDA (polydopamine) -wrapped cobaltosic oxide nanocubes
Putting 90 mg of cobaltosic oxide prepared in the first step and 40 mg of dopamine hydrochloride into 100 mL of 10mM Tris-buffer solution, and stirring for 3h at room temperature; then centrifugally separating the precipitate, centrifugally washing the precipitate for three times by using a water/ethanol mixed solution, and drying the precipitate for 12 hours at 65 ℃;
step three, preparing the porous carbon-coated cobaltous oxide by temperature control conversion
And (3) putting the product prepared in the second step into a tubular furnace, heating at the speed of 5 ℃/min, and keeping the temperature at the temperature of 500 ℃ for 3 hours to prepare the carbon-coated porous cobaltous oxide nanocube three-dimensional material with the shell-core structure.
The XRD pattern of the carbon-coated cobaltous oxide material prepared in this example is shown in fig. 1, and compared with a standard card, the carbon-coated cobaltous oxide material prepared in this example is illustrated. The scanning electron microscope image and the transmission electron microscope image are shown in FIGS. 2 and 3.
Example 2
As in example 1, except that,
fourthly, preparation of porous carbon-coated cobaltous oxide by hydrochloric acid etching
And dispersing the product prepared in the third step in a hydrochloric acid solution with the concentration of 0.1mol/L for etching for 3min, then washing with deionized water/ethanol to remove soluble impurities, centrifugally separating the obtained substance, and drying in vacuum at 65 ℃ to prepare the carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure.
The transmission electron microscope image of the carbon-coated porous cobaltous oxide nanocube three-dimensional material etched by hydrochloric acid in the embodiment is shown in fig. 4.
Example 3
As in example 1, except that,
fourthly, preparation of porous carbon-coated cobaltous oxide by hydrochloric acid etching
And dispersing the product prepared in the third step in a hydrochloric acid solution with the concentration of 0.1mol/L for etching for 6min, then washing by deionized water/ethanol to remove soluble impurities, centrifugally separating the obtained substance, and drying in vacuum at 65 ℃ to prepare the carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure.
The transmission electron microscope image of the carbon-coated porous cobaltous oxide nanocube three-dimensional material etched by hydrochloric acid in the embodiment is shown in fig. 5.
Example 4
As in example 1, except that,
fourthly, preparation of porous carbon-coated cobaltous oxide by hydrochloric acid etching
And dispersing the product prepared in the third step in a hydrochloric acid solution with the concentration of 0.1mol/L for etching for 12min, then washing with deionized water/ethanol to remove soluble impurities, centrifugally separating the obtained substance, and drying in vacuum at 65 ℃ to prepare the carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure.
The transmission electron microscope image of the carbon-coated porous cobaltous oxide nanocube three-dimensional material etched by hydrochloric acid in the embodiment is shown in fig. 6.
The process for preparing the carbon-coated porous cobaltous oxide nanocube three-dimensional material has the advantages of simple requirement on the whole reaction condition, low cost, greenness and environmental protection, and is more suitable for industrial production. The X-ray diffraction pattern of the prepared carbon-coated porous cobaltous oxide nanocube material with the shell-core structure is shown in figure 1, and the sample is single-phase cobaltous oxide (JCPDS: 48-1719). FIG. 2 is an SEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure prepared in example 1, wherein the cobaltous oxide surface is uniformly coated with a carbon layer and has obvious holes; FIG. 3 shows a TEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure prepared in example 1; FIG. 4 shows a TEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure obtained by 3min etching; FIG. 5 shows a TEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure obtained by 6min etching; FIG. 6 shows a TEM image of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure obtained by 12min etching, wherein the cobaltous oxide inside is completely etched, and only a carbon shell is left; FIG. 7 shows a cyclic voltammogram of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure prepared in example 1; FIG. 8 shows the electrochemical cycle diagram of the carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure prepared in example 1 at the current density of 0.2A/g.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (1)
1. A preparation method of a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure for improving the multiplying power performance of a lithium ion battery cathode material is characterized by comprising the following steps:
firstly, preparing cobaltosic oxide nanocubes by using a hydrothermal method
Dispersing cobalt nitrate hexahydrate in deionized water, magnetically stirring until the cobalt nitrate hexahydrate is transparent, adding sodium hydroxide into the solution, continuously stirring until the cobalt nitrate hexahydrate is transparent, transferring the obtained solution into a reaction kettle, reacting for 24 hours at 180 ℃, cooling to room temperature after the reaction is finished, centrifuging, centrifugally washing the obtained solid for a plurality of times by using an ethanol water solution, and drying the centrifuged solid to obtain a cobaltosic oxide nanocube;
secondly, coating the surface of the cobaltosic oxide nano cube prepared in the first step with PDA
Dissolving the cobaltosic oxide nanocube prepared in the first step and dopamine hydrochloride in 10mM tris (hydroxymethyl) aminomethane buffer solution, stirring for 3h at room temperature, centrifuging, centrifugally washing the obtained solid with an ethanol aqueous solution for several times, and drying the centrifuged solid to obtain the cobaltosic oxide nanocube with the surface coated with PDA;
thirdly, calcining the material obtained in the second step to obtain a carbon-coated porous cobaltous oxide nanocube three-dimensional material with a shell-core structure; the calcining condition is that the cobaltosic oxide nanocubes with the surfaces coated with the PDA obtained in the second step are kept at the constant temperature for 3 hours at the temperature rising rate of 5 ℃/min and the temperature of 500 ℃;
in the first step, the mass ratio of cobalt nitrate hexahydrate to sodium hydroxide is 4: 1;
in the second step, the concentration of cobaltosic oxide is 0.9g/mL, and the concentration of dopamine hydrochloride is 0.4 g/mL;
the carbon-coated porous cobaltous oxide nanocube three-dimensional material with the shell-core structure prepared by the preparation method has a plurality of mesopores, and the transmission path of lithium ions and electrons is improved, so that the rate capability of the material is improved.
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CN110600712B (en) * | 2019-10-08 | 2021-06-04 | 西京学院 | Carbon and nitrogen Co-doped Co3O4Composite material, preparation method and application thereof |
CN111233049A (en) * | 2020-01-19 | 2020-06-05 | 安徽师范大学 | Sulfur-loaded composite material of zinc cobaltate microspheres with multilayer mesoporous structure and preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
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