CN112259903A - Nitrogen-doped porous carbon loaded metal cobalt material and preparation method and application thereof - Google Patents
Nitrogen-doped porous carbon loaded metal cobalt material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 31
- 239000010941 cobalt Substances 0.000 title claims abstract description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 31
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- 238000000034 method Methods 0.000 claims abstract description 15
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims abstract description 10
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- 239000002243 precursor Substances 0.000 claims description 6
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- 239000007789 gas Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 229920001021 polysulfide Polymers 0.000 abstract description 13
- 239000005077 polysulfide Substances 0.000 abstract description 13
- 150000008117 polysulfides Polymers 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
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- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 229910007552 Li2Sn Inorganic materials 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 230000014233 sulfur utilization Effects 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a nitrogen-doped porous carbon loaded metal cobalt material and a preparation method and application thereof, and belongs to the field of lithium-sulfur batteries. The preparation method specifically comprises the following steps: placing porous carbon in a water vapor environment of flowing ammonia gas, pouring the porous carbon adsorbed with ammonia water into an ethyl acetate solution dissolved with cobalt acetylacetonate, standing, performing suction filtration, and drying; and finally, calcining the dried product to obtain the nitrogen-doped porous carbon-loaded metal cobalt material. The nitrogen-doped porous carbon loaded metal cobalt can adsorb polysulfide doubly by chemical adsorption and physical adsorption, reduces the dissolution of polysulfide in electrolyte, effectively inhibits the shuttling of polysulfide, and enhances the conductivity of the electrode material by porous carbon. The reaction kinetics process can be accelerated by doping nitrogen, and the porous carbon has a larger internal space, so that the volume expansion of the anode can be effectively relieved, and the stability of the battery is improved. Meanwhile, the diaphragm coated with the material is not easy to be punctured by dendrites to cause battery short circuit, and the safety of the lithium-sulfur battery is also guaranteed.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a nitrogen-doped porous carbon loaded metal cobalt material and a preparation method and application thereof.
Background
In recent years, with the increasing prominence of environmental problems and strong demands for battery endurance, many experts have begun to explore high energy density battery systems. The theoretical energy density of the energy storage system taking sulfur as the positive electrode of the battery and lithium as the negative electrode is as high as 2600Wh kg-1Lithium sulfur batteries are beginning to be the focus of research on energy storage devices. However, practical application of lithium-sulfur batteries is still hampered by inherent problems of shuttling effect, low sulfur utilization, severe volume change during cycling, and the like. Such as: the electronic/ionic conductance of the sulfur anode and the final discharge product is very poor, the volume expansion/shrinkage of the active substance is severe in the process of charge-discharge reaction, and the intermediate product polysulfide lithium of the reaction is easily dissolved in the organic electrolyte of the battery and then diffuses to the cathode to cause shuttle effect. How to greatly improve the practical energy density and the cycling stability of the lithium-sulfur battery has become one of the hot spots of the current research.
In response to the above problems, researchers have conducted a great deal of research work to explore various ways to improve electrochemical performance. The modification means are mainly focused on the following aspects: (1) designing a high-conductivity and porous structure material as a carrier of the sulfur anode, enhancing the conductivity of the electrode and inhibiting the diffusion of polysulfide; (2) the shuttle effect in the battery is inhibited by optimizing an electrolyte system, a diaphragm structure and a binder component; (3) the surface of the lithium metal negative electrode is protected, so that polysulfide and lithium are prevented from generating side reaction, the lithium dendrite is prevented from penetrating through the diaphragm to cause short circuit of the battery, and the stability and the safety of the lithium negative electrode are improved.
A porous conductive coating was built on a commercial separator to block shuttling of the poly lithium sulfide and to provide an additional conductive network. Various coating layers including carbon materials, metal oxides, polymers, composites thereof, and the like have been studied. Among the material choices for the modified membrane coating layer, carbon materials are the most common. The carbon coating layer not only inhibits shuttling of the lithium polysulfide but also activates the "inactive sulfur" that is not passed and remains on the separator. In addition, the porous conductive carbon coating layer may also serve as a second current collector, facilitating the reaction within the battery to proceed sufficiently. Various types of carbon materials are therefore incorporated into the membrane modification. However, after lithium polysulfide is adsorbed, it is difficult to continue to participate in the subsequent electrochemical reaction process. Therefore, the ideal separator coating material must have both good electrical conductivity, strong ability to adsorb polysulfide and certain catalytic ability, so as to reduce the activation energy and realize the ordered proceeding of the lithium polysulfide from the adsorption to the diffusion and finally to the conversion process.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention mainly aims to provide a preparation method of a nitrogen-doped porous carbon loaded metal cobalt material.
The invention also aims to provide the nitrogen-doped porous carbon-loaded metal cobalt material prepared by the method.
The invention further aims to provide application of the nitrogen-doped porous carbon-loaded metal cobalt material in a lithium-sulfur battery.
The invention further aims to provide a lithium-sulfur battery prepared from the nitrogen-doped porous carbon-supported metal cobalt material.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a nitrogen-doped porous carbon loaded metal cobalt material comprises the following steps:
(1) placing the porous carbon in a water vapor environment to obtain the porous carbon adsorbed with water vapor;
(2) placing the porous carbon adsorbed with the water vapor in an ammonia atmosphere to obtain porous carbon with ammonia water adsorbed in holes and on the surface;
(3) adding the porous carbon adsorbed with the ammonia water into an ethyl acetate solution dissolved with cobalt acetylacetonate, standing, performing suction filtration, and drying to obtain a precursor;
(4) and calcining the precursor in the flowing ammonia atmosphere to obtain the nitrogen-doped porous carbon loaded metal cobalt material.
Preferably, the porous carbon in the step (1) and the step (2) is washed by argon before absorbing water vapor and ammonia water, so that an inert gas environment is provided, and the porous carbon is cleaned while no impurity gas capable of influencing reaction exists in the porous carbon holes.
Preferably, the precursor in step (4) is calcined in an argon atmosphere to remove the impurity gas, and then calcined in an atmosphere of flowing ammonia gas.
Further preferably, the calcination temperature is 300 ℃ and the time is 1 h.
Preferably, the porous carbon with ammonia water adsorbed in the pores and on the surface obtained in the step (2) is placed in a clean fume hood to be spread, and is kept stand for a period of time to obtain the porous carbon with redundant ammonia water on the surface removed, and then the step (3) is carried out.
Preferably, the porous carbon in step (1) is one of ketjen black, carbon nanotube, mesoporous carbon, conductive carbon black, super P, RF carbon, expanded graphite, carbon nanofiber and carbon molecular sieve.
Preferably, the porous carbon adsorbed with water vapor of step (1) is prepared by the following method: the porous carbon is placed at 70-90 ℃ and heated for 0.5-2h, water vapor is adsorbed to the carbon holes, and in the high-temperature environment full of water vapor, the water vapor can be adsorbed by the porous carbon, so that the porous carbon adsorbed with the water vapor is obtained.
Preferably, the flow rate of the ammonia gas in the step (2) is 15-50 SCCM, and the time for introducing the ammonia gas is 0.5-3 h.
Preferably, the mass ratio of the porous carbon adsorbed with the ammonia water in the step (3) to the cobalt acetylacetonate is 0.5-10, and preferably 1.2-3: 1.
Preferably, the concentration of cobalt acetylacetonate in the cobalt acetylacetonate dissolved ethyl acetate solution is 0.5mg ml-1～10mg ml-1。
Preferably, the standing time is 3 to 24 hours.
Preferably, the calcination temperature in the step (4) is 400-1000 ℃, and the calcination time is 0.5-3 h.
A nitrogen-doped porous carbon loaded metal cobalt material is prepared by any one of the methods.
The nitrogen-doped porous carbon-loaded metal cobalt material is applied to a lithium-sulfur battery.
The lithium-sulfur battery is prepared from the nitrogen-doped porous carbon-loaded metal cobalt material.
The nitrogen-doped porous carbon loaded metal cobalt material can be used as a lithium-sulfur battery diaphragm material to remarkably improve the electrochemical performance of the battery. Nano-metal cobalt pairs and Li embedded in material and deposited in carbon pores2SnHas strong affinity to Li2SnThe shuttle effect can be mitigated by adsorption of (a). While nitrogen atom doped porous carbon, due to its porous structure and other chemisorption sites created by nitrogen doping, provides the necessary physisorption and chemisorption. Meanwhile, the porous carbon has a large internal space, so that the volume expansion of the anode can be effectively relieved, and the stability of the battery is improved. And the separator coated with the material is not easy to be punctured by dendrites to cause short circuit of the battery, so that the safety of the lithium-sulfur battery is guaranteed. Compared with the preparation of Co-doped MOF and N-doped MOF, the material of the invention has simple preparation process, cheap and easily obtained source materials and basically is a nontoxic and harmless inorganic substance. Provides a good idea for the commercial application of the lithium-sulfur battery.
Compared with the prior art, the invention has the following beneficial effects:
the nitrogen-doped porous carbon loaded metal cobalt material can obviously improve the electrochemical performance of a battery, and the nano metal cobalt and Li embedded into carbon holes in the material2SnThe porous carbon has strong affinity, can inhibit the dissolution of polysulfide in electrolyte, achieves the aim of slowing down the shuttle effect, and enhances the conductivity of the electrode material. The nitrogen doping also provides for Li in accelerating the kinetics of the redox reaction2SnChemical adsorption of (3). Compared with MOF, the lithium-sulfur battery prepared by using the material prepared by the method as the diaphragm has larger specific capacity and smaller capacity decay rate per circle. And the porous carbon of the invention uses commercial carbon, which has not been subjected to MOFAny chemical treatment, low cost, easy obtaining, green and safe. The separator coated with the material is not easy to be punctured by dendrites to cause short circuit of the battery, and the safety of the lithium-sulfur battery is also enhanced.
Drawings
Fig. 1 is an X-ray powder diffraction pattern of the separator material of nitrogen-doped porous carbon-supported metallic cobalt prepared in example 1.
FIG. 2a is a first cycle charge and discharge diagram of the lithium sulfur battery with KJ-600 and Co-800@ KJ obtained in example 2 as the positive electrode carrier.
FIG. 2b is a plot of the cyclic voltammograms of KJ-600 and Co-800@ KJ obtained in example 2 as lithium sulfur battery positive supports.
FIG. 3 is a graph showing the AC impedance (Nyquist) curves of the cell with KJ-600 as the separator modification material and the cell with Co-800@ KJ as the separator modification material obtained in example 3.
FIG. 4 is a long cycle plot of high loading for the cell with KJ-600 as the separator modification material and the cell with Co-800@ KJ as the separator modification material obtained in example 3.
Detailed Description
The present invention will be further described with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparing a nitrogen-doped porous carbon material: placing 100mg Ketjen black (KJ-600) in a vial, absorbing water vapor at 80 deg.C for 50 min, and placing KJ-600 in NH3Reacting in a tubular furnace with the airflow speed of about 30SCCM for 1 hour to obtain the nitrogen-doped porous carbon material.
The obtained nitrogen-doped porous carbon material was immersed in a saturated cobalt acetylacetonate/ethyl acetate solution (volume ratio 1:10) for 8 hours. Then transferring the sample into a glove box, filtering and drying the sample, and placing the sample into NH3Calcining the mixture for 1 hour at 800 ℃ in a tubular furnace with the airflow speed of about 50SCCM to obtain the nitrogen-doped porous carbon loaded metal cobalt material which is marked as Co-800@ KJ.
FIG. 1 is an XRD pattern of Co-800@ KJ obtained in this example. At 44.2 ° and 51.6 °, the two distinct diffraction peaks are replaced, which coincide with the (111) and (200) crystal planes of the face-centered cubic cobalt nanoparticles, respectively. The successful combination of the nitrogen-doped porous carbon and the metallic cobalt is proved.
Example 2
700mg of the nitrogen-doped porous carbon-loaded metal cobalt material Co-800@ KJ obtained in example 1 and 300mg of sulfur were mixed and then immersed at 155 ℃ for 10 hours, and then the mass ratio of the immersed mixed material, super P and polyvinylidene fluoride was 8: 1:1 as the positive electrode material, and assembling the positive electrode material, lithium metal and Celgard2400 diaphragm into a lithium-sulfur battery to be tested, wherein the active mass loading of all tests is 1-5mg cm-2. The KJ-600 was assembled into a lithium sulfur battery using the same method.
FIG. 2a is a first cycle charge and discharge diagram of the lithium sulfur battery with KJ-600 and Co-800@ KJ obtained in example 2 as the positive electrode carrier. FIG. 2b is a plot of the cyclic voltammograms of KJ-600 and Co-800@ KJ obtained in example 2 as lithium sulfur battery positive supports. Two typical platforms during the discharge of a lithium sulfur battery are shown in fig. 2a, wherein the first cycle charge-discharge capacity of the battery using Co-800@ KJ as the positive electrode carrier of the lithium sulfur battery is greater than KJ-600, indicating that the material is functioning and that a very low proportion of polysulfide anions diffuses into the electrolyte to enhance the electrochemical performance of the battery due to polarization degradation; as can be seen from FIG. 2b, the Co-800@ KJ lithium sulfur battery has two reduction peaks at 2.31V and 2.03V, corresponding to the conversion of elemental sulfur to Li2S4Conversion of (2), Li2S4To Li2And (4) converting S. Two oxidation peaks at 2.29V and 2.39V, corresponding to Li respectively2S to Li2S4Conversion of (2), Li2S4Conversion to elemental sulphur. The results also prove that the Co-800@ KJ material plays a catalytic role, reduces the reaction activation energy, thereby reducing the polarization effect of the battery and being beneficial to improving the performance of the lithium-sulfur battery.
Example 3
The nitrogen-doped porous carbon-supported metallic cobalt material Co-800@ KJ in example 1 and polyvinylidene fluoride (binder) are mixed according to a mass ratio of 6: 4 grinding in a mortar, adding a proper amount of N-methyl pyrrolidone (NMP) to obtain uniform slurry, coating the uniform slurry on one side of a Celgard2400 diaphragm, drying, cutting into a 19mm disk to be used as a diaphragm of a battery, wherein the material face faces to a positive electrode, the preparation of the positive electrode material selects the simplest original method, namely directly physically mixing pure sulfur and a binder, coating the mixture on an aluminum foil, and drying and cutting into pieces to be used as a pole piece. The KJ-600 is coated with a diaphragm by the same method to be assembled into the lithium-sulfur battery.
Fig. 3 and 4 are the ac impedance (Nyquist) curves of the lithium sulfur battery with KJ-600 as the membrane modification material and the lithium sulfur battery with Co-800@ KJ as the membrane modification material obtained in example 3, and the long cycle performance of the battery with the membrane coated with the nitrogen-doped porous carbon-loaded metal cobalt material (Co-800@ KJ) under high loading. The alternating current impedance result shows that the insertion of the Co-800@ KJ material intermediate layer reduces the internal charge transfer resistance and limits the diffusion of soluble polysulfide; as can be seen from FIG. 4, the cell in which the material was coated was found to have a sulfur loading of 3.4mg/cm even at this time2The cycle performance is still stable, the battery still maintains high initial discharge specific capacity of 1188.7mAh/g, and still has discharge specific capacity of 911.2mAh/g after stable cycle of 100 circles, the cycle attenuation of each time is very weak, the attenuation rate is only 0.23%/circle, the capacity retention rate is very high, and the battery performance is also extremely good. The coulombic efficiency of the cell remained close to 100% at all times, which also indicates that the Co-800@ KJ material still exerts its physical and chemical adsorption and electrocatalysis effects even at such high sulfur loadings, thus effectively suppressing the shuttle effect and thus improving the electrochemical performance of the cell, which provides a commercially viable method for manufacturing lithium sulfur cells.
Compared with the preparation of Co-doped MOF (such as CN 110078053A-a porous carbon material applied to a battery diaphragm coating and a preparation method and application thereof), the material has simple preparation process, cheap and easily obtained source materials, basically non-toxic and harmless inorganic matters and no need of using toxic organic matters. Provides a good idea for the commercial application of the lithium-sulfur battery. Compared with MOF, the lithium-sulfur battery prepared by using the material prepared by the method as the diaphragm has larger specific capacity and smaller capacity decay rate per circle. And the porous carbon of the invention uses commercial carbon which is not subjected to any chemical treatment, is cheap and easy to obtain and is green and safe compared with MOF. The separator coated with the material is not easy to be punctured by dendrites to cause short circuit of the battery, and the safety of the lithium-sulfur battery is also enhanced.
The above-mentioned embodiments only represent some preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present invention. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention. Therefore, the protection scope of the present patent application shall be subject to the appended claims.
Claims (10)
1. A preparation method of a nitrogen-doped porous carbon loaded metal cobalt material is characterized by comprising the following steps:
(1) placing the porous carbon in a water vapor environment to obtain the porous carbon adsorbed with water vapor;
(2) placing the porous carbon adsorbed with the water vapor in an ammonia atmosphere to obtain porous carbon adsorbed with ammonia water;
(3) adding the porous carbon adsorbed with the ammonia water into an ethyl acetate solution dissolved with cobalt acetylacetonate, standing, performing suction filtration, and drying to obtain a precursor;
(4) and calcining the precursor in the flowing ammonia atmosphere to obtain the nitrogen-doped porous carbon loaded metal cobalt material.
2. The preparation method according to claim 1, wherein the porous carbon in the steps (1) and (2) is washed by argon before absorbing water vapor and ammonia water; and (4) calcining the precursor in the argon atmosphere to remove impure gas, and then calcining in the flowing ammonia atmosphere.
3. The method according to claim 1, wherein the porous carbon in the step (1) is one of ketjen black, carbon nanotube, mesoporous carbon, conductive carbon black, super P, RF carbon, expanded graphite, carbon nanofiber, and carbon molecular sieve.
4. The production method according to claim 1, wherein the porous carbon adsorbed with water vapor of step (1) is produced by: and heating the porous carbon at 70-90 ℃ for 0.5-2h, and adsorbing water vapor into the carbon pores to obtain the porous carbon adsorbed with the water vapor.
5. The preparation method according to claim 1, wherein the flow rate of the ammonia gas in the step (2) is 15-50 SCCM, and the time for introducing the ammonia gas is 0.5-3 h.
6. The preparation method according to claim 1, wherein the mass ratio of the porous carbon adsorbed with the ammonia water in the step (3) to the cobalt acetylacetonate is 0.5 to 10; the concentration of the cobalt acetylacetonate in the ethyl acetate solution dissolved with the cobalt acetylacetonate is 0.5mg ml-1～10mg ml-1(ii) a The standing time is 3-24 hours.
7. The preparation method as claimed in claim 1, wherein the calcination temperature in step (4) is 400-1000 ℃ and the calcination time is 0.5-3 h.
8. A nitrogen-doped porous carbon-supported metallic cobalt material, characterized by being prepared by the method of any one of claims 1 to 7.
9. The use of the nitrogen-doped porous carbon-supported metallic cobalt material of claim 8 in a lithium-sulfur battery.
10. A lithium-sulfur battery prepared from the nitrogen-doped porous carbon-supported metallic cobalt material of claim 8.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112615008A (en) * | 2021-03-08 | 2021-04-06 | 浙江师范大学 | Positive modified material M-N-CNT for lithium-sulfur battery, preparation method thereof and battery |
| CN112928255A (en) * | 2021-01-25 | 2021-06-08 | 合肥工业大学 | Lithium-sulfur battery composite positive electrode material and preparation method and application thereof |
| CN113381120A (en) * | 2021-06-11 | 2021-09-10 | 中国科学院兰州化学物理研究所 | Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm |
| CN114759236A (en) * | 2022-04-28 | 2022-07-15 | 厦门大学 | Assembling and testing method of polysulfide flow battery based on membrane electrode |
| CN114975938A (en) * | 2022-06-08 | 2022-08-30 | 华南师范大学 | Cobalt-based metal compound mesoporous carbon sphere composite material and preparation method of cobalt-based metal compound mesoporous carbon sphere composite material as sodium-sulfur battery positive electrode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681091A (en) * | 2017-09-12 | 2018-02-09 | 北京理工大学 | A kind of lithium-sulfur cell functionalization composite diaphragm and preparation method thereof |
| CN108666570A (en) * | 2018-04-12 | 2018-10-16 | 深圳大学 | Porous carbon nanobelts lithium sulfur battery anode material and its preparation method and application |
| CN110323447A (en) * | 2019-08-07 | 2019-10-11 | 南昌大学 | A kind of lithium-sulphur cell positive electrode framework material and preparation method thereof and a kind of lithium sulfur battery anode material and a kind of lithium-sulfur cell |
| CN110931752A (en) * | 2019-12-09 | 2020-03-27 | 华南师范大学 | Nitrogen-doped porous carbon loaded metal nickel lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN111490259A (en) * | 2019-01-25 | 2020-08-04 | 苏州沃泰丰能电池科技有限公司 | Nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for zinc-air battery and preparation method thereof |
-
2020
- 2020-09-23 CN CN202011008895.5A patent/CN112259903A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681091A (en) * | 2017-09-12 | 2018-02-09 | 北京理工大学 | A kind of lithium-sulfur cell functionalization composite diaphragm and preparation method thereof |
| CN108666570A (en) * | 2018-04-12 | 2018-10-16 | 深圳大学 | Porous carbon nanobelts lithium sulfur battery anode material and its preparation method and application |
| CN111490259A (en) * | 2019-01-25 | 2020-08-04 | 苏州沃泰丰能电池科技有限公司 | Nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for zinc-air battery and preparation method thereof |
| CN110323447A (en) * | 2019-08-07 | 2019-10-11 | 南昌大学 | A kind of lithium-sulphur cell positive electrode framework material and preparation method thereof and a kind of lithium sulfur battery anode material and a kind of lithium-sulfur cell |
| CN110931752A (en) * | 2019-12-09 | 2020-03-27 | 华南师范大学 | Nitrogen-doped porous carbon loaded metal nickel lithium-sulfur battery positive electrode material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHENYU XING，等: ""Carbon-pore-sheathed cobalt nanoseeds: An exceptional and durable"", 《NANO ENERGY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112928255A (en) * | 2021-01-25 | 2021-06-08 | 合肥工业大学 | Lithium-sulfur battery composite positive electrode material and preparation method and application thereof |
| CN112615008A (en) * | 2021-03-08 | 2021-04-06 | 浙江师范大学 | Positive modified material M-N-CNT for lithium-sulfur battery, preparation method thereof and battery |
| CN113381120A (en) * | 2021-06-11 | 2021-09-10 | 中国科学院兰州化学物理研究所 | Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm |
| CN113381120B (en) * | 2021-06-11 | 2022-07-12 | 中国科学院兰州化学物理研究所 | Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm |
| CN114759236A (en) * | 2022-04-28 | 2022-07-15 | 厦门大学 | Assembling and testing method of polysulfide flow battery based on membrane electrode |
| CN114975938A (en) * | 2022-06-08 | 2022-08-30 | 华南师范大学 | Cobalt-based metal compound mesoporous carbon sphere composite material and preparation method of cobalt-based metal compound mesoporous carbon sphere composite material as sodium-sulfur battery positive electrode material |
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