CN114590842A - Preparation method of morphology-controllable cobalt nonaoctasulfide material and application of morphology-controllable cobalt nonasulfide material in electrode - Google Patents
Preparation method of morphology-controllable cobalt nonaoctasulfide material and application of morphology-controllable cobalt nonasulfide material in electrode Download PDFInfo
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- CN114590842A CN114590842A CN202111653470.4A CN202111653470A CN114590842A CN 114590842 A CN114590842 A CN 114590842A CN 202111653470 A CN202111653470 A CN 202111653470A CN 114590842 A CN114590842 A CN 114590842A
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- 239000000463 material Substances 0.000 title claims abstract description 91
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 42
- 239000010941 cobalt Substances 0.000 title claims abstract description 42
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 claims abstract description 31
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 47
- 229910021641 deionized water Inorganic materials 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 33
- 239000002244 precipitate Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 21
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 14
- 239000012621 metal-organic framework Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 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 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 abstract description 14
- 239000005077 polysulfide Substances 0.000 abstract description 14
- 150000008117 polysulfides Polymers 0.000 abstract description 14
- 238000012360 testing method Methods 0.000 description 16
- 239000002002 slurry Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 238000007599 discharging Methods 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a morphology-controllable cobalt octasulfide nonacobalt material and application of the morphology-controllable cobalt octasulfide nonacobalt material in an electrode. Co prepared by the method of the invention9S8The material can be used as a positive electrode material of a lithium sulfur/room temperature sodium sulfur battery to load elemental sulfur and adsorb and fix polysulfide, and can also be used for modifying a diaphragm of the lithium sulfur/room temperature sodium sulfur battery to block the shuttle of the polysulfide.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage and conversion, in particular to a preparation method of a morphology-controllable cobalt octasulfide material and application of the morphology-controllable cobalt octasulfide material in an electrode.
Background
Secondary batteries have received much attention as an advanced recyclable energy storage system as the demand for energy from human beings is continuously increasing. In the lithium ion battery that has been commercialized, it has been difficult to satisfy the demand of the human society for a high energy density secondary battery due to its low theoretical specific capacity of the positive electrode.
The lithium sulfur battery and the room temperature sodium sulfur battery both have higher energy density and are considered as battery energy systems with the most development potential, and in addition, the elemental sulfur has the advantages of small environmental pollution, large reserve, low price and the like, and has better commercial prospect. However, at present, both lithium-sulfur batteries and room-temperature sodium-sulfur batteries cannot enter a commercial stage, and the reasons for hindering the commercial use of the two batteries are similar to each other, and the biggest problem is the shuttle effect caused by the dissolution and diffusion of soluble intermediate products (lithium polysulfide and sodium polysulfide) in an electrolyte in the charging and discharging process.
Octacobalt (Co) sulfide9S8) Being a polar material, it can chemically block polysulfide shuttling, while its high conductivity also ensures that high coulombic efficiency can be maintained while effectively blocking polysulfides. Therefore, if the contact area between the cobalt octasulfide and polysulfide can be increased, the adsorption effect can be improved, and the mechanical structure is more stable.
Therefore, it is necessary to provide a technical solution to overcome the drawbacks of the prior art.
Disclosure of Invention
The invention aims to provide a preparation method and application of a morphology-controllable cobalt octasulfide electrode material, wherein the surface area of cobalt octasulfide is increased by improving a process, so that Co with different morphologies is prepared9S8A material. Co prepared by the method of the invention9S8The material can be used as a positive electrode material of a lithium sulfur/room temperature sodium sulfur battery to load elemental sulfur and adsorb and fix polysulfide, and can also be used for modifying a diaphragm of the lithium sulfur/room temperature sodium sulfur battery to block the shuttle of the polysulfide.
In order to achieve the aim, the invention provides a preparation method of a shape-controllable cobalt octasulfide material, which comprises the following steps,
step S1: preparing a mixed solution of cobalt salt and a metal organic framework ligand; taking a certain proportion of 2-methylimidazole (2-MIM) and cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), dissolving in deionized water with a certain volume to obtain a mixed solution of cobalt salt and a metal organic framework ligand;
step S2: preparing a precursor solution on the basis of the mixed solution prepared in the step S1 to obtain precursor powder;
step S3: mixing the obtained precursor powder with Thioacetamide (TAA) according to a certain proportion, dissolving in deionized water with a certain volume, and magnetically stirring at room temperature until the precursor powder and the thioacetamide are uniformly mixed to obtain a purple black suspension;
step S4: transferring the obtained suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 90-120 ℃ for 5-8h to obtain a second solution; centrifuging the obtained second solution and repeatedly washing with deionized water to obtain a second precipitate;
step S5: drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain a corresponding morphology structure of the cobalt nonaoctasulfide material;
in step S2, cobalt-containing metal organic framework structures of different morphologies are obtained by regulating and controlling the precursor, and the cobalt-containing metal organic framework structures are further vulcanized to obtain the cobalt octasulfide nonabaltate materials of different morphologies.
As a further improvement, in step S2, the mixed solution is magnetically stirred at room temperature for 5-10min to obtain a purple precursor solution; standing the obtained precursor solution for 1-3h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; and drying at 50-70 deg.C for 8-12h to obtain precursor powder. Thus obtaining single-blade boat-shaped Co9S8A material.
As a further improvement, in step S2, Cetyl Trimethyl Ammonium Bromide (CTAB) is added to the mixed solution in a certain proportion, and magnetic stirring is performed at room temperature for 15-30min to obtain a purple precursor solution; standing the obtained precursor solution for 5-1After 0h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; drying at 80-100 deg.C for 14-24h to obtain precursor powder; the mass fraction of CTAB in the mixed liquid is 0.0025 percent to 0.01 percent. Thus obtaining trilobate Co9S8A material.
Further, the obtained monolobal navicular Co9S8The length of the long axis of the material is 3-5 μm, and the length of the short axis is 0.8-1.5 μm.
Further, the obtained trilobal Co9S8The radius of the material is 4-6 μm.
Further, in the step S1, the mass ratio of the 2-methylimidazole, the cobalt nitrate hexahydrate and the deionized water is (2-5): 1: 140.
further, in the step S4, the mass ratio of the precursor powder, thioacetamide and deionized water is 1: (1.5-3.0): 250.
preferably, the temperature of the reaction in the step S5 is 100 ℃.
Preferably, the reaction time in the step S5 is 6 h.
The nonacobalt octasulfide material prepared by the method is applied to electrodes, and the obtained nonacobalt octasulfide material is used as an electrode material of a lithium-sulfur or sodium-sulfur secondary battery or a modified battery diaphragm. Namely, the method is applied to the anode material of the lithium-sulfur battery, the anode material of the room-temperature sodium-sulfur battery, the diaphragm modification of the lithium-sulfur battery and the diaphragm modification of the room-temperature sodium-sulfur battery.
As a further improvement scheme, when the cobalt octasulfide and the sublimed sulfur are compounded to be used as the positive electrode material of the lithium-sulfur battery, the positive electrode of the lithium-sulfur battery comprises a positive electrode current collector, and the negative electrode is metal lithium; coating the surface of a current collector with a positive electrode material, wherein the positive electrode material comprises a nonacobalt octasulfide material obtained by the method of any one of claims 1 to 7;
and when the cobalt octasulfide and the sublimed sulfur are compounded to be used as the positive electrode material of the sodium-sulfur battery, the positive electrode of the sodium-sulfur battery comprises a positive electrode current collector, and the negative electrode is metallic sodium; the surface of the current collector is coated with a positive electrode material, and the positive electrode material comprises the nonacobalt octasulfide material obtained by the method of any one of claims 1 to 7.
As a further improvement scheme, the octa-cobalt-sulfide modified microporous polypropylene diaphragm or glass fiber diaphragm is used for a lithium-sulfur battery or a room-temperature sodium-sulfur battery; the method for modifying the diaphragm selects a coating method or a hydrothermal deposition method.
Compared with the prior art, the invention has the following beneficial effects:
(1) co prepared by the method of the invention9S8The material has larger surface area and stable mechanical structure, can effectively load elemental sulfur when being used as the anode material of a lithium sulfur battery or a room temperature sodium sulfur battery, and simultaneously, because of Co9S8The material has high polarity, can be combined with polysulfide, and can effectively prevent the polysulfide from shuttling.
(2) The preparation method of the shape-controllable cobalt octasulfide electrode material provided by the invention has the advantages of controllable shape and simple preparation process, and is suitable for large-scale industrial production.
Drawings
FIG. 1 shows the contents of the one-blade boat Co of example 29S8Scanning electron microscope pictures of the materials.
FIG. 2 shows the three-lobed Co of example 49S8Scanning electron microscope pictures of the materials.
FIG. 3 shows the content of the one-blade boat Co obtained in example 29S8The lithium-sulfur battery taking the material as the cathode material has a charge-discharge specific capacity and coulombic efficiency curve chart of charging and discharging 200 times under 0.2C.
FIG. 4 shows the single blade boat Co obtained in example 29S8The charge-discharge specific capacity and coulombic efficiency curve chart of the room temperature sodium-sulfur battery taking the anode material is that the room temperature sodium-sulfur battery is charged and discharged for 200 times under 0.2C.
FIG. 5 shows the content of the one-blade boat Co obtained in example 39S8The material modified diaphragm lithium-sulfur battery has a charge-discharge specific capacity and coulombic efficiency curve chart of charging and discharging 200 times under 0.5C.
FIG. 6 shows the content of the one-blade boat Co obtained in example 39S8A charge-discharge specific capacity and coulombic efficiency curve chart of the room-temperature sodium-sulfur battery with the material modified diaphragm, wherein the charge-discharge specific capacity and coulombic efficiency curve chart is 200 times of charge-discharge at 0.2 ℃.
FIG. 7 shows the trilobe Co obtained in example 49S8The lithium-sulfur battery taking the material as the cathode material has a charge-discharge specific capacity and coulombic efficiency curve chart of charging and discharging 200 times under 0.5C.
FIG. 8 shows the trilobe Co obtained in example 49S8The charge-discharge specific capacity and coulombic efficiency curve chart of the room temperature sodium-sulfur battery taking the anode material is that the room temperature sodium-sulfur battery is charged and discharged for 200 times under 0.5C.
FIG. 9 shows the trilobe Co obtained in example 59S8The material modified diaphragm lithium-sulfur battery has a charge-discharge specific capacity and coulombic efficiency curve chart of charging and discharging 200 times under 0.2C.
FIG. 10 shows the trilobe Co obtained in example 59S8A charge-discharge specific capacity and coulombic efficiency curve chart of the room temperature sodium-sulfur battery with the material modified diaphragm, wherein the charge-discharge specific capacity and coulombic efficiency curve chart is 200 times of charge-discharge at 0.5 ℃.
FIG. 11 is a flow chart of a preparation method of a morphology-controllable cobalt octasulfide material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail by the following examples. It is to be understood that the invention may be embodied or carried out in various other specific embodiments, and that various changes or modifications may be made in the details of the following examples without departing from the spirit of the invention. It should be noted that, in the following embodiments, features in the embodiments may be combined with each other without conflict.
Applicants have found in their research that nonacobalt octasulfide (Co)9S8) Being a polar material, it can chemically block polysulfide shuttling, while its high conductivity also ensures that high coulombic efficiency can be maintained while effectively blocking polysulfides. On the basis, the invention provides a preparation method of a morphology-controllable cobalt octasulfide electrode material, which improves the adsorption effect of cobalt octasulfide and polysulfide by increasing the contact area of the cobalt octasulfide and the polysulfide and simultaneously enables the mechanical structure to be more mechanicalAnd (4) stabilizing.
Referring to fig. 11, a flow chart of a preparation method of a morphology-controllable cobalt octasulfide material of the present invention is shown, which comprises the following steps:
step S1: preparing a mixed solution of cobalt salt and a metal organic framework ligand; dissolving a certain proportion of 2-methylimidazole and cobalt nitrate hexahydrate in a certain volume of deionized water to obtain a mixed solution of a cobalt salt and a metal organic framework ligand;
step S2: preparing a precursor solution on the basis of the mixed solution prepared in the step S1 to obtain precursor powder;
step S3: mixing the obtained precursor powder with thioacetamide according to a certain proportion, dissolving in deionized water with a certain volume, and magnetically stirring at room temperature until the precursor powder and thioacetamide are uniformly mixed to obtain a purple black suspension;
step S4: transferring the obtained suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 90-120 ℃ for 5-8h to obtain a second solution; centrifuging the obtained second solution and repeatedly washing with deionized water to obtain a second precipitate;
step S5: drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain a cobalt octasulfide material with a corresponding morphology structure;
in step S2, cobalt-containing metal organic framework structures of different morphologies are obtained by regulating and controlling the precursor, and the cobalt-containing metal organic framework structures are further vulcanized to obtain the cobalt octasulfide nonabaltate materials of different morphologies.
In step S2, magnetically stirring the mixed solution obtained in step S1 at room temperature for 5-10min to obtain a purple precursor solution; standing the obtained precursor solution for 1-3h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; drying at 50-70 deg.C for 8-12h to obtain precursor powder; thus preparing the single-blade boat-shaped cobalt nonasulfide material.
In step S2, hexadecyl trimethyl ammonium bromide with a certain proportion is added into the mixed solution obtained in step S1, and magnetic stirring is carried out for 15-30min at room temperature to obtain a purple precursor solution; standing the obtained precursor solution for 5-10h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; drying at 80-100 deg.C for 14-24h to obtain precursor powder; thus obtaining a trilobal octa-cobalt sulfide material; wherein the mass fraction of the hexadecyl trimethyl ammonium bromide in the mixed solution is 0.0025-0.01 percent.
The method can be used for preparing the shape-controllable cobalt octasulfide material. The cobalt octasulfide material can be applied to electrodes, and specifically has the following four application scenes:
(1) the method is applied to the electrode material of the lithium-sulfur battery, and the specific test process is as follows: s @ Co prepared in an argon-protected glove box9S8For the positive electrode, Celgard 2500 was used as a separator, a metal lithium piece was used as a negative electrode, and LiNO was added in an amount of 0.1mol/L to 1M LiTFSI (DOL/DME ═ 1:1)3The battery was assembled as an electrolyte. In the charge and discharge test system, the charge and discharge test voltage is 1.5-3.0V.
(2) The method is applied to the lithium-sulfur battery diaphragm modification material, and the specific test process is as follows: sublimed sulfur as a positive electrode in an argon-protected glove box, Celgard 2500@ Co9S8As a separator, a lithium metal sheet was used as a negative electrode, and LiTFSI (DOL/DME: 1) of 1M was added with 0.1mol/L LiNO3The battery was assembled as an electrolyte. In the charge and discharge test system, the charge and discharge test voltage is 1.5-3.0V.
(3) The method is applied to the room-temperature sodium-sulfur battery electrode material, and the specific test process is as follows: s @ Co prepared in an argon-protected glove box9S8Is a positive electrode, Whatman GF/D is a diaphragm, a metal sodium sheet is a negative electrode, and 1M NaClO4(EC/DEC ═ 1:1) as an electrolyte. In the charge and discharge test system, the charge and discharge test voltage is 1.0-3.0V.
(4) The method is applied to the room-temperature sodium-sulfur battery electrode material, and the specific test process is as follows: in a glove box protected by argon, sublimed sulfur is taken as a positive electrode, WhatmanGF/D @ Co9S8As a separator, a metal sodium sheet as a negative electrode, 1M NaClO4(EC/DEC ═ 1:1) as an electrolyte. In the charge and discharge test system, the charge and discharge test voltage is 1.0-3.0V.
The technical scheme of the invention is further explained by specific examples.
Example 1
Example 1 provides a single blade boat Co9S8A method of preparing a material comprising the steps of:
s11, taking a certain proportion of 2-methylimidazole (2-MIM) and cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), dissolving in deionized water with a certain volume to obtain a mixed solution of cobalt salt and a metal organic framework ligand; the mass ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate to the deionized water is (2-5): 1: 140.
s12, magnetically stirring the mixed solution at room temperature for 5-10min to obtain a purple precursor solution; standing the obtained precursor solution for 1-3h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; and drying at 50-70 deg.C for 8-12h to obtain precursor powder.
S13, mixing the obtained precursor powder with Thioacetamide (TAA) in a certain proportion, dissolving in deionized water with a certain volume, and magnetically stirring at room temperature until the precursor powder and the thioacetamide are uniformly mixed to obtain a purple black suspension; the mass ratio of the precursor powder, thioacetamide and deionized water is 1: (1.5-3.0): 250.
s14, transferring the obtained suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 90-120 ℃ for 5-8h to obtain a second solution; the resulting second solution was centrifuged and repeatedly rinsed with deionized water to obtain a second precipitate.
S15, drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain unilobar navicular Co9S8A material.
In this embodiment, the following are specifically mentioned:
mixing 0.65g of dimethylimidazole and 0.29g of cobalt nitrate hexahydrate, dissolving in 40ml of deionized water, magnetically stirring at room temperature for 5min to obtain a purple precursor solution, standing the obtained precursor solution for 2h, centrifuging, repeatedly washing with deionized water to obtain a first precipitate, and drying at 70 ℃ for 12h to obtain precursor powder; mixing 0.06g of precursor powder and 0.15g of thioacetamide, dissolving in 15ml of deionized water, and magnetically stirring at room temperature to form uniform suspensionTransferring the suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 100 ℃ for 6 hours to obtain a second solution; centrifuging the obtained second solution and repeatedly washing with deionized water to obtain a second precipitate; drying the second precipitate at 70 deg.C for 12h to obtain unilobal boat-shaped Co9S8A material.
Example 2
Example 1 provides a single blade boat Co9S8The preparation method of the material is different from the preparation method of the material in example 1 in that:
mixing 0.65g of dimethylimidazole and 0.29g of cobalt nitrate hexahydrate, dissolving in 40ml of deionized water, magnetically stirring at room temperature for 10min to obtain a purple precursor solution, standing the obtained precursor solution for 2h, centrifuging, repeatedly washing with deionized water to obtain a first precipitate, and drying at 70 ℃ for 12h to obtain precursor powder; mixing 0.06g of precursor powder and 0.15g of thioacetamide, dissolving in 15ml of deionized water, magnetically stirring at room temperature to form uniform suspension, transferring the suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 100 ℃ for 6 hours to obtain a second solution; centrifuging the obtained second solution and repeatedly washing with deionized water to obtain a second precipitate; drying the second precipitate at 70 deg.C for 12 hr to obtain Co in the shape of single blade boat9S8A material. 30mg of sublimed sulphur was dissolved in CS2To the solution, 20mg of Navicon Co was added9S8Stirring the materials at room temperature until the materials are dried, transferring the mixture into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and preserving the heat at 155 ℃ for 12 hours to obtain S @ Co9S8A composite material. Mixing S @ Co9S8The composite material, the superconducting carbon black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, N-methyl pyrrolidone (NMP) is used as a diluent, stirring is carried out for 3 hours to prepare slurry, the prepared slurry is coated on a current collector by a blade coating method, and drying is carried out for 12 hours at 60 ℃ in a vacuum environment. And cutting the electrode plates into circular electrode plates with the diameter of 16mm, compacting, and assembling the battery for testing.
FIG. 1 shows a single blade boat Co obtained in this example9S8SEM image of material, length of single-blade boat can be seenThe axial length is about 4.7 μm and the minor axis length is about 1.3 μm. FIG. 3 shows a single blade boat Co obtained in this example9S8The lithium-sulfur battery taking the material as the positive electrode material has a charge-discharge specific capacity and coulombic efficiency curve chart of 200 times of charge and discharge at 0.2 ℃. The first discharge specific capacity of the obtained lithium-sulfur battery is 1587mAhg-1And the specific capacity after 200 cycles is 258mAhg-1。
FIG. 4 shows a view of the single-blade boat-shaped Co obtained in this example9S8The charge-discharge specific capacity and coulombic efficiency curve chart of the room temperature sodium-sulfur battery taking the anode material is that the room temperature sodium-sulfur battery is charged and discharged for 200 times under 0.2C.
Example 3
This example shows a single blade boat shaped Co prepared as in example 29S8The material is a raw material, and a blade coating method is adopted to modify the diaphragm, and the specific implementation is as follows:
subjecting a single blade to boat shape Co9S8The material, the superconducting carbon black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, N-methylpyrrolidone (NMP) is used as a diluent, stirring is carried out for 3 hours to prepare slurry, the prepared slurry is coated on a diaphragm by a blade coating method, and drying is carried out for 12 hours at 60 ℃ in a vacuum environment. Cut into circular membrane pieces with a diameter of 20 mm. Uniformly mixing sublimed sulfur, superconducting carbon black and PVDF according to the mass ratio of 7:2:1, stirring for 3 hours by using N-methylpyrrolidone (NMP) as a diluent to prepare slurry, coating the prepared slurry on a current collector by using a blade coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. And cutting into circular electrode plates with the diameter of 16mm, compacting, and assembling the battery for testing.
FIG. 5 shows the boat-shaped single blade Co obtained in this example9S8The material modified diaphragm lithium-sulfur battery has a charge-discharge specific capacity and coulombic efficiency curve chart of charging and discharging 200 times under 0.5C. FIG. 6 shows a single blade boat-shaped Co obtained in this example9S8A charge-discharge specific capacity and coulombic efficiency curve chart of the room-temperature sodium-sulfur battery with the material modified diaphragm, wherein the charge-discharge specific capacity and coulombic efficiency curve chart is 200 times of charge-discharge at 0.2 ℃.
Example 4
Example 4 provides a trilobal Co9S8A method of preparing a material comprising the steps of:
s21, taking a certain proportion of 2-methylimidazole (2-MIM) and cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), dissolving in deionized water with a certain volume to obtain a mixed solution of cobalt salt and a metal organic framework ligand; the mass ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate to the deionized water is (2-5): 1: 140.
s22, adding a certain proportion of Cetyl Trimethyl Ammonium Bromide (CTAB) into the mixed solution, and magnetically stirring at room temperature for 15-30min to obtain a purple precursor solution; standing the obtained precursor solution for 5-10h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; drying at 80-100 deg.C for 14-24 hr to obtain precursor powder; the mass fraction of CTAB in the mixed liquid is 0.0025 percent to 0.01 percent.
S23, mixing the obtained precursor powder with Thioacetamide (TAA) according to a certain proportion, dissolving in deionized water with a certain volume, and magnetically stirring at room temperature until the precursor powder and the thioacetamide are uniformly mixed to obtain a purple black suspension; the mass ratio of the precursor powder, thioacetamide and deionized water is 1: (1.5-3.0): 250.
s24, transferring the obtained suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 90-120 ℃ for 5-8h to obtain a second solution; the resulting second solution was centrifuged and repeatedly rinsed with deionized water to obtain a second precipitate.
S25, drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain trilobal Co9S8A material.
In this embodiment, the following are specific:
mixing 0.65g of dimethyl imidazole, 0.29g of cobalt nitrate hexahydrate and 0.002g of hexadecyl trimethyl ammonium bromide, dissolving the mixture in 40ml of deionized water, magnetically stirring the mixture at room temperature for 15min to obtain a purple precursor solution, standing the obtained precursor solution for 6h, centrifuging the precursor solution, repeatedly washing the precursor solution with deionized water to obtain a first precipitate, and drying the precipitate at 70 ℃ for 12h to obtain precursor powder; mixing 0.06g of precursor powder and 0.15g of thioacetamide, dissolving in 15ml of deionized water, magnetically stirring at room temperature to form uniform suspension, transferring the suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 100 DEG CReacting at the temperature of 6 hours to obtain a second solution; centrifuging the obtained second solution and repeatedly washing with deionized water to obtain a second precipitate; drying the second precipitate at 70 deg.C for 12h to obtain trilobate Co9S8A material. 30mg of sublimed sulphur was dissolved in CS2To the solution, 20mg of trilobate Co was added9S8Stirring the materials at room temperature until the materials are dried, transferring the mixture into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and preserving the heat at 155 ℃ for 12 hours to obtain S @ Co9S8A composite material. Mixing S @ Co9S8The composite material, the superconducting carbon black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, N-methyl pyrrolidone (NMP) is used as a diluent, stirring is carried out for 3 hours to prepare slurry, the prepared slurry is coated on a current collector by a blade coating method, and drying is carried out for 12 hours at 60 ℃ in a vacuum environment. And cutting the electrode plates into circular electrode plates with the diameter of 16mm, compacting, and assembling the battery for testing.
FIG. 2 shows the trilobal Co obtained in this example9S8SEM pictures of the material, it can be seen that the trilobes are 4.4 μm in diameter. FIG. 7 shows the trilobe Co prepared in this example9S8The lithium-sulfur battery taking the material as the cathode material has a charge-discharge specific capacity and coulombic efficiency curve chart of charging and discharging 200 times under 0.5C. FIG. 8 shows the trilobe Co prepared in this example9S8The charge-discharge specific capacity and coulombic efficiency curve chart of the room temperature sodium-sulfur battery taking the anode material is that the room temperature sodium-sulfur battery is charged and discharged for 200 times under 0.5C.
Example 5
This example is a trilobal Co prepared as in example 49S8The material is used as a raw material, and the diaphragm is modified by adopting a blade coating method, which is specifically implemented as follows:
mixing three leaves of flower Co9S8The material, the superconducting carbon black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, N-methylpyrrolidone (NMP) is used as a diluent, stirring is carried out for 3 hours to prepare slurry, the prepared slurry is coated on a diaphragm by a blade coating method, and drying is carried out for 12 hours at 60 ℃ in a vacuum environment. Cut into circular membrane pieces with a diameter of 20 mm. Sublimed sulfur, superconducting carbon black and PVDF are evenly mixed according to the mass ratio of 7:2:1, and N-methylpyrrole is usedAnd (3) stirring the mixture for 3 hours by using the ketoneketone (NMP) as a diluent to prepare slurry, coating the prepared slurry on a current collector by using a blade coating method, and drying the coated current collector for 12 hours at 60 ℃ in a vacuum environment. And cutting the electrode plates into circular electrode plates with the diameter of 16mm, compacting, and assembling the battery for testing.
FIG. 9 shows the trilobe Co prepared in this example9S8The material modified diaphragm lithium-sulfur battery has a charge-discharge specific capacity and coulombic efficiency curve chart of charging and discharging 200 times under 0.2C. FIG. 10 shows the trilobe Co prepared in this example9S8A charge-discharge specific capacity and coulombic efficiency curve chart of the room temperature sodium-sulfur battery with the material modified diaphragm, wherein the charge-discharge specific capacity and coulombic efficiency curve chart is 200 times of charge-discharge at 0.5 ℃.
Example 6
This example 6 provides a trilobal Co9S8The preparation method of the material is different from the preparation method of the material in example 4 in that:
mixing 0.65g of dimethyl imidazole, 0.29g of cobalt nitrate hexahydrate and 0.002g of hexadecyl trimethyl ammonium bromide, dissolving the mixture in 40ml of deionized water, magnetically stirring the mixture at room temperature for 20min to obtain a purple precursor solution, standing the obtained precursor solution for 6h, centrifuging the precursor solution, repeatedly washing the precursor solution with deionized water to obtain a first precipitate, and drying the precipitate at 70 ℃ for 12h to obtain precursor powder; mixing 0.06g of precursor powder and 0.15g of thioacetamide, dissolving in 15ml of deionized water, magnetically stirring at room temperature to form uniform suspension, transferring the suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 100 ℃ for 6 hours to obtain a second solution; centrifuging the obtained second solution and repeatedly washing with deionized water to obtain a second precipitate; drying the second precipitate at 70 deg.C for 12h to obtain trilobate Co9S8A material.
The specific examples described in this specification are merely illustrative of the technical solutions described in the present invention. Further modifications or additions may be made to the described embodiments or alternatives in a similar manner by those skilled in the art without departing from the spirit of the invention or exceeding the scope of the invention as defined by the appended claims. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A preparation method of a morphology-controllable nine cobalt octasulfide material is characterized by comprising the following steps:
step S1: preparing a mixed solution of cobalt salt and a metal organic framework ligand; dissolving a certain proportion of 2-methylimidazole and cobalt nitrate hexahydrate in a certain volume of deionized water to obtain a mixed solution of a cobalt salt and a metal organic framework ligand;
step S2: preparing a precursor solution on the basis of the mixed solution prepared in the step S1 to obtain precursor powder;
step S3: mixing the obtained precursor powder with thioacetamide according to a certain proportion, dissolving in deionized water with a certain volume, and magnetically stirring at room temperature until the precursor powder and the thioacetamide are uniformly mixed to obtain a purple black suspension;
step S4: transferring the obtained suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at 90-120 ℃ for 5-8h to obtain a second solution; centrifuging the obtained second solution and repeatedly washing with deionized water to obtain a second precipitate;
step S5: drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain a cobalt octasulfide material with a corresponding morphology structure;
in step S2, cobalt-containing metal organic framework structures of different morphologies are obtained by regulating and controlling the precursor, and the cobalt-containing metal organic framework structures are further vulcanized to obtain the cobalt octasulfide nonabaltate materials of different morphologies.
2. The preparation method of the shape-controllable nonacobalt octasulfide material as claimed in claim 1, wherein in step S2, the mixed solution obtained in step S1 is magnetically stirred at room temperature for 5-10min to obtain a purple precursor solution; standing the obtained precursor solution for 1-3h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; drying at 50-70 deg.C for 8-12h to obtain precursor powder; thus preparing the single-blade boat-shaped cobalt nonasulfide material.
3. The preparation method of the shape-controllable nonacobalt octasulfide material as claimed in claim 1, wherein in step S2, cetyl trimethyl ammonium bromide is added into the mixed solution obtained in step S1 in a certain proportion, and magnetic stirring is performed at room temperature for 15-30min to obtain a purple precursor solution; standing the obtained precursor solution for 5-10h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; drying at 80-100 deg.C for 14-24h to obtain precursor powder; thus obtaining a trilobal octa-cobalt sulfide material; wherein the mass fraction of the hexadecyl trimethyl ammonium bromide in the mixed solution is 0.0025-0.01 percent.
4. The preparation method of the shape-controllable cobalt nonaoctasulfide material as claimed in claim 2 or 3, wherein in step S1, the mass ratio of 2-methylimidazole, cobalt nitrate hexahydrate and deionized water is (2-5): 1: 140.
5. the preparation method of the shape-controllable nonacobalt octasulfide material as claimed in claim 2 or 3, wherein in step S3, the mass ratio of the precursor powder, thioacetamide and deionized water is 1: (1.5-3.0): 250.
6. the method for preparing morphology-controlled nonacobalt octasulfide material as claimed in claim 2, wherein the length of the long axis of the obtained single-blade boat-shaped nonacobalt octasulfide material is 3-5 μm, and the length of the short axis is 0.8-1.5 μm.
7. The preparation method of the morphology-controllable nonacobalt octasulfide material as claimed in claim 3, wherein the radius of the obtained trilobal nonacobalt octasulfide material is 4-6 μm.
8. Use of a nonacobalt octasulfide material prepared by the process of any one of claims 1 to 7 in an electrode, characterized in that the resulting nonacobalt octasulfide material is used as an electrode material for a lithium-sulfur or sodium-sulfur secondary battery or as a modified battery separator.
9. The use of the material of claim 8 in an electrode, wherein when the material of cobalt octasulfide is used as a positive electrode material of a lithium-sulfur battery in combination with sublimed sulfur, the positive electrode of the lithium-sulfur battery comprises a positive electrode current collector, and the negative electrode is metallic lithium; coating the surface of a current collector with a positive electrode material, wherein the positive electrode material comprises a nonacobalt octasulfide material obtained by the method of any one of claims 1 to 7;
and when the cobalt octasulfide and the sublimed sulfur are compounded to be used as the positive electrode material of the room-temperature sodium-sulfur battery, the positive electrode of the sodium-sulfur battery comprises a positive electrode current collector, and the negative electrode is metallic sodium; the surface of the current collector is coated with a positive electrode material, and the positive electrode material comprises the nonacobalt octasulfide material obtained by the method of any one of claims 1 to 7.
10. The application of the material of the nine cobalt octasulfide in the electrode, which is characterized in that the nine cobalt octasulfide is used for a lithium-sulfur battery or a room-temperature sodium-sulfur battery after modifying a microporous polypropylene diaphragm or a glass fiber diaphragm; the method for modifying the diaphragm selects a coating method or a hydrothermal deposition method.
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