CN114590842B - Preparation method of morphology-controllable cobalt octasulfide material and application of morphology-controllable cobalt octasulfide material in electrode - Google Patents
Preparation method of morphology-controllable cobalt octasulfide material and application of morphology-controllable cobalt octasulfide material in electrode Download PDFInfo
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- CN114590842B CN114590842B CN202111653470.4A CN202111653470A CN114590842B CN 114590842 B CN114590842 B CN 114590842B CN 202111653470 A CN202111653470 A CN 202111653470A CN 114590842 B CN114590842 B CN 114590842B
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- 239000000463 material Substances 0.000 title claims abstract description 84
- 239000010941 cobalt Substances 0.000 title claims abstract description 43
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 43
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 38
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 28
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 48
- 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
- 239000002244 precipitate Substances 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 23
- 238000011010 flushing procedure Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 16
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 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
- 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
- 239000000203 mixture Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 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
- 239000002131 composite material Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 2
- 229920001021 polysulfide Polymers 0.000 abstract description 13
- 239000005077 polysulfide Substances 0.000 abstract description 13
- 150000008117 polysulfides Polymers 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 description 16
- 239000002002 slurry Substances 0.000 description 12
- 238000010345 tape casting Methods 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003085 diluting agent 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
- 238000001000 micrograph Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 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
- 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 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect 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
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a shape-controllable cobalt octasulfide material and application of the cobalt octasulfide material in an electrode. The Co 9S8 material prepared by the method 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 shuttling of 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 are receiving attention as an advanced recyclable energy storage system as the demand for energy by humans increases. Among the lithium ion batteries that have been commercialized, it has been difficult to satisfy the demands of the human society for the high energy density secondary batteries due to the low theoretical specific capacity of the positive electrode.
The lithium sulfur battery and the room temperature sodium sulfur battery both have higher energy density, are considered as the battery energy system with the most development potential, and in addition, the sulfur simple substance has the advantages of small environmental pollution, large reserve, low price and the like, thereby having 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 preventing the commercial use of the two batteries have certain similarity, namely the biggest problem is a shuttle effect caused by the dissolution and diffusion of soluble intermediate products (lithium polysulfide and sodium polysulfide) in electrolyte in the charge and discharge processes.
Nine cobalt octasulfide (Co 9S8) as a polar material can chemically inhibit polysulfide shuttling, while its high conductivity also ensures that high coulombic efficiency can be maintained while effectively blocking polysulfide. 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, aiming at the technical problems existing in the prior art, a technical scheme is needed to be put forward in order to overcome the defects existing in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method and application of a shape-controllable cobalt octasulfide electrode material, wherein the surface area of cobalt octasulfide is increased by improving the process, so that Co 9S8 materials with different shapes are prepared. The Co 9S8 material prepared by the method 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 shuttling of polysulfide.
In order to achieve the aim, the invention provides a preparation method of a shape-controllable octa-sulfide nine-cobalt 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)2·6H2 O), dissolving in a certain volume of deionized water to obtain a mixed solution of cobalt salt and metal organic frame 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) in a certain proportion, dissolving in a certain volume of deionized water, and magnetically stirring at room temperature until the mixture is uniform to obtain a purple black suspension;
Step S4: transferring the obtained suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting for 5-8 hours at 90-120 ℃ to obtain a second solution; centrifuging the obtained second solution and repeatedly flushing with deionized water to obtain a second precipitate;
step S5: drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain the octa-nine-cobalt sulfide material with the corresponding morphology structure;
in step S2, cobalt-containing metal organic frame structures with different morphologies are obtained by regulating and controlling the precursor, and then vulcanized to obtain the octa-nine cobalt sulfide material with different morphologies.
As a further improvement scheme, in the step S2, the mixed solution is magnetically stirred for 5-10min at room temperature to obtain a purple precursor solution; standing the obtained precursor solution for 1-3h, centrifuging and repeatedly flushing with deionized water to obtain a first precipitate; and drying at 50-70deg.C for 8-12 hr to obtain precursor powder. The single-leaf boat-shaped Co 9S8 material is prepared.
As a further improvement scheme, in the step S2, adding a certain proportion of cetyltrimethylammonium bromide (CTAB) into the mixed solution, and magnetically stirring for 15-30min at room temperature to obtain a purple precursor solution; standing the obtained precursor solution for 5-10h, centrifuging and repeatedly flushing with deionized water to obtain a first precipitate; drying at 80-100deg.C for 14-24 hr to obtain precursor powder; the mass fraction of CTAB in the mixed solution is 0.0025% -0.01%. The trilobate Co 9S8 material is prepared.
Further, the length of the long axis of the obtained single-leaf boat-shaped Co 9S8 material is 3-5 μm, and the length of the short axis is 0.8-1.5 μm.
Further, the radius of the obtained trilobate Co 9S8 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 to 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 hours.
The application of the octa-cobalt sulfide material prepared by the method in the electrode uses the obtained octa-cobalt sulfide material as an electrode material of a lithium sulfur or sodium sulfur secondary battery or a modified battery diaphragm. Namely, the modified membrane is applied to a positive electrode material of a lithium sulfur battery, a positive electrode material of a room temperature sodium sulfur battery, membrane modification of the lithium sulfur battery and membrane modification of the room temperature sodium sulfur battery.
As a further improvement scheme, when the composite of the cobalt octasulfide and the sublimed sulfur is used as a positive electrode material of a lithium-sulfur battery, the positive electrode of the lithium-sulfur battery comprises a positive electrode current collector, and the negative electrode is metal lithium; the surface of the current collector is coated with a positive electrode material, and the positive electrode material comprises the octa-sulfide nine-cobalt material obtained by the method of any one of claims 1-7;
when the cobalt octasulfide and sublimed sulfur are compounded to be used as a sodium-sulfur battery positive electrode material, the sodium-sulfur battery positive electrode comprises a positive electrode current collector, and the negative electrode is sodium metal; the surface of the current collector is coated with a positive electrode material, and the positive electrode material comprises the octa-sulfide nine-cobalt material obtained by the method of any one of claims 1-7.
As a further improvement scheme, the modified microporous polypropylene membrane or glass fiber membrane is used for a lithium sulfur battery or a room temperature sodium sulfur battery after being subjected to the modification of the microporous polypropylene membrane or glass fiber membrane by the cobalt octasulfide; the membrane is modified by coating or hydrothermal deposition.
Compared with the prior art, the invention has the following beneficial effects:
(1) The Co 9S8 material prepared by the method has larger surface area and stable mechanical structure, can effectively load elemental sulfur when being used as a positive electrode material of a lithium sulfur battery or a room temperature sodium sulfur battery, and can be combined with polysulfide due to the fact that the Co 9S8 material has high polarity, so that polysulfide shuttling can be effectively prevented.
(2) The preparation method of the shape-controllable cobalt octasulfide electrode material provided by the invention is controllable in shape, simple in preparation process and suitable for large-scale industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of the single leaf boat Co 9S8 material of example 2.
Fig. 2 is a scanning electron microscope image of the trilobate Co 9S8 material of example 4.
Fig. 3 is a graph showing the specific charge/discharge capacity and coulombic efficiency of a lithium sulfur battery using the single-leaf boat-shaped Co 9S8 material prepared in example 2 as a positive electrode material, which was charged/discharged 200 times at 0.2C.
Fig. 4 is a graph showing the specific charge and discharge capacity and coulombic efficiency of a sodium sulfur cell at room temperature, in which the single-leaf boat-shaped Co 9S8 material prepared in example 2 was used as the positive electrode material, charged and discharged 200 times at 0.2C.
Fig. 5 is a graph showing specific charge/discharge capacity and coulombic efficiency of a lithium sulfur battery with a single-leaf boat-shaped Co 9S8 -modified separator prepared in example 3, charged/discharged 200 times at 0.5C.
FIG. 6 is a graph showing the specific charge/discharge capacity and coulombic efficiency of a single-leaf boat-shaped Co 9S8 -material-modified membrane prepared in example 3 at 0.2C for 200 times.
Fig. 7 is a graph showing the specific charge/discharge capacity and coulombic efficiency of a lithium-sulfur battery using the trilobal Co 9S8 material prepared in example 4 as a positive electrode material, charged/discharged 200 times at 0.5C.
Fig. 8 is a graph showing the specific charge and discharge capacity and coulombic efficiency of a sodium sulfur cell at room temperature, which uses the trilobate Co 9S8 material prepared in example 4 as the positive electrode material, charged and discharged 200 times at 0.5C.
Fig. 9 is a graph showing specific charge/discharge capacity and coulombic efficiency of a lithium-sulfur battery with a trilobal Co 9S8 material modified separator prepared in example 5 charged/discharged 200 times at 0.2C.
Fig. 10 is a graph showing the specific charge and discharge capacity and coulombic efficiency of a room temperature sodium sulfur battery with a trilobate Co 9S8 material modified membrane prepared in example 5 charged and discharged 200 times at 0.5C.
FIG. 11 is a flow chart of a method for preparing a shape-controllable cobalt octasulfide material.
Detailed Description
The present invention will be further described in detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It is to be understood that the invention may be practiced or carried out in other various embodiments and that various details of the examples that follow may be modified or changed from a different perspective without departing from the spirit of the invention. The following embodiments and features of the embodiments may be combined with each other without any conflict.
The applicant found in the study that, as a polar material, cobalt octasulphide (Co 9S8) was able to chemically prevent polysulfide shuttling, while its high conductivity also ensured that while effectively blocking polysulfides, a high coulombic efficiency was maintained. The invention provides a preparation method of a shape-controllable cobalt octasulfide electrode material on the basis, and the contact area of cobalt octasulfide and polysulfide is increased, so that the adsorption effect is improved, and the mechanical structure is more stable.
Referring to fig. 11, a flow chart of a preparation method of a morphology-controllable cobalt octasulfide material of the present invention is shown, comprising 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 and cobalt nitrate hexahydrate, and dissolving the mixture in a certain volume of deionized water to obtain a mixed solution of cobalt salt and a metal organic frame 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 in a certain proportion, dissolving in a certain volume of deionized water, and magnetically stirring at room temperature until the mixture is uniform to obtain a purple black suspension;
Step S4: transferring the obtained suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting for 5-8 hours at 90-120 ℃ to obtain a second solution; centrifuging the obtained second solution and repeatedly flushing with deionized water to obtain a second precipitate;
step S5: drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain the octa-nine-cobalt sulfide material with the corresponding morphology structure;
in step S2, cobalt-containing metal organic frame structures with different morphologies are obtained by regulating and controlling the precursor, and then vulcanized to obtain the octa-nine cobalt sulfide material with different morphologies.
In the step S2, magnetically stirring the mixed solution obtained in the 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 flushing with deionized water to obtain a first precipitate; drying at 50-70deg.C for 8-12 hr to obtain precursor powder; the single-leaf boat-shaped octasulfide nine-cobalt material is prepared.
In the step S2, adding a certain proportion of cetyltrimethylammonium bromide into the mixed solution obtained in the step S1, and magnetically stirring for 15-30min at room temperature to obtain a purple precursor solution; standing the obtained precursor solution for 5-10h, centrifuging and repeatedly flushing with deionized water to obtain a first precipitate; drying at 80-100deg.C for 14-24 hr to obtain precursor powder; the trilobate octa-cobalt sulfide material is prepared by the method; wherein the mass fraction of the cetyl trimethyl ammonium bromide in the mixed solution is 0.0025-0.01%.
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: in an argon-protected glove box, the prepared s@co 9S8 was positive, celgard 2500 as separator, lithium metal plate as negative electrode, and 1M LiTFSI (DOL/dme=1:1) with 0.1mol/L of LiNO 3 added as electrolyte to assemble the battery. In the charge-discharge test system, the charge-discharge test voltage is 1.5-3.0V.
(2) The method is applied to a lithium-sulfur battery diaphragm modification material, and the specific test process is as follows: in an argon-protected glove box, sublimed sulfur was used as a positive electrode, celgard 2500@co 9S8 as a separator, a metallic lithium sheet as a negative electrode, and 1M LiTFSI (DOL/dme=1:1) with 0.1mol/L of LiNO 3 added as an electrolyte to assemble the battery. In the charge-discharge test system, the charge-discharge test voltage is 1.5-3.0V.
(3) The method is applied to the electrode material of the sodium-sulfur battery at room temperature, and the specific test process is as follows: in an argon-protected glove box, the prepared s@co 9S8 was positive, WHATMANGF/D as separator, sodium metal sheet as negative, and 1M NaClO 4 (EC/dec=1:1) as electrolyte to assemble the battery. In the charge-discharge test system, the charge-discharge test voltage is 1.0-3.0V.
(4) The method is applied to the electrode material of the sodium-sulfur battery at room temperature, and the specific test process is as follows: in an argon-protected glove box, sublimed sulfur was positive electrode, WHATMANGF/d@co 9S8 as separator, metallic sodium sheet as negative electrode, and 1M NaClO 4 (EC/dec=1:1) as electrolyte to assemble the cell. In the charge-discharge test system, the charge-discharge test voltage is 1.0-3.0V.
The technical scheme of the invention is further described through the specific examples.
Example 1
The embodiment 1 provides a preparation method of a single-leaf boat-shaped Co 9S8 material, which comprises the following steps:
S11, taking a certain proportion of 2-methylimidazole (2-MIM) and cobalt nitrate hexahydrate (Co (NO 3)2·6H2 O), dissolving in a certain volume of deionized water to obtain a mixed solution of cobalt salt and metal organic frame ligand, wherein 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 flushing with deionized water to obtain a first precipitate; and drying at 50-70deg.C for 8-12 hr to obtain precursor powder.
S13, mixing the obtained precursor powder with Thioacetamide (TAA) according to a certain proportion, dissolving in a certain volume of deionized water, and magnetically stirring at room temperature until the mixture is uniform to obtain a purple-black suspension; the mass ratio of the precursor powder to the thioacetamide to the 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 for 5-8 hours at 90-120 ℃ to obtain a second solution; and centrifuging the obtained second solution and repeatedly flushing with deionized water to obtain a second precipitate.
S15, drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain the single-leaf boat-shaped Co 9S8 material.
In this embodiment, specifically, the method includes:
Mixing 0.65g of dimethyl imidazole 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 flushing with deionized water to obtain a first precipitate, and drying at 70 ℃ for 12h to obtain precursor powder; mixing 0.06g of precursor powder with 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 flushing with deionized water to obtain a second precipitate; and drying the obtained second precipitate at 70 ℃ for 12 hours to obtain the single-leaf boat-shaped Co 9S8 material.
Example 2
The present example 1 provides a method for preparing a single-leaf boat-shaped Co 9S8 material, which is different from example 1 in that:
Mixing 0.65g of dimethyl imidazole 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 flushing with deionized water to obtain a first precipitate, and drying at 70 ℃ for 12h to obtain precursor powder; mixing 0.06g of precursor powder with 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 flushing with deionized water to obtain a second precipitate; and drying the obtained second precipitate at 70 ℃ for 12 hours to obtain the single-leaf boat-shaped Co 9S8 material. 30mg of sublimed sulfur is dissolved in CS 2 solution, 20mg of single-leaf boat-shaped Co 9S8 material is added, stirring is carried out at room temperature until the mixture is dried, then the mixture is transferred into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and the temperature is kept at 155 ℃ for 12 hours, so that the S@Co 9S8 composite material is obtained. Uniformly mixing the S@Co 9S8 composite material, the superconducting carbon black and the PVDF according to the mass ratio of 7:2:1, stirring for 3 hours to prepare slurry, coating the prepared slurry on a current collector by using a knife coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Cutting into round electrode plates with the diameter of 16mm, compacting, and assembling the battery for testing.
FIG. 1 is an SEM image of a single-leaf boat Co 9S8 material prepared in this example, and it can be seen that the long axis length of the single-leaf boat is about 4.7 μm and the short axis length is about 1.3. Mu.m. Fig. 3 is a graph showing the specific charge and discharge capacity and coulombic efficiency of a lithium sulfur battery using the single-leaf boat-shaped Co 9S8 material prepared in this example as a positive electrode material, charged and discharged 200 times at 0.2C. The specific capacity of the lithium sulfur battery after the initial discharge is 1587mAhg -1, and the specific capacity after 200 circles is 258mAhg -1.
Fig. 4 is a graph showing the specific charge and discharge capacity and coulombic efficiency of a sodium sulfur battery with a single-leaf boat-shaped Co 9S8 material as the positive electrode material, which was prepared in this example, charged and discharged 200 times at 0.2C.
Example 3
In this example, the single-leaf boat-shaped Co 9S8 material prepared in example 2 was used as a raw material, and the diaphragm was modified by a knife coating method, and the specific implementation is as follows:
Uniformly mixing a single-leaf boat-shaped Co 9S8 material, superconducting carbon black and PVDF according to the mass ratio of 7:2:1, stirring for 3 hours to prepare slurry, coating the prepared slurry on a diaphragm by using a knife coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Cut into round membrane sheets of 20mm diameter. Mixing sublimed sulfur, superconducting carbon black and PVDF uniformly according to the mass ratio of 7:2:1, stirring for 3 hours by using N-methyl pyrrolidone (NMP) as a diluent to prepare slurry, coating the prepared slurry on a current collector by using a knife coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Cutting into round electrode plates with the diameter of 16mm, compacting, and assembling the battery for testing.
Fig. 5 is a graph showing specific charge and discharge capacity and coulombic efficiency of a lithium-sulfur battery with a single-leaf boat-shaped Co 9S8 material modified diaphragm prepared in this example charged and discharged 200 times at 0.5C. Fig. 6 is a graph of specific charge and discharge capacity and coulombic efficiency of a single-leaf boat-shaped Co 9S8 material modified membrane room temperature sodium-sulfur battery prepared in this example charged and discharged 200 times at 0.2C.
Example 4
The embodiment 4 provides a preparation method of a trilobate-shaped Co 9S8 material, which comprises the following steps:
S21, dissolving 2-methylimidazole (2-MIM) and cobalt nitrate hexahydrate (Co (NO 3)2·6H2 O) in a certain volume of deionized water to obtain a mixed solution of cobalt salt and a metal organic frame ligand, wherein 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 cetyltrimethylammonium bromide (CTAB) into the mixed solution, and magnetically stirring for 15-30min at room temperature to obtain a purple precursor solution; standing the obtained precursor solution for 5-10h, centrifuging and repeatedly flushing with deionized water to obtain a first precipitate; drying at 80-100deg.C for 14-24 hr to obtain precursor powder; the mass fraction of CTAB in the mixed solution is 0.0025% -0.01%.
S23, mixing the obtained precursor powder with Thioacetamide (TAA) according to a certain proportion, dissolving in a certain volume of deionized water, and magnetically stirring at room temperature until the mixture is uniform to obtain a purple-black suspension; the mass ratio of the precursor powder to the thioacetamide to the 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 for 5-8 hours at 90-120 ℃ to obtain a second solution; and centrifuging the obtained second solution and repeatedly flushing with deionized water to obtain a second precipitate.
S25, drying the obtained second precipitate at 60-100 ℃ for 8-12h to obtain the trilobate Co 9S8 material.
In this embodiment, specifically, the method includes:
Mixing 0.65g of dimethyl imidazole, 0.29g of cobalt nitrate hexahydrate and 0.002g of cetyltrimethylammonium bromide, dissolving in 40ml of deionized water, magnetically stirring at room temperature for 15min to obtain a purple precursor solution, standing the obtained precursor solution for 6h, centrifuging, repeatedly flushing with deionized water to obtain a first precipitate, and drying at 70 ℃ for 12h to obtain precursor powder; mixing 0.06g of precursor powder with 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 flushing with deionized water to obtain a second precipitate; and drying the obtained second precipitate at 70 ℃ for 12 hours to obtain the trilobate Co 9S8 material. 30mg of sublimed sulfur is dissolved in CS 2 solution, 20mg of clover-shaped Co 9S8 material is added, stirring is carried out at room temperature until the mixture is dried, then the mixture is transferred into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and the temperature is kept at 155 ℃ for 12 hours, so that the S@Co 9S8 composite material is obtained. Uniformly mixing the S@Co 9S8 composite material, the superconducting carbon black and the PVDF according to the mass ratio of 7:2:1, stirring for 3 hours to prepare slurry, coating the prepared slurry on a current collector by using a knife coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Cutting into round electrode plates with the diameter of 16mm, compacting, and assembling the battery for testing.
FIG. 2 is an SEM image of the trilobate Co 9S8 material prepared in this example, and it can be seen that the trilobate diameter is 4.4. Mu.m. Fig. 7 is a graph showing specific charge and discharge capacity and coulombic efficiency of a lithium-sulfur battery using the trilobal Co 9S8 material prepared in this example as a positive electrode material, charged and discharged 200 times at 0.5C. Fig. 8 is a graph of specific charge and discharge capacity and coulombic efficiency of a room temperature sodium-sulfur battery with a trilobate Co 9S8 material as a positive electrode material, prepared in this example, charged and discharged 200 times at 0.5C.
Example 5
In this embodiment, the trilobate Co 9S8 material prepared in example 4 is used as a raw material, and a knife coating method is used to modify the diaphragm, and the specific implementation is as follows:
Uniformly mixing a trilobate Co 9S8 material, superconducting carbon black and PVDF according to the mass ratio of 7:2:1, stirring for 3 hours to prepare slurry, coating the prepared slurry on a diaphragm by using a knife coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Cut into round membrane sheets of 20mm diameter. Mixing sublimed sulfur, superconducting carbon black and PVDF uniformly according to the mass ratio of 7:2:1, stirring for 3 hours by using N-methyl pyrrolidone (NMP) as a diluent to prepare slurry, coating the prepared slurry on a current collector by using a knife coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Cutting into round electrode plates with the diameter of 16mm, compacting, and assembling the battery for testing.
Fig. 9 is a graph of specific charge and discharge capacity and coulombic efficiency of a lithium-sulfur battery with a trilobal Co 9S8 material modified membrane prepared in this example charged and discharged 200 times at 0.2C. Fig. 10 is a graph of specific charge and discharge capacity and coulombic efficiency of a room temperature sodium-sulfur battery with a trilobate Co 9S8 material modified membrane prepared in this example charged and discharged 200 times at 0.5C.
Example 6
The present example 6 provides a preparation method of trilobate Co 9S8 material, which is different from the example 4 in that:
Mixing 0.65g of dimethyl imidazole, 0.29g of cobalt nitrate hexahydrate and 0.002g of cetyltrimethylammonium bromide, dissolving in 40ml of deionized water, magnetically stirring at room temperature for 20min to obtain a purple precursor solution, standing the obtained precursor solution for 6h, centrifuging, repeatedly flushing with deionized water to obtain a first precipitate, and drying at 70 ℃ for 12h to obtain precursor powder; mixing 0.06g of precursor powder with 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 flushing with deionized water to obtain a second precipitate; and drying the obtained second precipitate at 70 ℃ for 12 hours to obtain the trilobate Co 9S8 material.
The specific examples described in this specification are merely illustrative of the application as described. Those skilled in the art may make further modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the application or exceeding the scope of the application as defined in the accompanying claims. Therefore, it is intended that the application not be limited to the particular embodiment disclosed, but that the application will include all embodiments falling within the scope of the appended claims.
Claims (5)
1. The preparation method of the shape-controllable octa-sulfide nine-cobalt material is characterized by comprising the following steps of:
Step S1: preparing a mixed solution of cobalt salt and a metal organic framework ligand; taking a certain proportion of 2-methylimidazole and cobalt nitrate hexahydrate, and dissolving the mixture in a certain volume of deionized water to obtain a mixed solution of cobalt salt and a metal organic frame ligand; in the step S1, the mass ratio of the 2-methylimidazole, the cobalt nitrate hexahydrate and the deionized water is (2-5): 1:140;
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 in a certain proportion, dissolving in a certain volume of deionized water, and magnetically stirring at room temperature until the mixture is uniform to obtain a purple black suspension;
step S4: transferring the obtained suspension into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting for 5-8 hours at 90-120 ℃ to obtain a second solution; centrifuging the obtained second solution and repeatedly flushing with deionized water to obtain a second precipitate;
step S5: drying the obtained second precipitate at 60-100 ℃ to obtain 8-12 h, thereby obtaining the octa-nine-cobalt sulfide material with a corresponding morphology structure;
In the step S2, cobalt-containing metal organic frame structures with different morphologies are obtained by regulating and controlling the precursor, and then vulcanized to obtain the octa-nine cobalt sulfide material with different morphologies;
In the step S2, magnetically stirring the mixed solution obtained in the step S1 at room temperature for 5-10min to obtain a purple precursor solution; standing the obtained precursor solution for 1-3 h, centrifuging, and repeatedly washing with deionized water to obtain a first precipitate; drying at 50-70deg.C for 8-12 hr to obtain precursor powder; the single-leaf boat-shaped octasulfide nine cobalt material is prepared by the method;
In the step S2, adding a certain proportion of cetyltrimethylammonium bromide into the mixed solution obtained in the step S1, and magnetically stirring for 15-30min at room temperature to obtain a purple precursor solution; standing the obtained precursor solution for 5-10 h, centrifuging and repeatedly washing with deionized water to obtain a first precipitate; drying at 80-100deg.C for 14-24 h to obtain precursor powder; the trilobate octa-cobalt sulfide material is prepared by the method; wherein the mass fraction of the cetyl trimethyl ammonium bromide in the mixed solution is 0.0025% -0.01%.
2. The method for preparing the morphology-controllable cobalt octasulfide material according to claim 1, wherein in the step S3, the mass ratio of the precursor powder, thioacetamide and deionized water is 1: (1.5-3.0): 250.
3. The method for preparing the shape-controllable cobalt octasulfide material according to claim 1, wherein the length of a long axis of the obtained single-leaf boat-shaped cobalt octasulfide material is 3-5 μm, and the length of a short axis of the obtained single-leaf boat-shaped cobalt octasulfide material is 0.8-1.5 μm.
4. The method for preparing the morphology-controllable cobalt octasulfide material according to claim 1, wherein the radius of the obtained trilobate cobalt octasulfide material is 4-6 μm.
5. Use of the cobalt octasulfide material prepared by the method according to any one of claims 1 to 4 in an electrode, characterized in that the resulting cobalt octasulfide material is used as an electrode material for a lithium sulfur or sodium sulfur secondary battery or as a modified battery separator;
When the composite of the cobalt octasulfide and the sublimed sulfur is used as a lithium-sulfur battery positive electrode material, the lithium-sulfur battery positive electrode comprises a positive electrode current collector, and the negative electrode is metal lithium; the surface of the current collector is coated with a positive electrode material, and the positive electrode material comprises the octa-sulfide nine-cobalt material obtained by the method of any one of claims 1-4;
When the octa-cobalt sulfide and sublimed sulfur are compounded to be used as a room-temperature sodium-sulfur battery positive electrode material, the sodium-sulfur battery positive electrode comprises a positive electrode current collector, and the negative electrode is sodium metal; the surface of the current collector is coated with a positive electrode material, and the positive electrode material comprises the octa-sulfide nine-cobalt material obtained by the method of any one of claims 1-4;
After 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 membrane is modified by coating or hydrothermal deposition.
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