CN111874951B - Hollow tube heterojunction electrode material and preparation method and application thereof - Google Patents
Hollow tube heterojunction electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111874951B CN111874951B CN202010766584.9A CN202010766584A CN111874951B CN 111874951 B CN111874951 B CN 111874951B CN 202010766584 A CN202010766584 A CN 202010766584A CN 111874951 B CN111874951 B CN 111874951B
- Authority
- CN
- China
- Prior art keywords
- electrode material
- hollow tube
- hydrothermal reaction
- mixing
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 239000002073 nanorod Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 21
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 17
- 239000011565 manganese chloride Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000000034 method Methods 0.000 claims description 26
- 239000002344 surface layer Substances 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 4
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 229940079101 sodium sulfide Drugs 0.000 description 16
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 7
- 229940099607 manganese chloride Drugs 0.000 description 7
- 235000002867 manganese chloride Nutrition 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 4
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of electrode materials, in particular to a hollow tube heterojunction electrode material and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: carrying out first hydrothermal reaction after mixing cobalt chloride, urea and water for the first time to obtain a nanorod precursor; secondly, mixing the nanorod precursor with water to obtain nanorod precursor dispersion liquid; thirdly mixing the nanorod precursor dispersion liquid and a sodium sulfide aqueous solution, and carrying out a second hydrothermal reaction to obtain hollow tubular Co9S8(ii) a Mixing the hollow tubular Co9S8、MnCl2And mixing the hollow tube heterojunction electrode material with water for the fourth time, and carrying out a third hydrothermal reaction to obtain the hollow tube heterojunction electrode material. The hollow tube cobalt manganese binary sulfide is prepared by two-step ion exchange, the whole operation is simple and convenient, the universality is better, and the hollow tube heterojunction electrode material prepared by the preparation method also has higher specific capacity and better cycling stability.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a hollow tube heterojunction electrode material and a preparation method and application thereof.
Background
In recent years, new energy conversion devices having high efficiency, low cost, and environmental friendliness have received increasing attention, such as solar cells, fuel cells, hydrogen production by electrolysis of water, and supercapacitors. Among them, the super capacitor is considered to have the most practical application prospect due to the fact that the super capacitor has higher power density, longer service life and wider working temperature. However, the performance of the super capacitor is seriously affected by the electrode material, so that designing and synthesizing a novel high-performance electrode material becomes a research focus and difficulty in the field.
So far, transition metal oxides and sulfides have been widely studied as electrode materials for supercapacitors due to their multiple chemical states, high theoretical capacity and electrical conductivity. However, the redox reaction activity of the single-component transition metal compound has certain limitations, and the better development of the single-component transition metal compound in the electrode material of the super capacitor is restricted. In order to further improve the redox reactivity of the electrode material, researchers have provided a wider variety of reaction types by introducing two-component transition metal compounds, exhibiting very outstanding electrochemical activity. Among them, the bi-component transition metal sulfide represented by cobalt and manganese has a faster ion and electron transfer rate in the oxidation-reduction reaction process, so that the faraday capacity characteristic of the material can be enhanced, and the electrochemical performance is excellent. However, the construction of the special regular hollow tube morphology structure of the cobalt-manganese binary sulfide at present often depends on instruments and equipment, such as electrostatic spinning, vapor deposition and the like, but these methods have no universality and certain operation difficulty, so that a method for simply, conveniently and controllably preparing the hollow tube cobalt-manganese binary sulfide supercapacitor electrode material does not exist at present.
Disclosure of Invention
The invention aims to provide a hollow tube heterojunction electrode material and a preparation method and application thereof. The preparation method of the hollow tube heterojunction electrode material is simple to operate, the product appearance is controllable, the universality is good, and the prepared hollow tube heterojunction electrode material has high specific capacity and good cycling stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hollow tube heterojunction electrode material, which comprises the following steps:
carrying out first hydrothermal reaction after mixing cobalt chloride, urea and water for the first time to obtain a nanorod precursor;
secondly, mixing the nanorod precursor with water to obtain nanorod precursor dispersion liquid;
thirdly mixing the nanorod precursor dispersion liquid and a sodium sulfide aqueous solution, and carrying out a second hydrothermal reaction to obtain hollow tubular Co9S8;
Mixing the hollow tubular Co9S8、MnCl2And mixing the hollow tube heterojunction electrode material with water for the fourth time, and carrying out a third hydrothermal reaction to obtain the hollow tube heterojunction electrode material.
Preferably, the molar ratio of the cobalt chloride to the urea is (4-6): (4-6).
Preferably, the temperature of the first hydrothermal reaction is 100-150 ℃, and the time of the first hydrothermal reaction is 8-12 h.
Preferably, the concentration of the nanorod precursor dispersion liquid is (3.75-6.25) mg/mL;
the concentration of the sodium sulfide water solution is (20-40) mg/mL;
the mass ratio of the nanorod precursor in the nanorod precursor dispersion liquid to the sodium sulfide in the sodium sulfide aqueous solution is (3-5): (8-16).
Preferably, the temperature of the second hydrothermal reaction is 160-200 ℃, and the time of the second hydrothermal reaction is 6-12 h.
Preferably, the hollow tubular Co9S8And MnCl2The mass ratio of (80-120): (25-400).
Preferably, the temperature of the third hydrothermal reaction is 120-180 ℃, and the time of the third hydrothermal reaction is 8-16 h.
The invention also provides a hollow tube heterojunction electrode material prepared by the preparation method of the technical scheme, which comprises MnS and Co3S4;
The Co3S4Is a hollow tubular structure, and the MnS is positioned in the Co3S4An outer surface layer;
the MnS and Co3S4The heterojunction is formed at the interface of (a).
Preferably, the MnS and Co3S4The mass ratio of (1): (1.5 to 3).
The invention also provides application of the hollow tube heterojunction electrode material in the technical scheme in a super capacitor.
The invention provides a preparation method of a hollow tube heterojunction electrode material, which comprises the following steps: carrying out first hydrothermal reaction after mixing cobalt chloride, urea and water for the first time to obtain a nanorod precursor; secondly, mixing the nanorod precursor with water to obtain nanorod precursor dispersion liquid; thirdly mixing the nanorod precursor dispersion liquid and a sodium sulfide aqueous solution, and carrying out a second hydrothermal reaction to obtain hollow tubular Co9S8(ii) a Mixing the hollow tubular Co9S8、MnCl2And mixing the hollow tube heterojunction electrode material with water for the fourth time, and carrying out a third hydrothermal reaction to obtain the hollow tube heterojunction electrode material. The hollow tube cobalt-manganese binary sulfide is prepared by two-step ion exchange, the whole operation is simple and convenient, the universality is better, and the hollow tube heterojunction electrode material prepared by the preparation method also has higher specific capacity and better cycling stability;
the invention also provides a hollow tube heterojunction electrode material prepared by the preparation method of the technical scheme, which comprises MnS and Co3S4(ii) a The MnS is positioned on the outer surface of the hollow tube; the Co3S4Located on the inner surface and inside of the hollow tube; the MnS and Co3S4The heterojunction is formed at the interface of (a). The hollow tube heterojunction electrode material can generate a plurality of groups of oxidation reduction peaks in the electrochemical test process, so that electric quantity can be stored together, and the specific capacitance of the electrode material is improved; meanwhile, the hollow tube structure can be beneficial to the oxidation-reduction reaction of the electrode material under an external electric field and provides a channel for the transfer of electrons in the reaction process, so that the electron transfer is changed from a disordered state to a pipeline path for transfer, and the electron transfer is shortenedTime, thereby concentrating electrons and storing the electrons more quickly, so that the electrode material has higher specific capacitance; and the hollow tube structure is not easy to collapse in long-time oxidation-reduction reaction, so that the cycling stability of the electrode material is further improved.
Drawings
FIG. 1 is an XRD pattern of the hollow tube heterojunction electrode material prepared in examples 1-5;
FIG. 2 is a TEM, HRTEM and elemental mapping of the hollow tube heterojunction electrode material prepared in example 4; wherein a-b are TEM images, c-d are HRTEM images, and e-h are element maps;
FIG. 3 is a cyclic voltammetry curve of the hollow tube heterojunction electrode material prepared in examples 1-5;
FIG. 4 is a constant current charging and discharging curve diagram of the hollow tube heterojunction electrode material prepared in examples 1-5;
fig. 5 is a graph of the cycling stability of the hollow tube heterojunction electrode material prepared in example 4.
Detailed Description
The invention provides a preparation method of a hollow tube heterojunction electrode material, which comprises the following steps:
carrying out first hydrothermal reaction after mixing cobalt chloride, urea and water for the first time to obtain a nanorod precursor;
secondly, mixing the nanorod precursor with water to obtain nanorod precursor dispersion liquid;
thirdly mixing the nanorod precursor dispersion liquid and a sodium sulfide aqueous solution, and carrying out a second hydrothermal reaction to obtain hollow tubular Co9S8;
Mixing the hollow tubular Co9S8、MnCl2And mixing the hollow tube heterojunction electrode material with water for the fourth time, and carrying out a third hydrothermal reaction to obtain the hollow tube heterojunction electrode material.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, cobalt chloride, urea and water are firstly mixed and then subjected to a first hydrothermal reaction to obtain a nanorod precursor. In the present invention, the cobalt chloride is preferably cobalt chloride hexahydrate; the water is preferably deionized water. In the invention, the molar ratio of the cobalt chloride to the urea is preferably (4-6): (4-6), more preferably 5: 5. In the present invention, the volume ratio of the amount of the cobalt chloride to the water is preferably (4 to 6) mmol: 50mL, more preferably 5 mmol: 50 mL. In the present invention, the first mixing is preferably carried out under stirring, and the stirring is not particularly limited in the present invention and may be carried out by a process well known to those skilled in the art.
In the invention, the temperature of the first hydrothermal reaction is preferably 100-150 ℃, more preferably 110-140 ℃, and most preferably 120-130 ℃; the time of the first hydrothermal reaction is preferably 8-12 h, more preferably 9-11 h, and most preferably 10 h.
After the first hydrothermal reaction is finished, the method also preferably comprises the steps of cooling, centrifuging, washing and drying which are sequentially carried out; the cooling is not particularly limited in the present invention and may be carried out by a process known to those skilled in the art. The present invention is not limited to any particular centrifugation, and the solid-liquid separation can be carried out by a process known to those skilled in the art. In the invention, the washing comprises water washing and alcohol washing which are carried out in sequence; the water washing is preferably carried out by using deionized water; the alcohol washing is preferably carried out by using absolute ethyl alcohol. In the present invention, the temperature of the drying is preferably 60 ℃, and the drying time is not particularly limited, and the moisture is sufficiently removed by using a time known to those skilled in the art.
After obtaining the nanorod precursor, mixing the nanorod precursor with water for the second time to obtain a nanorod precursor dispersion liquid; in the present invention, the water is preferably deionized water. In the present invention, the second mixing is preferably performed under the condition of ultrasound, and the ultrasound is not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art. In the invention, the concentration of the nanorod precursor dispersion liquid is preferably (3.75-6.25) mg/mL, more preferably (4-6) mg/mL, and most preferably 5 mg/mL.
After the nano-rod precursor dispersion liquid is obtained, the nano-rod precursor dispersion liquid and a sodium sulfide aqueous solution are mixed for the third time, and a second hydrothermal reaction is carried out to obtain hollow tubular Co9S8. In the present invention, the concentration of the aqueous sodium sulfide solution is preferably (20 to 40) mg/mL, more preferably (25 to 35) mg/mL, and most preferably 30 mg/mL. In the present invention, the aqueous sodium sulfide solution is preferably prepared. In the present invention, the preparation process of the sodium sulfide aqueous solution is preferably: sodium sulfide nonahydrate was mixed with water to obtain an aqueous sodium sulfide solution. In the present invention, the mixing of the sodium sulfide nonahydrate and water is preferably performed under stirring, and the stirring is not particularly limited, and may be performed by a process well known to those skilled in the art, and the sodium sulfide nonahydrate is sufficiently dissolved in deionized water.
In the invention, the mass ratio of the nanorod precursor in the nanorod precursor dispersion liquid to the sodium sulfide in the sodium sulfide aqueous solution is preferably (3-5): (8-16), more preferably 4: 12.
In the present invention, the third mixing is preferably performed by dropping the sodium sulfide aqueous solution into the nanorod precursor dispersion liquid; the dropping process is not particularly limited, and may be a dropping process known to those skilled in the art.
After the third mixing is completed, the mixed solution obtained by the third mixing is preferably stirred for 20-40 min, and more preferably for 30 min.
In the invention, the temperature of the second hydrothermal reaction is preferably 160-200 ℃, more preferably 170-190 ℃, and most preferably 180 ℃; the time of the second hydrothermal reaction is preferably 6-12 h, and more preferably 8 h.
After the second hydrothermal reaction is finished, the method also preferably comprises the steps of sequentially centrifuging and drying products obtained by the second hydrothermal reaction; the present invention does not have any particular limitation on the centrifugation, and may employ a procedure well known to those skilled in the art and enable solid-liquid separation. In the present invention, the drying temperature is preferably 60 ℃, and the drying time is not particularly limited, so that sufficient moisture removal can be ensured.
Obtaining hollow tubular Co9S8Then, the invention leads the hollow tubular Co9S8、MnCl2And mixing the hollow tube heterojunction electrode material with water for the fourth time, and carrying out a third hydrothermal reaction to obtain the hollow tube heterojunction electrode material. In the present invention, the MnCl2Preferably anhydrous manganese chloride; the water is preferably deionized water. In the present invention, the hollow tubular Co9S8And MnCl2The mass ratio of (A) to (B) is preferably (80-120): (25-400), more preferably (90-110): (50-200), and most preferably 100: 100. In the present invention, the hollow tubular Co9S8The mass to water volume ratio of (5) to (120) mg: 50mL, more preferably (90-110) mg: 50mL, most preferably 100 mg: 50 mL. In the present invention, the fourth mixing is preferably performed by mixing hollow tubular Co9S8Mixing with water and mixing with manganese chloride. In the present invention, the fourth mixing is preferably performed under stirring conditions, and the stirring rate is not particularly limited in the present invention, and may be performed at a rate well known to those skilled in the art. In the invention, the stirring time is preferably 20-40 min, and more preferably 30 min.
In the invention, the temperature of the third hydrothermal reaction is preferably 120-180 ℃, more preferably 130-170 ℃, and most preferably 140-160 ℃; the time of the third hydrothermal reaction is preferably 8-16 h, more preferably 10-15 h, and most preferably 12 h.
After the third hydrothermal reaction is finished, the method also preferably comprises the steps of sequentially carrying out centrifugal washing and drying on a product system obtained after the third hydrothermal reaction; the present invention does not have any particular limitation on the process of the centrifugal washing, and the process well known to those skilled in the art may be used. In the present invention, the drying temperature is preferably 60 ℃, and the drying time is not particularly limited, so that sufficient moisture removal can be ensured.
The invention also provides the technical schemeThe hollow tube heterojunction electrode material prepared by the preparation method comprises MnS and Co3S4;
The Co3S4Is a hollow tubular structure, and the MnS is positioned in the Co3S4An outer surface layer of;
the MnS and Co3S4The heterojunction is formed at the interface of (a).
In the present invention, the MnS and Co3S4Is preferably 1: (1.5-3), more preferably 1: (2.0-2.5).
The invention also provides application of the hollow tube heterojunction electrode material in the technical scheme in a super capacitor. In the invention, the application of the hollow tube heterojunction electrode material in the supercapacitor is preferably that the hollow tube heterojunction electrode material is used as an electrode material of the supercapacitor. The method of the present invention is not particularly limited, and may be carried out by a method known to those skilled in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing 5mmol of cobalt chloride hexahydrate, 5mmol of urea and 50mL of deionized water under the condition of stirring, carrying out hydrothermal reaction on the obtained mixture at 120 ℃ for 10h, cooling to room temperature, centrifugally washing the mauve precipitate by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain a nanorod precursor;
mixing 200mg of nanorod precursor with 40mL of deionized water under an ultrasonic condition to obtain nanorod precursor dispersion liquid;
mixing 600mg of sodium sulfide nonahydrate and 20mL of deionized water under the stirring condition to obtain a sodium sulfide solution;
dropwise adding the sodium sulfide solution into the nanorod precursor dispersion liquid, stirring for 30min after dropwise adding, drying at 180 ℃ for 8h, centrifugally washing, and drying at 60 ℃ to obtain hollow tubular Co9S8;
100mg of hollow tubular Co9S8Mixing with 50mL of deionized water, adding 25mg of anhydrous manganese chloride, stirring for 30min to make the mixed solution uniform, carrying out hydrothermal reaction at 150 ℃ for 12h, centrifuging, washing, and drying at 60 ℃ to obtain the hollow tube heterojunction electrode material (marked as 25-MnS/Co)3S4Said MnS and Co3S4In a mass ratio of 1: 2.9).
Example 2
The preparation process is referred to example 1, except that the amount of the anhydrous manganese chloride is 50mg, and the hollow tube heterojunction electrode material (marked as 50-MnS/Co) is obtained3S4Said MnS and Co3S4The mass ratio of (1): 2.7).
Example 3
The preparation process is referred to example 1, except that the amount of the anhydrous manganese chloride is 100mg, and the hollow tube heterojunction electrode material (marked as 100-MnS/Co) is obtained3S4Said MnS and Co3S4The mass ratio of (1): 2.5).
Example 4
The preparation process is referred to example 1, except that the amount of the anhydrous manganese chloride is 200mg, and the hollow tube heterojunction electrode material (marked as 200-MnS/Co) is obtained3S4Said MnS and Co3S4The mass ratio of (1): 2.2).
Example 5
The preparation process refers to example 1, except that the amount of the anhydrous manganese chloride is 400mg, and the hollow tube heterojunction electrode material (marked as 400-MnS/Co) is obtained3S4Said MnS and Co3S4The mass ratio of (1): 1.5).
Test example
The hollow tube heterojunction electrode material prepared in the examples 1 to 5 is carried outXRD test, the test conditions are as follows: an Ultima IV type X-ray diffractometer produced by Japan science and science company is adopted, a Cu target Kalpha ray is adopted, the accelerating voltage is 40kV, the current is 40mA, the incident wavelength is 0.154nm, the scanning range is 10-90 degrees, the scanning speed is 5 degrees/min, and the phase diffraction spectrogram is searched and checked by Jade6.0 software; the test results are shown in FIG. 1, and it can be seen from FIG. 1 that the crystal phases finally prepared by different manganese ion addition amounts are MnS and Co3S4And at 35.2 DEG and 49.1 DEG 2 theta corresponding to the (200) and (220) crystallographic planes of the MnS phase (PDF #72-1534), and at 16.3 DEG, 31.6 DEG, 38.2 DEG and 55.2 DEG 2 theta corresponding to Co3S4The (111), (311), (400) and (440) crystal planes of the phase (PDF # 73-1703);
TEM, HRTEM and element mapping tests are carried out on the hollow tube heterojunction electrode material prepared in the example 4, a Titan G260-300 type objective spherical aberration comparison transmission electron microscope produced by FEI company in America is adopted in the testing process, and the accelerating voltage is 300 kV; the test results are shown in FIG. 2, wherein a to b are TEM images, c to d are HRTEM images, and e to h are elemental maps; from a to b, the electrode material obtained in example 4 has a hollow tubular structure; from c to d, it can be seen that the interplanar spacings of 0.168nm, 0.231nm and 0.256nm correspond to Co, respectively3S4Crystal (440), (400) and (311) planes, and interplanar spacings of 0.185nm and 0.273nm correspond to the (220) and (200) planes of MnS crystals; the distribution of S, Mn and Co can be seen from e-h, the three elements can be uniformly distributed on the hollow tube, mainly Co3S4The MnS particles are stacked on the tubular surface to form a heterogeneous interface;
electrochemical testing:
uniformly mixing the hollow tube heterojunction electrode material prepared in the embodiment 1-5, acetylene black and PVDF binder according to the mass ratio of 7:2:1, adding a small amount of NMP solvent, uniformly mixing, dropwise coating the uniformly mixed slurry on the surface of the processed foamed nickel, wherein the loading amount is 1mg, performing vacuum drying at 60 ℃ for 12h, pressing into a sheet by using a hydraulic machine under the pressure of 10MPa, and taking the sheet as a working electrode to be tested;
taking a counter electrode as a platinum sheet electrode, a reference electrode as an Hg/HgO electrode and electrolyte as 2M KOH to obtain a three-electrode system;
performing Cyclic Voltammetry (CV) test, constant current charging and discharging (GCD) test and cyclic stability test on the three-electrode system;
performing cyclic voltammetry testing: soaking the working electrode in the electrolyte for 1h, performing CV circulation for 1000 times for activation, and obtaining a test voltage with a voltage range of 0-0.6V and a scanning rate of 50mV s-1(ii) a As shown in fig. 3, it can be seen from fig. 3 that the hollow tube heterojunction electrode material prepared in example 4 has the largest CV curve area at the same scanning rate, which proves that it has the largest storage capacity.
Constant current charge and discharge test: the voltage window of the GCD is 0-0.55V, and the current density is 1 A.g-1(ii) a As shown in FIG. 4, it can be seen from FIG. 4 that the hollow tube heterojunction electrode material prepared in example 4 has the maximum specific capacity of 627F g-1;
And (3) testing the cycling stability: test objects: example 4 the hollow tubular heterojunction electrode material prepared in example 4 has a current density of 10A g-1Charge and discharge cycles 2000 cycles; as shown in FIG. 5, it can be seen from FIG. 5 that the capacitance gradually decreased with the increase of the number of cycles, and the first cycle capacitance was 567F g-1The capacitance also has 528F g after 2000 cycles-1The capacity retention rate is as high as 93.1%, and the method has high cycle stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a hollow tube heterojunction electrode material is characterized by comprising the following steps:
after cobalt chloride, urea and water are mixed for the first time, a first hydrothermal reaction is carried out to obtain a nanorod precursor;
secondly, mixing the nanorod precursor with water to obtain nanorod precursor dispersion liquid;
thirdly mixing the nanorod precursor dispersion liquid and a sodium sulfide aqueous solution, and carrying out a second hydrothermal reaction to obtain hollow tubular Co9S8;
Mixing the hollow tubular Co9S8、MnCl2And mixing the hollow tube heterojunction electrode material with water for the fourth time, and carrying out a third hydrothermal reaction to obtain the hollow tube heterojunction electrode material.
2. The method according to claim 1, wherein the molar ratio of the cobalt chloride to the urea is (4-6): (4-6).
3. The method according to claim 1 or 2, wherein the temperature of the first hydrothermal reaction is 100 to 150 ℃ and the time of the first hydrothermal reaction is 8 to 12 hours.
4. The method according to claim 1, wherein the nanorod precursor dispersion has a concentration of (3.75-6.25) mg/mL;
the concentration of the sodium sulfide aqueous solution is (20-40) mg/mL;
the mass ratio of the nanorod precursor in the nanorod precursor dispersion liquid to the sodium sulfide in the sodium sulfide aqueous solution is (3-5): (8-16).
5. The method according to claim 1 or 4, wherein the temperature of the second hydrothermal reaction is 160 to 200 ℃ and the time of the second hydrothermal reaction is 6 to 12 hours.
6. The method of claim 1, wherein the hollow tubular Co is prepared by9S8And MnCl2The mass ratio of (80-120): (25-400).
7. The preparation method according to claim 1 or 6, wherein the temperature of the third hydrothermal reaction is 120 to 180 ℃ and the time of the third hydrothermal reaction is 8 to 16 hours.
8. The hollow tube heterojunction electrode material prepared by the preparation method of any one of claims 1 to 7, which is characterized by comprising MnS and Co3S4;
The Co3S4Is a hollow tubular structure, and the MnS is positioned in the Co3S4An outer surface layer of;
the MnS and Co3S4The heterojunction is formed at the interface of (a).
9. The hollow-tube heterojunction electrode material of claim 8, wherein said MnS and Co3S4The mass ratio of (1): (1.5 to 3).
10. Use of the hollow tube heterojunction electrode material of claim 8 or 9 in a supercapacitor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010766584.9A CN111874951B (en) | 2020-08-03 | 2020-08-03 | Hollow tube heterojunction electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010766584.9A CN111874951B (en) | 2020-08-03 | 2020-08-03 | Hollow tube heterojunction electrode material and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111874951A CN111874951A (en) | 2020-11-03 |
CN111874951B true CN111874951B (en) | 2022-06-07 |
Family
ID=73205255
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010766584.9A Active CN111874951B (en) | 2020-08-03 | 2020-08-03 | Hollow tube heterojunction electrode material and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111874951B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112410816A (en) * | 2020-11-20 | 2021-02-26 | 武汉金特明新材料科技有限公司 | Electrocatalyst and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE867056A (en) * | 1977-05-16 | 1978-11-13 | Exxon Research Engineering Co | PROCESS FOR THE CATALYTIC TREATMENT OF HYDROCARBON CHARGES |
CN107346710A (en) * | 2017-09-09 | 2017-11-14 | 安徽师范大学 | It is a kind of to synthesize the method for nano flower array by the use of ion-exchange reactions and its be used as supercapacitor applications |
CN108682561A (en) * | 2018-05-28 | 2018-10-19 | 江苏大学 | A kind of electrode material for super capacitor and preparation method |
-
2020
- 2020-08-03 CN CN202010766584.9A patent/CN111874951B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE867056A (en) * | 1977-05-16 | 1978-11-13 | Exxon Research Engineering Co | PROCESS FOR THE CATALYTIC TREATMENT OF HYDROCARBON CHARGES |
CN107346710A (en) * | 2017-09-09 | 2017-11-14 | 安徽师范大学 | It is a kind of to synthesize the method for nano flower array by the use of ion-exchange reactions and its be used as supercapacitor applications |
CN108682561A (en) * | 2018-05-28 | 2018-10-19 | 江苏大学 | A kind of electrode material for super capacitor and preparation method |
Non-Patent Citations (3)
Title |
---|
A heterostuctured Co3S4/MnS nanotube array as a catalytic sulfur host for lithium–sulfur batteries;Yongpeng Li,et al.;《Electrochimica Acta》;20200110;第330卷;全文 * |
Co9S8 nanotubes synthesized on the basis of nanoscale Kirkendall effect and their magnetic and electrochemical properties;Zhenghua Wang,et al.;《CrystEngComm》;20100204;第12卷(第6期);全文 * |
General Formation of MxCo3-xS4 (M=Ni, Mn, Zn) Hollow Tubular Structures for Hybrid Supercapacitors;YuMing Chen,etl.;《Angewandte Chemie-International Edition》;20150901;第54卷(第36期);全文 * |
Also Published As
Publication number | Publication date |
---|---|
CN111874951A (en) | 2020-11-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108735522B (en) | CoNiO2/MXene composite material and preparation method and application thereof | |
CN111554896B (en) | Cobalt nickel selenide nitrogen doped amorphous carbon nano composite negative electrode material and preparation and application thereof | |
CN110853937A (en) | Preparation method of nickel-cobalt bimetallic selenide/carbon composite for supercapacitor | |
CN111900408B (en) | MoS for lithium ion battery2@ C composite negative electrode material and preparation method thereof | |
CN108598450B (en) | CoP/nitrogen-doped carbon/graphene nanocomposite and preparation method thereof | |
CN106057478B (en) | In the preparation method and applications of the coarse CuS nanosheet array of nickel foam Surface Creation | |
CN109546139A (en) | Metal sulfide/carbon composite material, preparation method and application thereof in battery cathode material | |
CN112830523B (en) | Molybdenum-doped cobaltosic oxide for super capacitor and preparation method thereof | |
CN107325295A (en) | Copper metal organic framework materials with super capacitor performance and preparation method and application | |
CN101847712B (en) | Method for depositing TiO2 on surface of multiwall carbon nano-tube for improving memory property of lithium ion | |
Li et al. | Unique 3D bilayer nanostructure basic cobalt carbonate@ NiCo–layered double hydroxide nanosheets on carbon cloth for supercapacitor electrode material | |
CN115232326A (en) | Metal organic framework material, preparation thereof and application thereof in electrode material | |
CN111874951B (en) | Hollow tube heterojunction electrode material and preparation method and application thereof | |
CN108231430B (en) | Polyvanadate organic-inorganic hybrid material nano-microsphere and preparation method thereof | |
KR102012106B1 (en) | Metal-organic composite comprising metal oxide and organic ligand, electrode for super-capacitor using the same, and method for preparing the same | |
CN108217725B (en) | Hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2Preparation method and application of O) material | |
CN112927947A (en) | Nickel-cobalt-sulfur electrode material based on yolk shell structure, preparation method and supercapacitor | |
CN109704303A (en) | A kind of compound biomass carbon material and its preparation and the application in lithium selenium cell coated separator | |
CN115010117B (en) | Preparation method and application of active metal modified carbon nano tube brush material | |
CN110931726A (en) | Lithium titanate negative electrode composite material, preparation method thereof and lithium ion battery | |
CN110197902A (en) | A kind of shelly-shaped sodium-ion battery positive material of porous structure split walnut and preparation method thereof | |
CN113120976B (en) | Ni4OHF7 electrode material and preparation method and application thereof | |
CN113764195B (en) | Lithium ion capacitor and preparation method thereof | |
CN115207305A (en) | Preparation method of molybdenum diselenide coated nitrogen-doped carbon nanotube composite material and lithium ion battery cathode material thereof | |
CN114094097A (en) | Preparation method of long-life high-power graphite composite material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |