CN110223849A - A kind of cobalt sulfide combination electrode material and its preparation method and application - Google Patents
A kind of cobalt sulfide combination electrode material and its preparation method and application Download PDFInfo
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- CN110223849A CN110223849A CN201910614106.3A CN201910614106A CN110223849A CN 110223849 A CN110223849 A CN 110223849A CN 201910614106 A CN201910614106 A CN 201910614106A CN 110223849 A CN110223849 A CN 110223849A
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- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000007772 electrode material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004744 fabric Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 16
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 238000004073 vulcanization Methods 0.000 claims description 14
- 239000002073 nanorod Substances 0.000 claims description 13
- 239000012265 solid product Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000002086 nanomaterial Substances 0.000 description 13
- 235000013495 cobalt Nutrition 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 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
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- H01G11/32—Carbon-based
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- 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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The present invention provides a kind of cobalt sulfide combination electrode materials and its preparation method and application, belong to electrode material technical field, the preparation method comprises the following steps: (1) carbon cloth being placed in the mixed solution including cobalt nitrate, ammonium fluoride, urea and water and carry out hydro-thermal reaction, cobaltosic oxide is grown on carbon cloth, obtains presoma；(2) presoma is mixed with sodium sulfide solution, carries out hydro-thermal reaction, obtains cobalt sulfide combination electrode material；The temperature of hydro-thermal reaction is 95~105 DEG C in the step (2), and the time is 4~6h.The present invention uses the above method, and obtained cobalt sulfide combination electrode material is more coarse compared with the surface of cobaltosic oxide, and the electric conductivity of electrode material is greatly improved, so that prior art Co3O4Electrode material causes the restricted problem of charge/discharge capacity to be resolved because electric conductivity is bad.
Description
Technical field
The present invention relates to electrode material technical fields more particularly to a kind of cobalt sulfide combination electrode material and preparation method thereof
And application.
Background technique
Supercapacitor is a kind of new type of energy storage device of performance between battery and traditional capacitor, has power close
The advantages that degree is high, charge/discharge speed is fast, long service life, no pollution to the environment, is one of most promising green energy resource.
The basic structure of supercapacitor includes the diaphragm between anode, cathode and two electrodes, electrolyte fill up by
Two gaps that the two electrodes and diaphragm are separated, as shown in Figure 1.According to energy storage mechanism, supercapacitor is main
Be divided into 1. double layer capacitor: by charge electrode surface centrifugation, i.e., using being formed between electrode and electrolyte
Electric double layer realizes the storage and release of energy, and capacitance is mainly related with the surface area of electrode material；2. the counterfeit electricity of faraday
Container: chemistry suction, desorption or oxygen by the way that high reversible occurs on the two-dimentional or quasi- two-dimensional space in electrode surface or body phase
Change reduction reaction (faraday's reaction) and carrys out energy storage.Fake capacitance is not only generated in electrode surface, but also can be generated in electrode interior, because
And there is capacitance more higher than electric double layer capacitance and energy density.
In order to further increase the energy density of supercapacitor, a kind of model electrochemical capacitor-is developed in recent years
Asymmetric Supercapacitor, as shown in Fig. 2, different electrode materials is respectively adopted in two electrode, and energy storage mechnism is completely not
Together, one of electrode (cathode) stores energy using electric double layer, another electrode (anode) is then stored by fake capacitance
With conversion energy, therefore Asymmetric Supercapacitor has the double characteristic of battery and electric double layer concurrently.
Asymmetric Supercapacitor takes full advantage of capacitance characteristic of the different materials under different voltages section, keeps work electric
Pressure is widened, while battery electrode can store more charges, and therefore, energy density is much larger than symmetric form supercapacitor
Energy density.According to energy storage mechnism it is found that the system that cathode (double layer electrodes), which is, to be influenced performance of the supercapacitor and further promoted
About factor.
As the electrode material of supercapacitor, carbon material is with its excellent electric conductivity, chemical stability and high-ratio surface
Product is widely applied, but lesser specific capacitance limits its performance boost.Previous RuO2Chemical stability is good, specific capacitance
Height, but it is expensive and be difficult to large-scale use in practice.Cheap with high specific capacitance, natural resources storage level is big
Transition metal oxide (MnO2、Co3O4、TiO2, NiO etc.) become research hotspot.Co therein3O4It is stored up with excellent electronics
A kind of standby ability, it is considered to be ideal electrode of super capacitor alternative materials.In recent years, configurations, pattern are not
Same Co3O4It is prepared out and is studied as electrode material one after another, including aeroge, membrane material and hollow sub-microsphere etc..It grinds
Study carefully discovery, nano transition metal oxides can greatly shorten electrolyte ion transmission path, be conducive to substance transfer, thus greatly
It is big to improve specific capacitance.But current existing Co3O4Electrode material electric conductivity is poor, still has larger gap apart from its theory specific capacitance,
So as to cause Co3O4Application of the electrode material in supercapacitor is restricted.
Summary of the invention
The purpose of the present invention is to provide a kind of cobalt sulfide combination electrode materials and its preparation method and application, and the present invention mentions
The cobalt sulfide combination electrode material of confession has the porous structure of bigger serface, effectively increases the electric conductivity and electricity of electrode material
Capacity.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of cobalt sulfide combination electrode material, comprising the following steps:
(1) carbon cloth is placed in the mixed solution including cobalt nitrate, ammonium fluoride, urea and water and carries out hydro-thermal reaction, in carbon cloth
Upper growth cobaltosic oxide, obtains presoma；
(2) presoma is mixed with sodium sulfide solution, carries out hydro-thermal reaction, obtains cobalt sulfide combination electrode material；
The temperature of hydro-thermal reaction is 95~105 DEG C in the step (2), and the time is 4~6h.
Preferably, the amount ratio of cobalt nitrate in the step (1), ammonium fluoride, urea and water be 8~12mmol:18~
24mmol:45~55mmol:45~55mL.
Preferably, the temperature of hydro-thermal reaction is 115~125 DEG C in the step (1), and the time is 4.5~5.5h.
Preferably, the concentration of sodium sulfide solution is 0.18~0.24mol/L in the step (2).
It preferably, further include that the solid product of hydro-thermal reaction is dried after hydro-thermal reaction in the step (2).
The present invention provides the cobalt sulfide combination electrode materials that preparation method described in above-mentioned technical proposal is prepared, including
The surface of carbon cloth and the vulcanization cobalt nanorod for being attached to the carbon cloth surfaces, the vulcanization cobalt nanorod has porous structure, hole
Diameter is 300~500nm, and the shape in hole is class ellipse, and porosity is 40~60%.
Preferably, the length of the vulcanization cobalt nanorod is 3~5 μm, and diameter is 0.2~0.4 μm.
The present invention also provides the cobalt sulfide combination electrode materials described in above-mentioned technical proposal in Asymmetric Supercapacitor
In application.
The present invention provides a kind of preparation methods of cobalt sulfide combination electrode material, comprising the following steps: (1) sets carbon cloth
Hydro-thermal reaction is carried out in the mixed solution for including cobalt nitrate, ammonium fluoride, urea and water, cobaltosic oxide is grown on carbon cloth, is obtained
To presoma；(2) presoma is mixed with sodium sulfide solution, carries out hydro-thermal reaction, obtains cobalt sulfide combination electrode material；
The temperature of hydro-thermal reaction is 95~105 DEG C in the step (2), and the time is 4~6h.The present invention first four oxidation of growth on carbon cloth
Three cobalts obtain presoma, and presoma and sodium sulfide solution are then carried out hydro-thermal reaction, by controlling hydrothermal reaction condition,
In hydrothermal reaction process, sulphur atom enters Co3O4Nano material replaced in oxygen atom, and formd centainly in this process
Lacking oxygen defect, obtained porous structure, a large amount of open diffusion admittance can be provided for ion, promote carrier concentration
It is promoted, the electric conductivity of electrode material is greatly improved, so that prior art Co3O4Electrode material is led because electric conductivity is bad
The restricted problem of charge/discharge capacity is caused to be resolved.Embodiment the result shows that, Co provided by the invention3O4At vulcanization reaction
After reason, the chemical property ratio Co of obtained cobalt sulfide combination electrode material3O4It is greatly improved, area capacitance
Reach 2F/cm2。
In addition, cobalt sulfide combination electrode material prepared by the present invention has excellent cycle life, after 10000 times recycle
Capacitor maintenance dose be up to 85% or more, have good cyclical stability.
For preparation method of the present invention using transition metal oxide as presoma, the manufacture craft of electrode material is simple,
It is easy to control, and hydrothermal temperature is low, the time is short, more safety and economy.
The surface of cobalt sulfide combination electrode material prepared by the present invention is more coarse, provides more for the storage of anode ion
Exceptional space and effectively buffer charge/discharge process in volume change, substantially expand power supply pole surface reaction carry out
Specific surface area；The carrier concentration of cobalt sulfide (CoS) has obtained great promotion, while also improving the expansion of the lithium ion of electrode
Dissipate coefficient and efficiency for charge-discharge.
Detailed description of the invention
Fig. 1 is supercapacitor structures schematic diagram；
Fig. 2 is Asymmetric Supercapacitor structural schematic diagram；
The XRD diagram of cobalt sulfide in the cobalt sulfide combination electrode material that Fig. 3 is prepared for embodiment 1；
Fig. 4 is the EDS energy spectrum diagram for the cobalt sulfide combination electrode material that embodiment 1 is prepared；
Fig. 5 is the Co3O4 nanometer material and finally obtained cobalt sulfide combination electrode that 1 step of embodiment (2) obtains
The SEM of material schemes；
Fig. 6 is the TEM figure for the cobalt sulfide combination electrode material that embodiment 1 is prepared；
Fig. 7 is the cobaltosic oxide composite material and finally obtained cobalt sulfide combination electrode that 1 step of embodiment (2) obtains
Material is 100mVs in scanning speed-1When cathode cycle characteristics comparison diagram；
Fig. 8 is the cathode cycle characteristics figure for the cobalt sulfide combination electrode material that embodiment 1 is prepared；
Fig. 9 is the stable circulation linearity curve for the cobalt sulfide combination electrode material that embodiment 1 is prepared.
Specific embodiment
The present invention provides a kind of preparation methods of cobalt sulfide combination electrode material, comprising the following steps:
(1) carbon cloth is placed in the mixed solution including cobalt nitrate, ammonium fluoride, urea and water and carries out hydro-thermal reaction, in carbon cloth
Upper growth cobaltosic oxide, obtains presoma；
(2) presoma is mixed with sodium sulfide solution, carries out hydro-thermal reaction, obtains cobalt sulfide combination electrode material；
The temperature of hydro-thermal reaction is 95~105 DEG C in the step (2), and the time is 4~6h.
Without specified otherwise, raw material of the present invention is all from commercial goods well known to those skilled in the art.
Carbon cloth is placed in the mixed solution including cobalt nitrate, ammonium fluoride, urea and water and carries out hydro-thermal reaction by the present invention, in carbon
Cobaltosic oxide is grown on cloth, obtains presoma.
The present invention does not have particular/special requirement to the preparation method of the mixed solution including cobalt nitrate, ammonium fluoride, urea and water,
Directly each raw material is uniformly mixed.In the present invention, the amount ratio of the cobalt nitrate, ammonium fluoride, urea and water is preferably 8
~12mmol:18~24mmol:45~55mmol:45~55mL, further preferably 10mmol:20mmol:50mmol:
50mL。
After obtaining mixed solution, carbon cloth is placed in the mixed solution and carries out hydro-thermal reaction by the present invention, raw on carbon cloth
Long cobaltosic oxide, obtains presoma.
In the present invention, the thickness of the carbon cloth is preferably 1mm.The present invention does not have special want to the size of the carbon cloth
It asks, using size well known to those skilled in the art.In a specific embodiment of the present invention, the size of the carbon cloth is preferred
For 2cm × 3cm, conductive substrates of the carbon cloth of the present invention as electrode.Carbon cloth is preferably immersed in mixed solution by the present invention
Carry out hydro-thermal reaction.
In the present invention, the temperature of the hydro-thermal reaction is preferably 115~125 DEG C, and further preferably 120 DEG C；Hydro-thermal
The time of reaction is preferably 4.5~5.5h, further preferably 5h.In hydrothermal reaction process of the present invention, cobalt nitrate and urea
Cobaltosic oxide is generated in carbon cloth surfaces slow reaction under the action of ammonium fluoride, obtains presoma.Ammonium fluoride of the present invention
As buffer, the speed of reaction can be adjusted, it is ensured that generate nano-cobaltic-cobaltous oxide in carbon cloth surfaces.After hydro-thermal reaction,
The present invention preferably dries the solid product of hydro-thermal reaction.In the present invention, the temperature of the drying is preferably 50~55
℃.The present invention does not have particular/special requirement to the time of the drying, can reach and be completely dried.
After obtaining presoma, the present invention mixes the presoma with sodium sulfide solution, carries out hydro-thermal reaction, is vulcanized
Cobalt combination electrode material.
In the present invention, the solvent of the sodium sulfide solution is preferably water, and the concentration of the sodium sulfide solution is preferably
0.18~0.24mol/L, further preferably 0.2mol/L.The present invention does not have special want to the dosage of the sodium sulfide solution
It asks, it can be by presoma thorough impregnation.The present invention is not special to the hybrid mode of the presoma and sodium sulfide solution
It is required that using hybrid mode well known to those skilled in the art.
In the present invention, the temperature of the hydro-thermal reaction is 95~105 DEG C, preferably 100 DEG C；The hydro-thermal reaction when
Between be 4~6h, further preferably 5h.The present invention by the condition of control hydro-thermal reaction, in hydrothermal reaction process sulphur atom into
Enter Co3O4Nano material and the oxygen atom in having replaced, and certain Lacking oxygen defect is formd in this process, increase electricity
The specific surface area of pole material.
After hydro-thermal reaction, it is also preferable to include the solid products to hydro-thermal reaction to be dried by the present invention.In the present invention, institute
Stating dry temperature is preferably 50~55 DEG C.The present invention does not have particular/special requirement to the time of the drying, can be realized completely dry
It is dry.
The present invention first grows cobaltosic oxide on carbon cloth, obtains presoma, then mixes presoma and sodium sulfide solution
It closes and carries out hydro-thermal reaction, by controlling hydrothermal reaction condition, in hydrothermal reaction process, sulphur atom enters Co3O4Nano material is set
Oxygen atom in having changed, and certain Lacking oxygen defect is formd in this process, porous structure has been obtained, can have been mentioned for ion
For largely open diffusion admittance, promoting the promotion of carrier concentration, the electric conductivity of electrode material is greatly improved, so that
Prior art Co3O4Electrode material causes the restricted problem of charge/discharge capacity to be resolved because electric conductivity is bad.
The present invention also provides the cobalt sulfide combination electrode material that preparation method described in above-mentioned technical proposal is prepared, packets
Carbon cloth and the vulcanization cobalt nanorod for being attached to the carbon cloth surfaces are included, the surface of the vulcanization cobalt nanorod has porous structure,
Aperture is 300~500nm, and the shape in hole is class ellipse, and porosity is 40~60%.
In the present invention, the length of the vulcanization cobalt nanorod is preferably 3~5 μm, and diameter is preferably 0.2~0.4 μm.This
The surface for inventing the vulcanization cobalt nanorod has porous structure, and a large amount of open diffusion admittance can be provided for ion, is promoted
The electric conductivity of the promotion of carrier concentration, electrode material is greatly improved, in addition, a large amount of porous structure also helps table
The progress of face reaction, and provide more exceptional spaces for the storage of anode ion and effectively buffer in charge/discharge process
Volume change.
The present invention separately provides cobalt sulfide combination electrode material described in above-mentioned technical proposal in Asymmetric Supercapacitor
Application.In the present invention, the mode of the application preferably includes: using the cobalt sulfide combination electrode material as asymmetric super
The negative electrode material of grade capacitor uses；The present invention does not have particular/special requirement to the concrete application mode of the negative electrode material, using this
Known to the technical staff of field.
Cobalt sulfide combination electrode material provided by the invention and its preparation method and application is carried out below with reference to embodiment
Detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
A kind of preparation method of CoS combination electrode material, comprising the following steps:
(1) deionized water of the cobalt nitrate of 10mmol, the ammonium fluoride of 20mmol, the urea of 50mmol and 50mL are mixed into water
Solution；
(2) by mixed aqueous solution and 2cm × 3cm, it is put into reaction kettle that carry out hydro-thermal anti-simultaneously with a thickness of the carbon cloth of 1mm
It answers, hydrothermal temperature is 120 DEG C, and time 5h grows Co3O4 nanometer material on carbon cloth, obtains presoma；
(3) sodium sulfide solution of 0.2mol/L is prepared, and is put into reaction kettle after being mixed with presoma and carries out hydro-thermal reaction,
Wherein, hydrothermal temperature is 100 DEG C, reaction time 5h, generates cobalt sulfide nano material, then will grow has nano-sulfur
The conductive carbon for changing cobalt is arranged in drying in 50 DEG C of baking ovens, obtains CoS combination electrode material.
CoS combination electrode material sample prepared by embodiment 1 carries out XRD test, and by the standard of spectrogram and cobalt sulfide
Spectrogram is compared, as a result as shown in Figure 3.Fig. 3 shows, sample at the angle of diffraction (2 θ) is 30.625 °, 35.302 °, 46.927 °,
54.440 ° and 74.663 ° there is strong diffraction maximum, these strong spectral peaks be belonging respectively to (100) of cobalt sulfide, (101), (102),
(110) and the crystal face diffraction of (202), it was demonstrated that laboratory sample is the CoS (JCPDS NO.65-3418) of spinel structure.
The present invention has also carried out further ingredient point to cobalt sulfide combination electrode material using X-ray energy spectrometer (EDS)
Analysis, as a result as shown in Figure 4.Fig. 4 is the spectrogram and percentage composition of energy disperse spectroscopy (EDS).Wherein, S element and Co member in spectrogram
Mass ratio (37.78:62.22) between element generally conforms to the mass ratio (S:Co=32:59) of CoS material, and S element
The ratio between atomicity between Co element is 52.75:47.25, is also closer to the ratio of 1:1, further demonstrates and be grown in
Material main component above carbon cloth is CoS.
The CoS combination electrode material that the presoma and step (3) obtain to 1 step of embodiment (2) obtains carries out respectively
SEM test, test results are shown in figure 5.Fig. 5 a is the different amplifications for the persursor material that carbon cloth is prepared by hydro-thermal method
Magnification optical photo, Fig. 5 b are then to carry out hydro-thermal method on the basis of persursor material to vulcanize the CoS combination electrode material drawn
Material.Every carbon fiber surface of carbon cloth known to Fig. 5 b has all been covered with CoS nanometer rods, these nanorod lengths are about 4 μm, average straight
Diameter reaches 0.2 μm, and wherein CoS nanorod surfaces are relatively rough, the Co with Fig. 5 a3O4The smooth surface of the nanometer rods of nano material
And pointed end has significantly comparison, shows sulphur atom at high temperature under high pressure and enters Co3O4Nano material is simultaneously replaced
In oxygen atom, and form certain Lacking oxygen defect in this process.Fig. 5 b shows, the carbon of nanometer rods and high conductivity
Fibre compact connection, may significantly promote the capacitive property of combination electrode material.
The present invention has also carried out transmission electron microscope (TEM) test to finally obtained cobalt sulfide combination electrode material, as a result such as
Shown in Fig. 6.CoS nanometer rods are relatively rough as can see from Figure 6；In SAED diffraction pattern (lower left corner) visible diffraction spot compared with
To show annular shape in a jumble, illustrate that CoS is polycrystalline structure and has more defect.The upper right corner is CoS nanometer rods
HRTEM schemes, and left side lattice fringe thickens on HRTEM figure, and crystallinity is declined, and is also implied that in CoS nanorod surfaces
More defect is formd, porous structure has been obtained.
The presoma (i.e. carbon cloth and the cobaltosic oxide being grown on carbon cloth) that is obtained respectively with the step (2) and finally
Cathode of the obtained cobalt sulfide combination electrode material as Asymmetric Supercapacitor is 100mVs in scanning speed-1Condition
Lower carry out cyclic voltammetry, test results are shown in figure 7.It can be seen from figure 7 that under identical voltage value, CoS nano material
Current density be higher than Co from far away3O4Nano material shows Co3O4After vulcanization reaction is handled, the electricity of obtained CoS
Chemical property ratio Co3O4It is greatly improved, is computed, area capacitance reaches 2F/cm2。
Fig. 8 is cathode cycle characteristics figure of the cobalt sulfide combination electrode material of the preparation of embodiment 1 under different scanning speed,
It can be seen from the figure that sweep cyclic voltammetry curve under speed different and all show symmetric characteristics, and when sweeping speed from 10mV/
Shape is also able to maintain symmetry when s increases to 200mV/s, shows Co3O4What nano material obtained after vulcanization reaction
CoS combination electrode material has good redox reversible and higher capacitance.
Fig. 9 is that cobalt sulfide complex chemical compound nano material prepared by embodiment 1 is followed in the case where 200mV/s sweeps speed through 10000 times
Capacity retention after ring, it can be seen from the figure that the capacitor maintenance dose after 10000 circulations is up to 85% or more, the electricity
It is great to have good cyclical stability.
Embodiment 2
A kind of preparation method of CoS combination electrode material, comprising the following steps:
(1) deionized water of the cobalt nitrate of 8mmol, the ammonium fluoride of 24mmol, the urea of 45mmol and 50mL are mixed into water
Solution；
(2) by mixed aqueous solution and 2cm × 3cm, it is put into reaction kettle that carry out hydro-thermal anti-simultaneously with a thickness of the carbon cloth of 1mm
It answers, hydrothermal temperature is 115 DEG C, and time 4.5h grows Co3O4 nanometer material on carbon cloth, obtains presoma；
(3) sodium sulfide solution of 0.18M is prepared, and is put into reaction kettle after being mixed with presoma and carries out hydro-thermal reaction,
In, hydrothermal temperature is 95 DEG C, reaction time 6h, generates cobalt sulfide nano material, then will grow has nanometer vulcanization
The conductive carbon of cobalt is arranged in drying in 50 DEG C of baking ovens, obtains CoS combination electrode material.
Embodiment 3
A kind of preparation method of CoS combination electrode material, comprising the following steps:
(1) deionized water of the cobalt nitrate of 12mmol, the ammonium fluoride of 22mmol, the urea of 53mmol and 45mL are mixed into water
Solution；
(2) by mixed aqueous solution and 2cm × 3cm, it is put into reaction kettle that carry out hydro-thermal anti-simultaneously with a thickness of the carbon cloth of 1mm
It answers, hydrothermal temperature is 125 DEG C, and time 5.5h grows Co3O4 nanometer material on carbon cloth, obtains presoma；
(3) 0.24M vulcanized sodium Na is prepared2S solution, and be put into reaction kettle after being mixed with presoma and carry out hydro-thermal reaction,
Wherein, hydrothermal temperature is 105 DEG C, reaction time 4h, generates cobalt sulfide nano material, then will grow has nano-sulfur
The conductive carbon for changing cobalt is arranged in drying in 50 DEG C of baking ovens, obtains CoS combination electrode material.
The cobalt sulfide complex chemical compound nano material prepared to embodiment 2 and 3 is tested for the property, the results show that when sweeping
When speed is 10mV/s, the capacitor of embodiment 2 and embodiment 3 respectively reaches 0.48F/cm2And 0.51F/cm2, the two is in 200mV/s
Sweep under speed through 10000 times circulation after maintenance dose be up to 80% or more.
By above embodiments and attached drawing it is found that cobalt sulfide combination electrode material rough surface prepared by the present invention, have compared with
Big surface area is conducive to the progress of surface reaction, as the negative electrode material of Asymmetric Supercapacitor, has biggish capacitor
Amount and good cyclical stability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of cobalt sulfide combination electrode material, which comprises the following steps:
(1) carbon cloth is placed in the mixed solution including cobalt nitrate, ammonium fluoride, urea and water and carries out hydro-thermal reaction, it is raw on carbon cloth
Long cobaltosic oxide, obtains presoma；
(2) presoma is mixed with sodium sulfide solution, carries out hydro-thermal reaction, obtains cobalt sulfide combination electrode material；
The temperature of hydro-thermal reaction is 95~105 DEG C in the step (2), and the time is 4~6h.
2. preparation method according to claim 1, which is characterized in that cobalt nitrate in the step (1), ammonium fluoride, urea with
The amount ratio of water is 8~12mmol:18~24mmol:45~55mmol:45~55mL.
3. preparation method according to claim 1, which is characterized in that the temperature of hydro-thermal reaction is 115 in the step (1)
~125 DEG C, the time is 4.5~5.5h.
4. preparation method according to claim 1, which is characterized in that the concentration of sodium sulfide solution is in the step (2)
0.18~0.24mol/L.
5. preparation method according to claim 1, which is characterized in that after hydro-thermal reaction further include pair in the step (2)
The solid product of hydro-thermal reaction is dried.
6. the cobalt sulfide combination electrode material that any one of Claims 1 to 5 preparation method is prepared, which is characterized in that
Including carbon cloth and the vulcanization cobalt nanorod for being attached to the carbon cloth surfaces, the surface of the vulcanization cobalt nanorod has porous knot
Structure, aperture are 300~500nm, and the shape in hole is class ellipse, and porosity is 40~60%.
7. cobalt sulfide combination electrode material according to claim 6, which is characterized in that the length of the vulcanization cobalt nanorod
It is 3~5 μm, diameter is 0.2~0.4 μm.
8. application of the described in any item cobalt sulfide combination electrode materials of claim 6~7 in Asymmetric Supercapacitor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403180A (en) * | 2020-02-26 | 2020-07-10 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Nickel hydroxide/cobalt disulfide composite material and preparation method and application thereof |
| CN114604903A (en) * | 2022-04-07 | 2022-06-10 | 苏州大学 | Cobalt sulfide/reduced graphene oxide compound and application thereof in gas sensor |
| CN114604902A (en) * | 2022-03-31 | 2022-06-10 | 江苏大学 | Manganese-doped cobalt sulfide particles and preparation method and application thereof |
| CN114724865A (en) * | 2022-01-07 | 2022-07-08 | 五邑大学 | Cobaltosic sulfide nano material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108190969A (en) * | 2018-03-01 | 2018-06-22 | 广东工业大学 | A kind of preparation method of cobalt sulfide nano material |
| CN109616332A (en) * | 2018-12-06 | 2019-04-12 | 五邑大学 | A kind of preparation method vulcanizing cobaltosic oxide combination electrode material |
| KR20190041240A (en) * | 2017-10-12 | 2019-04-22 | 국민대학교산학협력단 | Electrode for supercapacitor and manufacturing method thereof |
-
2019
- 2019-07-09 CN CN201910614106.3A patent/CN110223849A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190041240A (en) * | 2017-10-12 | 2019-04-22 | 국민대학교산학협력단 | Electrode for supercapacitor and manufacturing method thereof |
| CN108190969A (en) * | 2018-03-01 | 2018-06-22 | 广东工业大学 | A kind of preparation method of cobalt sulfide nano material |
| CN109616332A (en) * | 2018-12-06 | 2019-04-12 | 五邑大学 | A kind of preparation method vulcanizing cobaltosic oxide combination electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 陈家辉: ""非对称超级电容器的制备及其性能研究"", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技II辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403180A (en) * | 2020-02-26 | 2020-07-10 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Nickel hydroxide/cobalt disulfide composite material and preparation method and application thereof |
| CN114724865A (en) * | 2022-01-07 | 2022-07-08 | 五邑大学 | Cobaltosic sulfide nano material and preparation method and application thereof |
| CN114604902A (en) * | 2022-03-31 | 2022-06-10 | 江苏大学 | Manganese-doped cobalt sulfide particles and preparation method and application thereof |
| CN114604902B (en) * | 2022-03-31 | 2024-04-12 | 江苏大学 | Manganese doped cobalt sulfide particles and preparation method and application thereof |
| CN114604903A (en) * | 2022-04-07 | 2022-06-10 | 苏州大学 | Cobalt sulfide/reduced graphene oxide compound and application thereof in gas sensor |
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