CN113410067A - In-situ synthesis NiS2Method for preparing/ZIF-67 composite material and application thereof - Google Patents
In-situ synthesis NiS2Method for preparing/ZIF-67 composite material and application thereof Download PDFInfo
- Publication number
- CN113410067A CN113410067A CN202110681290.0A CN202110681290A CN113410067A CN 113410067 A CN113410067 A CN 113410067A CN 202110681290 A CN202110681290 A CN 202110681290A CN 113410067 A CN113410067 A CN 113410067A
- Authority
- CN
- China
- Prior art keywords
- nis
- zif
- composite material
- mixed solution
- mixing
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims description 16
- 238000003786 synthesis reaction Methods 0.000 title claims description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 54
- 238000002156 mixing Methods 0.000 claims abstract description 46
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000003990 capacitor Substances 0.000 claims abstract description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 11
- 239000012498 ultrapure water Substances 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000004201 L-cysteine Substances 0.000 claims description 3
- 235000013878 L-cysteine Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal chalcogenide Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- 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
- H01G11/24—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
- H01G11/84—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
-
- 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
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides an in-situ synthesis method of NiS2A method of making a/ZIF-67 composite, the method comprising: mixing Ni (NO)3)2·6H2Mixing O and urea, dissolving in ultrapure water, adding L-cysteine, performing hydrothermal reaction, centrifuging, washing, and vacuum drying for 15h to obtain hollow spherical NiS2(ii) a Mixing Co (NO)3)2·6H2O mixed solution and NiS2Mixing the mixed solution, pouring into 2-methylimidazole mixed solution to obtain preformed product mixed solution, standing at room temperature, centrifuging, washing, and vacuum drying to obtain NiS2the/ZIF-67 composite material also provides application of the composite material to a super capacitor anode. NiS prepared by the invention2the/ZIF-67 composite material has electrochemical properties such as high specific capacitance, good circulation stability and the like.
Description
Technical Field
The invention belongs to the technical field of electrode materials of supercapacitors, and particularly relates to in-situ synthesis of NiS2A method for preparing/ZIF-67 composite material and application thereof.
Background
With the increasing dependence on fossil energy such as coal, oil, natural gas and the like, human beings exploit and use the fossil energy excessively, which leads to a series of problems such as global warming, serious environmental destruction, day-by-day reduction of fossil resources and the like, and thus, the wide attention of the human society is brought forward. Renewable energy is an environment-friendly energy source, and the research and the use of the renewable energy have become a practical and popular research direction since the new century. The key of research is to improve the utilization rate and the conversion rate of renewable energy sources, so that the energy storage capacity of all the existing energy storage devices must be improved to a certain degree. Supercapacitors are the direction of research that has evolved gradually in recent years, with great potential. The super capacitor has unique property, is greatly different from the traditional capacitor and battery in the aspects of principle and function use, has no large light capacity, and can charge and discharge at high speed, which is different from the other two devices. It is considered to be a more promising energy storage device than the other two devices. The transition metal compound has advantages of high specific capacitance, high energy density, low cost, low toxicity, and the like, and thus has been a popular research for electrode materials. The transition metal chalcogenide is regarded as an inorganic functional material with a great application prospect as an electrode material for storing charges through the Faraday reaction of metal ions. Metal-Organic Frameworks (MOFs) are materials with a porous network framework structure formed by coordination of Metal ions and Organic ligands. ZIF-67 is a zeolitic imidazolate framework material consisting essentially of Co2+The material is generated by reacting with an organic ligand with an imidazole ring structure, is a special member in MOFs materials, and has better thermal stability and chemical stability. The two types of materials are compounded to have higher theoretical capacity and good stability, so that the NiS2ZIF-67 composite materialThe material has great research value when being applied to the anode material of the super capacitor.
As electrode materials for supercapacitors, NiS2Has the advantages of high specific capacitance, high energy density and the like. But the mechanical strength is low, and the volume is easy to expand and contract in the charging and discharging processes, so that the stability is poor, and the practical application of the super capacitor is limited. While the ZIF-67 material has high specific surface area and excellent chemical stability, but the application of the ZIF-67 material is limited by high resistance, low conductivity and low stability, and the capacitance of the ZIF-67 material is generally low. When the ZIF-67 material is singly taken as an electrode material, the performance is difficult to achieve a desired effect.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide an in-situ synthesis method of NiS, which aims at overcoming the defects of the prior art2Method and application of/ZIF-67 composite material and NiS prepared by method2the/ZIF-67 composite material has electrochemical properties such as high specific capacitance, good circulation stability and the like.
In order to solve the technical problems, the invention adopts the technical scheme that: in-situ synthesis NiS2A method of making a/ZIF-67 composite, the method comprising:
s1, mixing Ni (NO)3)2·6H2Dissolving O and urea after mixing in ultrapure water, stirring and mixing for 5-15 min, adding L-cysteine, magnetically stirring and mixing for 40-70 min, performing hydrothermal reaction at 140 ℃ for 24h, centrifuging, washing a precipitate with ultrapure water for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, volatilizing the absolute ethyl alcohol, and performing vacuum drying at 70 ℃ for 15h to obtain the hollow spherical NiS2；
S2、Co(NO3)2·6H2Dissolving O in methanol a, mixing for 15min under magnetic stirring to obtain Co (NO)3)2·6H2O mixed solution, and hollow spherical NiS obtained in S12Dissolving in methanol b, and magnetically stirring and mixing for 25-45 min to obtain NiS2Dissolving 2-methylimidazole in methanol c, and magnetically stirring for 10-20 minAfter min, obtaining 2-methylimidazole mixed solution, and mixing the Co (NO)3)2·6H2O mixed solution and said NiS2Mixing and stirring the mixed solution, pouring the mixed solution into the 2-methylimidazole mixed solution, and mixing and stirring the mixed solution to obtain a preformed product mixed solution;
wherein, Co (NO)3)2·6H2Carrying out subsequent reaction on the O mixed solution and the 2-methylimidazole mixed solution to generate a ZIF-67 material;
s3, standing the mixed solution of the preformed products obtained in the S2 for 24 hours at room temperature, centrifuging, washing the precipitate with methanol for 3 to 6 times, and drying in vacuum at the temperature of 60 ℃ for 12 hours to obtain NiS2a/ZIF-67 composite material.
Preferably, Ni (NO) as described in S13)2·6H2The molar ratio of O, urea and L-cysteine is 1:1: 4.
Preferably, the rotation speed of the centrifugation in the S1 is 2500 r/min-5000 r/min, and the centrifugation time is 5 min-15 min.
Preferably, the hollow spherical NiS in S12The average inner diameter of the inner layer is 1.8 to 2.5 μm.
Preferably, Co (NO) in the preform mixture in S23)2·6H2O, hollow spherical NiS2And the molar ratio of 2-methylimidazole is 1 (0.3-0.7): 4.
preferably, said Co (NO) in S23)2·6H2Co (NO) in O mixed liquor3)2·6H2The dosage ratio of O to methanol a is 1 mmol: 20 mL; the NiS2Hollow spherical NiS in mixed liquid2And the dosage ratio of the methanol b is (0.3-0.7) mmol: 10 mL; the dosage ratio of the 2-methylimidazole to the methanol c in the 2-methylimidazole mixed solution is 4 mmol: 20 mL.
Preferably, the rotation speed of the centrifugation in the S3 is 2000r/min to 4000r/min, and the centrifugation time is 5min to 15 min.
Preferably, the NiS2The specific surface area of the/ZIF-67 composite material is 547.70m2/g～765.18m2/g。
The invention also provides the NiS synthesized in situ2Use of/ZIF-67 composite material, said NiS2the/ZIF-67 composite material is used for the positive electrode of the super capacitor.
Compared with the prior art, the invention has the following advantages:
firstly, nickel nitrate, urea and L-cysteine are used as raw materials, and a hydrothermal method is used for preparing hollow spherical NiS2Then, cobalt nitrate and 2-methylimidazole are used for standing reaction, and the prepared hollow spherical NiS is added in the process of synthesizing ZIF-672In NiS2A layer of ZIF-67 is grown in situ on the surface to prepare NiS2The ZIF-67 composite material has a brand-new morphology structure of hollow spheres wrapped by ZIFs, can improve the cycle stability and rate capability of the material while maintaining higher specific capacitance, on one hand, the structure greatly improves the specific surface area of an electrode material, increases active sites of redox reaction, enhances the charge transfer rate, and has better conductivity, on the other hand, the wrapping structure reduces the expansion and contraction of the material in the reaction process, reduces the influence of volume expansion on the cycle performance of the electrode, improves the stability of the material, and has great application value on the electrochemical performance of a super capacitor2the/ZIF-67 composite material has electrochemical properties such as high specific capacitance, good circulation stability and the like.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic representation of a hollow spherical NiS prepared in example 1 of the present invention2And NiS2SEM image of/ZIF-67 composite material.
FIG. 2 shows NiS prepared in example 1 of the present invention2ZIF-67 composite material, ZIF-67 analog spectrum and NiS2XRD pattern of standard spectrum.
FIG. 3 shows the hollow spherical NiS prepared in example 1 of the present invention2And NiS2N of/ZIF-672Adsorption-desorption isotherm plot.
FIG. 4 shows NiS prepared in example 1 of the present invention2Constant current charge and discharge curve diagram of the/ZIF-67 composite material.
FIG. 5 is the bookNiS prepared in inventive example 22SEM image of/ZIF-67 composite material.
FIG. 6 shows NiS prepared in example 2 of the present invention2XRD pattern of/ZIF-67 composite material.
FIG. 7 shows NiS prepared in example 2 of the present invention2N of/ZIF-672Adsorption-desorption isotherm plot.
FIG. 8 shows NiS prepared in example 2 of the present invention2Constant current charge and discharge curve diagram of the/ZIF-67 composite material.
FIG. 9 is NiS prepared according to example 2 of the present invention2Cycle stability profile of/ZIF-67 composite.
FIG. 10 shows NiS prepared in example 3 of the present invention2SEM image of/ZIF-67 composite material.
FIG. 11 shows NiS prepared in example 3 of the present invention2XRD pattern of/ZIF-67 composite material.
FIG. 12 shows NiS prepared in example 3 of the present invention2N of/ZIF-672Adsorption-desorption isotherm plot.
FIG. 13 shows NiS prepared in example 3 of the present invention2Constant current charge and discharge curve diagram of the/ZIF-67 composite material.
Detailed Description
Example 1
In situ Synthesis of NiS of this example2A method of making a/ZIF-67 composite, the method comprising:
s1, mixing 1mmol of Ni (NO)3)2·6H2Dissolving O and 1mmol of urea after mixing in 70mL of ultrapure water, stirring and mixing for 5-15 min, adding 4mmol of L-cysteine, magnetically stirring and mixing for 50min, performing hydrothermal reaction for 24h at the temperature of 140 ℃, centrifuging for 10min at the rotation speed of 4000r/min, washing the precipitate with ultrapure water for 4 times, washing with absolute ethyl alcohol for 4 times, volatilizing the absolute ethyl alcohol, and drying in vacuum at the temperature of 70 ℃ for 15h to obtain the hollow spherical NiS with the average inner diameter of 2.0 mu m2；
S2, 1mmol of Co (NO)3)2·6H2Dissolving O in 20mL of methanol a, and magnetically stirring and mixing for 15min to obtainCo(NO3)2·6H2O mixture, 0.3mmol of hollow spherical NiS obtained in S12Dissolving in 10mL of methanol b, and magnetically stirring for 35min to obtain NiS2Dissolving 4mmol 2-methylimidazole in 20mL methanol c, mixing under magnetic stirring for 15min to obtain 2-methylimidazole mixed solution, and mixing with Co (NO)3)2·6H2O mixed solution and said NiS2Mixing and stirring the mixed solution, pouring the mixed solution into the 2-methylimidazole mixed solution, and mixing and stirring the mixed solution to obtain a preformed product mixed solution;
s3, standing the mixed solution of the pre-formed product obtained in the S2 at room temperature for 24 hours, centrifuging the mixed solution at the rotating speed of 3000r/min for 10 minutes, washing the precipitate with methanol for 4 times, and drying the precipitate in vacuum at the temperature of 60 ℃ for 12 hours to obtain the mixed solution with the specific surface area of 765.18m2NiS of/g2a/ZIF-67 composite material.
FIG. 1 shows the hollow spherical NiS prepared in this example2And NiS2SEM image of/ZIF-67 composite material, wherein a in FIG. 1 is the hollow spherical NiS in the step S12And b is NiS prepared in step S32a/ZIF-67 composite; as can be seen from FIG. 1, NiS2The inner diameter of the hollow sphere structure is 2.33 μm; NiS2the/ZIF-67 composite material is formed by NiS2The dosage of (A) is less, the hollow sphere is covered by a plurality of ZIF-67, and the spherical structure is not formed.
FIG. 2 shows the NiS prepared in this example2ZIF-67 composite material, ZIF-67 analog spectrum and NiS2XRD pattern of standard spectrum, NiS as shown in FIG. 22XRD spectra of/ZIF-67 composites were similar to simulated ZIF-67 structures, NiS, between 5 and 302The diffraction peaks of/ZIF-67 at 2 θ of 7.38 °, 10.46 °, 12.82 °, 16.56 °, 18.16 °, 22.28 ° and 24.68 ° coincide with the characteristic peaks of the ZIF-67 structure. It is also apparent that NiS2The diffraction peaks of the/ZIF-67 composite at 31.48 °, 35.48 °, 38.84 °, 45.16 ° and 53.44 ° 2 θ can be attributed to the (200), (210), (211), (220) and (311) plane cubic phases NiS2(JCPDSno.89-1495). Therefore, from the XRD results, the composition of the composite material can be determined asNiS2a/ZIF-67 composite material.
FIG. 3 shows the hollow spherical NiS prepared in this example2And NiS2N of/ZIF-672Adsorption-desorption isotherm plot. In FIG. 3, a is the hollow spherical NiS in step S12(in FIG. 3a, curve A is a desorption curve, curve B is an adsorption curve), and B is the NiS prepared in step S32the/ZIF-67 composite material (in figure 3B, a curve A is a desorption curve, and a curve B is an adsorption curve); according to the result of the BET test, NiS2Has a specific surface area of 1.89m2/g，NiS2The specific surface area of the/ZIF-67 composite material is 765.18m2G, description of NiS2ZIF-67 composite material and NiS2The specific surface area is greatly improved.
This example also provides the above-described in situ synthesized NiS2Use of/ZIF-67 composite material, said NiS2the/ZIF-67 composite material is used for the positive electrode of the super capacitor.
FIG. 4 shows the in situ synthesis of NiS in this example2Constant current charge and discharge curve diagram of the/ZIF-67 composite material. NiS2The current density of the/ZIF-67 composite material is 0.5 A.g-1、1A·g-1、2A·g-1、5A·g-1And 10A. g-1Specific time capacitance of 723.33F g-1，672.44F·g-1，597.33F·g-1，462.22F·g-1And 320 F.g-1The electrode is shown to have a high specific capacitance.
Example 2
In situ Synthesis of NiS of this example2A method of making a/ZIF-67 composite, the method comprising:
s1, mixing 1mmol of Ni (NO)3)2·6H2Dissolving O and 1mmol of urea after mixing in 70mL of ultrapure water, stirring and mixing for 5min, adding 4mmol of L-cysteine, magnetically stirring and mixing for 40min, performing hydrothermal reaction at 140 ℃ for 24h, centrifuging at 2500r/min for 5min, washing the precipitate with ultrapure water for 3 times, washing with absolute ethanol for 3 times, volatilizing the absolute ethanol, and vacuum drying at 70 ℃ for 15h to obtain the final productHollow spherical NiS with average inner diameter of 1.8 mu m2；
S2, 1mmol of Co (NO)3)2·6H2Dissolving O in 20mL of methanol a, and magnetically stirring and mixing for 15min to obtain Co (NO)3)2·6H2O mixture, 0.5mmol of hollow spherical NiS obtained in S12Dissolving in 10mL of methanol b, and magnetically stirring for 25min to obtain NiS2Dissolving 4mmol 2-methylimidazole in 20mL methanol c, mixing for 10min under magnetic stirring to obtain 2-methylimidazole mixed solution, and mixing with Co (NO)3)2·6H2O mixed solution and said NiS2Mixing and stirring the mixed solution, pouring the mixed solution into the 2-methylimidazole mixed solution, and mixing and stirring the mixed solution to obtain a preformed product mixed solution;
s3, standing the mixed solution of the pre-formed product obtained in the S2 at room temperature for 24 hours, centrifuging the mixed solution at the rotating speed of 2000r/min for 5 minutes, washing the precipitate with methanol for 3 times, and drying the washed precipitate in vacuum at the temperature of 60 ℃ for 12 hours to obtain the mixed solution with the specific surface area of 577.16m2NiS of/g2a/ZIF-67 composite material.
FIG. 5 shows the NiS prepared in this example2SEM image of/ZIF-67 composite Material, NiS prepared in this example2ZIF-67 composite material in NiS2When the input amount is 0.5mmol, ZIF-67 uniformly grows in the hollow spherical NiS2The ZIF-67 has good coating effect on NiS2Uniformly grown on the surface of (2), NiS2The surface of the spherical structure of (a) changes from being relatively smooth to being filled with wrinkles.
FIG. 6 shows NiS prepared in this example2XRD pattern of/ZIF-67 composite, as shown, NiS2XRD spectra of/ZIF-67 composites were similar to simulated ZIF-67 structures, NiS, between 5 and 302The diffraction peaks of the ZIF-67 at 2 theta of 7.38 degrees, 10.46 degrees, 12.82 degrees, 16.56 degrees, 18.16 degrees, 22.28 degrees and 24.68 degrees are matched with the characteristic peak of the ZIF-67 structure, and NiS2The diffraction peaks of/ZIF-67 at 2 θ 31.48 °, 35.48 °, 38.84 °, 45.16 ° and 53.44 ° can be attributed to (200), (210), (211), (220) and (311) plane cubic phases NiS2(JCPDSno.89-1495)And (5) characterization of peaks.
FIG. 7 shows the NiS prepared in this example2N of/ZIF-672The adsorption-desorption isotherm graph (curve A is the desorption curve and curve B is the adsorption curve in FIG. 7) can be obtained according to the BET test results, NiS2The specific surface area of the/ZIF-67 composite material is 577.16m2/g。
NiS synthesized in situ in this example2the/ZIF-67 composite material is used for the positive electrode of the super capacitor, and is shown in figure 8 at 0.5A-g-1、1A·g-1、2A·g-1、5A·g-1And 10A. g-1At a current density of (2), NiS2The specific capacitance of/ZIF-67 is 1442.22F g respectively-1、1297.78F·g-1、911.11F·g-1、604.44F·g-1And 391.11F g-1The electrode has a very high specific capacitance.
FIG. 9 shows NiS prepared in this example2Cyclic stability profile, NiS, of/ZIF-67 composite2The specific capacitance of the/ZIF-67 composite material is 110% of the initial specific capacitance after 4000 cycles, which shows that the introduction of the ZIF-67 material can effectively relieve the problems of volume collapse and the like caused by volume expansion and contraction of nickel sulfide in the cyclic charge-discharge process, thereby improving the cyclic stability of the material.
Example 3
In situ Synthesis of NiS of this example2A method of making a/ZIF-67 composite, the method comprising:
s1, mixing 1mmol of Ni (NO)3)2·6H2Dissolving O and 1mmol of urea after mixing in 70mL of ultrapure water, stirring and mixing for 15min, adding 4mmol of L-cysteine, magnetically stirring and mixing for 70min, performing hydrothermal reaction at 140 ℃ for 24h, centrifuging at 5000r/min for 15min, washing the precipitate with ultrapure water for 5 times, washing with absolute ethanol for 5 times, volatilizing the absolute ethanol, and vacuum drying at 70 ℃ for 15h to obtain the hollow spherical NiS with the average inner diameter of 2.5 mu m2；
S2, 1mmol of Co (NO)3)2·6H2Dissolving O in 20mL of methanol a, and magnetizingStirring and mixing for 15min to obtain Co (NO)3)2·6H2O mixture, 0.7mmol of hollow spherical NiS obtained in S12Dissolving in 10mL of methanol b, and magnetically stirring for 45min to obtain NiS2Dissolving 4mmol 2-methylimidazole in 20mL methanol c, magnetically stirring for 20min to obtain 2-methylimidazole mixed solution, and mixing the Co (NO) with the mixed solution3)2·6H2O mixed solution and said NiS2Mixing and stirring the mixed solution, pouring the mixed solution into the 2-methylimidazole mixed solution, and mixing and stirring the mixed solution to obtain a preformed product mixed solution;
s3, standing the pre-formed mixed solution obtained in S2 at room temperature for 24h, centrifuging at 4000r/min for 15min, washing the precipitate with methanol for 6 times, and vacuum drying at 60 deg.C for 12h to obtain a specific surface area of 547.70m2NiS of/g2a/ZIF-67 composite material.
FIG. 10 shows NiS prepared in this example2SEM image of/ZIF-67 composite Material, NiS prepared in this example2ZIF-67 composite material in NiS2When the input amount is 0.7mmol, ZIF-67 grows in NiS2On the hollow ball, a small part of hollow NiS2The ball is not covered by ZIF-67.
FIG. 11 shows NiS prepared in this example2XRD pattern of/ZIF-67 composite material; as shown, NiS2XRD spectra of/ZIF-67 composites were similar to simulated ZIF-67 structures, NiS, between 5 and 302The diffraction peaks of the ZIF-67 at 2 theta of 7.38 degrees, 10.46 degrees, 12.82 degrees, 16.56 degrees, 18.16 degrees, 22.28 degrees and 24.68 degrees are matched with the characteristic peak of the ZIF-67 structure, and NiS2The diffraction peaks of/ZIF-67 at 2 θ 31.48 °, 35.48 °, 38.84 °, 45.16 ° and 53.44 ° can be attributed to (200), (210), (211), (220) and (311) plane cubic phases NiS2(JCPDSno.89-1495).
FIG. 12 shows NiS prepared in this example2N of/ZIF-672The adsorption-desorption isotherm graph (curve A is the desorption curve and curve B is the adsorption curve in FIG. 12) can be obtained from the BET test results, NiS2Ratio of/ZIF-67 compositeSurface area 547.70m2/g。
NiS synthesized in situ in this example2the/ZIF-67 composite material is used for the positive electrode of the super capacitor, as shown in figure 13, and the current density is 0.5A-g-1，1A·g-1，2A·g-1，5A·g-1And 10A. g-1When the specific capacitance is 674.33F g-1，593.78F·g-1，476.44F·g-1，302.22F·g-1And 177.78 F.g-1The electrode has a high specific capacitance.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (9)
1. In-situ synthesis NiS2A method of forming a/ZIF-67 composite, the method comprising:
s1, mixing Ni (NO)3)2·6H2Dissolving O and urea after mixing in ultrapure water, stirring and mixing for 5-15 min, adding L-cysteine, magnetically stirring and mixing for 40-70 min, performing hydrothermal reaction at 140 ℃ for 24h, centrifuging, washing a precipitate with ultrapure water for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, volatilizing the absolute ethyl alcohol, and performing vacuum drying at 70 ℃ for 15h to obtain the hollow spherical NiS2；
S2、Co(NO3)2·6H2Dissolving O in methanol a, mixing for 15min under magnetic stirring to obtain Co (NO)3)2·6H2O mixed solution, and hollow spherical NiS obtained in S12Dissolving in methanol b, and magnetically stirring and mixing for 25-45 min to obtain NiS2Dissolving 2-methylimidazole in methanol c, magnetically stirring for 10-20 min to obtain 2-methylimidazole mixed solution, and adding Co (NO) into the mixed solution3)2·6H2O mixed solution and said NiS2Mixing the mixed solution, stirring, pouring into the 2-methylimidazole mixed solution, and mixingMixing and stirring to obtain a preformed product mixed solution;
s3, standing the mixed solution of the preformed products obtained in the S2 for 24 hours at room temperature, centrifuging, washing the precipitate with methanol for 3 to 6 times, and drying in vacuum at the temperature of 60 ℃ for 12 hours to obtain NiS2a/ZIF-67 composite material.
2. The in-situ synthesis NiS of claim 12A method of manufacturing a/ZIF-67 composite material, characterized in that Ni (NO) is described in S13)2·6H2The molar ratio of O, urea and L-cysteine is 1:1: 4.
3. The in-situ synthesis NiS of claim 12The method for preparing the ZIF-67 composite material is characterized in that the rotation speed of centrifugation in S1 is 2500 r/min-5000 r/min, and the centrifugation time is 5 min-15 min.
4. The in-situ synthesis NiS of claim 12A method of forming a ZIF-67 composite material, wherein the hollow spherical NiS is formed in S12The average inner diameter of the inner layer is 1.8 to 2.5 μm.
5. The in-situ synthesis NiS of claim 12A method for producing a ZIF-67 composite material, characterized in that Co (NO) is contained in the preform mixture in S23)2·6H2O, hollow spherical NiS2And the molar ratio of 2-methylimidazole is 1 (0.3-0.7): 4.
6. the in-situ synthesis NiS of claim 12A method of manufacturing a/ZIF-67 composite material, characterized in that Co (NO) is described in S23)2·6H2Co (NO) in O mixed liquor3)2·6H2The dosage ratio of O to methanol a is 1 mmol: 20 mL; the NiS2Hollow spherical NiS in mixed liquid2And the dosage ratio of the methanol b is (0.3-0.7) mmol: 10 mL; the dosage ratio of 2-methylimidazole to methanol c in the 2-methylimidazole mixed solution is 4mmol：20mL。
7. The in-situ synthesis NiS of claim 12The method for preparing the ZIF-67 composite material is characterized in that the centrifugal rotation speed in S3 is 2000 r/min-4000 r/min, and the centrifugal time is 5 min-15 min.
8. The in-situ synthesis NiS of claim 12Method for manufacturing/ZIF-67 composite material, characterized in that said NiS is manufactured by a method comprising2The specific surface area of the/ZIF-67 composite material is 547.70m2/g～765.18m2/g。
9. An in situ synthesized NiS as claimed in any one of claims 1 to 82Use of/ZIF-67 composite material, characterized in that said NiS2the/ZIF-67 composite material is used for the positive electrode of the super capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110681290.0A CN113410067A (en) | 2021-06-19 | 2021-06-19 | In-situ synthesis NiS2Method for preparing/ZIF-67 composite material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110681290.0A CN113410067A (en) | 2021-06-19 | 2021-06-19 | In-situ synthesis NiS2Method for preparing/ZIF-67 composite material and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113410067A true CN113410067A (en) | 2021-09-17 |
Family
ID=77681699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110681290.0A Pending CN113410067A (en) | 2021-06-19 | 2021-06-19 | In-situ synthesis NiS2Method for preparing/ZIF-67 composite material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113410067A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114381009A (en) * | 2022-01-25 | 2022-04-22 | 东北电力大学 | Fixed-point transformation strategy design synthesis of NiXCo1-XMethod for producing (E) -MOF @ LDH |
| CN114464786A (en) * | 2022-01-09 | 2022-05-10 | 福建师范大学 | Electrode material of potassium ion battery and preparation method and application thereof |
| CN114715954A (en) * | 2022-03-21 | 2022-07-08 | 东北电力大学 | Preparation method and application of NiMn-LDH material after three-dimensional flower-ball-shaped partial vulcanization |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413635A (en) * | 2015-11-02 | 2016-03-23 | 江苏省海洋资源开发研究院(连云港) | Preparation method for metal organic framework material in core-shell structure |
| CN108963274A (en) * | 2018-06-30 | 2018-12-07 | 河南师范大学 | A kind of preparation method of New-type bifunctional elctro-catalyst and its application in zinc and air cell |
| WO2018226158A1 (en) * | 2017-06-05 | 2018-12-13 | Agency For Science, Technology And Research | A core-shell composite |
| CN109449009A (en) * | 2018-10-29 | 2019-03-08 | 安徽师范大学 | One-dimensional manganese dioxide nano pipe@ZIF-67 nucleocapsid heterojunction structure composite material and preparation method and application |
| CN111072986A (en) * | 2019-12-18 | 2020-04-28 | 江汉大学 | Synthesis method of amorphous ZIF and core-shell structure ZIF-67@ amorphous ZIF and electrode manufactured by same |
-
2021
- 2021-06-19 CN CN202110681290.0A patent/CN113410067A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413635A (en) * | 2015-11-02 | 2016-03-23 | 江苏省海洋资源开发研究院(连云港) | Preparation method for metal organic framework material in core-shell structure |
| WO2018226158A1 (en) * | 2017-06-05 | 2018-12-13 | Agency For Science, Technology And Research | A core-shell composite |
| CN108963274A (en) * | 2018-06-30 | 2018-12-07 | 河南师范大学 | A kind of preparation method of New-type bifunctional elctro-catalyst and its application in zinc and air cell |
| CN109449009A (en) * | 2018-10-29 | 2019-03-08 | 安徽师范大学 | One-dimensional manganese dioxide nano pipe@ZIF-67 nucleocapsid heterojunction structure composite material and preparation method and application |
| CN111072986A (en) * | 2019-12-18 | 2020-04-28 | 江汉大学 | Synthesis method of amorphous ZIF and core-shell structure ZIF-67@ amorphous ZIF and electrode manufactured by same |
Non-Patent Citations (1)
| Title |
|---|
| LU, M; YUAN, XP; WANG, GS;ET AL.: ""Synthesis of nickel chalcogenide hollow spheres using an L-cysteine-assisted hydrothermal process for efficient supercapacitor electrodes"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114464786A (en) * | 2022-01-09 | 2022-05-10 | 福建师范大学 | Electrode material of potassium ion battery and preparation method and application thereof |
| CN114381009A (en) * | 2022-01-25 | 2022-04-22 | 东北电力大学 | Fixed-point transformation strategy design synthesis of NiXCo1-XMethod for producing (E) -MOF @ LDH |
| CN114715954A (en) * | 2022-03-21 | 2022-07-08 | 东北电力大学 | Preparation method and application of NiMn-LDH material after three-dimensional flower-ball-shaped partial vulcanization |
| CN114715954B (en) * | 2022-03-21 | 2023-06-20 | 东北电力大学 | Preparation method and application of NiMn-LDH material after three-dimensional flower-sphere-shaped partial vulcanization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hou et al. | Hollow dodecahedral Co3S4@ NiO derived from ZIF-67 for supercapacitor | |
| CN113410067A (en) | In-situ synthesis NiS2Method for preparing/ZIF-67 composite material and application thereof | |
| Li et al. | Reduced graphene oxide wrapped MOFs-derived cobalt-doped porous carbon polyhedrons as sulfur immobilizers as cathodes for high performance lithium sulfur batteries | |
| CN108231426B (en) | Molybdenum disulfide/porous carbon nanosphere composite material and preparation method thereof | |
| CN110690057B (en) | Nickel intercalation manganese dioxide-based flexible symmetrical quasi-solid supercapacitor material and preparation method and application thereof | |
| Chen et al. | Rational design of polar/nonpolar mediators toward efficient sulfur fixation and enhanced conductivity | |
| CN107758641A (en) | A kind of three-dimensional nitrogen sulphur codope porous carbon materials and preparation method and purposes | |
| CN110473712B (en) | MOF derived nanosheet intercalation material, and preparation method and application thereof | |
| CN113299484B (en) | Preparation method of CCO/CoNiMn-LDH composite material and application of CCO/CoNiMn-LDH composite material in super capacitor | |
| Song et al. | Morphologies of thienyl based bimetallic metal-organic frameworks controlled by solvents for high specific capacitance supercapacitor | |
| CN112017868B (en) | Mesoporous hollow carbon micron cage material and preparation method and application thereof | |
| CN107804833A (en) | A kind of three-dimensional netted nitrogen phosphorus sulphur codope porous carbon materials and preparation method and purposes | |
| CN114664569A (en) | Boron-doped cobalt-nickel flexible electrode material and preparation method thereof | |
| CN106847539A (en) | A kind of composite of the carbon coating cobalt molybdic acid hydridization manganese dioxide heterojunction structure of ultracapacitor | |
| CN110444407B (en) | Preparation method and application of core-shell porous nickel sulfide electrode material based on metal organic framework | |
| CN112357900A (en) | High-density nitrogen, oxygen and chlorine co-doped carbon particle material, and preparation method and application thereof | |
| CN104167296A (en) | Method for preparing nanoelectrode material of super capacitor | |
| CN110157006B (en) | Preparation of bimetallic phosphide material, preparation and application of electrode material containing bimetallic phosphide material | |
| Zhang et al. | Design and synthesis of Co3S4@ CoCH/NF for high performance asymmetric supercapacitors | |
| Liu et al. | Conducting polymer-functionalized mesoporous metal-organic frameworks for high-performance Li-S battery | |
| Wang et al. | Salen-based porous aromatic frameworks with multi-active sites as anode materials for lithium-ion batteries | |
| CN109192532A (en) | A kind of electrode material for super capacitor and preparation method thereof | |
| CN113205964A (en) | ZIF-67@ LDHs electrode material applied to supercapacitor and preparation method thereof | |
| CN112927947A (en) | Nickel-cobalt-sulfur electrode material based on yolk shell structure, preparation method and supercapacitor | |
| CN109920654B (en) | Preparation method of graphene/carbon nanosheet electrode |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210917 |