CN110767467B - NiCoZnP hollow microsphere material and preparation method thereof - Google Patents
NiCoZnP hollow microsphere material and preparation method thereof Download PDFInfo
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- CN110767467B CN110767467B CN201911201323.6A CN201911201323A CN110767467B CN 110767467 B CN110767467 B CN 110767467B CN 201911201323 A CN201911201323 A CN 201911201323A CN 110767467 B CN110767467 B CN 110767467B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 140
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 70
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 13
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 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 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 28
- 239000013543 active substance Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000000840 electrochemical analysis Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 229910000474 mercury oxide Inorganic materials 0.000 description 7
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 241001124569 Lycaenidae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000004769 chrono-potentiometry Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- ATYNVYNPWGEMMI-UHFFFAOYSA-H nickel(2+);carbonate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Ni+2].[Ni+2].[Ni+2].[O-]C([O-])=O ATYNVYNPWGEMMI-UHFFFAOYSA-H 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
Abstract
The invention discloses a NiCoZnP hollow microsphere material and a preparation method thereof, belonging to the technical field of conductive composite materials, the method comprises the steps of placing foamed nickel in an acetone solvent for ultrasonic treatment, then soaking in an acid solution, taking out for ultrasonic treatment, and drying for later use; mixing zinc nitrate, nickel nitrate, cobalt nitrate, urea and sodium hypophosphite, adding into a container containing isopropanol water solution, stirring, adding the above processed foamed nickel, and keeping the temperature at 90-180 deg.C for 9-18 h; centrifuging, washing and drying to obtain the product; the invention prepares NiCoZnP by one-step hydrothermal and phosphorization, has hollow NiCoZnP microsphere active substance with excellent electrochemical properties such as high capacity, good cycle performance, reasonable pore size distribution and the like, and has simple process and easy operation; electrochemical tests show that the NiCoZnP electrode material has excellent electrochemical performance, and the specific capacitance of the NiCoZnP electrode material can reach 938F/g.
Description
Technical Field
The invention relates to the technical field of conductive composite materials, in particular to a NiCoZnP hollow microsphere material and a preparation method thereof.
Background
With the development of scientific technology, modern science and technology society needs to store and use energy of different scales, so that it is necessary to design large and small energy systems, wherein the electric energy storage systems have attracted great interest in the past decades. The super capacitor is also called as a super capacitor or an electrochemical double-layer capacitor, and is an energy storage device with high power density, high charging and discharging speed and long service life. It can supplement or replace batteries in electrical energy storage and collection applications when a high rate of electrical energy delivery or absorption is required. Small supercapacitors can be integrated with microelectronic devices, either as stand-alone power sources or as efficient energy storage units, as a complement to batteries and energy harvesters, making these devices more widely used in many industries.
It is well known that the performance of electrochemical devices is mainly related to the electrochemical activity and the kinetic properties of the electrode materials. To improve the performance of the capacitor, it is necessary not only to improve the effective contact between the electrolyte and the electrode material, but also to improve the fast transport rate of ions/electrons at the electrode and electrode/electrolyte interface. Therefore, it is very important to prepare an active material having high conductivity.
In recent years, metal phosphides have become an emerging class of electrode materials and are applied to supercapacitors, exhibiting outstanding electrochemical performance. However, the materials still face the problems of poor rate performance and unstable long cycle, and the large-scale application of the materials is severely restricted. Compared with single metal phosphide, the electrochemical property of the ternary metal phosphide is greatly improved by introducing other ions to form the ternary metal phosphide, the ternary metal phosphide presents richer redox active sites, and the electrochemical conductivity and stability are remarkably improved, so that the aims of improving the conductivity and the capacitive performance of the material are fulfilled. The transition metal element has a rich valence state, and thus exhibits a high faraday capacitance during an electrochemical redox reaction. However, the preparation method of the ternary metal phosphide composite material is complex and is not suitable for large-batch production. Therefore, the preparation method of the conductive composite material with simple development method and strong practicability has great significance for developing high-performance super capacitors.
Disclosure of Invention
The invention aims to provide a NiCoZnP hollow microsphere material and a preparation method thereof, which aim to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a NiCoZnP hollow microsphere material, which takes zinc nitrate, nickel nitrate and cobalt nitrate as precursors, and generates the NiCoZnP hollow microsphere material by hydrothermal phosphorization and foam nickel as a template.
Further, the preparation method of the NiCoZnP hollow microsphere material comprises the following steps:
(1) pretreating foamed nickel: putting the foamed nickel into an acetone solvent for ultrasonic treatment, then soaking the foamed nickel in an acid solution, taking out the foamed nickel for ultrasonic treatment, and drying the foamed nickel for later use;
(2) mixing zinc nitrate, nickel nitrate, cobalt nitrate, urea and sodium hypophosphite, adding into a container filled with isopropanol water solution, stirring, adding the foam nickel treated in the step (1), and keeping the temperature at 90-180 ℃ for 9-18 h.
Further, the acid solution is a 1mol/L HCl solution.
Further, the second sonication was performed in deionized water and ethanol solution, respectively.
Further, the two times of ultrasonic treatment are both 15 min.
Further, the nickel nitrate is nickel nitrate hexahydrate, the cobalt nitrate is cobalt nitrate hexahydrate, and the zinc nitrate is zinc nitrate hexahydrate.
Furthermore, the molar ratio of the zinc nitrate, the nickel nitrate and the cobalt nitrate to the urea and the sodium hypophosphite is 1:1:1:120: 6.
Further, the volume ratio of isopropanol to water in the isopropanol aqueous solution is 3: 1.
Further, the method also comprises the step (3), after the heat preservation is finished, cooling to room temperature, respectively centrifuging three times by using deionized water and ethanol solution, and drying for 12 hours at the temperature of 60 ℃ to obtain the NiCoZnP hollow microsphere material loaded on the foamed nickel;
and (4) washing the foamed nickel loaded with the NiCoZnP hollow microspheres for several times by using deionized water and absolute ethyl alcohol, and drying at 60 ℃.
The invention also provides a NiCoZnP hollow microsphere material prepared by the preparation method.
The invention discloses the following technical effects:
the electrode material prepared by the method has excellent electrochemical performance in an aqueous super capacitor. The metal phosphide becomes an emerging electrode material and is applied to a super capacitor, and the super capacitor shows excellent electrochemical performance. However, the materials still face the problems of poor rate performance and unstable long cycle, and the large-scale application of the materials is severely restricted. Compared with single metal phosphide, the electrochemical property of the ternary metal phosphide is greatly improved by introducing other ions to form the ternary metal phosphide, the ternary metal phosphide presents richer redox active sites, and the electrochemical conductivity and stability are remarkably improved, so that the aims of improving the conductivity and the capacitive performance of the material are fulfilled.
The invention prepares NiCoZnP hollow microsphere material by one-step hydrothermal and phosphorization, and the principle of microsphere formation is as follows: the formation of the metal carbonate hydroxide starts from the nucleation evolution of the single metal nickel carbonate hydroxide to flower-shaped microspheres, then the metal carbonate hydroxide nanorods nucleate and grow on the nano-plates of the flower-shaped microspheres through the local dissolution-recrystallization action, and become metal phosphide through the one-step phosphorization action, finally the hollow microspheres are formed, and the hollow microspheres have excellent electrochemical properties such as high capacity, good cycle performance, reasonable pore size distribution and the like, and are simple in process and easy to operate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an SEM image of the NiCoZnP microsphere material obtained in example 5 at 20000 times;
FIG. 2 is a circular layout of the NiCoZnP electrode material obtained in example 5 at different scanning speeds, wherein the number of the electrode materials is 2mv/s, 5mv/s, 10mv/s, 20mv/s, and 50mv/s in sequence from top to bottom;
FIG. 3 is a constant current charge and discharge diagram of the NiCoZnP electrode material obtained in example 5 under different current densities;
FIG. 4 is an AC impedance diagram of the NiCoZnP electrode material obtained in example 5
Fig. 5 is an SEM image of the NiCoZnP electrode material obtained in example 3 at 20000 times.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
Example 1
A preparation method of a NiCoZnP hollow microsphere material comprises the following steps:
1. pretreating foamed nickel, soaking the foamed nickel in an acetone solution for 15min by ultrasonic treatment to remove oil stains on the surface, then soaking the foamed nickel in 1mol/L HCl for 15min to remove an oxide layer on the surface, respectively performing ultrasonic treatment in deionized water and an ethanol solution for 15min, and putting the foamed nickel into a vacuum drying oven to be dried for later use;
2. weighing 1.5mmol nickel nitrate hexahydrate, 1.5mmol cobalt nitrate hexahydrate, 1.5mmol zinc nitrate hexahydrate, 180mmol urea and 9mmol sodium hypophosphite, dissolving in 60ml isopropanol water solution (the volume ratio of isopropanol to deionized water is 3:1), and stirring for 30 min;
3. transferring the solution to a 100ml hydrothermal kettle, adding the treated nickel foam, and keeping the temperature at 150 ℃ for 12 hours;
4. cooling to room temperature, respectively centrifuging three times by using deionized water and alcohol, and drying at 60 ℃ for 12h to obtain a hollow NiCoZnP microsphere electrode material loaded on foamed nickel;
5. the foamed nickel loaded with the active substances is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried for standby at 60 ℃.
And (3) performance testing:
the test instrument is Shanghai Chenghua CHI660E, and the electrode material is tested by a three-electrode method, wherein the electrolyte is 6mol/L KOH, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a platinum sheet, and the electrochemical performance tests of Cyclic Voltammetry (CV), alternating current impedance (EIS) and timing potential (GCD) are respectively carried out.
Example 2
A preparation method of a NiCoZnP hollow microsphere material comprises the following steps:
1. pretreating foamed nickel, soaking the foamed nickel in an acetone solution for 15min by ultrasonic treatment to remove oil stains on the surface, then soaking the foamed nickel in 1mol/L HCl for 15min to remove an oxide layer on the surface, respectively performing ultrasonic treatment in deionized water and an ethanol solution for 15min, and putting the foamed nickel into a vacuum drying oven to be dried for later use;
2. weighing 1.5mmol nickel nitrate hexahydrate, 1.5mmol cobalt nitrate hexahydrate, 1.5mmol zinc nitrate hexahydrate, 180mmol urea and 9mmol sodium hypophosphite, dissolving in 60ml isopropanol water solution (the volume ratio of isopropanol to deionized water is 3:1), and stirring for 30 min;
3. transferring the solution to a 100ml hydrothermal kettle, adding the treated nickel foam, and keeping the temperature at 90 ℃ for 12 hours;
4. cooling to room temperature, respectively centrifuging three times by using deionized water and alcohol, and drying at 60 ℃ for 12h to obtain a hollow NiCoZnP microsphere electrode material loaded on foamed nickel;
5. the foamed nickel loaded with the active substances is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried for standby at 60 ℃.
And (3) performance testing:
the test instrument is Shanghai Chenghua CHI660E, and the electrode material is tested by a three-electrode method, wherein the electrolyte is 6mol/L KOH, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a platinum sheet, and the electrochemical performance tests of Cyclic Voltammetry (CV), alternating current impedance (EIS) and timing potential (GCD) are respectively carried out.
Example 3
A preparation method of a NiCoZnP hollow microsphere material comprises the following steps:
1. pretreating foamed nickel, soaking the foamed nickel in an acetone solution for 15min by ultrasonic treatment to remove oil stains on the surface, then soaking the foamed nickel in 1mol/L HCl for 15min to remove an oxide layer on the surface, respectively performing ultrasonic treatment in deionized water and an ethanol solution for 15min, and putting the foamed nickel into a vacuum drying oven to be dried for later use;
2. weighing 1.5mmol nickel nitrate hexahydrate, 1.5mmol cobalt nitrate hexahydrate, 1.5mmol zinc nitrate hexahydrate, 180mmol urea and 9mmol sodium hypophosphite, dissolving in 60ml isopropanol water solution (the volume ratio of isopropanol to deionized water is 3:1), and stirring for 30 min;
3. transferring the solution to a 100ml hydrothermal kettle, adding the treated nickel foam, and keeping the temperature at 180 ℃ for 12 hours;
4. cooling to room temperature, respectively centrifuging three times by using deionized water and alcohol, and drying at 60 ℃ for 12h to obtain a hollow NiCoZnP microsphere electrode material loaded on foamed nickel;
5. the foamed nickel loaded with the active substances is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried for standby at 60 ℃.
And (3) performance testing:
the test instrument is Shanghai Chenghua CHI660E, and the electrode material is tested by a three-electrode method, wherein the electrolyte is 6mol/L KOH, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a platinum sheet, and the electrochemical performance tests of Cyclic Voltammetry (CV), alternating current impedance (EIS) and timing potential (GCD) are respectively carried out.
Example 4
A preparation method of a NiCoZnP hollow microsphere material comprises the following steps:
1. pretreating foamed nickel, soaking the foamed nickel in an acetone solution for 15min by ultrasonic treatment to remove oil stains on the surface, then soaking the foamed nickel in 1mol/L HCl for 15min to remove an oxide layer on the surface, respectively performing ultrasonic treatment in deionized water and an ethanol solution for 15min, and putting the foamed nickel into a vacuum drying oven to be dried for later use;
2. weighing 1.5mmol nickel nitrate hexahydrate, 1.5mmol cobalt nitrate hexahydrate, 1.5mmol zinc nitrate hexahydrate, 180mmol urea and 9mmol sodium hypophosphite, dissolving in 60ml isopropanol water solution (the volume ratio of isopropanol to deionized water is 3:1), and stirring for 30 min;
3. transferring the solution to a 100ml hydrothermal kettle, adding the treated nickel foam, and keeping the temperature at 120 ℃ for 9 hours;
4. cooling to room temperature, respectively centrifuging three times by using deionized water and alcohol, and drying at 60 ℃ for 12h to obtain a hollow NiCoZnP microsphere electrode material loaded on foamed nickel;
5. the foamed nickel loaded with the active substances is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried for standby at 60 ℃.
And (3) performance testing:
the test instrument is Shanghai Chenghua CHI660E, and the electrode material is tested by a three-electrode method, wherein the electrolyte is 6mol/L KOH, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a platinum sheet, and the electrochemical performance tests of Cyclic Voltammetry (CV), alternating current impedance (EIS) and timing potential (GCD) are respectively carried out.
Example 5
A preparation method of a NiCoZnP hollow microsphere material comprises the following steps:
1. pretreating foamed nickel, soaking the foamed nickel in an acetone solution for 15min by ultrasonic treatment to remove oil stains on the surface, then soaking the foamed nickel in 1mol/L HCl for 15min to remove an oxide layer on the surface, respectively performing ultrasonic treatment in deionized water and an ethanol solution for 15min, and putting the foamed nickel into a vacuum drying oven to be dried for later use;
2. weighing 1.5mmol nickel nitrate hexahydrate, 1.5mmol cobalt nitrate hexahydrate, 1.5mmol zinc nitrate hexahydrate, 180mmol urea and 9mmol sodium hypophosphite, dissolving in 60ml isopropanol water solution (the volume ratio of isopropanol to deionized water is 3:1), and stirring for 30 min;
3. transferring the solution to a 100ml hydrothermal kettle, adding the treated nickel foam, and keeping the temperature at 120 ℃ for 12 hours;
4. cooling to room temperature, respectively centrifuging three times by using deionized water and alcohol, and drying at 60 ℃ for 12h to obtain a hollow NiCoZnP microsphere electrode material loaded on foamed nickel;
5. the foamed nickel loaded with the active substances is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried for standby at 60 ℃.
And (3) performance testing:
the test instrument was Shanghai Chenghua CHI660E, and the electrode material was tested by a three-electrode method, in which the electrolyte was 6mol/L KOH, the reference electrode was a mercury/mercury oxide electrode, and the counter electrode was a platinum sheet, and electrochemical performance tests of Cyclic Voltammetry (CV), alternating current impedance (EIS), and chronopotentiometry (GCD) were performed, respectively, and the results are shown in FIGS. 2 to 4.
Electrochemical tests show that the NiCoZnP electrode material has excellent electrochemical performance, and the specific capacitance of the NiCoZnP electrode material can reach 938F/g.
FIG. 1 is an SEM image of the NiCoZnP microsphere material obtained in example 5 at 20000 times, and it can be seen that the material is in the shape of hollow microsphere, wherein the size of the hollow microsphere is 3.3 μm, the wall thickness is 0.3 μm, and the morphology and the size are uniform.
Example 6
A preparation method of a NiCoZnP hollow microsphere material comprises the following steps:
1. pretreating foamed nickel, soaking the foamed nickel in an acetone solution for 15min by ultrasonic treatment to remove oil stains on the surface, then soaking the foamed nickel in 1mol/L HCl for 15min to remove an oxide layer on the surface, respectively performing ultrasonic treatment in deionized water and an ethanol solution for 15min, and putting the foamed nickel into a vacuum drying oven to be dried for later use;
2. weighing 1.5mmol nickel nitrate hexahydrate, 1.5mmol cobalt nitrate hexahydrate, 1.5mmol zinc nitrate hexahydrate, 180mmol urea and 9mmol sodium hypophosphite, dissolving in 60ml isopropanol water solution (the volume ratio of isopropanol to deionized water is 3:1), and stirring for 30 min;
3. transferring the solution to a 100ml hydrothermal kettle, adding the treated nickel foam, and keeping the temperature at 120 ℃ for 15 h;
4. cooling to room temperature, respectively centrifuging three times by using deionized water and alcohol, and drying at 60 ℃ for 12h to obtain a hollow NiCoZnP microsphere electrode material loaded on foamed nickel;
5. the foamed nickel loaded with the active substances is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried for standby at 60 ℃.
And (3) performance testing:
the test instrument is Shanghai Chenghua CHI660E, and the electrode material is tested by a three-electrode method, wherein the electrolyte is 6mol/L KOH, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a platinum sheet, and the electrochemical performance tests of Cyclic Voltammetry (CV), alternating current impedance (EIS) and timing potential (GCD) are respectively carried out.
Example 7
A preparation method of a NiCoZnP hollow microsphere material comprises the following steps:
1. pretreating foamed nickel, soaking the foamed nickel in an acetone solution for 15min by ultrasonic treatment to remove oil stains on the surface, then soaking the foamed nickel in 1mol/L HCl for 15min to remove an oxide layer on the surface, respectively performing ultrasonic treatment in deionized water and an ethanol solution for 15min, and putting the foamed nickel into a vacuum drying oven to be dried for later use;
2. weighing 1.5mmol nickel nitrate hexahydrate, 1.5mmol cobalt nitrate hexahydrate, 1.5mmol zinc nitrate hexahydrate, 180mmol urea and 9mmol sodium hypophosphite, dissolving in 60ml isopropanol water solution (the volume ratio of isopropanol to deionized water is 3:1), and stirring for 30 min;
3. transferring the solution to a 100ml hydrothermal kettle, adding the treated nickel foam, and keeping the temperature at 120 ℃ for 18 h;
4. cooling to room temperature, respectively centrifuging three times by using deionized water and alcohol, and drying at 60 ℃ for 12h to obtain a hollow NiCoZnP microsphere electrode material loaded on foamed nickel;
5. the foamed nickel loaded with the active substances is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried for standby at 60 ℃.
And (3) performance testing:
the test instrument is Shanghai Chenghua CHI660E, and the electrode material is tested by a three-electrode method, wherein the electrolyte is 6mol/L KOH, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a platinum sheet, and the electrochemical performance tests of Cyclic Voltammetry (CV), alternating current impedance (EIS) and timing potential (GCD) are respectively carried out.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A preparation method of a NiCoZnP hollow microsphere material is characterized in that zinc nitrate, nickel nitrate and cobalt nitrate are used as precursors, urea and sodium hypophosphite are added, hydrothermal phosphorization is carried out, and foam nickel is used as a template to generate the NiCoZnP hollow microsphere material;
the preparation method of the NiCoZnP hollow microsphere material comprises the following steps:
(1) pretreating foamed nickel: putting the foamed nickel into an acetone solvent for ultrasonic treatment, then soaking the foamed nickel in an acid solution, taking out the foamed nickel, putting the foamed nickel into deionized water or an ethanol solution for ultrasonic treatment, and drying the foamed nickel for later use;
(2) mixing zinc nitrate, nickel nitrate, cobalt nitrate, urea and sodium hypophosphite, adding into a container filled with isopropanol water solution, stirring, adding the foam nickel treated in the step (1), and keeping the temperature at 90-180 ℃ for 9-18 h;
the molar ratio of the zinc nitrate, the nickel nitrate and the cobalt nitrate to the urea to the sodium hypophosphite is 1:1:1:120: 6.
2. The preparation method of the NiCoZnP hollow microsphere material of claim 1, wherein the acid solution is 1mol/L HCl solution.
3. The preparation method of the NiCoZnP hollow microsphere material according to claim 1, wherein the two times of ultrasonic treatment are both 15 min.
4. The preparation method of the NiCoZnP hollow microsphere material of claim 1, wherein the nickel nitrate is nickel nitrate hexahydrate, the cobalt nitrate is cobalt nitrate hexahydrate, and the zinc nitrate is zinc nitrate hexahydrate.
5. The method for preparing a NiCoZnP hollow microsphere material according to claim 1, wherein the volume ratio of isopropanol to water in the isopropanol aqueous solution is 3: 1.
6. The preparation method of the NiCoZnP hollow microsphere material according to claim 1, characterized by further comprising the step (3), after the heat preservation is finished, cooling to room temperature, centrifuging three times respectively by using deionized water and ethanol solution, and drying for 12h at 60 ℃ to obtain the NiCoZnP hollow microsphere material loaded on the foamed nickel;
and (4) washing the foamed nickel loaded with the NiCoZnP hollow microspheres for several times by using deionized water and absolute ethyl alcohol, and drying at 60 ℃.
7. A NiCoZnP hollow microsphere material, characterized in that, it is prepared by the preparation method of any claim 1-6.
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Application publication date: 20200207 Assignee: Guangxi Xiaoli New Energy Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044534 Denomination of invention: A NiCoZnP hollow microsphere material and its preparation method Granted publication date: 20210907 License type: Common License Record date: 20231030 |