CN109243850B - Ni-Co oxide nanocrystalline and controllable synthesis method and application thereof - Google Patents
Ni-Co oxide nanocrystalline and controllable synthesis method and application thereof Download PDFInfo
- Publication number
- CN109243850B CN109243850B CN201811310079.2A CN201811310079A CN109243850B CN 109243850 B CN109243850 B CN 109243850B CN 201811310079 A CN201811310079 A CN 201811310079A CN 109243850 B CN109243850 B CN 109243850B
- Authority
- CN
- China
- Prior art keywords
- synthesis method
- oxide
- oxide nanocrystals
- controllable synthesis
- coo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910017709 Ni Co Inorganic materials 0.000 title claims abstract description 46
- 229910003267 Ni-Co Inorganic materials 0.000 title claims abstract description 46
- 229910003262 Ni‐Co Inorganic materials 0.000 title claims abstract description 46
- 238000001308 synthesis method Methods 0.000 title claims abstract description 21
- 239000002159 nanocrystal Substances 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- UMYZHWLYICNGRQ-UHFFFAOYSA-N ethanol;heptane Chemical compound CCO.CCCCCCC UMYZHWLYICNGRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000004886 process control Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 14
- 239000006260 foam Substances 0.000 description 13
- 239000003990 capacitor Substances 0.000 description 11
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000011232 storage material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 229910003266 NiCo Inorganic materials 0.000 description 4
- -1 Polytetrafluoroethylene Polymers 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005303 weighing Methods 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
- H01G11/24—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
- H01G11/46—Metal oxides
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to the field of material chemistry, in particular to Ni-Co oxide nanocrystals and a controllable synthesis method and application thereof. The Ni-Co oxide nanocrystalline with a solid sphere structure is controllably synthesized by changing the synthesis conditions such as the amount of the solvent, the calcination temperature and the like and the process. The preparation process is simple, the process control is strong, the synthesis time is short, and the method has good industrial application prospect. Meanwhile, the Ni-Co oxide nanocrystalline prepared by the method has excellent performance of a solid asymmetric flexible supercapacitor, can be bent, can be rapidly charged and discharged, has high-efficiency electric energy storage performance, and has important guiding significance for the technical development of renewable energy sources.
Description
Technical Field
The invention relates to the field of material chemistry, in particular to the field of synthesis and application of nanocrystals, and more particularly relates to a Ni-Co oxide nanocrystal and a controllable synthesis method and application thereof.
Background
Ni-Co oxide refers to an oxide having NiCo2O4A compound oxide of the formula. Since the composite compound has excellent conductivity and electrochemical activity, the research on the Ni — Co oxide has been a hot problem in the field of material chemistry, particularly in the research field of supercapacitors in recent years.
For example, NiCo having a spinel structure as disclosed in the prior art has been disclosed2O4Black nano-powder. NiCo disclosed by T.Y.Wei et al2O4Gel, NiCo, published by H.L.Wang et al2O4A nanowire. And NiCo disclosed by G.Q.Zhang et al2O4Nanoneedles, and the like.
Different NiCo2O4The structure may provide different electrical properties, that is, the electrical properties of the nanocrystals have a large dependence on the nanocrystal structure and size. Therefore, controlling the formation of nanocrystalline structures through a careful, controllable synthesis method is an important means and method for obtaining nanocrystals with different electrical properties and the like. In other words, different nanocrystal structures may exhibit different electrical properties, and therefore, for a new electrical application, it is crucial to find a nanocrystal structure that satisfies the requirements and a controllable synthesis method for obtaining the nanocrystal structure.
With the popularization of portable electronic devices and the vigorous development of electric automobiles, people have higher and higher requirements on the performance of energy storage materials, but the development of the energy storage materials is lagged. On one hand, the energy density of the energy storage material is insufficient, so that the service time of the electric appliance is too short, the charging is frequent, serious inconvenience is brought to daily use, and the use of the electric automobile is also greatly limited. On the other hand, the power of the energy storage material is insufficient, so that the charging time of the energy storage material is too long.
In recent years, with the rise of wearable portable electronic devices, the problems of insufficient energy density and insufficient power of energy storage materials are more prominent. Meanwhile, due to the introduction of "wearable", a new requirement is put on the energy storage device, namely, the energy storage device is required to have flexibility.
Literature research shows that the transition metal is widely applied to energy storage materials due to good reversibility and high reaction speed in the oxidation and reduction processes. For example, Yaning et al found Fe2O3The mixture of nanoclusters and rGO has good properties as the negative electrode of a flexible supercapacitor, and has high energy density and power density. Can show that the graphene composite material has better current activity, which is mainly related to graphiteThe graphene serves as a framework structure to be a good carrier, and meanwhile, the graphene has excellent conductivity.
Therefore, the energy storage material manufactured by using the transition metal has the potential of preparing a flexible super capacitor. Therefore, the research and development of an efficient synthesis method of the transition metal nanocrystalline with a special structure is a hot spot of the current research, and particularly, the method has important significance and great challenges for an electrode material which can be used for an all-solid-state asymmetric flexible supercapacitor.
Disclosure of Invention
The invention aims to solve the technical problem of disclosing an electrode material which can be used for an all-solid-state asymmetric flexible supercapacitor, thereby meeting the requirements of wearable portable electronic equipment on an energy storage device and providing a basis for the development of the wearable portable electronic equipment.
In order to solve the technical problems, the invention discloses Ni-Co oxide nanocrystals which are solid nanosphere-shaped structures.
Furthermore, the invention also discloses that the Ni-Co oxide nanocrystal is a solid nano spherical structure with the diameter of 3-5 nm.
Meanwhile, the invention also discloses a controllable synthesis method of the Ni-Co oxide nanocrystal, which comprises the following steps:
s1: mixing Ni (CH)3COO)2·4H2O、Co(CH3COO)2·4H2Adding O into a mixed solution of Oleic Acid (OA), dodecylamine and Octadecene (ODE);
s2: gradually heating to 180 ℃;
s3: keeping the temperature at 180 ℃ for reaction to obtain a precursor containing Ni-Co oxide nanocrystals;
s4: dispersing, settling and centrifuging;
s5: gradually heating to 350 ℃;
s6: and calcining at 350 ℃ to obtain the Ni-Co oxide nanocrystal.
Meanwhile, Ni (CH) is further disclosed in the present invention3COO)2·4H2O、Co(CH3COO)2·4H2O, Oleic Acid (OA), dodecylamine and Octadecene (ODE) are added in the ratio of Ni (CH)3COO)2·4H2When O is 3.62mmol, Co (CH)3COO)2·4H2The amount of O added was 1.81mmol, the amount of ODE added was 10mL, the amount of dodecylamine added was 5mL, and the amount of OA added was 5 mL.
Preferably, the temperature rising rate in the step S2 is 3-4 ℃ min-1。
Further preferably, the reaction is carried out in step S3 for 18 hours while maintaining the temperature at 180 ℃.
In a preferred embodiment, the step S4 uses an absolute ethanol-n-heptane mixed solution for dispersion and sedimentation. Further preferably, the mixing volume ratio of the absolute ethyl alcohol to the n-heptane is 1: 1.
Further preferably, the step S4 further includes washing after the dispersion sedimentation and the centrifugation.
In a preferred technical scheme, the washing adopts an absolute ethyl alcohol-n-heptane mixed solution. Further preferably, the mixing volume ratio of the absolute ethyl alcohol to the n-heptane is 1: 1.
As another preferable technical means, the temperature rise rate in the step S5 is 10 ℃ min-1。
And as a preferable technical means, the calcination is performed for 1 hour under the condition of keeping the temperature at 350 ℃ in the step S6.
Finally, the invention also discloses application of the Ni-Co oxide nanocrystalline in a solid asymmetric flexible supercapacitor electrode material.
The Ni-Co oxide nanocrystalline prepared by the invention has excellent performance of a solid asymmetric flexible super capacitor, can be bent, can be rapidly charged and discharged, and has high-efficiency electric energy storage performance. Through detection, the performance of the flexible super capacitor is superior to that of the current commercial asymmetric flexible super capacitor, and the flexible super capacitor has important guiding significance for the technical development of renewable energy sources.
Meanwhile, the Ni-Co oxide nanocrystalline with a solid sphere structure is controllably synthesized by a controllable synthesis method through changing the synthesis conditions such as the amount of a solvent, the calcination temperature and the like and a process. The preparation process is simple, the process control is strong, the synthesis time is short, the standard of industrial production is met, and the method has good industrial application prospect.
Drawings
FIG. 1 is a TEM image of Ni-Co oxide nanocrystals synthesized in the present invention.
FIG. 2 is a chart of Cyclic Voltammetry (CV) of Ni-Co oxide nanocrystals synthesized in accordance with the present invention.
FIG. 3 is a constant current charge and discharge (GCD) diagram of Ni-Co oxide nanocrystals synthesized by the present invention.
FIG. 4 is a cyclic voltammogram of a Ni-Co oxide nanocrystal synthesized in accordance with the present invention when unbent; the photograph is shown in the unbent state.
FIG. 5 is a cyclic voltammogram of the Ni-Co oxide nanocrystals synthesized in accordance with the present invention after being bent; the picture therein is a representation of the state of the bend detection.
Detailed Description
In order that the invention may be better understood, we now provide further explanation of the invention with reference to specific examples.
Example 1
0.9008g of Ni (CH) were weighed at room temperature (25. + -. 5 ℃ C.)3COO)2·4H2O and 0.4509g of Co (CH)3COO)2·4H2O was poured into a Teflon liner containing 10mL of Octadecene (ODE), 5mL of dodecylamine, and 5mL of Oleic Acid (OA), magnetically stirred for 15min and placed in a stainless steel reaction kettle, and the kettle lid was tightened. Placing in an oven, adjusting the temperature to 180 deg.C, and heating at 3-4 deg.C/min-1After the temperature reached 180 ℃, the reaction was continued for 18 hours. After the reaction is finished, cooling to room temperature, opening the reaction kettle, adding a proper amount of absolute ethyl alcohol-n-heptane (the volume ratio is 1:1) for dispersion, and centrifugally separating solids. Washing the solid with n-heptane-anhydrous ethanol (volume ratio 1:1), vacuum drying in a vacuum drying oven overnight, placing in a muffle furnace, adjusting temperature to 350 deg.C, and heating at 10 deg.C/min-1，And when the temperature reaches 350 ℃, continuously calcining for 1 hour to obtain the Ni-Co oxide nanocrystalline.
Example 2
The Ni-Co oxide nanocrystal product obtained in example 1 was examined by a Transmission Electron Microscope (TEM), and the result is shown in fig. 1, from which fig. 1 it can be seen that the Ni-Co oxide nanocrystal has a solid sphere nanocrystal structure and a diameter of 3-5 nm.
Example 3
The electrochemical properties of the Ni-Co oxide nanocrystal sample (hereinafter referred to as sample) obtained in example 1 were tested in a two-electrode system by cyclic voltammetry and constant current charge-discharge methods, and the specific procedure was as follows:
the electrochemical experiments were carried out on an electrochemical workstation model CHI660d, using a two-electrode test system, the corresponding positive electrode being a sample-modified nickel foam electrode as obtained herein. The negative electrode is a foam nickel electrode modified by active carbon. All potentials herein are relative to RHE. The electrolyte was a 3M KOH solution. All electrochemical tests were performed at 25 ℃. At each experiment, all electrodes were tested in 3M KOH solution.
The preparation method of the sample modified foam nickel comprises the following steps:
before each test, the foamed nickel is cut into the size of 1cm multiplied by 5cm, ultrasonically cleaned for 15min by deionized water, ultrasonically cleaned for 15min by ethanol, and dried for 2h at 50 ℃ for standby.
40mg of Ni-Co oxide nanocrystals and 7.5mg of acetylene black were ground in a mortar for 15 min. Then adding a proper amount of isopropanol, and continuing to grind for 15 min. Finally, 1-2 drops of Polytetrafluoroethylene (PTFE) emulsion are added and are dropped on the surface of the foam nickel to be used before after being stirred slightly. After drying at 50 ℃ for 2h, the electrochemical test was waited for.
40mg of activated carbon and 7.5mg of acetylene black were ground in a mortar for 15 min. Then adding a proper amount of isopropanol, and continuing to grind for 15 min. Finally, 1-2 drops of Polytetrafluoroethylene (PTFE) emulsion are added and are dropped on the surface of the foam nickel to be used before after being stirred slightly. After drying at 50 ℃ for 2h, the electrochemical test was waited for.
And (3) carrying out cyclic voltammetry and constant current charge and discharge tests on the modified sample foamed nickel in the two-electrode system. The detection results are shown in FIGS. 2 and 3. Test knotThe results show that the Ni-Co oxide nanocrystals showed excellent supercapacitor performance, and the current densities of the Ni-Co oxide nanocrystals were 5mA cm/cm, respectively, as calculated from FIG. 3-2、10mA cm-2、15mA cm-2、20mA cm-2And 25mA cm-2When the specific capacitance is 330.8mF cm-2、300.6mF cm-2、278.5mF cm-2、251.3mF cm-2And 212.0mF cm-2。
Example 4
Testing the flexibility of a Ni-Co oxide nanocrystalline device (hereinafter referred to as a device) by assembling an all-solid flexible asymmetric capacitor device and comparing cyclic voltammograms before and after bending; the specific process is as follows:
the electrochemical experiments were carried out on an electrochemical workstation model CHI660d, using a two-electrode test system, the corresponding positive electrode being a sample-modified nickel foam electrode as obtained herein. The negative electrode is a foam nickel electrode modified by active carbon. All potentials herein are relative to RHE. The electrolyte was a 3M KOH solution. All electrochemical tests were performed at 25 ℃. At each experiment, all electrodes were tested in 3M KOH solution.
The preparation method of the sample modified foam nickel comprises the following steps:
before each test, the foamed nickel is cut into the size of 1cm multiplied by 5cm, ultrasonically cleaned for 15min by deionized water, ultrasonically cleaned for 15min by ethanol, and dried for 2h at 50 ℃ for standby.
40mg of Ni-Co oxide nanocrystals and 7.5mg of acetylene black were ground in a mortar for 15 min. Then adding a proper amount of isopropanol, and continuing to grind for 15 min. Finally, 1-2 drops of Polytetrafluoroethylene (PTFE) emulsion are added and are dropped on the surface of the foam nickel to be used before after being stirred slightly. And drying at 50 ℃ for 2h, and waiting for the assembly of the all-solid-state flexible asymmetric capacitor.
40mg of activated carbon and 7.5mg of acetylene black were ground in a mortar for 15 min. Then adding a proper amount of isopropanol, and continuing to grind for 15 min. Finally, 1-2 drops of Polytetrafluoroethylene (PTFE) emulsion are added and are dropped on the surface of the foam nickel to be used before after being stirred slightly. And drying at 50 ℃ for 2h, and waiting for the assembly of the all-solid-state flexible asymmetric capacitor.
The assembly method of the all-solid-state flexible asymmetric capacitor device comprises the following steps:
two 1cm multiplied by 4cm polyvinyl chloride (PVC) sheets are taken, 3-5 drops of a mixed solution of 3M KOH and polyethylene glycol are slowly dropped on one of the two sheets, and the whole PVC sheet is paved. And placing the foam nickel modified with the sample and the foam nickel modified with the activated carbon at two ends of the PVC sheet, and weighing about 1cm to ensure that the foam nickel is immersed in the mixed solution of 3M KOH and polyethylene glycol. Then another PVC sheet is carefully covered to be completely overlapped, and the whole device is wrapped by the preservative film to prevent liquid leakage. After drying at 50 ℃ for 12h, the electrochemical test is waited for.
And (3) carrying out cyclic voltammetry test on the all-solid-state flexible asymmetric capacitor device in the two-electrode system, and then bending the all-solid-state flexible asymmetric capacitor device to carry out cyclic voltammetry test, wherein the detection result is shown in the figure 4 and the figure 5. The test result shows that the cyclic voltammogram (figure 4) when the device is not bent is not obviously different from the cyclic voltammogram (figure 5) after the device is bent, which indicates that the capacitance performance of the device is not obviously changed before and after the device is bent, and the flexibility performance is good.
What has been described above is a specific embodiment of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (12)
- A controllable synthesis method of Ni-Co oxide nanocrystals is characterized in that the Ni-Co oxide nanocrystals are solid nanosphere-shaped structures with the diameter of 3-5nm, and the controllable synthesis method specifically comprises the following steps:s1: mixing Ni (CH)3COO)2∙4H2O、Co(CH3COO)2∙4H2Adding O into a mixed solution of Oleic Acid (OA), dodecylamine and Octadecene (ODE);s2: gradually heating to 180 ℃;s3: keeping the temperature at 180 ℃ for reaction to obtain a precursor containing Ni-Co oxide nanocrystals;s4: dispersing, settling and centrifuging;s5: gradually heating to 350 ℃;s6: and calcining at 350 ℃ to obtain the Ni-Co oxide nanocrystal.
- 2. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 1, wherein: ni (CH)3COO)2∙4H2O、Co(CH3COO)2∙4H2O, Oleic Acid (OA), dodecylamine and Octadecene (ODE) are added in the ratio of Ni (CH)3COO)2∙4H2When O is 3.62mmol, Co (CH)3COO)2∙4H2The amount of O added was 1.81mmol, the amount of ODE added was 10mL, the amount of dodecylamine added was 5mL, and the amount of OA added was 5 mL.
- 3. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 1, wherein: in the step S2, the heating rate is 3-4 ℃ min-1。
- 4. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 1, wherein: in step S4, an absolute ethanol-n-heptane mixed solution is used for dispersion and sedimentation.
- 5. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 4, wherein: the mixing volume ratio of the absolute ethyl alcohol to the n-heptane is 1: 1.
- 6. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 1, wherein: step S4 includes washing after dispersion sedimentation and centrifugation.
- 7. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 6, wherein: the washing adopts an absolute ethyl alcohol-n-heptane mixed solution.
- 8. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 7, wherein: the volume ratio of the absolute ethyl alcohol to the n-heptane is 1: 1.
- 9. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 1, wherein: in the step S5, the temperature rise rate is 10 ℃ min-1。
- 10. The controllable synthesis method of Ni-Co oxide nanocrystals according to claim 1, wherein: the reaction time in step S6 was 1 hour.
- 11. The Ni-Co oxide nanocrystal prepared by the controlled synthesis method of the Ni-Co oxide nanocrystal according to any one of claims 1 to 10, characterized in that: the Ni-Co oxide nanocrystal is a solid nanosphere structure with the diameter of 3-5 nm.
- 12. Use of the Ni-Co oxide nanocrystals according to claim 11 in solid-state asymmetric flexible supercapacitor electrode materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811310079.2A CN109243850B (en) | 2018-11-05 | 2018-11-05 | Ni-Co oxide nanocrystalline and controllable synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811310079.2A CN109243850B (en) | 2018-11-05 | 2018-11-05 | Ni-Co oxide nanocrystalline and controllable synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109243850A CN109243850A (en) | 2019-01-18 |
| CN109243850B true CN109243850B (en) | 2020-11-27 |
Family
ID=65076827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811310079.2A Active CN109243850B (en) | 2018-11-05 | 2018-11-05 | Ni-Co oxide nanocrystalline and controllable synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109243850B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1568285A (en) * | 2001-10-12 | 2005-01-19 | 韩国Nano技术株式会社 | Synthesis of mono-disperse and highly crystalline nano-particles of metals, alloys, metal-oxides, and multi-metallic oxides without a size-selection process |
| CN101433965A (en) * | 2008-12-17 | 2009-05-20 | 厦门大学 | Method for preparing monodisperse nickel nanoparticle |
| CN104477949A (en) * | 2014-12-31 | 2015-04-01 | 西安交通大学 | Method for preparing single-dispersion MgO nano-particle |
| CN108136369A (en) * | 2016-06-07 | 2018-06-08 | 株式会社Lg化学 | Catalyst for oxidative dehydrogenation and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105513836B (en) * | 2016-01-14 | 2018-07-24 | 河南师范大学 | A kind of preparation method of electrode material for super capacitor nickel, cobalt composite nanometer oxide |
| CN106006763A (en) * | 2016-05-19 | 2016-10-12 | 青岛大学 | Method for preparing nickel cobaltate nanocrystalline assembly |
| CN107128981B (en) * | 2017-06-12 | 2018-07-13 | 南京晓庄学院 | Ni-M-O-H is nanocrystalline and its controllable type synthetic method and the application in preparing ultracapacitor |
| CN108097269B (en) * | 2017-12-19 | 2018-10-30 | 南京晓庄学院 | A kind of ultra-thin porous Ce-Ni-O-S nanometer sheets and its preparation method and application |
-
2018
- 2018-11-05 CN CN201811310079.2A patent/CN109243850B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1568285A (en) * | 2001-10-12 | 2005-01-19 | 韩国Nano技术株式会社 | Synthesis of mono-disperse and highly crystalline nano-particles of metals, alloys, metal-oxides, and multi-metallic oxides without a size-selection process |
| CN101433965A (en) * | 2008-12-17 | 2009-05-20 | 厦门大学 | Method for preparing monodisperse nickel nanoparticle |
| CN104477949A (en) * | 2014-12-31 | 2015-04-01 | 西安交通大学 | Method for preparing single-dispersion MgO nano-particle |
| CN108136369A (en) * | 2016-06-07 | 2018-06-08 | 株式会社Lg化学 | Catalyst for oxidative dehydrogenation and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Improved size-tunable synthesis of monodisperse NiO nanoparticles";Lang, Fengpei; Sun, Delong; Liu, Jingbing;et al.;《MATERIALS LETTERS》;20161015;第181卷;第328-330页 * |
| "金属氧化物和金属铜纳米晶的合成及性质研究";张品华;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20130815;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109243850A (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Su et al. | Asymmetric electrochemical supercapacitor, based on polypyrrole coated carbon nanotube electrodes | |
| Aghazadeh et al. | Template-free preparation of vertically-aligned Mn3O4 nanorods as high supercapacitive performance electrode material | |
| Huang et al. | Facilely synthesized porous ZnCo 2 O 4 rodlike nanostructure for high-rate supercapacitors | |
| Hu et al. | Polyaniline/SnO2 nanocomposite for supercapacitor applications | |
| Kazazi | Effect of electrodeposition current density on the morphological and pseudocapacitance characteristics of porous nano-spherical MnO2 electrode | |
| Li et al. | Hydrothermal synthesis and characterization of litchi-like NiCo2Se4@ carbon microspheres for asymmetric supercapacitors with high energy density | |
| Wang et al. | Enhanced electrochemical capacitance of NiO loaded on TiO2 nanotubes | |
| Van Hoa et al. | Rapid and efficient synthesis of high-porous reduced graphene oxide/NiCo2S4 nanocomposites for supercapacitor application | |
| Wan et al. | Three-dimensional cotton-like nickel nanowire@ Ni–Co hydroxide nanosheet arrays as binder-free electrode for high-performance asymmetric supercapacitor | |
| CN104124434A (en) | Multi-edge MoS2 nanosheet/graphene electrochemical lithium storage composite electrode and preparation method thereof | |
| CN107311119A (en) | Hollow nanoprisms material of the cobalt nickel of four selenizing two and its preparation method and application | |
| CN114005683A (en) | CoZn-MOF/NiCo2O4Preparation method of @ CNTs/rGO composite electrode material | |
| CN107221458B (en) | Nickel complex is the carbon dope nickel oxide combination electrode material and preparation method thereof of precursor | |
| Xu et al. | Synthesis of Co 3 S 4 nanosheets and their superior supercapacitor property | |
| Jin et al. | Rational design of nickel‑cobalt sulfide nanorods grown on graphene with high performance for supercapacitors | |
| CN110634688A (en) | Preparation method and application of composite film electrode with CoZn-S nano particles inserted in graphene | |
| Ouyang et al. | Integrated electrode of PPy/Ni (OH) 2 composite on nickel foam with enhanced electrochemical performance for hybrid supercapacitors | |
| Yu et al. | A cobalt-based metal–organic framework electrodeposited on nickel foam as a binder-free electrode for high-performance supercapacitors | |
| Yu et al. | Modifying the Zn Anode with Nano-Silica: A Strategy to Realize Dendrite-Free Zinc-Ion Hybrid Supercapacitors | |
| CN106783233B (en) | CuCo2S4The preparation method of nano-particle | |
| Chen et al. | Hybrid manganese oxide films for supercapacitor application prepared by sol–gel technique | |
| CN104124435B (en) | Multiple edge MoS2nanometer sheet/Graphene electrochemistry storage sodium combination electrode and preparation method | |
| Huang et al. | Low temperature synthesis of MnO2/graphene nanocomposites for supercapacitors | |
| CN109243850B (en) | Ni-Co oxide nanocrystalline and controllable synthesis method and application thereof | |
| CN110655112B (en) | Manganese oxide positive electrode material of water-based battery and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |