CN109273289A - Solvent method prepares Ni-based cobalt acid magnesium base composite material and its application - Google Patents
Solvent method prepares Ni-based cobalt acid magnesium base composite material and its application Download PDFInfo
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- CN109273289A CN109273289A CN201810864129.5A CN201810864129A CN109273289A CN 109273289 A CN109273289 A CN 109273289A CN 201810864129 A CN201810864129 A CN 201810864129A CN 109273289 A CN109273289 A CN 109273289A
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to combination electrode material preparation technical field, it is related to a kind of solvent heat legal system nickel for base cobalt acid magnesium base composite material and its application.The method of the invention includes:, with magnesium salts and cobalt salt etc. for raw material, through solvent thermoprecipitation, by adjusting precipitating reagent and magnesium salts, the content of cobalt salt and its dependent variable, presoma cobalt acid Development of Magnesium Electrode Materials to be made after calcining using urea as precipitating reagent；Again through a step solvent thermal reaction, the content and its dependent variable of nickel salt, molybdenum salt are adjusted, cobalt acid magnesium combination electrode material is made after calcining.Nickel molybdate is loaded in presoma cobalt acid Development of Magnesium Electrode Materials, the electric conductivity of material can be increased, internal resistance is reduced, improves the chemical property of composite material.The present invention uses solvent-thermal method, at low cost, easy to operate；Made electrode material purity is high, crystal form is good, impurity content is few, pattern is good, is evenly distributed, it is easy to accomplish industrialization；Have benefited from special physicalchemical structure, can be applied to electrode material for super capacitor, is suitble to industrialized production.
Description
Technical field
The invention belongs to combination electrode material preparation technical fields, are related to the synthesis of nanometer combined electrode material, especially relate to
And a kind of solvent heat legal system nickel is for base cobalt acid magnesium base composite material and its application.
Background technique
In recent years, while the progress of science and technology and fast-developing society, demand of the people to the energy is also increasingly urgent to.For
Meet the needs of productivity, people increase the yield to traditional energy (coal, petroleum, natural gas etc.), but produce water
Resource pollution, desertification of land, greenhouse effects etc. seriously threaten the environmental problem of human survival and development.So far, scientific research personnel
It studies the novel energy energetically to replace traditional energy, successfully develops the New Energies such as hybrid power, fuel cell, chemical cell
Source device, but the problems such as generally existing service life is short, temperature characterisitic is poor.In face of problem above, by the continuous of scientific research personnel
Environmentally protective and efficient new energy device is developed in effort --- supercapacitor.Supercapacitor is between traditional electricity
A kind of novel energy storage apparatus between container and rechargeable battery, it had not only had the characteristic of capacitor fast charging and discharging, but also had
There is the energy storage characteristic of battery.According to different energy storage mechnisms, supercapacitor can be divided into double layer capacitor and faraday is quasi-
Capacitor two major classes.Wherein, double layer capacitor is mainly adsorbed by pure electrostatic charge in electrode surface to generate storage
Energy；Faradic pseudo-capacitor mainly passes through pseudo capacitance active electrode material (such as transition metal oxide and macromolecule
Polymer) surface and surface nearby occur reversible redox reaction and generate pseudo capacitance, to realize to energy
Storage and conversion.In addition, supercapacitor is made of collector, electrode material, electrolyte and diaphragm, wherein electrode material is shadow
The principal element of its performance is rung, therefore scientific research personnel's emphasis studies it.
Cobalt acid magnesium (MgCo2O4) it is the product that magnesia closes cobalt sesquioxide, it is black powder under room temperature.Cobalt acid magnesium belongs to
Isometric system, space group Fd3m, crystalline field stability is relatively good, lattice constant α=8.123.Because its is at low cost, source
Extensively, chemical property is good, environmentally friendly, is widely applied in catalysis industry, the activity as electrochemical capacitor
Electrode material also has great application prospect.
Nickel molybdate is light green color or white solid, is slightly soluble in hot water.Nickel Chloride aqueous solution, precipitating can be added by potassium molybdate
After obtain, since preparation condition difference can must contain the nickel molybdate of the different crystallizations water, such as: acted on by thermal chlorination nickel and sodium molybdate
2/3rds molybdic acid hydrate nickel (NiMoO of yellow4·2/3H2O)；Anhydrous molybdic acid nickel is precipitated as in aqueous solution from boiling；From cold soln
In five molybdic acid hydrate nickel (NiMoO of green precipitate object4·5H2O)；It is light blue for reacting with ammonia water and generating complex.China
Mo resource yield occupies second place of the world, and using resources advantage, the novel molybdic acid salt material of developmental research pushes it to lead in each industry
Application in domain, will be with important economic value and social value.
Hydro-thermal method is since low energy consumption, raw material is easy to get, pollutes the advantages that few, always by it is believed that being synthesis inorganic particle material
The effective ways of material.Cobalt acid magnesium and nickel molybdate are obtained into the nanometer combined electrode material with synergistic effect through water-heat process, it can
With chemical properties such as the charge and discharge, cyclical stability, temperature characterisitic and the service lifes that improve electrode material.The present invention passes through water
Thermal method prepares cobalt acid magnesium combination electrode material, and carries out controllable adjustment to pattern.
Summary of the invention
To solve the above problems, it is an object of the invention to elder generations passes through solvent heat using urea as precipitating reagent
Method prepares presoma nanometer cobalt acid Development of Magnesium Electrode Materials, then cobalt acid magnesium combination electrode material is made through the simple solvent-thermal method of a step
Material.
Technical solution: it using urea as precipitating reagent, using magnesium salts and cobalt salt as raw material, through hydrothermal deposition, is precipitated by adjusting
Presoma cobalt acid Development of Magnesium Electrode Materials is made in agent and magnesium salts, the content of cobalt salt and its dependent variable after high-temperature calcination；Again through step letter
Cobalt acid magnesium compound electric is made by adjusting the content and its dependent variable of nickel salt and molybdenum salt in single hydro-thermal reaction after high-temperature calcination
Pole material.
A kind of solvent-thermal method prepares Ni-based cobalt acid magnesium (MgCo2O4@NiMoO4) composite material, include the following steps:
A, clipped nickel foam the pretreatment of nickel foam: is sequentially placed into 1 mol/L hydrochloric acid solution, acetone and deionized water
In, ultrasonic cleaning；
B, it is loaded with the preparation of the nickel foam of presoma cobalt acid magnesium:
B1, magnesium salts, cobalt salt and urea are weighed respectively, and solvent is added, magnetic agitation makes its uniform dissolution, wherein the magnesium salts,
Cobalt salt, urea and solvent mole, volume ratio be the mmol:4~14 of 1~4 mmol:2~9 mmol:50~90 mL, preferably 3
Mmol:6 mmol:14 mmol:90 mL；Mixed solution and pretreated nickel foam are transferred to polytetrafluoroethyllining lining
In reaction kettle, 3~10h, preferably 120 DEG C reaction 8h are reacted under the conditions of 100~160 DEG C；
B2, nickel foam is taken out after being cooled to room temperature, it is neutral to eluent pH value with deionized water and washes of absolute alcohol respectively, 50
~90 DEG C of 10~26h of drying, preferably 80 DEG C are dried for 24 hours；
B3, the nickel foam after drying is placed in Muffle furnace with the heating rate of 5 DEG C/min in 300~450 DEG C of calcining 1h~3h,
It is preferred that 400 DEG C of calcining 2h, after cooling to obtain the final product；
C, the preparation of Ni-based cobalt acid magnesium combination electrode material:
C1, nickel salt and molybdenum salt are weighed respectively, solvent is added, magnetic agitation makes its uniform dissolution, wherein the nickel salt, molybdenum salt with it is molten
Agent mole, volume ratio be the mmol:50~90 of 1~3 mmol:1~3 mL, preferably 2 mmol:2 mmol:80 mL；It will mixing
Solution and the nickel foam for being loaded with presoma cobalt acid magnesium are transferred in the reaction kettle of polytetrafluoroethyllining lining, under the conditions of 100~150 DEG C
React 4~12h, preferably 130 DEG C reaction 12h；
C2, nickel foam is taken out after being cooled to room temperature, it is neutral to eluent pH value with deionized water and washes of absolute alcohol respectively,
Under the conditions of 50~80 DEG C dry 10~for 24 hours, preferably 80 DEG C dry for 24 hours；
C3, the nickel foam after drying is placed in Muffle furnace with the heating rate of 5 DEG C/min in 350~500 DEG C of calcining 1h~3h,
It is preferred that 400 DEG C of calcining 2h, after cooling to obtain the final product.
In a more excellent disclosed example of the invention, the nickel foam of cutting described in step A is having a size of 1 × 1 cm.
In a more excellent disclosed example of the invention, magnesium salts described in step B1 be Magnesium dichloride hexahydrate, magnesium nitrate hexahydrate or
When any one in four acetate hydrate magnesium, the solvent is deionized water or dehydrated alcohol.
It is described molten when magnesium salts described in step B1 is bitter salt (toxic) in a more excellent disclosed example of the invention
Agent is deionized water.
In a more excellent disclosed example of the invention, cobalt salt described in step B1 be cobalt chloride hexahydrate, cabaltous nitrate hexahydrate or
When any one in four acetate hydrate cobalts, the solvent is deionized water or dehydrated alcohol.
It is described molten when cobalt salt described in step B1 is Cobalt monosulfate heptahydrate (toxic) in a more excellent disclosed example of the invention
Agent is deionized water.
In a more excellent disclosed example of the invention, nickel salt described in step C1 is Nickel dichloride hexahydrate (toxic), six hydration nitre
When any one in sour nickel (low toxicity), nickel acetate tetrahydrate (toxic) or six hydration nickel sulfate (toxic), the solvent is to go
Ionized water.
It is described when molybdenum salt described in step C1 is two molybdic acid hydrate sodium or potassium molybdate in a more excellent disclosed example of the invention
Solvent is deionized water.
The present invention first as precipitating reagent and utilizes solvent-thermal method, proportion and other reaction conditions by feed change using urea
Synthesize presoma cobalt acid magnesium.The urea that different content is added in precipitation process can play the role of steric hindrance, reduce particle
Between directly contact, reduce surface tension, reduce surface can, so that reduce disperse system causes because of the effect of hydrogen bond or Van der Waals force
The degree of aggregation keeps dispersion relatively stable, effectively regulates and controls to the size of nanoparticle and whole pattern.It connects
Get off, recycles solvent-thermal method, molybdic acid is synthesized on presoma cobalt acid magnesium by the proportion and other reaction conditions of feed change
Nickel.During synthesizing nickel molybdate, synthesis condition is continued to optimize, so as to improve the chemical property of integral material.Meanwhile it closing
Cobalt acid magnesium is securely fixed at nickel molybdate later, cobalt acid magnesium pattern Collapse Deformation can be prevented, and increase the work of integral material
Property site, to improve the capacitance of electrode material.
The Ni-based cobalt acid magnesium combination electrode material that the method is prepared, product are evenly distributed according to the present invention, having a size of
15~20 μm, there is one layer of apparent nickel molybdate to be supported on cobalt acid magnesium, so that cobalt acid magnesium is closely connected with foam nickel base, be not easy
It falls off.
The Ni-based cobalt acid magnesium combination electrode material that the method is prepared according to the present invention, purity is high, crystal form is good, impurity
Content is few, pattern is good, is evenly distributed.
Another object of the present invention, the Ni-based cobalt acid magnesium combination electrode material that the method is prepared according to the present invention
Material, as the electrode of supercapacitor, can be applied to the electrode material for assembling all solid state Asymmetric Supercapacitor, has
The advantages that specific capacitance is high, stable circulation is good, the service life is long, operating temperature range is wide.
Reagent used in the present invention is all that analysis is pure, is commercially available.
Beneficial effect
The present invention synthesizes cobalt acid magnesium combination electrode material (MgCo using solvent-thermal method in nickel foam2O4@NiMoO4/ NF), preparation
Process route is simple, at low cost, easy to control, combined coefficient is high；In addition, nickel molybdate further increase participate in electrode it is anti-
The active site answered increases the electric conductivity of integral material, reduces the internal resistance of electrode, and material overall performance is made to go out preferably electricity
Chemical property.The made electrode material purity is high of the present invention, crystal form is good, impurity content is few, pattern is good, is evenly distributed, it is easy to accomplish
Industrialization；Have benefited from special physicalchemical structure, can satisfy future source of energy needs, is expected to play great function.
Detailed description of the invention
Fig. 1 is Fourier transform infrared spectroscopy (FTIR), wherein
A is presoma cobalt acid Development of Magnesium Electrode Materials prepared by the present invention,
B is Ni-based cobalt acid magnesium combination electrode material prepared by the present invention.
Fig. 2 is X ray diffracting spectrum (XRD), wherein
A is presoma cobalt acid Development of Magnesium Electrode Materials prepared by the present invention,
B is Ni-based cobalt acid magnesium combination electrode material prepared by the present invention.
Fig. 3 is Ni-based cobalt acid magnesium combination electrode material scanning electron microscope (SEM) figure prepared by the present invention.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand
The present invention, but the invention is not limited to following embodiments.
Embodiment 1
3 mmol Magnesium dichloride hexahydrates, 6 mmol cobalt chloride hexahydrates and 14 mmol urea are weighed respectively at room temperature in beaker,
90 mL deionized waters are added, magnetic agitation makes its uniform dissolution, is then transferred to mixed solution and the nickel foam handled well
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 8h at a temperature of 120 DEG C and is washed, in 80 DEG C of perseverances
Dried in warm baking oven for 24 hours, later in Muffle furnace with the heating rate of 5 DEG C/min in 400 DEG C of temperature lower calcination 2h, obtain presoma
Cobalt acid magnesium (MgCo2O4/ NF), FTIR is as shown in figure 1 shown in a, and for XRD spectrum as shown in a in Fig. 2, which meets cobalt acid magnesium
XRD standard card (JCPDS NO. 02-1073, α=8.123), illustrate successfully to prepare cobalt acid magnesium.Later to presoma
Cobalt acid magnesium is loaded, and is first weighed 2 mmol Nickelous nitrate hexahydrates and 2 mmol, bis- molybdic acid hydrate sodium in beaker, is added 80
ML deionized water, magnetic agitation make its uniform dissolution, then shift mixed solution with the nickel foam for being loaded with presoma cobalt acid magnesium
Into the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 12h at a temperature of 130 DEG C and is washed, in 80
Dried for 24 hours in DEG C constant temperature oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 400 DEG C of temperature lower calcination 2h, obtain cobalt
Sour magnesium combination electrode material (MgCo2O4@NiMoO4/ NF), FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2, SEM
As shown in Figure 3.With MgCo2O4@NiMoO4/ NF carries out constant current charge-discharge directly as working electrode under three-electrode system,
Its specific capacitance is 1648.3 F g-1。
Embodiment 2
2 mmol magnesium nitrate hexahydrates, 4 mmol cabaltous nitrate hexahydrates and 6 mmol urea are weighed respectively at room temperature in beaker,
60 mL deionized waters are added, magnetic agitation makes its uniform dissolution, is then transferred to mixed solution and the nickel foam handled well
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 10h at a temperature of 100 DEG C and is washed, in 60 DEG C
12h is dried in constant temperature oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 300 DEG C of temperature lower calcination 3h, obtain forerunner
Body cobalt acid magnesium (MgCo2O4/ NF), FTIR is as shown in figure 1 shown in a, and for XRD spectrum as shown in a in Fig. 2, which meets cobalt acid
The XRD standard card (JCPDS NO. 02-1073, α=8.123) of magnesium, illustrates successfully to prepare cobalt acid magnesium.Later to forerunner
Body cobalt acid magnesium is loaded, and is first weighed 1 mmol Nickel dichloride hexahydrate and 1 mmol potassium molybdate in beaker, is added 60 mL and go
Ionized water, magnetic agitation make its uniform dissolution, are then transferred to mixed solution with the nickel foam for being loaded with presoma cobalt acid magnesium poly-
In the reaction kettle of tetrafluoroethene liner, reaction kettle is put into baking oven after reacting 6h at a temperature of 100 DEG C and is washed, in 60 DEG C of constant temperature
12h is dried in baking oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 350 DEG C of temperature lower calcination 3h, it is multiple to obtain cobalt acid magnesium
Composite electrode material (MgCo2O4@NiMoO4/ NF), FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2, SEM such as Fig. 3
It is shown.With MgCo2O4@NiMoO4/ NF carries out constant current charge-discharge, than electricity directly as working electrode under three-electrode system
Holding is 840.3 F g-1。
Embodiment 3
1 mmol, tetra- acetate hydrate magnesium, 2 mmol, tetra- acetate hydrate cobalt and 4 mmol urea are weighed respectively at room temperature in beaker,
50 mL dehydrated alcohols are added, magnetic agitation makes its uniform dissolution, is then transferred to mixed solution and the nickel foam handled well
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 4h at a temperature of 130 DEG C and is washed, in 50 DEG C of perseverances
18h is dried in warm baking oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 350 DEG C of temperature lower calcination 2h, obtain presoma
Cobalt acid magnesium (MgCo2O4/ NF), FTIR is as shown in figure 1 shown in a, and for XRD spectrum as shown in a in Fig. 2, which meets cobalt acid magnesium
XRD standard card (JCPDS NO. 02-1073, α=8.123), illustrate successfully to prepare cobalt acid magnesium.Later to presoma
Cobalt acid magnesium is loaded, and is first weighed 1 mmol nickel acetate tetrahydrate and 1 mmol, bis- molybdic acid hydrate nickel in beaker, is added 50
ML deionized water, magnetic agitation make its uniform dissolution, then shift mixed solution with the nickel foam for being loaded with presoma cobalt acid magnesium
Into the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 8h at a temperature of 150 DEG C and is washed, in 50 DEG C
18h is dried in constant temperature oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 450 DEG C of temperature lower calcination 1.5h, obtain cobalt
Sour magnesium combination electrode material (MgCo2O4@NiMoO4/ NF), FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2, SEM
As shown in Figure 3.With MgCo2O4@NiMoO4/ NF carries out constant current charge-discharge directly as working electrode under three-electrode system,
Its specific capacitance is 1442.3 F g-1。
Embodiment 4
2 mmol bitter salts, 2 mmol Cobalt monosulfate heptahydrates and 8 mmol urea are weighed respectively at room temperature in beaker,
80 mL deionized waters are added, magnetic agitation makes its uniform dissolution, is then transferred to mixed solution and the nickel foam handled well
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 3h at a temperature of 150 DEG C and is washed, in 70 DEG C of perseverances
26h is dried in warm baking oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 450 DEG C of temperature lower calcination 1h, obtain presoma
Cobalt acid magnesium (MgCo2O4/ NF), FTIR is as shown in figure 1 shown in a, and for XRD spectrum as shown in a in Fig. 2, which meets cobalt acid magnesium
XRD standard card (JCPDS NO. 02-1073, α=8.123), illustrate successfully to prepare cobalt acid magnesium.Later to presoma
Cobalt acid magnesium is loaded, and is first weighed 1 mmol six hydration nickel sulfate and 2 mmol, bis- molybdic acid hydrate nickel in beaker, is added 70
ML deionized water, magnetic agitation make its uniform dissolution, then shift mixed solution with the nickel foam for being loaded with presoma cobalt acid magnesium
Into the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 10h at a temperature of 120 DEG C and is washed, in 70
Dry 10h in DEG C constant temperature oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 500 DEG C of temperature lower calcination 1h, obtain cobalt
Sour magnesium combination electrode material (MgCo2O4@NiMoO4/ NF), FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2, SEM
As shown in Figure 3.With MgCo2O4@NiMoO4/ NF carries out constant current charge-discharge directly as working electrode under three-electrode system,
Its specific capacitance is 1163.5 F g-1。
Embodiment 5
4 mmol Magnesium dichloride hexahydrates, 9 mmol, tetra- acetate hydrate cobalt and 10 mmol urea are weighed respectively at room temperature in beaker,
85 mL deionized waters are added, magnetic agitation makes its uniform dissolution, is then transferred to mixed solution and the nickel foam handled well
In the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 5h at a temperature of 160 DEG C and is washed, in 90 DEG C of perseverances
10h is dried in warm baking oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 400 DEG C of temperature lower calcination 2h, obtain presoma
Cobalt acid magnesium (MgCo2O4/ NF), FTIR is as shown in figure 1 shown in a, and for XRD spectrum as shown in a in Fig. 2, which meets cobalt acid magnesium
XRD standard card (JCPDS NO. 02-1073, α=8.123), illustrate successfully to prepare cobalt acid magnesium.Later to presoma
Cobalt acid magnesium is loaded, and is first weighed 3 mmol Nickel dichloride hexahydrates and 3 mmol, bis- molybdic acid hydrate nickel in beaker, is added 90
ML deionized water, magnetic agitation make its uniform dissolution, then shift mixed solution with the nickel foam for being loaded with presoma cobalt acid magnesium
Into the reaction kettle of polytetrafluoroethyllining lining, reaction kettle is put into baking oven after reacting 4h at a temperature of 110 DEG C and is washed, in 80 DEG C
16h is dried in constant temperature oven, later in Muffle furnace with the heating rate of 5 DEG C/min in 450 DEG C of temperature lower calcination 1h, obtain cobalt acid
Magnesium combination electrode material (MgCo2O4@NiMoO4/ NF), FTIR is as shown in figure 1 shown in b, and XRD spectrum is as shown in b in Fig. 2, and SEM is such as
Shown in Fig. 3.With MgCo2O4@NiMoO4/ NF carries out constant current charge-discharge directly as working electrode under three-electrode system,
Specific capacitance is 794 F g-1。
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (10)
1. a kind of solvent-thermal method prepares Ni-based cobalt acid magnesium (MgCo2O4@NiMoO4) composite material, which is characterized in that including walking as follows
It is rapid:
The pretreatment of nickel foam: clipped nickel foam is sequentially placed into 1 mol/L hydrochloric acid solution, acetone and deionized water,
Ultrasonic cleaning；
It is loaded with the preparation of the nickel foam of presoma cobalt acid magnesium:
B1, magnesium salts, cobalt salt and urea are weighed respectively, and solvent is added, magnetic agitation makes its uniform dissolution, wherein the magnesium salts,
Cobalt salt, urea and solvent mole, volume ratio be the mmol:4~14 of 1~4 mmol:2~9 mmol:50~90 mL；It will mixing
Solution and pretreated nickel foam are transferred in the reaction kettle of polytetrafluoroethyllining lining, under the conditions of 100~160 DEG C react 3~
10h；
B2, nickel foam is taken out after being cooled to room temperature, it is neutral to eluent pH value with deionized water and washes of absolute alcohol respectively, 50
~90 DEG C of 10~26h of drying, preferably 80 DEG C are dried for 24 hours；
B3, the nickel foam after drying is placed in Muffle furnace with the heating rate of 5 DEG C/min in 300~450 DEG C of calcining 1h~3h,
It is preferred that 400 DEG C of calcining 2h, after cooling to obtain the final product；
The preparation of Ni-based cobalt acid magnesium combination electrode material:
C1, nickel salt and molybdenum salt are weighed respectively, solvent is added, magnetic agitation makes its uniform dissolution, wherein the nickel salt, molybdenum salt with it is molten
Agent mole, volume ratio be the mmol:50~90 of 1~3 mmol:1~3 mL, preferably 2 mmol:2 mmol:80 mL；It will mixing
Solution and the nickel foam for being loaded with presoma cobalt acid magnesium are transferred in the reaction kettle of polytetrafluoroethyllining lining, under the conditions of 100~150 DEG C
React 4~12h, preferably 130 DEG C reaction 12h；
C2, nickel foam is taken out after being cooled to room temperature, it is neutral to eluent pH value with deionized water and washes of absolute alcohol respectively,
Under the conditions of 50~80 DEG C dry 10~for 24 hours, preferably 80 DEG C dry for 24 hours；
C3, the nickel foam after drying is placed in Muffle furnace with the heating rate of 5 DEG C/min in 350~500 DEG C of calcining 1h~3h,
It is preferred that 400 DEG C of calcining 2h, after cooling to obtain the final product.
2. solvent-thermal method prepares Ni-based cobalt acid magnesium (MgCo according to claim 12O4@NiMoO4) composite material, feature exists
In: magnesium salts, cobalt salt and urea are weighed described in step B1 respectively, and solvent is added, magnetic agitation makes its uniform dissolution, wherein described
Magnesium salts, cobalt salt, urea and solvent mole, volume ratio be 3 mmol:6 mmol:14 mmol:90 mL；By mixed solution and in advance
Processed nickel foam is transferred in the reaction kettle of polytetrafluoroethyllining lining, reacts 8h at 120 DEG C.
3. solvent-thermal method according to claim 1 or claim 2 prepares Ni-based cobalt acid magnesium (MgCo2O4@NiMoO4) composite material, it is special
Sign is: when magnesium salts described in step B1 is any one in Magnesium dichloride hexahydrate, magnesium nitrate hexahydrate or four acetate hydrate magnesium,
The solvent is deionized water or dehydrated alcohol.
4. solvent-thermal method according to claim 1 or claim 2 prepares Ni-based cobalt acid magnesium (MgCo2O4@NiMoO4) composite material, it is special
Sign is: when magnesium salts described in step B1 is bitter salt, the solvent is deionized water.
5. solvent-thermal method according to claim 1 or claim 2 prepares Ni-based cobalt acid magnesium (MgCo2O4@NiMoO4) composite material, it is special
Sign is: when cobalt salt described in step B1 is any one in cobalt chloride hexahydrate, cabaltous nitrate hexahydrate or four acetate hydrate cobalts,
The solvent is deionized water or dehydrated alcohol.
6. solvent-thermal method according to claim 1 or claim 2 prepares Ni-based cobalt acid magnesium (MgCo2O4@NiMoO4) composite material, it is special
Sign is: when cobalt salt described in step B1 is Cobalt monosulfate heptahydrate, the solvent is deionized water.
7. solvent-thermal method prepares Ni-based cobalt acid magnesium (MgCo according to claim 12O4@NiMoO4) composite material, feature exists
In: nickel salt described in step C1 is appointing in Nickel dichloride hexahydrate, Nickelous nitrate hexahydrate, nickel acetate tetrahydrate or six hydration nickel sulfate
When anticipating a kind of, the solvent is deionized water.
8. solvent-thermal method prepares Ni-based cobalt acid magnesium (MgCo according to claim 12O4@NiMoO4) composite material, feature exists
In: when molybdenum salt described in step C1 is two molybdic acid hydrate sodium or potassium molybdate, the solvent is deionized water.
9. Ni-based cobalt acid magnesium base composite material made from -8 any the methods according to claim 1.
10. a kind of application of composite material described in claim 9, it is characterised in that:, can as the electrode of supercapacitor
Applied to the electrode material for assembling all solid state Asymmetric Supercapacitor.
Priority Applications (1)
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| CN110212174A (en) * | 2019-05-13 | 2019-09-06 | 福建江夏学院 | Cobalt acid magnesium and N doping tin dioxide composite material and preparation method thereof, purposes |
| CN113830838A (en) * | 2021-07-26 | 2021-12-24 | 江汉大学 | Preparation method and application of magnesium cobaltate |
| CN114974929A (en) * | 2022-05-17 | 2022-08-30 | 河南师范大学 | Preparation method of bar-shaped structure cobalt-magnesium double hydroxide/foamed nickel supercapacitor electrode |
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| CN114974929A (en) * | 2022-05-17 | 2022-08-30 | 河南师范大学 | Preparation method of bar-shaped structure cobalt-magnesium double hydroxide/foamed nickel supercapacitor electrode |
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