CN107591251A - A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof - Google Patents
A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof Download PDFInfo
- Publication number
- CN107591251A CN107591251A CN201710573126.1A CN201710573126A CN107591251A CN 107591251 A CN107591251 A CN 107591251A CN 201710573126 A CN201710573126 A CN 201710573126A CN 107591251 A CN107591251 A CN 107591251A
- Authority
- CN
- China
- Prior art keywords
- nico
- nimoo
- core
- nanometer sheet
- chip arrays
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to electrode material to synthesize field, there is provided a kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof, the present invention include nickel foam, are grown in the NiCo of foam nickel surface2O4Nanometer sheet and it is grown in NiCo2O4The NiMoO on nanometer sheet surface4Nanometer sheet, NiMoO4Nanometer sheet and NiCo2O4Nanometer sheet forms core shell structure.Material of the present invention is core-shell nano chip arrays structure, and its pattern is the cellular nano piece of stacking, the electrode material by composite directly as ultracapacitor, possesses height ratio capacity and cyclical stability, NiCo2O4@NiMoO4The specific capacity of core-shell nano chip arrays material is 6.91F cm‑2, it is 5mA cm in current density‑2When, capability retention is 76% after 5000 charge and discharge cycles；And simultaneously, the purity height of the material, good crystalline, favorable reproducibility possess more preferable specific capacity and cyclical stability, and preparation method is simple, mild condition, cost are low；Particularly suitable for being used as electrode material in ultracapacitor and Asymmetric Supercapacitor.
Description
Technical field
The invention belongs to electrode material to synthesize field, is related to a kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano piece
Array material and preparation method thereof.
Background technology
By energy resource consumption and the ever-increasing promotion of environmental protection demand, sustainable development and regenerative resource and related
The energy generate electricity, storage and protection technique are paid high attention to, ultracapacitor due to its high power density, long circulation life and
Fast charge/discharge speed and be considered as excellent energy storing device.Research for ultracapacitor, is mainly concentrated
In the design and preparation of electrode material, in view of that rapidly reversible redox can occur is anti-for transition metal oxide electrode material
Should, and then energy storage and conversion are carried out, while there is high power density and theoretical specific capacity, attract many researchs
The research interest of person.Transition bimetallic oxide electrode material possesses lead more excellent than transition single metal oxides electrode material
Electrical and energy-storage property, the specific capacitance of the transition single metal oxides material of one-component is small, and cyclical stability is poor, therefore seeks
It is very crucial to look for the compound of different materials, and the structure design of transition bimetallic material and shape characteristic are in electrochemistry
The application of aspect is vital.Present invention selection cobalt acid nickel and nickel molybdate prepare core-shell nano sheet material.
At present, the conventional preparation method of cobalt acid nickel has sol-gal process, coprecipitation, mechanochemical reaction and hydro-thermal method etc.,
Appearance structure mainly includes nano wire, nanometer rods, spherical etc.；The chemical reaction of sol-gal process is easily carried out, temperature needed for reaction
It is low, but the reaction time is longer, such as Publication No.：CN102092797B patent document；Coprecipitation and mechanochemical reaction synthesis
The simple and reaction time is short, but homogeneity is bad, easily reunites, such as Publication No.：CN104291385A, CN104659358A and
The patent documents such as CN103318978B；And hydro-thermal method can save the time of materials synthesis, synthesized material has homogeneity
And repeatability, such as Publication No.：CN105399150A patent document.The conventional preparation method of nickel molybdate has template, sunk
Shallow lake method, microwave assisting method etc., common appearance structure are nano wire, nanotube, nanometer rods etc.；Prepared with template spherical
Powder body material, chemically react and easily carry out, but the time that the reaction needs is longer, such as Publication No.：CN10344937A patent text
Offer；The microwave assisting method time is short, such as Publication No.：CN102502891A patent document；The work of precipitating reagent is added in the precipitation method
Reunion or the uneven phenomenon of component occurs with so that material, such as Publication No. CN101439882A patent document；Greatly
Majority research is all nanowire composite structures (such as Publication No. prepared：CN106356198A patent document) and nanometer rods answer
Close structure (such as Publication No.：CN105914051A, CN104282446A patent document).
The present invention has synthesized NiCo using hydro-thermal method2O4@NiMoO4The nanometer sheet composite construction of core shell structure, nanometer sheet heap
The core shell structure that pile is formed is more beneficial for contact of the material with electrolyte ion, and then lifts the utilization rate of whole material, in addition
The nanometer sheet material is directly used in electro-chemical test, it is not necessary to the addition of extra binding agent, and then utilize both collaborations
Effect causes whole composite to have excellent chemical property.
The content of the invention
It is an object of the invention to provide a kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material, should
Core shell structure design of the material based on electrode material, the material synthesized in nickel foam can directly apply to electrochemistry survey
The addition of binding agent has been reduced or remitted in examination, the design of core shell structure, is advantageous to contact and reduction ion diffusion resistance of the material with electrolyte
Power, and then the electric conductivity of composite and cyclical stability are got a promotion, improve chemical property.The present invention utilizes steaming
Water as solvent is evaporated, nickel foam is collector, adds the preparation that urea, ammonium fluoride and corresponding metal salt carry out material, is prepared
Method is simple, and cost is low.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material, it is characterised in that including nickel foam,
It is grown in the NiCo of foam nickel surface2O4Nanometer sheet and it is grown in NiCo2O4The NiMoO on nanometer sheet surface4Nanometer sheet, it is described
NiMoO4Nanometer sheet and NiCo2O4Nanometer sheet forms core shell structure.
Above-mentioned soap-free emulsion polymeization formulation NiCo2O4@NiMoO4The preparation method of core-shell nano chip arrays material, it is characterised in that：Bag
Include following steps：
It is collector that step (1), which chooses nickel foam, standby after cleaning；
Step (2) is according to mol ratio 1:0.5:5:The ratio of (25~35) weigh cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate,
Urea and ammonium fluoride are simultaneously dissolved in distilled water, obtain mixed solution A (pink)；
Nickel foam is placed in crystallizing kettle inner bag by step (3), and pour into step (2) preparation mixed solution A, in 90 DEG C~
Crystallization 5~8 hours at 100 DEG C；
Step (4) treats that crystallizing kettle is down to room temperature, is washed successively with deionized water and absolute ethyl alcohol, is subsequently placed in 45 DEG C~50
DEG C baking oven in dry 1~1.5 hour, obtain NiCo2O4Presoma；
The NiCo that step (5) prepares step (4)2O4Presoma calcines 6~8 in air atmosphere in 300 DEG C~400 DEG C
Hour, the NiCo that must be grown in nickel foam2O4Nanometer sheet film；
Step (6) is according to mol ratio 1:1 ratio weighs Nickelous nitrate hexahydrate and two molybdic acid hydrate sodium and is dissolved in distillation
In water, mixed solution B (light green color) is obtained；
Growth prepared by step (5) is had NiCo by step (7)2O4The nickel foam of nanometer sheet film is placed in crystallizing kettle inner bag,
And pour into the mixed solution B of step (6) preparation, the crystallization 2-8 hours at 140 DEG C~160 DEG C；
Step (8) treats that crystallizing kettle is down to room temperature, is washed successively with deionized water and absolute ethyl alcohol, is subsequently placed in 45 DEG C~50
DEG C baking oven in dry 1~1.5 hour, obtain NiCo2O4@NiMoO4Presoma；
The NiCo that step (9) prepares step (8)2O4@NiMoO4Presoma is forged in argon atmosphere in 350 DEG C~450 DEG C
Burn 7~10 hours, that is, be prepared into soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material.
Further, in the step (1), nickel foam is successively using acetone, hydrochloric acid, deionized water and absolute ethyl alcohol difference
Supersound washing 15~20 minutes, then by nickel foam be placed in vacuum drying chamber 45~50 DEG C dry 0.5~1 hour it is standby.
In the step (6), Nickelous nitrate hexahydrate elder generation ultrasonic dissolution adds in distilled water, then by two molybdic acid hydrate sodium
Enter ultrasonic dissolution in solution.
In the step (5), the heating rate of calcining is 1.0~2.5 DEG C/min.
In the step (9), the heating rate of calcining is 1.0~2.0 DEG C/min.
Soap-free emulsion polymeization formulation NiCo provided by the invention2O4@NiMoO4The purity height of core-shell nano chip arrays material, good crystalline,
Favorable reproducibility, and the preparation method is simple, mild condition, cost are low；Soap-free emulsion polymeization formulation NiCo of the present invention2O4@NiMoO4Nucleocapsid
Nano-chip arrays Material growth is in foamed nickel current collector, NiCo2O4With NiMoO4Pattern is in nanometer sheet, forms core shell structure,
When not only there is high specific capacitance, also excellent cyclical stability, and being applied to asymmetric super capacitor, electricity is also expanded
Pressure applies section, improves power density and energy density；Particularly suitable for ultracapacitor and asymmetric super capacitor
In device (being assembled with activated carbon), as electrode material.
To sum up, the beneficial effects of the present invention are：
1st, soap-free emulsion polymeization formulation NiCo provided by the invention2O4@NiMoO4The purity of core-shell nano chip arrays material is high, crystalline form
Good, favorable reproducibility, possess more preferable specific capacity and cyclical stability, and the preparation method is simple, mild condition, cost are low.
2nd, the present invention provides soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material is core-shell nano chip arrays
Structure, its pattern are the cellular nano piece of stacking, and this arrangement enhances the electric conductivity of composite and stability；By composite wood
Expect the electrode material directly as ultracapacitor, possess height ratio capacity and cyclical stability, NiCo2O4@NiMoO4Core-shell nano
The specific capacity of chip arrays material is 6.91F cm-2, it is 5mA cm in current density-2When, capacity is protected after 5000 charge and discharge cycles
Holdup is 76%；And single NiCo2O4The specific capacity of material is only 1.55cm-2, and be 5mA cm in current density-2When,
Capability retention is only 57% after 5000 charge and discharge cycles；As can be seen here, the growth of Shell Materials of the present invention greatly improves
The specific capacity and cyclical stability of whole composite, both cooperative effects are not fully exerted.
3rd, the present invention for fake capacitance electrode material provides a kind of new core shell structure system material, energy storage with
There is potential application value in conversion.
Brief description of the drawings
Fig. 1 is soap-free emulsion polymeization formulation NiCo of the present invention2O4@NiMoO4The preparating mechanism figure of core-shell nano chip arrays material.
Fig. 2 (a) is NiCo in embodiment 12O4And NiCo2O4@NiMoO4XRD.
Fig. 2 (b) is NiCo in embodiment 12O4And NiCo2O4@NiMoO4EDS figure.
Fig. 3 is NiCo in Examples 1 and 22O4And NiCo2O4@NiMoO4SEM figure, wherein, (a) is NiCo2O4, (b) be
NiCo2O4@NiMoO4(2h), (c) are NiCo2O4@NiMoO4(4h), (d) are NiCo2O4@NiMoO4(6h), (e) are NiCo2O4@
NiMoO4(8h)。
Fig. 4 is NiCo in embodiment 12O4@NiMoO4TEM figure.
Fig. 5 is that Ni foam sweeping speed are 10mV s in embodiment 1-1Under CV figure.
Fig. 6 (a) is NiCo in embodiment 12O4And NiCo2O4@NiMoO4In the identical CV figures swept under speed and current density.
Fig. 6 (b) is NiCo in embodiment 12O4And NiCo2O4@NiMoO4In the identical CP figures swept under speed and current density.
Fig. 6 (c) is NiCo in embodiment 22O4@NiMoO4Area specific capacity and quality specific volume under different current densities
Spirogram.
Fig. 7 (a) is NiCo in embodiment 22O4@NiMoO4In the identical CV figures swept under speed and current density.
Fig. 7 (b) is NiCo in embodiment 22O4@NiMoO4In the identical CP figures swept under speed and current density.
Fig. 8 is NiCo in embodiment 22O4@NiMoO4Area specific volume spirogram under different current densities.
Fig. 9 (a) is NiCo in embodiment 12O4And NiCo2O4@NiMoO4Nyquist diagram.
Fig. 9 (b) is NiCo in embodiment 12O4And NiCo2O4@NiMoO4Circulation figure under different current densities.
Figure 10 (a) is NiCo in embodiment 12O4@NiMoO4The naive model figure of //AC Asymmetric Supercapacitor.
Figure 10 (b) is NiCo in embodiment 12O4@NiMoO4In sweep speed it is 10mV s with activated carbon electrodes-1CV figure.
Figure 10 (c) is NiCo in embodiment 12O4@NiMoO4//AC is in 10mV s-1The CV in different voltage windows schemes down.
Figure 10 (d) is NiCo in embodiment 12O4@NiMoO4//AC sweeps speed in the case where voltage window is 0-1.6V in difference
CV schemes.
Figure 10 (e) is NiCo in embodiment 12O4@NiMoO4//AC is under 0-1.6V voltage window, different current densities
Under CP figure.
Figure 10 (f) is NiCo in embodiment 12O4@NiMoO4//AC is 5A g in current density-1Under circulation figure.
Figure 10 (g) is NiCo in embodiment 12O4@NiMoO4The energy density of //AC devices and saturation effect curve
Figure.
Embodiment
In order to be best understood from the object, technical solutions and advantages of the present invention, with reference to the accompanying drawings and examples to this
Invention is further elaborated on.
Embodiment 1
The present embodiment provides soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material, its preparation method include
Following steps：
(1) 1*1cm is chosen2Nickel foam, clean nickel foam；
(2) 0.2910g cabaltous nitrate hexahydrates, 0.1454g Nickelous nitrate hexahydrates, 2.1021g urea and 0.1852g fluorine are weighed
Change ammonium to be dissolved in 50mL distilled water, obtain the mixed solution of pink；
(3) nickel foam is placed in 100mL crystallizing kettle inner bags, and pours into the mixed solution of step (2) preparation, at 95 DEG C
Crystallization 6 hours；
(4) treat that crystallizing kettle is down to room temperature, deionized water and absolute ethyl alcohol washing, are finally placed in 45 DEG C and dry 1 hour successively；
(5) the cobalt acid nickel presoma for preparing step (4) is calcined 6 hours for 300 DEG C under air atmosphere, obtains NiCo2O4Nanometer
Piece film；
(6) 0.2908g Nickelous nitrate hexahydrates are weighed and the molybdic acid hydrate sodium of 0.2419g bis- is dissolved in 50mL distilled water,
Obtain light green solution；
(7) growth prepared by step (5) there is into NiCo2O4The nickel foam of nanometer sheet film is placed in 100mL crystallizing kettle inner bags
In, and the light green solution poured into step (6), crystallization 4 hours at 140 DEG C；
(8) treat that crystallizing kettle is down to room temperature, deionized water and absolute ethyl alcohol washing, are finally placed in 45 DEG C and dry 1 hour successively；
(9) NiCo for preparing step (8)2O4@NiMoO4Presoma is calcined 8 hours for 350 DEG C under argon atmosphere, is obtained
Soap-free emulsion polymeization formulation NiCo2O4@NiMoO4(4h) core-shell nano chip arrays material.
NiCo prepared by embodiment 12O4@NiMoO4The brief mechanism of core-shell nano chip arrays material is as shown in Figure 1.
NiCo prepared by embodiment 12O4And NiCo2O4@NiMoO4Composition as shown in Fig. 2 SEM figures respectively such as Fig. 3 (a) and
Shown in 3 (c), NiCo2O4Pattern is in nanometer sheet film, and appropriate NiMoO is covered on nanometer sheet film4Nanometer sheet.
Above-mentioned electrode material is tested into its chemical property directly as working electrode under three-electrode system, it is sweet with saturation
Mercury electrode is reference electrode, and platinum electrode is to electrode, 6mol L-1KOH is electrolyte, and it is entered in occasion China electrochemical workstation
Row CV, CP, EIS are tested.
It is illustrated in figure 4 NiCo in embodiment 12O4@NiMoO4TEM figure, as can be seen from FIG., NiCo2O4Received by some
Rice grain is formed, NiMoO4It has been covered in NiCo2O4Surface, be not to be completely covered, present core shell structure.
It is illustrated in figure 5 the CV figures of Ni foam in embodiment 1, it is seen that it is to neglect that its capacity to whole electrode, which provides,
Slightly.
It is respectively NiCo in embodiment 1 as shown in Fig. 6 (a) and 6 (b)2O4And NiCo2O4@NiMoO4Speed and electricity are swept identical
CV and CP figures under current density, scheme from CV as can be seen that both having a pair of redox peaks, NiCo2O4@NiMoO4CV it is bent
Line area is bigger, it was demonstrated that it has far above NiCo2O4Capacity, can also be drawn by CP curves, under same current density,
NiCo2O4@NiMoO4Possess and longer put a time, it is seen that lifting of the design of this core shell structure for specific capacitance has
Very big benifit.
As Fig. 6 (c) show NiCo in embodiment 12O4@NiMoO4Area specific capacity under different current densities, respectively
For 6.91,5.31,5.85,5.39,5.03,4.55 and 3.91F cm-2, corresponding specific discharge capacity be 1974,1800,1671,
1540th, 1437,1300 and 1117F g-1It is 5,10,20,40,60,80 and 100mA cm in current density-2When.
As Fig. 9 (a) show NiCo in embodiment 12O4And NiCo2O4@NiMoO4Nyquist diagram, the latter (0.43 Ω)
With than the former (0.87 Ω) lower resistance and subvertical oblique line, show the latter have more preferable electric transmission power and
Ion-diffusibility.
As Fig. 9 (b) show NiCo in embodiment 12O4And NiCo2O4@NiMoO4It is respectively 20mA cm in current density-2
With 40mA cm-2The lower figure for carrying out 5000 circulations, the former capability retention are 57%, and the latter 76%, it is seen then that
NiCo2O4@NiMoO4Possess more preferable cyclical stability.
As Figure 10 (a) show NiCo in embodiment 12O4@NiMoO4With the Asymmetric Supercapacitor of activated carbon composition
Illustraton of model, NiCo2O4@NiMoO4As positive electrode, activated carbon is as negative material.
As Figure 10 (b) show NiCo in embodiment 12O4@NiMoO4In sweep speed it is 10mV s with activated carbon-1Under
CV curves, each under different voltage windows, both combinations can be assembled into Asymmetric Supercapacitor.
As Figure 10 (c) show NiCo in embodiment 12O4@NiMoO4//AC devices are 10mV s sweeping speed-1It is lower to be in not
With the CV curves under voltage window, with the 1.8V that increases to of voltage window, there is polarization in whole asymmetric unit, and explanation has
Effect voltage window is 1.6V.
As Figure 10 (d) show NiCo in embodiment 12O4@NiMoO4//AC is in the case where voltage window is 0-1.6V in difference
The CV figures of speed are swept, figure is class rectangle shape, and whole curve does not distort significantly, with the increase voltage linear for sweeping speed
Relation.
As Figure 10 (e) show NiCo in embodiment 12O4@NiMoO4//AC is under 0-1.6V voltage window, different electricity
CP figures under current density, charging and discharging curve have a generally triangular shape shape.
As Figure 10 (f) show NiCo in embodiment 12O4@NiMoO4//AC is 5A g in current density-1Under circulation figure,
After 4000 circulations, capability retention shows that whole Asymmetric Supercapacitor has good cycle performance 87%.
As Figure 10 (g) show NiCo in embodiment 12O4@NiMoO4//AC energy density and saturation effect curve
Figure, is 47Wh kg in energy density-1When, power density is 0.4kW kg-1；And energy density can reach 11Wh kg-1Even if
It is 5kW kg in high power density-1When；Compared to the prior art, NiCo2O4@NiMoO4//AC has shown high energy density
And power density, this is all attributed to the result that each component material acts synergistically under excellent structure design.
Embodiment 2
Soap-free emulsion polymeization formulation NiCo is provided in the present embodiment2O4@NiMoO4Core-shell nano chip arrays material, play preparation process bag
Include following steps：Wherein, in step (7), crystallization is respectively 2,6 and 8 hours, and other steps are respectively obtained without viscous with embodiment 1
Tie formulation NiCo2O4@NiMoO4(2h)、NiCo2O4@NiMoO4(6h) and NiCo2O4@NiMoO4(8h) core-shell nano chip arrays material
Material.
NiCo under 2h, 6h and 8h prepared by embodiment 22O4@NiMoO4Composition as shown in Fig. 2 SEM as respectively such as Fig. 3
(b), shown in 3 (d) and 3 (e), its pattern is in NiCo2O4Not same amount NiMoO is covered on nano thin-film4Nanometer sheet, with
The extension of hydro-thermal time, NiMoO4The stacking amount of nanometer sheet is also being constantly increasing, and then influences the pattern of whole electrode material
And chemical property.
By the NiCo under 2h, 6h and 8h2O4@NiMoO4Electrode tests it directly as working electrode under three-electrode system
Chemical property, using saturated calomel electrode as reference electrode, platinum electrode is to electrode, 6mol L-1KOH is electrolyte, in occasion China
CV and CP tests are carried out in electrochemical workstation to it.
It is illustrated in figure 7 the NiCo of 2h, 6h and 8h in embodiment 22O4@NiMoO4Swept identical under speed and current density
CV (a) and CP (b) figures, all there are a pair of obvious redox peaks, and with the increase of hydro-thermal time, CV curves integration
Area occurrence law changes, and CP can also prove the regular result that material is shown under the hydro-thermal time just, i.e. 6h is an advantage over
8h and 2h, and 2h is inferior to 8h.
It is illustrated in figure 8 the NiCo of 2h, 6h and 8h in embodiment 22O4@NiMoO4The area under different current densities
Specific capacity, it is 10,20 and 40mA cm in current density-2Under, 2h specific capacity is 3.41,2.82 and 2.30F cm-2；6h ratio
Capacity is 5.90,5.32 and 4.46F cm-2；8h specific capacity is 3.96,3.60 and 2.98F cm-2；It can thus be concluded that work as hydro-thermal
When time is 2h, a small amount of NiMoO4Nanometer sheet is covered in NiCo2O4On nanometer sheet film so that integrate the electrochemistry of material
Can be relative to single stratum nucleare NiCo2O4Increase, with hydro-thermal time lengthening to 8h, substantial amounts of NiMoO4Nanometer sheet covers
In NiCo2O4On nano thin-film so that the effective rate of utilization of material reduces, and is under 4h the hydro-thermal time under optimal conditions relative to being
The capacity for preparing material it is low, but overall specific capacity is all above core layer material NiCo2O4's.
The present invention provides soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material purity height, good crystalline, cost
It is low, obtained after hydro-thermal and annealing can be directly in nickel foam, characterization test, knot are carried out as electrode material
Fruit shows that material is also to have shown excellent cyclical stability by the core shell structure of nanometer sheet stacking, simultaneous electrochemical test,
High specific capacitance, energy density and power density, the potential application prospect in terms of energy storage.Finally illustrate, it is above-mentioned
Embodiment is intended merely to be illustrated this programme, but is not restricted to this programme, while without departing from appended claims
Certain change can be made on the basic scope of the present invention limited.
The foregoing is only a specific embodiment of the invention, any feature disclosed in this specification, except non-specifically
Narration, can alternative features equivalent by other or with similar purpose replaced；Disclosed all features or all sides
Method or during the step of, in addition to mutually exclusive feature and/or step, can be combined in any way.
Claims (6)
- A kind of 1. soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material, it is characterised in that including nickel foam, life Grow the NiCo in foam nickel surface2O4Nanometer sheet and it is grown in NiCo2O4The NiMoO on nanometer sheet surface4Nanometer sheet, it is described NiMoO4Nanometer sheet and NiCo2O4Nanometer sheet forms core shell structure.
- 2. the soap-free emulsion polymeization formulation NiCo as described in claim 12O4@NiMoO4The preparation method of core-shell nano chip arrays material, it is special Sign is, comprises the following steps：It is collector that step (1), which chooses nickel foam, standby after cleaning；Step (2) is according to mol ratio 1:0.5:5:The ratio of (25~35) weighs cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, urea With ammonium fluoride and be dissolved in distilled water, obtain mixed solution A；Nickel foam is placed in crystallizing kettle inner bag by step (3), and pours into the mixed solution A of step (2) preparation, in 90 DEG C~100 Crystallization 5~8 hours at DEG C；Step (4) treats that crystallizing kettle is down to room temperature, is washed successively with deionized water and absolute ethyl alcohol, is subsequently placed in 45 DEG C~50 DEG C Dried 1~1.5 hour in baking oven, obtain NiCo2O4Presoma；The NiCo that step (5) prepares step (4)2O4Presoma is calcined 6~8 hours in air atmosphere in 300 DEG C~400 DEG C, The NiCo2O4 nanometer sheet films that must be grown in nickel foam；Step (6) is according to mol ratio 1:1 ratio weighs Nickelous nitrate hexahydrate and two molybdic acid hydrate sodium and is dissolved in distilled water, Obtain mixed solution B；Growth prepared by step (5) is had NiCo by step (7)2O4The nickel foam of nanometer sheet film is placed in crystallizing kettle inner bag, and is fallen Enter the mixed solution B of step (6) preparation, the crystallization 2~8 hours at 140 DEG C~160 DEG C；Step (8) treats that crystallizing kettle is down to room temperature, is washed successively with deionized water and absolute ethyl alcohol, is subsequently placed in 45 DEG C~50 DEG C Dried 1~1.5 hour in baking oven, obtain NiCo2O4@NiMoO4Presoma；The NiCo that step (9) prepares step (8)2O4@NiMoO4Presoma calcines 7 in argon atmosphere in 350 DEG C~450 DEG C ~10 hours, that is, it is prepared into soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material.
- 3. the soap-free emulsion polymeization formulation NiCo as described in claim 22O4@NiMoO4Core-shell nano chip arrays material, it is characterised in that institute To state in step (1), nickel foam distinguishes supersound washing 15~20 minutes using acetone, hydrochloric acid, deionized water and absolute ethyl alcohol successively, Then by nickel foam be placed in vacuum drying chamber 45~50 DEG C dry 0.5~1 hour it is standby.
- 4. the soap-free emulsion polymeization formulation NiCo as described in claim 22O4@NiMoO4Core-shell nano chip arrays material, it is characterised in that institute State in step (6), Nickelous nitrate hexahydrate elder generation ultrasonic dissolution is in distilled water, then two molybdic acid hydrate sodium are added in solution and surpassed Sound dissolves.
- 5. the soap-free emulsion polymeization formulation NiCo as described in claim 22O4@NiMoO4Core-shell nano chip arrays material, it is characterised in that institute State in step (5), the heating rate of calcining is 1.0~2.5 DEG C/min.
- 6. the soap-free emulsion polymeization formulation NiCo as described in claim 22O4@NiMoO4Core-shell nano chip arrays material, it is characterised in that institute State in step (9), the heating rate of calcining is 1.0~2.0 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710573126.1A CN107591251A (en) | 2017-07-14 | 2017-07-14 | A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710573126.1A CN107591251A (en) | 2017-07-14 | 2017-07-14 | A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107591251A true CN107591251A (en) | 2018-01-16 |
Family
ID=61041759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710573126.1A Pending CN107591251A (en) | 2017-07-14 | 2017-07-14 | A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107591251A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108597898A (en) * | 2018-04-10 | 2018-09-28 | 宁波大学 | A kind of preparation method of cobalt sulfide zinc nano material |
| CN108806995A (en) * | 2018-06-08 | 2018-11-13 | 上海应用技术大学 | A kind of g-C3N4@NiCo2O4The preparation method of nucleocapsid |
| CN108831755A (en) * | 2018-06-25 | 2018-11-16 | 上海应用技术大学 | A kind of preparation method of electrode for capacitors multi-element composite material |
| CN109273289A (en) * | 2018-08-01 | 2019-01-25 | 江苏大学 | Solvent method prepares Ni-based cobalt acid magnesium base composite material and its application |
| CN109599564A (en) * | 2018-11-27 | 2019-04-09 | 东华大学 | Cobalt acid nickel array self-supporting large area air electrode and its preparation and application |
| CN109768224A (en) * | 2019-01-11 | 2019-05-17 | 五邑大学 | A kind of preparation method based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery |
| CN109911947A (en) * | 2019-02-22 | 2019-06-21 | 中国科学院山西煤炭化学研究所 | A kind of NiCo2O4@NiMoO4Core-shell structure and preparation method thereof |
| CN110085453A (en) * | 2019-04-10 | 2019-08-02 | 南京航空航天大学 | The preparation method and application of the hud typed Ni-Co LDH@Ni-Mn LDH of carbon nanotube foam support |
| CN110400699A (en) * | 2019-07-22 | 2019-11-01 | 安徽理工大学 | A kind of nano flower-like Ni@NiMoO4@Ni3S2Micro-, nano-electrode material preparation method and application |
| CN111146442A (en) * | 2019-12-27 | 2020-05-12 | 东华大学 | High-performance nickel-zinc battery positive electrode material CoXNi1-XMoO4And their preparation and use |
| US11183343B1 (en) | 2020-08-15 | 2021-11-23 | United Arab Emirates University | Composite material for supercapacitor electrodes |
| CN116764638A (en) * | 2023-06-28 | 2023-09-19 | 广东工业大学 | Integral foam nickel-loaded NiCo 2 O 4 Preparation method of nano-sheet array |
| US11767601B1 (en) | 2022-06-29 | 2023-09-26 | King Fahd University Of Petroleum And Minerals | NiMoO4 nanoflowers on nickel foam as electrocatalysts for water oxidation |
| WO2023207813A1 (en) * | 2022-04-29 | 2023-11-02 | 一汽奔腾轿车有限公司 | Preparation method for multi-stage nanosheet array nico2o4/rgo/nf and application as electrode |
| CN117316656A (en) * | 2023-11-13 | 2023-12-29 | 延安大学 | Preparation method and application of multi-element doped molybdate@cobaltate nano-array hybridized core-shell structure material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282446A (en) * | 2014-11-08 | 2015-01-14 | 安徽师范大学 | Nanometer material with nickel cobaltate@nickel molybdate core shell structure as well as preparation method and application of nanometer material |
| CN104377040A (en) * | 2014-11-19 | 2015-02-25 | 江苏合志锂硫电池技术有限公司 | Electrode applied to electrochemical energy storage device and preparation method thereof |
| CN104701036A (en) * | 2015-03-27 | 2015-06-10 | 吉林化工学院 | Research of super-capacitor electrode material based on graded flowerlike NiCo2O4 |
| CN106128801A (en) * | 2016-06-08 | 2016-11-16 | 东华大学 | A kind of ultracapacitor NiCo2o4the preparation method of based composites |
| CN106219616A (en) * | 2016-07-18 | 2016-12-14 | 合肥工业大学 | A kind of molybdenum dioxide/cobalt acid nickel classification hybrid nanostructure array and preparation method thereof |
-
2017
- 2017-07-14 CN CN201710573126.1A patent/CN107591251A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282446A (en) * | 2014-11-08 | 2015-01-14 | 安徽师范大学 | Nanometer material with nickel cobaltate@nickel molybdate core shell structure as well as preparation method and application of nanometer material |
| CN104377040A (en) * | 2014-11-19 | 2015-02-25 | 江苏合志锂硫电池技术有限公司 | Electrode applied to electrochemical energy storage device and preparation method thereof |
| CN104701036A (en) * | 2015-03-27 | 2015-06-10 | 吉林化工学院 | Research of super-capacitor electrode material based on graded flowerlike NiCo2O4 |
| CN106128801A (en) * | 2016-06-08 | 2016-11-16 | 东华大学 | A kind of ultracapacitor NiCo2o4the preparation method of based composites |
| CN106219616A (en) * | 2016-07-18 | 2016-12-14 | 合肥工业大学 | A kind of molybdenum dioxide/cobalt acid nickel classification hybrid nanostructure array and preparation method thereof |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108597898A (en) * | 2018-04-10 | 2018-09-28 | 宁波大学 | A kind of preparation method of cobalt sulfide zinc nano material |
| CN108806995B (en) * | 2018-06-08 | 2019-09-27 | 上海应用技术大学 | A kind of g-C3N4@NiCo2O4The preparation method of core-shell structure |
| CN108806995A (en) * | 2018-06-08 | 2018-11-13 | 上海应用技术大学 | A kind of g-C3N4@NiCo2O4The preparation method of nucleocapsid |
| CN108831755A (en) * | 2018-06-25 | 2018-11-16 | 上海应用技术大学 | A kind of preparation method of electrode for capacitors multi-element composite material |
| CN108831755B (en) * | 2018-06-25 | 2020-06-19 | 上海应用技术大学 | Preparation method of capacitor electrode multi-component composite material |
| CN109273289A (en) * | 2018-08-01 | 2019-01-25 | 江苏大学 | Solvent method prepares Ni-based cobalt acid magnesium base composite material and its application |
| CN109599564B (en) * | 2018-11-27 | 2022-09-06 | 东华大学 | Nickel cobaltate array self-supporting large-area air electrode and preparation and application thereof |
| CN109599564A (en) * | 2018-11-27 | 2019-04-09 | 东华大学 | Cobalt acid nickel array self-supporting large area air electrode and its preparation and application |
| CN109768224B (en) * | 2019-01-11 | 2021-09-03 | 五邑大学 | Preparation method of lithium ion battery cathode based on in-situ growth of copper oxide/nickel cobaltate nanowire composite material |
| CN109768224A (en) * | 2019-01-11 | 2019-05-17 | 五邑大学 | A kind of preparation method based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery |
| CN109911947A (en) * | 2019-02-22 | 2019-06-21 | 中国科学院山西煤炭化学研究所 | A kind of NiCo2O4@NiMoO4Core-shell structure and preparation method thereof |
| CN109911947B (en) * | 2019-02-22 | 2020-09-08 | 中国科学院山西煤炭化学研究所 | NiCo2O4@NiMoO4Core-shell structure and preparation method thereof |
| CN110085453A (en) * | 2019-04-10 | 2019-08-02 | 南京航空航天大学 | The preparation method and application of the hud typed Ni-Co LDH@Ni-Mn LDH of carbon nanotube foam support |
| CN110400699B (en) * | 2019-07-22 | 2022-02-15 | 安徽理工大学 | Preparation method and application of nano flower-shaped Ni @ NiMoO4@ Ni3S2 micro-nano electrode material |
| CN110400699A (en) * | 2019-07-22 | 2019-11-01 | 安徽理工大学 | A kind of nano flower-like Ni@NiMoO4@Ni3S2Micro-, nano-electrode material preparation method and application |
| CN111146442A (en) * | 2019-12-27 | 2020-05-12 | 东华大学 | High-performance nickel-zinc battery positive electrode material CoXNi1-XMoO4And their preparation and use |
| US11183343B1 (en) | 2020-08-15 | 2021-11-23 | United Arab Emirates University | Composite material for supercapacitor electrodes |
| WO2023207813A1 (en) * | 2022-04-29 | 2023-11-02 | 一汽奔腾轿车有限公司 | Preparation method for multi-stage nanosheet array nico2o4/rgo/nf and application as electrode |
| US11767601B1 (en) | 2022-06-29 | 2023-09-26 | King Fahd University Of Petroleum And Minerals | NiMoO4 nanoflowers on nickel foam as electrocatalysts for water oxidation |
| CN116764638A (en) * | 2023-06-28 | 2023-09-19 | 广东工业大学 | Integral foam nickel-loaded NiCo 2 O 4 Preparation method of nano-sheet array |
| CN117316656A (en) * | 2023-11-13 | 2023-12-29 | 延安大学 | Preparation method and application of multi-element doped molybdate@cobaltate nano-array hybridized core-shell structure material |
| CN117316656B (en) * | 2023-11-13 | 2024-04-16 | 延安大学 | Preparation method and application of multi-element doped molybdate@cobaltate nano-array hybridized core-shell structure material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107591251A (en) | A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof | |
| CN108054019B (en) | NiCo of laminated structure2S4@NixCo(1-x)(OH)2Preparation method and application of composite material | |
| CN105097299B (en) | Cobaltosic oxide/NiCoAl double-layered hydroxides composites and preparation method thereof | |
| CN104616915B (en) | A kind of preparation method of graphene ruthenium-oxide composite | |
| CN106206065A (en) | A kind of electrode material for super capacitor MnO2the preparation method of@PDA nano composite material | |
| CN109148160A (en) | A kind of core-shell structure manganese cobalt/cobalt oxide@nickel cobalt oxide composite material and preparation method and application | |
| CN109616331A (en) | A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof | |
| CN108773859A (en) | A kind of vulcanization nano material and its preparation method and application | |
| CN109741966A (en) | A kind of Ni with core-shell structure feature6MnO8@carbon nano tube compound material and its preparation method and application | |
| CN112830523B (en) | Molybdenum-doped cobaltosic oxide for super capacitor and preparation method thereof | |
| CN110310835A (en) | A kind of nano flower-like NiS@NiCo2S4Micro-, nano-electrode material and its preparation method and application | |
| CN106449136B (en) | Alpha-nickel hydroxide cobalt electrode material and the preparation method and application thereof | |
| CN106449138B (en) | Carbon-coated cobalt molybdate mesh nano chip arrays material, preparation method and application | |
| CN109767924A (en) | A kind of LDH based super capacitor combination electrode material and preparation method and purposes | |
| CN109786135A (en) | A kind of copper oxide@nickel molybdate/foam copper combination electrode material and preparation method thereof | |
| CN105742625B (en) | Nano-electrode material with sandwich and its preparation method and application | |
| CN107195470A (en) | Nanotube-shaped composite of nickel cobalt iron ternary metal oxide and preparation method thereof | |
| Wu et al. | Nickel-cobalt oxide nanocages derived from cobalt-organic frameworks as electrode materials for electrochemical energy storage with redox electrolyte | |
| Luo et al. | Preparation of NiMoO4 nanoarrays electrodes with optimized morphology and internal crystal water for efficient supercapacitors and water splitting | |
| Zhang et al. | Self-sacrificial growth of hierarchical P (Ni, Co, Fe) for enhanced asymmetric supercapacitors and oxygen evolution reactions | |
| CN101399120A (en) | Novel hybrid supercapacitor | |
| CN107195482A (en) | A kind of nanometer rods array composite and its preparation method and application | |
| CN104992847B (en) | A kind of Asymmetric Supercapacitor with high power density and preparation method thereof | |
| CN104779066B (en) | The super capacitor of a kind of rattan shape cobalt acid nickel as positive electrode and preparation method thereof | |
| CN112038106B (en) | Electrode material, preparation method thereof and supercapacitor electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180116 |