CN109473289A - A kind of flower-like nanometer composite material and preparation method and a kind of electrode material and preparation method thereof - Google Patents
A kind of flower-like nanometer composite material and preparation method and a kind of electrode material and preparation method thereof Download PDFInfo
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- CN109473289A CN109473289A CN201811319122.1A CN201811319122A CN109473289A CN 109473289 A CN109473289 A CN 109473289A CN 201811319122 A CN201811319122 A CN 201811319122A CN 109473289 A CN109473289 A CN 109473289A
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- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 239000007772 electrode material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 73
- 239000010439 graphite Substances 0.000 claims abstract description 73
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002114 nanocomposite Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 9
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000005253 cladding Methods 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000008240 homogeneous mixture Substances 0.000 description 5
- 230000000873 masking effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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
-
- 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)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of flower-like nanometer composite materials, are obtained by the Material cladding for including nickel hydroxide, class graphite phase carbon nitride and graphene oxide；The pattern of the flower-like nanometer composite material is in flower-shaped.When flower-like nanometer composite material provided by the invention is as electrode material for super capacitor, there is preferable chemical property.Embodiment the result shows that, flower-like nanometer composite material provided by the invention as electrode material have preferable cyclical stability, after 1000 charge and discharge cycles, the capacity retention ratio of electrode material shows good stable circulation performance up to 74.3%；In addition, flower-like nanometer composite material energy density with higher provided by the invention, specific capacitance is 473.3F/g~543.8F/g under the current density condition of 1A/g.
Description
Technical field
The present invention relates to field of nanometer material technology, more particularly to a kind of flower-like nanometer composite material and preparation method and one
Kind electrode material and preparation method thereof.
Background technique
As modern humans society is fast-developing, environmental pollution and energy crisis have become what human development must face
Two big difficult challenges.Supercapacitor is wide due to its high power density, the service life cycle of length and use temperature range
The research hotspot to cope with challenges is become, however super capacitor energy density is low, limits it and further develops.Therefore it seeks
New electrode active material is looked for improve the energy density of supercapacitor, is the project that scientific worker presently the most pays close attention to.
Currently used electrode material for super capacitor is carbon-based material, conducting polymer and metal oxide.Graphene
Most hot carbon-based material electrode is studied as current, various excellent physical and chemical performances are liked by researcher, still
Agglomeration caused by the intermolecular Van der Waals force of carbon-based material is the problem that current researcher must capture；Conducting polymer is one
The novel electrode material of kind, can obtain corresponding polymer architecture, but its cycle performance is unstable by MOLECULE DESIGN；
Although metal oxide can provide biggish capacitor, single metal oxide is also unstable.Therefore, how one is provided
The composite electrode material for super capacitor of kind energy density height and good cycling stability, is this field researcher's urgent need to resolve
Problem.
Summary of the invention
The present invention provides a kind of flower-like nanometer composite material and preparation method and a kind of electrode material and its preparation sides
Method, flower-like nanometer composite material provided by the invention have preferable cyclical stability and energy density as electrode material.
In order to reach the goals above, the present invention provides a kind of flower-like nanometer composite materials, by including nickel hydroxide, class stone
The Material cladding of black phase carbon nitride and graphene oxide obtains；The specific surface area of the flower-like nanometer composite material be 170~
190m2/g。
Preferably, the mass ratio of the nickel hydroxide, class graphite phase carbon nitride and graphene oxide be 15~17:0.5~
1.5:0.5~1.5.
The present invention also provides the preparation methods of flower-like nanometer composite material described in above-mentioned technical proposal, including following step
It is rapid:
(1) adjusted after mixing nickel nitrate, graphite oxide and class graphite phase carbon nitride in water mixed liquor pH value to 9~
11, obtain dispersion liquid；
(2) in confined conditions, the dispersion liquid that the step (1) obtains is heated, it is multiple obtains flower-like nanometer
Condensation material.
Preferably, the regulator that the mixed liquor pH value is adjusted in the step (1) is ammonium hydroxide, and the concentration of the ammonium hydroxide is
10~15mol/L.
Preferably, the temperature heated in the step (2) is 170~190 DEG C, and the time is 6~14h.
Preferably, in the step (1) class graphite phase carbon nitride preparation method the following steps are included:
(a) urea is subjected to calcination processing, is dispersed in water after calcined product grinding, obtains suspension；
(b) in confined conditions, the suspension that the step (a) obtains is heated, obtains class graphite-phase nitrogen
Change carbon.
Preferably, the temperature of calcination processing is 500~600 DEG C in the step (a), and the time is 2.5~3.5h.
Preferably, the temperature heated in the step (b) is 170~190 DEG C, and the time is 9~11h.
The present invention also provides a kind of electrode materials, including matrix and active constituent；The active constituent is above scheme
The flower-like nanometer composite material that preparation method described in the flower-like nanometer composite material or above scheme is prepared.
The present invention also provides the preparation methods of electrode material described in above-mentioned technical proposal, comprising the following steps:
Flower-like nanometer composite material is coated on matrix, then through dry and compressing tablet process, obtains electrode material.
The present invention provides a kind of flower-like nanometer composite materials, by including nickel hydroxide, class graphite phase carbon nitride and oxidation
The Material cladding of graphene obtains；The specific surface area of the flower-like nanometer composite material is 170~190m2/g.The present invention passes through
Nickel hydroxide, class graphite phase carbon nitride (g-C3N4) and graphene oxide (RGO) tri compound, RGO provide big specific surface area and
High conductivity can shorten the transmission path of ion and electronics, g-C3N4In the form of N doping with RGO electronics coupled, g-
C3N4Band gap can be opened and adjust conduction type, change the electronic structure of RGO, improve the free carrier density of RGO, from
And the electric conductivity and stability of electrode material are improved, Ni (OH)2High specific capacitance is provided；Flower-like nanometer provided by the invention is multiple
Condensation material takes full advantage of Ni (OH)2、g-C3N4With the advantage of RGO so that flower-like nanometer composite material provided by the invention
When as electrode material for super capacitor, there is preferable chemical property.Embodiment the result shows that, it is provided by the invention flower-shaped
Nanocomposite has preferable cyclical stability, after 1000 charge and discharge cycles, electrode material as electrode material
Capacity retention ratio up to 74.3%, show good stable circulation performance；In addition, flower-like nanometer provided by the invention is compound
Material energy density with higher, specific capacitance is 473.3F/g~543.8F/g under the current density condition of 1A/g.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of flower-like nanometer composite material provided by the invention；
Fig. 2 is the reacting flow chart of present invention preparation class graphite phase carbon nitride；
Fig. 3 is stratiform C prepared by the present invention3N4The scanning electron microscope (SEM) photograph of polymer；
Fig. 4 is the scanning electron microscope (SEM) photograph of class graphite phase carbon nitride prepared by the present invention；
Fig. 5 is the FT-IR spectrogram for the flower-like nanometer composite material that the embodiment of the present invention 1~5 is prepared；
Fig. 6 is the XRD diagram for the flower-like nanometer composite material that the embodiment of the present invention 1~5 is prepared；
Fig. 7 be the flower-like nanometer composite material for preparing of the embodiment of the present invention 1 as electrode material following at different rates
Ring volt-ampere curve figure；
Fig. 8 be the embodiment of the present invention 1 prepare flower-like nanometer composite material as electrode material under different current densities
GCD curve graph；
Fig. 9 be the embodiment of the present invention 1 prepare flower-like nanometer composite material as electrode material under 5A/g current density
Cyclical stability curve graph；
Figure 10 be the flower-like nanometer composite material that is prepared of the embodiment of the present invention 1~5 as electrode material in 10mV/s
Cyclic voltammetry curve figure under rate；
Figure 11 is that the flower-like nanometer composite material that the embodiment of the present invention 1~5 is prepared is hindered as the exchange of electrode material
Anti- figure；
Figure 12 is that the flower-like nanometer composite material that the embodiment of the present invention 1~5 is prepared is electric in 1A/g as electrode material
Constant current charge-discharge curve graph under current density.
Specific embodiment
The present invention provides a kind of flower-like nanometer composite materials, by including nickel hydroxide, class graphite phase carbon nitride and oxidation
The Material cladding of graphene obtains；The specific surface area of the flower-like nanometer composite material is 170~190m2/g。
In the present invention, the nickel hydroxide, class graphite phase carbon nitride (are write a Chinese character in simplified form are as follows: g-C3N4) and graphene oxide (write a Chinese character in simplified form
Are as follows: RGO) three kinds of materials are combined with each other by electronics coupled, the nickel hydroxide, class graphite phase carbon nitride and graphene oxide
Mass ratio be preferably 15~17:0.5~1.5:0.5~1.5, further preferably 16:1:1.In the present invention, described flower-shaped
The pattern of nanocomposite is in flower-shaped, and structure is as shown in Figure 1, as shown in Figure 1, flower-like nanometer composite material provided by the invention
It is not be overlapped between piece and piece, so that flower-like nanometer composite material provided by the invention has biggish specific surface area, and then be conducive to
Improve the chemical property of flower-like nanometer composite material.In the present invention, the specific surface area of the flower-like nanometer composite material is
170~190m2/ g, preferably 175~185m2/ g, more preferably 180m2/g。
The present invention passes through Ni (OH)2、g-C3N4With RGO tri compound, RGO provides big specific surface area and high conductivity,
The transmission path of ion and electronics, g-C can be shortened3N4In the form of N doping with RGO electronics coupled, g-C3N4It can open
Band gap simultaneously adjusts conduction type, changes the electronic structure of RGO, improves the free carrier density of RGO, to improve electrode material
The electric conductivity and stability of material, Ni (OH)2High specific capacitance is provided, flower-like nanometer composite material provided by the invention is sufficiently sharp
With Ni (OH)2、g-C3N4With the advantage of RGO so that flower-like nanometer composite material provided by the invention is as super capacitor
When device electrode material, there is preferable chemical property.
The present invention also provides the preparation methods of flower-like nanometer composite material described in above-mentioned technical proposal, including following step
It is rapid:
(1) mixed liquor pH value will be adjusted after nickel nitrate, graphite oxide and class graphite phase carbon nitride in water dispersion mixing to 9
~11, obtain dispersion liquid；
(2) in confined conditions, the dispersion liquid that the step (1) obtains is heated, it is multiple obtains flower-like nanometer
Condensation material.
The present invention mixes nickel nitrate, graphite oxide and class graphite phase carbon nitride in water, obtains mixed liquor.
In the present invention, the preparation method of the class graphite phase carbon nitride preferably includes following steps:
(a) urea is subjected to calcination processing, is dispersed in water after calcined product grinding, obtains suspension；
(b) in confined conditions, the suspension that the step (a) obtains is heated, obtains class graphite-phase nitrogen
Change carbon.
Urea is carried out calcination processing by the present invention, is dispersed in water after calcined product grinding, is obtained suspension.
In the present invention, the temperature of the calcination processing is preferably 500~600 DEG C, and further preferably 550~600 DEG C,
The time of the calcination processing is preferably 2.5~3.5h, further preferably 3h.
The present invention is in calcination process, and the urea, which first polymerize, generates melamine, and then melamine polymerize generation again
Stratiform C3N4Polymer.In the present invention, the urea generates stratiform C3N4The reaction of polymer is as shown in Figure 2.As shown in Figure 2,
Urea first occurs addition polymerization and generates melamine, and then deamination polycondensation generation stratiform C occurs again for melamine3N4Polymer.
The stratiform C that the present invention will obtain3N4It is dispersed in water after polymer grinding, obtains suspension.
In the present invention, the concentration of the suspension is preferably 2~3mg/mL, further preferably 2.5mg/mL.
After obtaining suspension, in confined conditions, the suspension is heated by the present invention, obtains class graphite-phase
Carbonitride.
In the present invention, the confined condition is preferably provided by closed reactor.In the present invention, the heat treatment
Temperature is preferably 170~190 DEG C, and further preferably 180 DEG C, the time is preferably 6~14h, further preferably 8~12h, more
Preferably 12h.
The present invention in particular during a heating process, stratiform C3N4Physical change occurs for the appearance structure of polymer, forms class graphite
Phase carbon nitride (g-C3N4).In the present invention, stratiform C before the heat treatment3N4The pattern of polymer is as shown in figure 3, at heating
Class graphite phase carbon nitride (the g-C obtained after reason3N4) pattern it is as shown in Figure 4.As can be seen from figs. 3 and 4 the present invention passes through heating
Processing, not only increases class graphite phase carbon nitride (g-C3N4) specific surface area, and increase the work on graphite phase carbon nitride surface
Property site, be conducive to graphene it is compound.
In the present invention, the graphite oxide is preferably prepared by the improved Hummers method of graphite, the graphite
Partial size is preferably 300~350 mesh, further preferably 325 mesh.
After obtaining class graphite phase carbon nitride, the present invention is by the class graphite phase carbon nitride, nickel nitrate and graphite oxide in water
Middle mixing, obtains mixed liquor.
In the present invention, the mass ratio of the nickel nitrate, graphite oxide and class graphite phase carbon nitride is preferably according to hydroxide
The mass ratio of nickel, class graphite phase carbon nitride and graphene oxide is configured, in the present invention, the nickel hydroxide, class graphite
The mass ratio of phase carbon nitride and graphene oxide is preferably 15~17:0.5~1.5:0.5~1.5, further preferably 16:1:
1。
The present invention preferably first by graphite oxide and class graphite phase carbon nitride ultrasonic mixing in water, is then stirred with nickel nitrate again
Mix mixing.In the present invention, the ultrasonic mixing power is preferably 500~550W, further preferably 520~540W, ultrasound
The mixed time is preferably 25~35min, further preferably 30min；It is described to be stirred preferably magnetic agitation mixing, institute
Stating the time being stirred is preferably 25~35min, further preferably 30min.
After obtaining the mixed liquor of nickel nitrate, graphite oxide and class graphite phase carbon nitride, the present invention adjusts the pH of mixed
Value obtains dispersion liquid to 9~11.
In the present invention, the pH value of the dispersion liquid is 9~11, preferably 10.In the present invention, the mixed liquor is adjusted
The regulator of pH value is preferably ammonium hydroxide, and the concentration of the ammonium hydroxide is preferably 10~15mol/L, further preferably 12~14mol/
L, more preferably 13.38mol/L.
After obtaining dispersion liquid, in confined conditions, dispersion liquid is heated by the present invention, and it is compound to obtain flower-like nanometer
Material.
The present invention preferably in a kettle heats dispersion liquid.In the present invention, the temperature of the heat treatment
Preferably 170~190 DEG C of degree, further preferably 180 DEG C, the time is preferably 6~14h, further preferably 8~12h, more excellent
It is selected as 12h.
In particular during a heating process, the graphite oxide (GO) is reduced to graphene oxide (RGO), the Ni to the present invention
(OH)2、g-C3N4, tri- kinds of substances of RGO be combined with each other by electronics coupled, formed flower-like nanometer composite material.
After the completion of heat treatment, the present invention preferably carries out cooling treatment to the reaction solution after heating, obtains coolant liquid.At this
In invention, the target temperature after cooling is preferably room temperature, and cooling specific embodiment is not particularly limited in the present invention,
Using the type of cooling well-known to those skilled in the art.
After obtaining coolant liquid, the present invention is preferably successively filtered coolant liquid, Washing of Filter Cake and drying process, is spent
Shape nanocomposite.In the present invention, the drying is preferably freeze-dried.The present invention is to filtering, Washing of Filter Cake and drying
Specific embodiment be not particularly limited, using method well-known to those skilled in the art.
The present invention also provides a kind of electrode material, including matrix and active constituent, the active constituent is above-mentioned technology
The flower-like nanometer composite wood that preparation method described in flower-like nanometer composite material or above-mentioned technical proposal described in scheme is prepared
Material.
In the present invention, mass content of the flower-like nanometer composite material in electrode material be preferably 75%~
85%, further preferably 80%.
The present invention also provides the preparation methods of electrode material described in above-mentioned technical proposal, comprising the following steps:
Flower-like nanometer composite material is coated on matrix, then through dry and compressing tablet process, obtains electrode material.
After the present invention preferably mixes flower-like nanometer composite material, ptfe emulsion and acetylene black, it is coated in matrix
On.In the present invention, the mass ratio of the flower-like nanometer composite material, ptfe emulsion and acetylene black be preferably 7.5~
8.5:1:1 further preferably 8:1:1.
In the present invention, the hybrid mode of the flower-like nanometer composite material, ptfe emulsion and acetylene black is preferred
For ground and mixed, the specific embodiment of ground and mixed is not particularly limited in the present invention, ripe using those skilled in the art institute
The method known.
In the present invention, described matrix is preferably foam nickel screen.The present invention is by flower-like nanometer composite material, polytetrafluoroethylene (PTFE)
The mixture of lotion and acetylene black is online coated in nickel foam, and the mixture is preferred in the online coating quality concentration of nickel foam
For 3~5mg/cm2。
After the completion of coating, coat is dried in the present invention, and the temperature of the drying is preferably 55~65 DEG C, further
Preferably 60 DEG C；The time of the drying is preferably 25~35min, further preferably 30min.
After the completion of drying, the present invention obtains electrode material to coat and foam nickel screen progress compressing tablet process after drying
Material.In the present invention, the pressure of the compressing tablet process is preferably 18~22MPa, further preferably 20MPa；At the tabletting
The time of reason is preferably 2min.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1
Using the graphite powder of 325 mesh as raw material, graphite oxide (GO) is prepared using improved Hummers method.Urea is ground,
It moves into crucible, wraps up crucible with masking foil, in 500 DEG C of calcining 3h of Muffle furnace high-temperature, in deionized water by product grinding
Ultrasonic disperse forms suspension, obtains the solution of 2.5mg/mL.It moves into the reaction kettle of polytetrafluoroethylene (PTFE), 180 DEG C of reaction 10h are obtained
To class graphite phase carbon nitride (g-C3N4).The graphite oxide (GO) of 50mg and the class graphite phase carbon nitride (g- of 50mg are weighed respectively
C3N4), it is ultrasonically treated in 100ml deionized water, ultrasonic time 30min, ultrasonic power 540W, obtains the outstanding of 1mg/mL
Supernatant liquid, by Ni (OH)2、g-C3N4It is that 16:1:1 is calculated and to weigh suitable nickel nitrate configuration nickel nitrate water-soluble with RGO mass ratio
Nickel nitrate aqueous solution is moved into graphite oxide (GO) and class graphite phase carbon nitride (g-C by liquid3N4) mixed liquor in, magnetic agitation shape
At homogeneous mixture solotion, a certain amount of concentrated ammonia liquor is added, adjusts solution ph 10 or so；Solution is transferred in polytetrafluoroethylene (PTFE)
In the reaction kettle of lining, room temperature is naturally cooled to after 180 DEG C of reaction 12h；Product separation, washing, drying, it is compound to obtain flower-like nanometer
Material, the specific surface area for the flower-like nanometer composite material that embodiment 1 obtains are 188m2/g。
Embodiment 2
Using the graphite powder of 325 mesh as raw material, graphite oxide (GO) is prepared using improved Hummers method.Urea is ground,
It moves into crucible, wraps up crucible with masking foil, in 500 DEG C of calcining 3h of Muffle furnace high-temperature, in deionized water by product grinding
Ultrasonic disperse forms suspension, obtains the solution of 2.5mg/mL.It moves into the reaction kettle of polytetrafluoroethylene (PTFE), 185 DEG C of reaction 10h are obtained
To class graphite phase carbon nitride (g-C3N4).The graphite oxide (GO) of 50mg and the class graphite phase carbon nitride (g- of 50mg are weighed respectively
C3N4), it is ultrasonically treated in 100ml deionized water, ultrasonic time 30min, ultrasonic power 540W, obtains the outstanding of 1mg/mL
Supernatant liquid, by Ni (OH)2、g-C3N4, RGO mass ratio be that 16:1:1 calculates and weigh suitable nickel nitrate configuration nickel nitrate aqueous solution,
Nickel nitrate aqueous solution is moved into graphite oxide (GO) and class graphite phase carbon nitride (g-C3N4) mixed liquor in, magnetic agitation is formed
Concentrated ammonia liquor is added in homogeneous mixture solotion, and adjusting solution ph is 11；Solution is transferred in the reaction kettle of polytetrafluoroethyllining lining,
Room temperature is naturally cooled to after 180 DEG C of reaction 14h；Product separation, washing, drying, obtain flower-like nanometer composite material, embodiment 2
The specific surface area of obtained flower-like nanometer composite material is 180m2/g。
Embodiment 3
Using the graphite powder of 325 mesh as raw material, graphite oxide (GO) is prepared using improved Hummers method.Urea is ground,
It moves into crucible, wraps up crucible with masking foil, in 550 DEG C of calcining 3h of Muffle furnace high-temperature, in deionized water by product grinding
Ultrasonic disperse forms suspension, obtains the solution of 2.5mg/mL.It moves into the reaction kettle of polytetrafluoroethylene (PTFE), 180 DEG C of reaction 10h are obtained
To class graphite phase carbon nitride (g-C3N4).The graphite oxide (GO) of 50mg and the class graphite phase carbon nitride (g- of 50mg are weighed respectively
C3N4), it is ultrasonically treated in 100ml deionized water, ultrasonic time 30min, ultrasonic power 540W, obtains the outstanding of 1mg/mL
Supernatant liquid, by Ni (OH)2、g-C3N4, RGO mass ratio be that 15.5:1:1 is calculated and to weigh suitable nickel nitrate configuration nickel nitrate water-soluble
Nickel nitrate aqueous solution is moved into graphite oxide (GO) and class graphite phase carbon nitride (g-C by liquid3N4) mixed liquor in, magnetic agitation shape
At homogeneous mixture solotion, concentrated ammonia liquor is added, adjusting solution ph is 9；Solution is transferred in the reaction kettle of polytetrafluoroethyllining lining,
Room temperature is naturally cooled to after 180 DEG C of reaction 10h；Product separation, washing, drying, obtain flower-like nanometer composite material, embodiment 3
The specific surface area of obtained flower-like nanometer composite material is 185m2/g。
Embodiment 4
Using the graphite powder of 325 mesh as raw material, graphite oxide (GO) is prepared using improved Hummers method.Urea is ground,
It moves into crucible, wraps up crucible with masking foil, in 600 DEG C of calcining 3h of Muffle furnace high-temperature, in deionized water by product grinding
Ultrasonic disperse forms suspension, obtains the solution of 2.5mg/mL.It moves into the reaction kettle of polytetrafluoroethylene (PTFE), 180 DEG C of reaction 10h are obtained
To class graphite phase carbon nitride (g-C3N4).The graphite oxide (GO) of 50mg and the class graphite phase carbon nitride (g- of 50mg are weighed respectively
C3N4), it is ultrasonically treated in 100ml deionized water, ultrasonic time 30min, ultrasonic power 540W, obtains the outstanding of 1mg/mL
Supernatant liquid, by Ni (OH)2、g-C3N4, RGO mass ratio be that 16.5:1:1 is calculated and to weigh suitable nickel nitrate configuration nickel nitrate water-soluble
Nickel nitrate aqueous solution is moved into graphite oxide (GO) and class graphite phase carbon nitride (g-C by liquid3N4) mixed liquor in, magnetic agitation shape
At homogeneous mixture solotion, concentrated ammonia liquor is added, adjusting solution ph is 10；Solution is transferred to the reaction kettle of polytetrafluoroethyllining lining
In, room temperature is naturally cooled to after 180 DEG C of reaction 8h；Product separation, washing, drying, obtain flower-like nanometer composite material, embodiment
The specific surface area of 4 obtained flower-like nanometer composite materials is 178m2/g。
Embodiment 5
Using the graphite powder of 325 mesh as raw material, graphite oxide (GO) is prepared using improved Hummers method.Urea is ground,
It moves into crucible, wraps up crucible with masking foil, in 500 DEG C of calcining 3h of Muffle furnace high-temperature, in deionized water by product grinding
Ultrasonic disperse forms suspension, obtains the solution of 2.5mg/mL.It moves into the reaction kettle of polytetrafluoroethylene (PTFE), 180 DEG C of reaction 10h are obtained
To class graphite phase carbon nitride (g-C3N4).The graphite oxide (GO) of 50mg and the class graphite phase carbon nitride (g- of 50mg are weighed respectively
C3N4), it is ultrasonically treated in 100ml deionized water, ultrasonic time 30min, ultrasonic power 540W, obtains the outstanding of 1mg/mL
Supernatant liquid, by Ni (OH)2、g-C3N4, RGO mass ratio be that 16:1:1 calculates and weigh suitable nickel nitrate configuration nickel nitrate aqueous solution,
Nickel nitrate aqueous solution is moved into graphite oxide (GO) and class graphite phase carbon nitride (g-C3N4) mixed liquor in, magnetic agitation is formed
Concentrated ammonia liquor is added in homogeneous mixture solotion, and adjusting solution ph is 10；Solution is transferred in the reaction kettle of polytetrafluoroethyllining lining,
Room temperature is naturally cooled to after 180 DEG C of reaction 6h；Product separation, washing, drying, obtain flower-like nanometer composite material, and embodiment 5 obtains
The specific surface area of the flower-like nanometer composite material arrived is 180m2/g。
Structural characterization and performance test
The flower-like nanometer composite material that Examples 1 to 5 is prepared carries out SEM test, test result with Fig. 1 class
Seemingly, it is no longer repeated herein.
In the present invention, the reaction time of class graphite phase carbon nitride, nickel nitrate and graphite oxide is 12h in embodiment 1, real
Applying example 2 is 14h, and embodiment 3 is 10h, and embodiment 4 is 8h, and embodiment 5 is 6h, is stated for convenience, and embodiment 1 is used " 12h "
It indicates, embodiment 2 is indicated with " 14h ", and embodiment 3 is indicated with " 10h ", and embodiment 4 is indicated with " 8h ", " 6h " table of embodiment 5
Show.
The test of FT-IR spectrogram, test result such as Fig. 5 are carried out to the flower-like nanometer composite material that Examples 1 to 5 is prepared
It is shown, wherein " 12h " represents embodiment 1, and " 14h " represents embodiment 2, and " 10h " represents embodiment 3, and " 8h " represents embodiment 4,
" 6h " represents embodiment 5.As shown in Figure 5, flower-like nanometer composite material has been prepared in the embodiment of the present invention 1~5.
XRD test is carried out to the flower-like nanometer composite material that Examples 1 to 5 is prepared, test results are shown in figure 6,
Wherein, " 12h " represents embodiment 1, and " 14h " represents embodiment 2, and " 10h " represents embodiment 3, and " 8h " represents embodiment 4, " 6h "
Represent embodiment 5.It will be appreciated from fig. 6 that flower-like nanometer composite material has been prepared in the embodiment of the present invention 1~5.
Test, test method can be carried out to the electrochemistry for the flower-like nanometer composite material that embodiment 1 is prepared are as follows: will
The flower-like nanometer composite material and ptfe emulsion and acetylene black (AR) that embodiment 1 is prepared are according to mass ratio 8:1:1
Mixing, is tuned into paste after grinding, equably smear and be bonded in that nickel foam is online, and 20MPa pressure lower sheeting is simultaneously kept 60 after 2min
DEG C vacuum drying 0.5h, be prepared into area be 1cm × 1cm electrode slice.For the electrode material of supercapacitor, its electricity is tested
Chemical property.Electrochemical property test uses the three-electrode system of standard, platinum plate electrode (15mm × 15mm) and saturation calomel electricity
Pole (SCE) is respectively as auxiliary electrode and reference electrode.Electrolyte is 6molL-1KOH solution, test before electrode need to balance
24h。
According to the test method of 1 chemical property of embodiment, the flower-like nanometer composite wood that embodiment 2~5 is prepared
The electrochemistry of material can be carried out test.
The flower-like nanometer composite material that embodiment 1 provides as electrode material cyclic voltammetry curve at different rates such as
Shown in Fig. 7, as shown in Figure 7, with the increase of sweep speed, electrode polarization is serious, and oxidation peak is mobile to positive direction, reduction peak to
Negative direction is mobile, and the potential difference Δ E and peak point current of oxidation peak and reduction peak increase, and increase electrode electro Chemical reaction can not
Inverse property.With increase of the sweep speed from 10mV/s to 200mV/s, the specific capacitance of 1 electrode material of embodiment declines therewith, but real
That applies 1 electrode material of example still has oxidation, reduction peak under big sweep speed, illustrates that 1 electrode material invertibity of embodiment is good
It is good.
GCD curve graph of the flower-like nanometer composite material that embodiment 1 provides as electrode material under different current densities
As shown in figure 8, as shown in Figure 8, with the increase of current density, the specific capacitance of 1 electrode material of embodiment is substantially reduced, and electrode
The discharge time of material reduces with the increase of current density, remains to discharge under conditions of 10A/g, illustrates electrode material i.e.
Make to remain to work normally in the case where larger current density.It is calculated by formula in 1A/g, 2A/g, 5A/g, 10A/g electricity
Specific capacitance under current density is respectively as follows: 543.8F/g, 540.7F/g, 423.1F/g, 353.6F/g.I.e. with the increasing of current density
Greatly, the specific capacitance of sample constantly reduces, this is caused by electrode material polarization.
Cyclical stability of the flower-like nanometer composite material that embodiment 1 provides as electrode material under 5A/g current density
Curve is as shown in figure 9, as shown in Figure 9, when cycle-index is when within 50 times, specific capacitance is gradually increased, and is recycled at latter 500 times
In, specific capacitance is almost undamped；And after 1000 charge and discharge cycles, before the specific capacitance of electrode material is by recycling
423.1F/g is reduced to 314.5F/g, and capacity retention ratio shows good stable circulation performance up to 74.3%.
Cyclic voltammetric of the flower-like nanometer composite material that Examples 1 to 5 provides as electrode material under 10mV/s rate
Curve is as shown in Figure 10, wherein " 12h " represents embodiment 1, and " 14h " represents embodiment 2, and " 10h " represents embodiment 3, " 8h " generation
Table embodiment 4, " 6h " represent embodiment 5.As shown in Figure 10, the oxidation peak of 1 electrode material of embodiment and the current potential of reduction peak are equal
It is smaller, illustrate that its oxygen evolution potential is higher, the charge efficiency of electrode is higher；Oxidation peak current is up to 0.13A, illustrates embodiment 1
The chemical property of electrode material is improved, and has preferable high rate performance.By calculating it is found that Examples 1 to 5 electrode material
The potential difference Δ E of material is respectively as follows: 0.269V, 0.285V, 0.293V, 0.308V, 0.331V, i.e. 1 electrode material Δ E value of embodiment
Minimum illustrates that the flower-like nanometer composite material that embodiment 1 provides has relatively best electrochemical reaction can as electrode material
Inverse property.
The flower-like nanometer composite material that Examples 1 to 5 provides is as shown in figure 11 as the AC impedance figure of electrode material,
In, " 12h " represents embodiment 1, and " 14h " represents embodiment 2, and " 10h " represents embodiment 3, and " 8h " represents embodiment 4, " 6h " generation
Table embodiment 5.As shown in Figure 11, Examples 1 to 5 electrode material is in high frequency region starting point and the solution resistance value of real axis intersection point point
Not Wei 0.401 Ω, 0.405 Ω, 0.459 Ω, 0.460 Ω, 0.468 Ω, the solution resistance of 5 electrode material of embodiment is maximum, real
The solution resistance for applying 1 electrode material of example is minimum.It is generally believed that the size and charge transfer resistance of half circular diameter are directly proportional, putting
It can be seen that half circular diameter of 1 electrode material of embodiment is minimum in big figure, show its charge transfer resistance minimum.Embodiment simultaneously
1 electrode material has the smallest Warburg impedance in the maximum slope of low frequency range straight line.
The flower-like nanometer composite material that Examples 1 to 5 provides is filled as constant current of the electrode material under 1A/g current density
Discharge curve is as shown in figure 12, wherein and " 12h " represents embodiment 1, and " 14h " represents embodiment 2, and " 10h " represents embodiment 3,
" 8h " represents embodiment 4, and " 6h " represents embodiment 5.As shown in Figure 12, current density of the Examples 1 to 5 electrode material in 1A/g
Under the conditions of specific capacitance be respectively as follows: 543.8F/g, 523.1F/g, 510.4F/g, 485.9F/g, 473.3F/g.Implemented by comparison
Known to the electrode material of example 1~5 five kind: the specific capacitance highest of 1 electrode material of embodiment.
In conclusion flower-like nanometer composite material provided by the invention has preferable stable circulation performance and higher energy
Metric density, flower-like nanometer composite material provided by the invention is under 5A/g current density, after 1000 charge and discharge cycles, electricity
The capacity retention ratio of pole material is up to 74.3%；Potential difference Δ E of the electrode material provided by the invention under 10mV/s rate are as follows:
0.269V~0.331V；Electrode material provided by the invention under the current density condition of 1A/g specific capacitance be 473.3F/g~
543.8F/g。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of flower-like nanometer composite material is answered by the material for including nickel hydroxide, class graphite phase carbon nitride and graphene oxide
Conjunction obtains；The specific surface area of the flower-like nanometer composite material is 170~190m2/g。
2. flower-like nanometer composite material according to claim 1, which is characterized in that the nickel hydroxide, class graphite-phase nitrogen
The mass ratio for changing carbon and graphene oxide is 15~17:0.5~1.5:0.5~1.5.
3. a kind of preparation method of flower-like nanometer composite material as claimed in claim 1 or 2, comprising the following steps:
(1) mixed liquor pH value is adjusted after mixing nickel nitrate, graphite oxide and class graphite phase carbon nitride in water to 9~11, is obtained
To dispersion liquid；
(2) in confined conditions, the dispersion liquid that the step (1) obtains is heated, obtains flower-like nanometer composite wood
Material.
4. preparation method according to claim 3, which is characterized in that adjust the mixed liquor pH value in the step (1)
Regulator be ammonium hydroxide, the concentration of the ammonium hydroxide is 10~15mol/L.
5. preparation method according to claim 3, which is characterized in that the temperature heated in the step (2) is 170
~190 DEG C, the time is 6~14h.
6. preparation method according to claim 3 or 4, which is characterized in that class graphite phase carbon nitride in the step (1)
Preparation method the following steps are included:
(a) urea is subjected to calcination processing, is dispersed in water after calcined product grinding, obtains suspension；
(b) in confined conditions, the suspension that the step (a) obtains is heated, obtains class graphite phase carbon nitride.
7. preparation method according to claim 6, which is characterized in that the temperature of calcination processing is 500 in the step (a)
~600 DEG C, the time is 2.5~3.5h.
8. preparation method according to claim 6, which is characterized in that the temperature heated in the step (b) is 170
~190 DEG C, the time is 9~11h.
9. a kind of electrode material, including matrix and active constituent；The active constituent is any one of claim 1~2 flower
The flower-like nanometer composite material that any one of shape nanocomposite or claim 3~8 preparation method are prepared.
10. the preparation method of electrode material described in claim 9, comprising the following steps:
Flower-like nanometer composite material is coated on matrix, then through dry and compressing tablet process, obtains electrode material.
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| CN111957335A (en) * | 2020-07-30 | 2020-11-20 | 太原理工大学 | Graphite phase carbon nitride composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111957335A (en) * | 2020-07-30 | 2020-11-20 | 太原理工大学 | Graphite phase carbon nitride composite material and preparation method and application thereof |
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