CN108538610A - A kind of preparation method and purposes of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material - Google Patents
A kind of preparation method and purposes of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material Download PDFInfo
- Publication number
- CN108538610A CN108538610A CN201810118594.4A CN201810118594A CN108538610A CN 108538610 A CN108538610 A CN 108538610A CN 201810118594 A CN201810118594 A CN 201810118594A CN 108538610 A CN108538610 A CN 108538610A
- Authority
- CN
- China
- Prior art keywords
- nickel
- nitrogen
- preparation
- porous carbon
- composite material
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material and preparation methods and purposes, and described method includes following steps：S1：Pyridine, hexachlorobutadiene and nickel source are subjected to confined reaction under the reaction pressure of superatmospheric；S2：After reaction, pressure release obtains sample to normal pressure after dry；S3：Sample is taken to carry out confined reaction under the reaction pressure of superatmospheric with urea liquid；S4：After reaction, pressure release after centrifugal drying, obtains sample to normal pressure；S4：The sample is subjected to high-temperature process under inert gas protection, to obtain the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material and preparation method.The three-dimensional globular nitrogen-doped carbon material has excellent chemical property, so as to be applied to chemical energy storage field, especially ultracapacitor field, has good industrialized value.
Description
Technical field
The present invention provides a kind of three-dimensional globular nitrogen-doped porous carbon materials and nickel oxide can be used for ultracapacitor
The preparation method and purposes of composite material, belong to inorganic functional material field, belong to inorganic composite materials field.
Background technology
As society continues to develop, energy problem is increasingly notable, and the mankind increasingly tend to for clean energy resource and can be again
The development and utilization in production-goods source.Demand of the people to the energy and require it is growing, energy supply shortage increasingly increase with people
There is serious contraventions between long energy demand.
Ultracapacitor is a kind of novel energy storage device, have power density is high, the charging time is short, have extended cycle life,
The advantages that environmentally protective, can be applicable on energy storage device, dynamic power system and many electronic equipments.According to energy storage mechnism
Difference, ultracapacitor are broadly divided into two classes:One kind is the double layer capacitor (EDLCs) using carbon material as electrode material,
By forming Helmholtz layers between electrode and electrolyte, electric energy is stored for electrostatically；Another kind of is with metal oxide
With faraday's capacitor that conducting polymer is electrode material, also known as pseudocapacitor or pseudocapacitors, using redox reaction,
Electrochemically store electric energy.The performance of ultracapacitor with its used in electrode material it is closely related, currently used three
Kind electrode material (carbon material, metal oxide, conducting polymer) respectively has advantage and disadvantage:Carbon material simple production process, price are low
Honest and clean, good cycle, but specific capacity is relatively low；Metal oxide and conducting polymer specific capacity are high, but of high cost, cyclical stability
It is bad.Studies have shown that above-mentioned different types of electrode material is carried out compound the shortcomings that can not only making up homogenous material, simultaneously
The mutual supplement with each other's advantages that can also realize material property, obtain device combination electrode material must have concurrently high power capacity, excellent cycling with it is forthright again
The super capacitor of energy.
Different electrode materials shows different electrochemical behaviors because it is with different characteristics, but on the whole,
The capacitance behavior of electrode material is influenced by its specific surface area and aperture.Recent studies indicate that the surface of porous carbon material
Chemical property is also an important factor for influencing its specific capacitance value, and it is a kind of into one to carry out Heteroatom doping to porous carbon electrode material
Step improves the effective ways of its capacitance behavior.It is concentrated for the Heteroatom doping research of porous carbon material for supercapacitor is main
In N doping, boron doping, phosphorus doping and oxygen doping etc..
Metal oxide materials ultracapacitor has many advantages, such as high power density, high specific capacitance, and its disadvantage is:
Quick faraday's reaction in charge and discharge process can cause material to undergo phase transition, volume expansion and dusting, largely reduced electrode
The high rate performance and cycle performance of material.
Therefore, the advantages of complex carbon material and metal oxide materials are come in combination with the two is as one studied now
Hot spot.Carbon material after compound while improving specific capacitance, keeps the original performance of carbon material.
In the early time there are also the research about carbon-based nickel oxide, for blended metal oxide and heteroatomic carbon-based multiple
Research that condensation material influences electrode material performance is comparatively also fewer can be for example listed below：
CN105460983A discloses a kind of preparation method of ultracapacitor cobalt acid nickel nano material, and steps are as follows:
(1) nickel nitrate, cobalt nitrate and urea are add to deionized water, are stirred under room temperature, so that solution is uniformly mixed, obtain solution A；
(2) sodium cetanesulfonate is added in solution A and micro KNO3, ultrasound is allowed to uniformly mixed, obtains solution B；(3) by solution
B is transferred in reaction kettle, carries out incubating solvent thermal response, is washed, and drying obtains presoma；(4) presoma is passed through in air
After 360 DEG C of -390 DEG C of constant temperature heat treatments, cobalt acid nickel nano material is obtained.The cobalt acid nickel nano material purity height of the present invention compares table
Area is big (68m2/g)；In charge-discharge test, in current density test, when current density is 1A/g, specific capacity value reaches
Relatively high value 2080F/g, specific capacity still maintains 93% or more after 3500 charge-discharge tests, can be used as super
Capacitor electrode material uses.
The CN102364811B present invention discloses a kind of nickel carbon supercapacitor activation method and device, and instruction is sent out by PC machine
It is respectively at charged state and discharge condition to MCU controls half activation unit；The both ends of DC charging power supply simultaneously connect chargeable
Battery, rechargeable battery connect PC machine by n activation unit of busbar parallel connection, each activation unit through communication bus；Individually
Activation unit includes nickel carbon supercapacitor, MCU, switching tube, inductance, current sensor；When charging, rechargeable battery is super to nickel carbon
Grade capacitor provides energy, and the electric energy of inductance charges to nickel carbon supercapacitor；When electric discharge, discharge current returns to the super electricity of nickel carbon
Container, rechargeable battery absorb the energy released when the electric discharge of nickel carbon supercapacitor；Impact of the charging unit to power grid can be reduced
Effect, the effectively save energy reduce the probability that electric energy is converted into thermal energy, avoid the accident caused by temperature, prevent to nickel
Injury caused by carbon supercapacitor.
CN102509614B is to be by nickel hydroxide the present invention relates to a kind of preparation method of high-energy nickel/carbon super capacitor
The positive plate of main active substances, alkali metal hydroxide aqueous electrolyte and hydrogen storing alloy powder are main living with active carbon material
Property material composition mixing negative plate and diaphragm seal constituted in stainless steel or engineering plastics shell, have energy storage density
Greatly, the features such as discharge power is high.This ultracapacitor operating voltage reaches 65Wh/kg up to 1.3V, maximum energy storage density, can be wide
General electrical source of power, vehicle cold-starting electrical source of power, the electrical source of power of military hardware, such as aviation applied to electric bus
Space flight, fighter plane, submarine, naval vessels etc. equip electricity container, portable device high-capacity are also applicable in, such as pen
Remember this computer, mobile phone, electric-tool container etc..Application field is related to vehicle, traffic, industry, aviation, military affairs, consumption
Electronics, green energy resource etc. have very extensive application prospect.
2014410174751.5 the invention discloses a kind of hydrotalcite/multi-walled carbon nanotube/nickel foam three-dimensional multistage structures
Thin-film electrode material and preparation method thereof.The present invention first synthesizes nickel aluminum water cunning using the method for growth in situ in foam nickel base
Stone thin-film material, then multi-walled carbon nanotube is grown on its surface, it is hydrophilized to obtain multi-wall carbon nano-tube periosteum/nickel foam
After processing, then hydro-thermal in situ synthesis is used, it is thin to obtain nickel aluminum hydrotalcite/multi-walled carbon nanotube/nickel foam three-dimensional multistage structure
Membrane material.The microstructure of the thin-film material is：Multi-walled carbon nanotube is grown in nickel foam substrate, and nickel aluminum hydrotalcite is grown in
Multi-wall carbon nano-tube pipe outer wall, this structure are known as " three-dimensional multistage structure ".The structure is close with thin-film material by foam nickel base
It is bonded one, it is not easily to fall off, it can be directly used as electrode, and large specific surface area, therefore be adapted for use as electrochemical capacitance electrode material
Material.
Although as described above, disclosing various carbon materials (such as carbon nanotube and graphene) and nickel oxide in the prior art
Compound method, but these have some disadvantages in the prior art, such as of high cost, synthetic method is excessively complicated etc., and
For can magnanimity synthesis nickel oxide and N doping carbon plate it is compound, obtain the composite material report of N doping carbon plate and nickel oxide
And it is few.
Therefore, how to design a kind of simple, economy can magnanimity synthetic method prepare N doping carbon plate and Nie's oxidation
The composite material of object, to play synergistic effect between the two, the electrochemistry for changing composite material energy density, promoting material
Performance, and apply it in ultracapacitor, there is highly important research significance, this is also exactly that the present invention is accomplished
Basis and power where.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of three-dimensional globular nitrogen-doped porous carbons
The preparation method and purposes of material and nickel oxide composite material, can prepare novel composite material, especially can be used for
The composite material in ultracapacitor field.
The purpose of the present invention is realized using following technical scheme：
Specifically, technical scheme of the present invention and content are related to a kind of three-dimensional globular nitrogen-doped porous carbon material and nickel oxygen
Compound composite material and preparation method and purposes.
More particularly it relates to following many aspects.
The first aspect, the present invention relates to a kind of three-dimensional globular nitrogen-doped porous carbon materials and nickel oxide composite material
Preparation method, described method includes following steps：
S1：Pyridine, hexachlorobutadiene and nickel source are subjected to confined reaction under the reaction pressure of superatmospheric；
S2：After reaction stops, removal reaction excess of solvent obtains sample after drying；
S3：Gained sample is mixed with urea liquid, and carries out confined reaction under the reaction pressure of superatmospheric；
S4：After reaction stops, high speed centrifugation obtains sample after drying；
S5：The sample is subjected to high-temperature process under inert gas protection, it is porous to obtain the three-dimensional globular N doping
Carbon material and nickel oxide composite material.
In the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material of the present invention, in step S1
In, reaction temperature is 140-260 DEG C, may be, for example, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C or 260 DEG C, excellent
It is selected as 180-220 DEG C, most preferably 200 DEG C.
In the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material of the present invention, at the high temperature
The temperature of reason is 700-1100 DEG C, preferably 700-900 DEG C, most preferably 800 DEG C.
In the three-dimensional globular nitrogen-doped porous carbon material of the present invention and the preparation method of nickel oxide composite material,
In step sl, the reaction pressure is 1-5MPa, may be, for example, 1MPa, 2MPa, 3MPa, 4MPa or 5MPa.
In the three-dimensional globular nitrogen-doped porous carbon material of the present invention and the preparation method of nickel oxide composite material,
In step sl, the reaction time is 2-10 hours, may be, for example, 2 hours, 4 hours, 6 hours, 8 hours or 10 hours, preferably 5
Hour.
In the three-dimensional globular nitrogen-doped porous carbon material of the present invention and the preparation method of nickel oxide composite material,
In step sl,
In the three-dimensional globular nitrogen-doped porous carbon material of the present invention and the preparation method of nickel oxide composite material, in step
In rapid S3, the high-temperature process time is 1-3 hours, be may be, for example, 1 hour, 2 hours or 3 hours.
In the three-dimensional globular nitrogen-doped porous carbon material of the present invention and the preparation method of nickel oxide composite material, in step
It is elemental nickel, nickel acetate, nickel acetate (four water), nickelous-nickelic oxide, nickel sulfate, nickel nitrate and six water nickel nitrates that nickel source is obtained in rapid S1
Deng most preferably elemental nickel.
In the three-dimensional globular nitrogen-doped porous carbon material of the present invention and the preparation method of nickel oxide composite material,
In step s 4, the inert gas is nitrogen or argon gas.
The inventors discovered that when using preparation method so, the three-dimensional ball with superior electrical performance can be obtained
Shape nitrogen-doped porous carbon material and nickel oxide composite material, and when changing certain technological parameters, energy-storage property is caused to have
It significantly reduces.
The second aspect, the present invention relates to the three-dimensional globular nitrogen-doped porous carbon material obtained by above-mentioned preparation method with
Nickel oxide composite material.
The inventors discovered that the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material are with excellent
Electric property has a good application prospect and industrial so as to be applied to electrochemical energy storage, especially ultracapacitor field
Change potentiality.
Therefore, in terms of third, the present invention relates to the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide are compound
Purposes of the material in preparing capacitor.
In the described on the way of the present invention, the three-dimensional globular nitrogen-doped porous carbon material is used with nickel oxide composite material
To prepare electrode for capacitors.
4th aspect, it is multiple with nickel oxide comprising the three-dimensional globular nitrogen-doped porous carbon material that the present invention relates to one kind
The electrode for capacitors of condensation material, especially electrode of super capacitor.
Inventors discovered through research that including the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material
Electrode for capacitors there is good chemical property, such as large capacity, high power, long-life, of low cost, environmental-friendly etc.
Superior performance, so as to be applied to capacitor especially ultracapacitor field.
5th aspect, the invention further relates to a kind of preparation methods of electrode for capacitors, and described method includes following steps：
(A) three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material, acetylene black and PTFE (polytetrafluoros are weighed
Ethylene) lotion, appropriate N-methyl pyrrolidones is added, is uniformly mixed, when being stirred continuously into starchiness, is coated onto in nickel foam；
The nickel foam that (B) will coat three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material is dried,
Drying, tabletting are to get to the electrode for capacitors.
Wherein, in the preparation method of electrode for capacitors of the present invention, in the step (A), the three-dimensional globular
The mass ratio of nitrogen-doped porous carbon material and nickel oxide composite material, acetylene black and PTFE emulsion is 80:10:10.
Wherein, in the preparation method of electrode for capacitors of the present invention, in the step (A), the PTFE (poly- four
Vinyl fluoride) lotion is electrode preparation field commonly known raw material, can be commercially-available by multiple channel, herein no longer one by one
It repeats.
Wherein, in the preparation method of electrode for capacitors of the present invention, in the step (A), the n-formyl sarcolysine that is added
The dosage of base pyrrolidones is not particularly limited, and dosage belongs to the routine techniques of capacitor area, herein no longer one by one
It repeats.
Wherein, in the preparation method of electrode for capacitors of the present invention, the preparation manipulation of the step (B) belongs to capacitance
Conventional technical means in device field, this is no longer going to repeat them.
As described above, the present invention provides a kind of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material and
Preparation method and use, the three-dimensional globular nitrogen-doped porous carbon material have excellent electrification with nickel oxide composite material
Performance is learned, there is huge application potential and industrial value in energy storage field.
Description of the drawings
Fig. 1 is the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material obtained by the embodiment of the present invention 1
Scanning electron microscope (SEM) photograph (SEM).
Fig. 2 is the Raman of the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material of the embodiment of the present invention 1
Figure.
Fig. 3 is the XPS of the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material of the embodiment of the present invention 1
Figure.
Fig. 4 is the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material obtained by the embodiment of the present invention 1
XPS high-resolution C1s spectrograms.
Fig. 5 is the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material obtained by the embodiment of the present invention 1
XPS high resolution N1s spectrograms.
Fig. 6 is the XPS high of the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material of the embodiment of the present invention 1
Resolution, N i 2p spectrograms.
Fig. 7 is the XRD of the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material of the embodiment of the present invention 1
Figure.
Fig. 8 is the N of the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material of the embodiment of the present invention 12It inhales
Desorption curve.
Fig. 9 is using the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material in the embodiment of the present invention
Prepared by C1, C8-10 CV comparison diagram of the electrode of super capacitor under 100mV/s sweep speeds.
Figure 10 is using the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material in the embodiment of the present invention
Prepared by C1, C5-7 CV comparison diagram of the electrode of super capacitor under 100mV/s sweep speeds.
Figure 11 is using the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material in the embodiment of the present invention
Prepared by C1-4 CV comparison diagram of the electrode of super capacitor under 100mV/s sweep speeds.
Figure 12 is the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material C1 using the embodiment of the present invention 1
Prepared by electrode for capacitors the charging and discharging curve under current density.
Figure 13 is the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material C1 using the embodiment of the present invention 1
Prepared by electrode for capacitors the cyclic voltammogram under different scanning rates.
Specific implementation mode
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not constitutes any type of any restriction to the real protection scope of the present invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
Embodiment 1
S1：28ml pyridines, 2ml hexachlorobutadienes and 0.5g nickel sources are carried out under the reaction pressure of superatmospheric closed
Reaction；
S2：After reaction stops, removal reaction excess of solvent obtains sample after drying；
S3：Gained sample is mixed with urea liquid, and carries out confined reaction under the reaction pressure of superatmospheric；
S4：After reaction stops, high speed centrifugation obtains sample after drying；
S5：The sample is carried out to 800 DEG C of processing of high temperature under inert gas protection, obtains the three-dimensional globular N doping
Porous carbon materials and nickel oxide composite material.It is named as C1.
Embodiment 2-4：The investigation of step S3 high temperature treatment temperatures
In addition to 800 DEG C of high-temperature process temperature in step S3 are replaced with 600 DEG C, 700 DEG C and 900 DEG C respectively, Qi Tacao
Work is constant, to sequentially be carried out a C2-C4.
Embodiment 5-7：The investigation of reaction raw materials ratio in step S1
Except by addition to the mass ratio of the elemental nickel in the raw material of step S1, other operations are constant, the quality of elemental nickel be 0g,
1g, 2g, to sequentially be carried out a C5-C7.
Embodiment 8-10：Reaction raw materials reaction ratio in step S1
Except by addition to the reaction ratio of the solvent heat in step S1, other operations are constant, pyridine and hexachlorobutadiene it is anti-
It is 24 to answer ratio according to this：6,26：4,29：1, and sequentially it is carried out a C8-C10.
Embodiment 11-14：The investigation in reaction time in step S1
Except by addition to the reaction time in the raw material of step S1, other operations are constant, the reaction time be followed successively by 160 DEG C, 180
DEG C, 200 DEG C, 220 DEG C, and sequentially carry out C11-C14.
Embodiment 15-18：The investigation in reaction time in step S3
Except by addition to the reaction time in the raw material of step S3, other operations are constant, the reaction time be followed successively by 160 DEG C, 180
DEG C, 200 DEG C, 220 DEG C, and sequentially carry out C15-C18.
Embodiment 19-23：The investigation of the concentration of raw material in step S3
Except by addition to the concentration of the raw material urea of step S3, other operations are constant, urea concentration be followed successively by 2mol/kg,
6mol/kg, 10mol/kg, 14mol/kg, 18mol/kg, and sequentially carry out C19-C23.
The preparation of electrode for capacitors
The preparation method of the electrode for capacitors includes the following steps：
(A) three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material, acetylene black, PTFE (polytetrafluoros are weighed
Ethylene) (three's mass ratio is 80 to lotion:10:10) appropriate N-methyl pyrrolidones, is added, is uniformly mixed, is stirred continuously and is slurried
When paste, it is coated onto in nickel foam；
The nickel foam that (B) will coat three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material is dried,
Drying, tabletting are to get to the electrode for capacitors.
Microscopic sdIBM-2+2q.p.approach
The three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material to 1 gained of embodiment have carried out more
The microscopic sdIBM-2+2q.p.approach of a means of different, it is as a result as follows：
1, it is the three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material obtained by the embodiment of the present invention 1
Scanning electron microscope (SEM) photograph (SEM).From SEM figures it can be seen that the material is three-dimensional globular structure.
2, from the Raman of Fig. 2 figures as can be seen that C1 three-dimensional globulars nitrogen-doped porous carbon material and nickel oxide composite material
It is a kind of three-dimensional structure that defect level is larger, the larger three-dimensional porous structure of this defect level makes material have more hole
Road structure, the electric conductivity of reinforcing material and the wellability of electrolyte.
3, schemed by the XPS of Fig. 3 it is found that thus being calculated containing C element, N element, Ni elements and O elements, root in the C1
The content of four kinds of elements is respectively 85.59%, 9.06%, 0.22%, 4.86%, the content of Cl elements is seldom, can ignore not
Meter.
4, by the XPS of Fig. 4 figure it is found that bond energy 284.85eV be C-C keys, 286.39eV be C-N keys.
5, by the XPS of Fig. 5 figure it is found that bond energy 398.49eV be pyridine nitrogen, 399.49eV is pyrroles N, and 400.9eV is stone
The nitrogen of inkization.
6, by the XPS of Fig. 6 figures it is found that bond energy in 873.95eV and 860.93 is Ni keys, bond energy in 855.16eV and
881.903eV being Ni-O keys.
7, can be seen that three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material from the XRD diagram of Fig. 7 is one
Kind undefined structure, this undefined structure is more advantageous to the quick embedded and export of ion or proton, suitable for doing electrode material,
There are the diffraction maximums of Ni and NiO in material simultaneously, corresponding with XPS, illustrate the oxidation that simple substance Ni and Ni is implicitly present in material
Object.
8, by the N of Fig. 82Adsorption desorption curve is it is found that C1 three-dimensional globulars nitrogen-doped porous carbon material and nickel oxide composite wood
The specific surface area of material is larger, reaches 235m2/g.Pore-size distribution is mainly in micropore and mesoporous state simultaneously.
Above-mentioned all characterizations of C2-C10 obtained by embodiment 2-10 are all highly identical to C1, and (there is only measurement experiment mistakes
Difference), therefore under the premise of height is similar, each collection of illustrative plates is no longer listed one by one.
Electrochemical property test
1, Fig. 9 is C1, the three-dimensional globular nitrogen-doped porous carbon material of C8-10 and electricity prepared by nickel oxide composite material
The CV figures under the sweep speed of 100mV/s of container electrode.It can be seen from the figure that C1 compares, other materials have higher
Specific capacitance.
2, prepared by Figure 10 is C1, and the three-dimensional globular nitrogen-doped porous carbon material of C5-C7 is with nickel oxide composite material
Electrode for capacitors is schemed in the CV under the sweep speed of 100mV/s.It can be seen from the figure that C1 compares, other materials have more
High specific capacitance.
3, prepared by Figure 11 is C1, and the three-dimensional globular nitrogen-doped porous carbon material of C2-C4 is with nickel oxide composite material
Electrode for capacitors is schemed in the CV under the sweep speed of 100mV/s.It can be seen from the figure that C1 compares, other materials have more
High specific capacitance.
4, Figure 12 is the constant current charge-discharge curve (20A/g, 10A/g, 5A/g, 2A/g, 1A/g) of C1.From constant current charge and discharge
It is close in the electric current of 20A/g it will be seen that it is 183.6F/g that C1 is computed capacitance under the current density of 1A/g in the figure of electricity
Spend charge and discharge, be computed capacitance and remain as 109.1F/g, to demonstrate the material can in charge and discharge under high current density,
Show excellent charge-discharge performance.
4, Figure 13 is the cyclic voltammetry curve under the different scanning rates of C1.We can from cyclic voltammetry curve
Go out, for C1 under the sweep speed of 1mV/s, it is that 218.8F/g is computed under the sweep speed of 100mV/s to be computed capacitance
Capacitance still has 124.2F/g, still protects time good rectangle to demonstrate the material under the rate that exposes thoroughly, illustrates to show
Excellent electric double layer performance is gone out.
By above-mentioned Fig. 4-6 as it can be seen that the obtained three-dimensional globular nitrogen-doped porous carbon material of the method for the present invention and nickel oxide
Composite material has excellent chemical property, the electrode material of capacitor especially ultracapacitor is thus can be used as, in electricity
Chemical field has a good application prospect and industrial production potential.
The microscopic sdIBM-2+2q.p.approach of composite material obtained by other embodiments
A, the characterization of C2-C6 is found, microscopic pattern height is similar to C1, while also height is similar for its chemical property
In the chemical property of C1.But due to high similarity and for simplicity, no longer list one by one herein all microcosmic
Phenogram and chemical property figure.
In conclusion selection of the present invention by suitable reactants and condition, and synthesize and obtained three-dimensional globular N doping
Porous carbon materials and nickel oxide composite material, by the study found that the composite material has excellent chemical property, tool
There are good industrial applications potentiality and market value.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limitation protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or modification, all these equivalent forms equally fall within and are protected defined by the application the appended claims
Within the scope of shield.
Claims (10)
1. a kind of preparation method of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material, which is characterized in that institute
The method of stating includes the following steps：
S1：Pyridine, hexachlorobutadiene and nickel source are subjected to confined reaction under the reaction pressure of superatmospheric；
S2：After reaction stops, removal reaction excess of solvent obtains sample after drying；
S3：Gained sample is mixed with urea liquid, and carries out confined reaction under the reaction pressure of superatmospheric；
S4：After reaction stops, high speed centrifugation obtains sample after drying；
S5：The sample is subjected to high-temperature process under inert gas protection, obtains the three-dimensional globular nitrogen-doped porous carbon
Material and nickel oxide composite material.
2. preparation method as described in claim 1, which is characterized in that in step sl, reaction temperature is 140-260 DEG C.
3. preparation method as claimed in claim 1 or 2, which is characterized in that in step s 2, the example reaction time is 2-10h.
4. preparation method as claimed in claim 3, which is characterized in that in step s 5, the temperature of the high-temperature process is
700-1100℃。
5. preparation method as claimed in claim 4, which is characterized in that in step sl, the pyridine and hexachlorobutadiene
Volume ratio is 1:1~15:1 or 1:1~1:15.
6. preparation method as claimed in claim 5, which is characterized in that in step sl, the mass ratio of the pyridine and nickel source
It is 3:1 or 6:1~30:1,.
7. preparation method as claimed in claim 6, which is characterized in that in step sl, described to be containing nickel source：Elemental nickel, vinegar
Sour nickel, nickel acetate (four water), nickelous-nickelic oxide, nickel sulfate, nickel nitrate or six water nickel nitrates.
8. preparation method as claimed in claim 7, which is characterized in that in step s3, a concentration of 1mol/L of urea liquid
~15mol/L.
9. the three-dimensional globular nitrogen-doped porous carbon material and nickel that are obtained such as preparation method described in any item of the claim 1 to 8
The purposes of oxide composite, which is characterized in that the composite material is used for electrode for capacitors.
10. the preparation method of electrode for capacitors as claimed in claim 9, which is characterized in that described method includes following steps：
(A) three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material and acetylene black are weighed, appropriate N-methyl is added
Pyrrolidones is uniformly mixed, appropriate PTFE (polytetrafluoroethylene (PTFE)) lotion is added, when being stirred continuously into starchiness, is coated onto nickel foam
On；
The nickel foam that (B) will coat three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material is dried, dries,
Tabletting is to get to the electrode for capacitors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810118594.4A CN108538610A (en) | 2018-02-06 | 2018-02-06 | A kind of preparation method and purposes of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810118594.4A CN108538610A (en) | 2018-02-06 | 2018-02-06 | A kind of preparation method and purposes of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108538610A true CN108538610A (en) | 2018-09-14 |
Family
ID=63485891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810118594.4A Pending CN108538610A (en) | 2018-02-06 | 2018-02-06 | A kind of preparation method and purposes of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108538610A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110867325A (en) * | 2019-11-12 | 2020-03-06 | 温州大学 | Nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere as well as preparation method and application thereof |
| CN115394562A (en) * | 2022-08-23 | 2022-11-25 | 深圳市乐汇通科技有限公司 | Nitrogen-doped porous carbon-loaded pompon NiO composite electrode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509786A (en) * | 2011-10-11 | 2012-06-20 | 北京化工大学 | Porous metal oxide-carbon composite thin film electrode and preparation method thereof |
| CN104966625A (en) * | 2015-07-31 | 2015-10-07 | 西安科技大学 | N-doped porous carbon/NiO composite material and preparation method therefor |
| CN105591090A (en) * | 2016-03-04 | 2016-05-18 | 河源广工大协同创新研究院 | Preparation method of zinc oxide/nitrogen-doped carbon composite material capable of being used for lithium ion battery negative electrode |
-
2018
- 2018-02-06 CN CN201810118594.4A patent/CN108538610A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509786A (en) * | 2011-10-11 | 2012-06-20 | 北京化工大学 | Porous metal oxide-carbon composite thin film electrode and preparation method thereof |
| CN104966625A (en) * | 2015-07-31 | 2015-10-07 | 西安科技大学 | N-doped porous carbon/NiO composite material and preparation method therefor |
| CN105591090A (en) * | 2016-03-04 | 2016-05-18 | 河源广工大协同创新研究院 | Preparation method of zinc oxide/nitrogen-doped carbon composite material capable of being used for lithium ion battery negative electrode |
Non-Patent Citations (3)
| Title |
|---|
| 石油化学工业部化工设计院主编: "《氮肥工艺设计手册 理化数据分册》", 31 December 1977, 化学工业出版社 * |
| 蔺洁: ""Fe_N_C复合材料的宏量合成及其在能量储存与转换中的应用研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 黄玉媛等编: "《精细化工配方常用原料手册》", 31 March 1998, 广东科技出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110867325A (en) * | 2019-11-12 | 2020-03-06 | 温州大学 | Nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere as well as preparation method and application thereof |
| CN115394562A (en) * | 2022-08-23 | 2022-11-25 | 深圳市乐汇通科技有限公司 | Nitrogen-doped porous carbon-loaded pompon NiO composite electrode material and preparation method thereof |
| CN115394562B (en) * | 2022-08-23 | 2024-03-29 | 深圳市乐汇通科技有限公司 | Nitrogen-doped porous carbon-loaded pompon NiO composite electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106744794B (en) | A kind of sheet nitrogen-phosphor codoping porous carbon materials and preparation method thereof and purposes | |
| Li et al. | Porous nanotubes derived from a metal-organic framework as high-performance supercapacitor electrodes | |
| CN106206065B (en) | A kind of electrode material for super capacitor MnO2The preparation method of@PDA nanocomposites | |
| Zhang et al. | Synthesis of honeycomb-like NiS2/NiO nano-multiple materials for high performance supercapacitors | |
| Ye et al. | In-situ growth of Se-doped NiTe on nickel foam as positive electrode material for high-performance asymmetric supercapacitor | |
| CN104008888A (en) | Preparation method of composite material and electrode slice for super capacitor | |
| Guo et al. | Facile fabrication of CoNi-Layered Double Hydroxide/NiCo2S4/Reduced Graphene Oxide composites by in situ hydrothermal growth strategy for supercapacitor performance | |
| CN108545712A (en) | A method of synthesizing multi-stage porous carbon material with salt template carbonization ZIF-8 | |
| CN107804833A (en) | A kind of three-dimensional netted nitrogen phosphorus sulphur codope porous carbon materials and preparation method and purposes | |
| Wu et al. | Hierarchical mesoporous MoO2 sphere as highly effective supercapacitor electrode | |
| Yang et al. | Nanoengineering of ZnCo2O4@ CoMoO4 heterogeneous structures for supercapacitor and water splitting applications | |
| Liu et al. | Mesoporous NH4NiPO4· H2O for high-performance flexible all-solid-state asymmetric supercapacitors | |
| Chang et al. | Synthesis of hierarchical hollow urchin-like HGRs/MoS2/MnO2 composite and its excellent supercapacitor performance | |
| CN109036860A (en) | A kind of ferroso-ferric oxide/single angle combination electrode material and preparation method thereof | |
| Liu et al. | Hexadecyl trimethyl ammonium bromide assisted growth of NiCo 2 O 4@ reduced graphene oxide/nickel foam nanoneedle arrays with enhanced performance for supercapacitor electrodes | |
| Luo et al. | Preparation of NiMoO4 nanoarrays electrodes with optimized morphology and internal crystal water for efficient supercapacitors and water splitting | |
| CN108538610A (en) | A kind of preparation method and purposes of three-dimensional globular nitrogen-doped porous carbon material and nickel oxide composite material | |
| Rutavi et al. | Two‐step electrodeposition of Hausmannite sulphur reduced graphene oxide and cobalt‐nickel layered double hydroxide heterostructure for high‐performance supercapacitor | |
| CN106710891B (en) | A kind of NiCo2O4The preparation method of/absorbent charcoal composite material | |
| CN108666144A (en) | A kind of three-dimensional flower-shaped cobalt hydroxide-graphene composite material and preparation method thereof | |
| Zhao et al. | Fabrication of 3D micro-flower structure of ternary Ni-Co-Cu hydroxide based on Co-MOF for advanced asymmetric supercapacitors | |
| Li et al. | MnO2 nanosilks self-assembled micropowders: facile one-step hydrothermal synthesis and their application as supercapacitor electrodes | |
| CN114709086A (en) | Nickel-based metal organic framework layered nanosheet array material and preparation and application thereof | |
| CN100552841C (en) | Composite super capacitor and manufacture method thereof based on cobalt oxide and ruthenium-oxide | |
| Song et al. | Facile synthesis of γ-MnO2/rice husk-based-activated carbon and its electrochemical properties |
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 |
Application publication date: 20180914 |
|
| RJ01 | Rejection of invention patent application after publication |