CN106683907A - Graphene/phthalocyanine supercapacitor electrode material, and preparation method thereof - Google Patents
Graphene/phthalocyanine supercapacitor electrode material, and preparation method thereof Download PDFInfo
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- CN106683907A CN106683907A CN201611179205.6A CN201611179205A CN106683907A CN 106683907 A CN106683907 A CN 106683907A CN 201611179205 A CN201611179205 A CN 201611179205A CN 106683907 A CN106683907 A CN 106683907A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a graphene/phthalocyanine supercapacitor electrode material, and a preparation method thereof. The method mainly comprises the following steps: obtaining graphene oxide (GO) through the chemical oxidation method, and using p-phenylenediamine (pPD) as a reducing agent to obtain reduced GO-pPD (rGO-pPD) under the action of strong ammonia water; and carrying out azo-coupling reaction of the rGO-pPD and 2,9,16,23-tetraamino nickel (II) phthalocyanine (NiTAPc) with outstanding photoelectric property to obtain a covalently grafted binary composite material, i.e., rGO-p-Pc. The material and the preparation method thereof provided by the invention have the advantages that the method is simple and convenient to operate, and the yield rate reaches 95%; and the specific capacitance of the electrode material reaches 600F.g<-1>, and the cyclic stability is high.
Description
Technical field
The invention belongs to electrode material for super capacitor preparation field, and in particular to a kind of super electricity of graphene/nickel phthalocyanine
Container electrode material and preparation method thereof.
Background technology
Increasing proportion is occupied in human lives with various electronic products, people are lasting to the electricity of power supply
Property, charge rate and security have requirement higher, it is therefore desirable to exploitation charge-discharge velocity with more Large Copacity and faster
Storing up electricity product.Ultracapacitor（supercapacitor）It is a kind of novel energy-storing for connecting traditional capacitor and battery
Device, with high power density, the long life, it is safe the characteristics of.The species of electrode material is influence performance of the supercapacitor
Principal element, current electrode material mainly includes：Carbon-based material, metal（Hydrogen）Oxygen/sulfide and conducting polymer, this
Outward, some nitrogenous abundant materials are equally applicable for wherein.Phthalocyanine（Phthalocyanines, Pcs）It is nitrogenous abundant chemical combination
Thing, used as the derivative of porphyrin, the big ring conjugated structure of plane of the electronics of phthalocyanine 18 is allowed to have very excellent photoelectric activity, phthalein
Cyanines can be coordinated with nearly all metal, in metal phthalocyanine, when central atom is some transition elements such as Co, Ni, in electricity
These elements can occur the change of valence state under field action；The abundant N atoms of phthalocyanine can also provide certain fake capacitance；Additionally, phthalein
There is certain semiconductor property after cyanines doping, this 3 points be metal phthalocyanine in electrode material for super capacitor applying and provide
Advantage.
After after CNTs/ metal phthalocyanine compounds are applied into ultracapacitor, Ozoemena etc. by nitrogenous abundant Co () composite of azepine phthalocyanine and graphene oxide GO is used as supercapacitor positive electrode, GO/ carbon blacks are used as negative pole, Yi Jizhong
Property Na2SO4The aqueous solution is assembled into Asymmetric Supercapacitor as electrolyte.Under bipolar electrode test system, the material has height
Specific capacitance（500 F·g-1）, energy density（44 W·h·kg-1）And power density（31 kW·kg-1）.The material
Fake capacitance mostly come from the N that enriches in oxy radical, Co azepine phthalocyanines on GO and central coordinated metal Co () oxygen
Change reduction act.
The research of carbon material and one or more fake capacitance Material cladding is very more.Relevant carbon material/metal phthalocyanine is combined
Thing is made in the report of electrode material, mainly multi-walled carbon nano-tubes, being combined between graphene oxide and metal phthalocyanine, and reduces
The research of Graphene/metal phthalocyanine combination electrode material is still blank.The present invention is first by functionalization reduced graphene（rGO-
pPD）With tetramino W metal phthalocyanine（NiTAPc）The compound electrode material as ultracapacitor.
The content of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of graphene/nickel phthalocyanine electrode of super capacitor material
Material and preparation method thereof, the method is answered reduced graphene and ammonobase phthalocyanine using Diazotization-coupling reaction simple and easy to apply
Close ,-N=N- the double bonds for being generated can be with phthalocyanine ring or the p-phenylenediamine of functionalization graphene（pPD）Phenyl ring is conjugated, and is conducive to electricity
The transmission of lotus, can be used as electrode material.
The purpose of the present invention is achieved through the following technical solutions.
The present invention passes through diazonium coupling method（azo-coupling reaction）By the reduction of p-phenylenediamine functionalization
Graphene（rGO-pPD）With tetramino W metal phthalocyanine（NiTAPc）Covalent coupling gets up.
The present invention is composited and including following synthesis step with Graphene and nickel phthalocyanine.First, by graphene oxide with right
Phenylenediamine（pPD）Functionalization is reduced and carried out, the reduced graphene rGO-pPD of p-phenylenediamine functionalization is finally given.2nd, with urine
Element, 4- nitrophthalic acids, nickel salt, ammonium chloride are raw material, with ammonium molybdate as catalyst, tetranitro are prepared using organic solvent
Nickel phthalocyanine（NiTNPc）.3rd, NiTNPc is reduced to tetra amino nickel phthalocyanine with gentle reducing agent（NiTAPc）.4th, by function
Change rGO-pPD carries out Diazotization-coupling reaction and is finally produced in organic solvent with the diazonium salt solution of the NiTAPc for preparing
Thing, the functionalization graphene of nickel phthalocyanine covalence graft（rGO-p-Pc）.
A kind of preparation method of graphene/nickel phthalocyanine electrode material for super capacitor, specifically includes following steps：
（1）The preparation of functionalization reduced graphene：Graphene oxide is dispersed in water, p-phenylenediamine is added, ultrasonic disperse,
Then add concentrated ammonia liquor, 70 ~ 100 DEG C of 6 ~ 24 h of reaction to be washed after the completion of reaction, dried in the case of backflow, obtain functionalization also
Former Graphene；Concentrated ammonia liquor is added in the preparation process of functionalization reduced graphene, is conducive to the carrying out of necleophilic reaction；
（2）The preparation of tetranitro nickel phthalocyanine：Urea, 4- nitrophthalic acids, nickel salt, ammonium chloride are sequentially added to flask
In, catalyst ammonium molybdate and solvent nitrobenzene are added under counterflow condition, 20 ~ 60 min are reacted at being heated to 120 ~ 170 DEG C, then
Filtered after being warming up to 170 ~ 200 DEG C of 3 ~ 8 h of reaction, washing, then filter cake is soaked in watery hydrochloric acid boils, filtered, added
NaOH solution is heated to 60 ~ 95 DEG C and is released to without ammonia, and product centrifugation, washing is dried, and obtains tetranitro nickel phthalocyanine；
（3）The preparation of tetra amino nickel phthalocyanine：Tetranitro nickel phthalocyanine is dispersed in water, Na is added2S·9H2O, at 40 ~ 60 DEG C
4 ~ 10 h of reaction, product is washed, and is dried, and obtains 2,9,16,23- tetra amino nickel phthalocyanines（2,9,16,23-tetraamino
Nickel (II) phthalocyanine, NiTAPc）；
（4）The preparation of graphene/nickel phthalocyanine electrode material for super capacitor：Functionalization reduced graphene is dispersed in N, N- diformazans
In base formamide DMF, ice bath after ultrasound obtains rGO-pPD organic dispersions；Tetra amino nickel phthalocyanine is scattered in watery hydrochloric acid, it is cold
But, NaNO is added2The aqueous solution, obtains NiTAPc diazonium salt solutions；NiTAPc diazonium salt solutions are added to organic point of rGO-pPD
In dispersion liquid, the h of magnetic agitation 6 ~ 24, filtering, washing is dried, and obtains graphene/nickel phthalocyanine electrode material for super capacitor.
Preferably, step（1）The time of the ultrasonic disperse is 1h.
Preferably, step（1）The graphene oxide is 1 with the mass ratio of p-phenylenediamine:3~3:1, more preferably
1：1；Graphene oxide is 5 with the mass ratio of concentrated ammonia liquor:1~3:1, more preferably 4:1.
Preferably, step（1）The concentrated ammonia liquor concentration is 25%.
Preferably, step（2）The nickel salt is Nickel dichloride hexahydrate or nickel sulfate, more preferably six chloride hydrates
Nickel.
Preferably, step（2）The urea, 4- nitrophthalic acids, nickel salt, ammonium chloride, ammonium molybdate optimum quality ratio
For（85~100）：（60~70）：（18~22）：（6~8）：（0.8~1.5）, more preferably 93:64:20:7:1.
Preferably, step（2）The concentration of the watery hydrochloric acid is 0.5mol/L ~ 2mol/L, more preferably 1mol/L.
Preferably, step（2）The time boiled is 10min ~ 60min, more preferably 30min.
Preferably, step（3）The tetranitro nickel phthalocyanine and Na2S·9H2O mass ratioes are 1:8~1:3, more preferably
1:5。
Preferably, step（3）The washing is with watery hydrochloric acid, sodium hydroxide solution, deionized water cyclic washing.
Preferably, step（4）Middle diazonium coupling process solvent for use is general polarity organic solvent, such as N, N- dimethyl
Formamide（DMF）, and carry out other dewater treatment without to product.
Preferably, step（4）The tetra amino nickel phthalocyanine is 1 with the mol ratio of watery hydrochloric acid:1.5~1:5, tetra amino nickel phthalein
Cyanines and NaNO2Mol ratio be 4:5~5:4；Tetra amino nickel phthalocyanine, watery hydrochloric acid, NaNO2Aqueous solution optimum mole ratio is 2:5:2.
A kind of graphene/nickel phthalocyanine electrode material for super capacitor, the electrode as obtained in above-described preparation method
Mass ratio shared by nickel phthalocyanine is 5% ~ 95% in material.
Compared with prior art, the invention has the advantages that and technique effect：
1st, reaction raw materials of the invention are easy to get, simple to operate, and reaction condition is gentle, and yield is up to 95% under optimum condition.
2nd, the present invention replaces hypertoxic hydrazine hydrate with p-phenylenediamine to reduce simultaneously functional graphene oxide, with environmental protection
Property.
3rd, diazonium coupling process of the present invention can be in general polarity solvent such as N,N-dimethylformamide（DMF）In enter
OK, and without to product other dewater treatment is carried out.
4th, the specific capacitance of graphene/nickel phthalocyanine electrode material for super capacitor of the invention has reached 600Fg-1, circulation
Good stability.
Brief description of the drawings
Fig. 1 is the ESEM of rGO-p-Pc composites（SEM）Figure.
Fig. 2 is the discharge and recharge of rGO-p-Pc composites（GCD）Figure.
Fig. 3 is the cyclic voltammetric of rGO-p-Pc composites（CV）Figure.
Fig. 4 is comparison diagram before and after rGO-p-Pc composites discharge and recharge 1000 times.
Fig. 5 is the preparation flow figure of rGO-p-Pc composites.
Specific embodiment
Specific implementation of the invention is described in further detail below in conjunction with example and accompanying drawing, but implementation of the invention
Mode not limited to this.
Embodiment 1
（1）Functionalization reduced graphene（rGO-pPD）Preparation：Weigh graphene oxide（GO）300 mg, are scattered in 300 ml
In deionized water, 900 mg p-phenylenediamine are added（pPD）, after ultrasonic 1h, it is 25wt% that 240 μ l concentration are added in the case of backflow
Concentrated ammonia liquor, 70 DEG C of 6 h of reaction, washs after the completion of reaction, dries, and obtains functionalization reduced graphene（rGO-pPD）.
（2）Tetranitro nickel phthalocyanine（NiTNPc）Preparation：By urea（8.5g）, 4- nitrophthalic acids（6.0 g）, sulphur
Sour nickel（1.8 g）, ammonium chloride（0.6 g）Sequentially add in flask, catalyst ammonium molybdate is added under counterflow condition（0.08g）And
10 ml nitro benzene solvents, 120 DEG C are heated to 3 DEG C/min, react 20 min；System is heated to 170 with 5 DEG C/min
DEG C, filtered after 3 h of reaction, washing；Filter cake is soaked in 250mL0.5mol/L watery hydrochloric acid and boils 10min, filtered, added
250mL1mol/L NaOH solutions are heated to 60 DEG C and are released to without ammonia, and product centrifugation, washing is dried, and obtains tetranitro nickel phthalocyanine
（NiTNPc）.
（3）Tetra amino nickel phthalocyanine（NiTAPc）Preparation：5 g NiTNPc are dispersed in 100 ml deionized waters, are added
Na2S·9H2The g of O 40, react 4 h at 40 DEG C, product is washed, and dry, and obtain 2,9,16,23- tetra amino nickel phthalocyanines
（NiTAPc）.
（4）Synthesize the functionalization graphene of nickel phthalocyanine covalence graft（rGO-p-Pc）：By functionalization reduced graphene（rGO-
pPD）0.5mg is scattered in 0.5 ml DMFs, ice bath 20min after ultrasonic 1h, obtains the organic dispersions of rGO-pPD
Liquid；10 mg2,9,16,23- tetra amino nickel phthalocyanines are scattered in the molL of 400 μ l 1-1Watery hydrochloric acid in, be cooled to 0 DEG C, then
Add 300 μ l 3.1 × 10-4mol/L NaNO2The aqueous solution, obtains NiTAPc diazonium salt solutions.The NiTAPc diazols that will be prepared
Solution is added into rGO-pPD organic dispersions, the h of magnetic agitation 6, filtering, and washing is dried, and obtains the work(of nickel phthalocyanine covalence graft
Can graphite alkene（rGO-p-Pc）9.7mg, i.e. graphene/nickel phthalocyanine electrode material for super capacitor.Yield is computed to be up to
92.4%, specific capacitance is up to 498F/g under the current density of 0.2A/g, and specific capacitance also retains original after the circle of circulation 1000
72.5%。
Embodiment 2
（1）Functionalization reduced graphene（rGO-pPD）Preparation：Weigh graphene oxide（GO）300 mg, are scattered in 300 ml
In deionized water, 100 mg p-phenylenediamine are added（pPD）, after ultrasonic 1h, it is 25 wt that 400 μ l concentration are added in the case of backflow
The concentrated ammonia liquor of %, 100 DEG C of 24 h of reaction, washs after the completion of reaction, dries, and obtains functionalization reduced graphene（rGO-pPD）.
（2）Tetranitro nickel phthalocyanine（NiTNPc）Preparation：By urea（10.0g）, 4- nitrophthalic acids（7.0 g）、
Nickel dichloride hexahydrate（2.2 g）, ammonium chloride（0.8 g）Sequentially add into flask, catalyst ammonium molybdate is added under counterflow condition
（0.15g）And 10 ml nitro benzene solvents, 170 DEG C are heated to 3 DEG C/min, react 60 min；System is added with 5 DEG C/min
Heat is filtered, washing to 200 DEG C after 8 h of reaction；Filter cake is soaked in 250mL2mol/L watery hydrochloric acid and boils 60min, filtered,
Add 250mL1mol/L NaOH solutions and be heated to 95 DEG C to without ammonia releasing, product centrifugation, washing is dried, and obtains tetranitro
Nickel phthalocyanine（NiTNPc）.
（3）Tetra amino nickel phthalocyanine（NiTAPc）Preparation：The g of NiTNPc 5 are dispersed in 100 ml deionized waters, are added
Na2S·9H2The g of O 15, react 10 h at 60 DEG C, product is washed, and dry, and obtain 2,9,16,23- tetra amino nickel phthalocyanines
（NiTAPc）.
（4）Synthesize the functionalization graphene of nickel phthalocyanine covalence graft（rGO-p-Pc）：By the mg of functionalization rGO-pPD 190
In being scattered in equipped with 190 ml DMFs, ice bath 20min after ultrasonic 1h obtains rGO-pPD organic dispersions；Will
10 mg2,9,16,23- tetra amino nickel phthalocyanines are scattered in the molL of 1000 μ l 1-1Watery hydrochloric acid in, be cooled to 0 DEG C, add 220
μl 3.1×10-4mol/L NaNO2The aqueous solution, obtains NiTAPc diazonium salt solutions.The NiTAPc diazonium salt solutions that will be prepared add
Enter into rGO-pPD organic dispersions, the h of magnetic agitation 24, filter, washing is dried, and obtains the functionalization of nickel phthalocyanine covalence graft
Graphene（rGO-p-Pc）188mg, i.e. graphene/nickel phthalocyanine electrode material for super capacitor.It is computed yield and is up to 94.0 %,
Specific capacitance is up to 450F/g under the current density of 0.2A/g, and specific capacitance also retains original 85.5% after the circle of circulation 1000.
Embodiment 3：
（1）Functionalization reduced graphene（rGO-pPD）Preparation：Weigh graphene oxide（GO）300 mg, are scattered in 300 ml
In deionized water, 500 mg p-phenylenediamine are added（pPD）, after ultrasonic 1h, it is 25 wt that 320 μ l concentration are added in the case of backflow
The concentrated ammonia liquor of %, 85 DEG C of 15 h of reaction, washs after the completion of reaction, dries, and obtains functionalization reduced graphene（rGO-pPD）.
（2）Tetranitro nickel phthalocyanine（NiTNPc）Preparation：By urea（9.25g）, 4- nitrophthalic acids（6.5 g）、
Nickel dichloride hexahydrate（2.0 g）, ammonium chloride（0.7 g）Sequentially add into flask, catalyst ammonium molybdate is added under counterflow condition
（0.115g）And 10 ml nitro benzene solvents, 145 DEG C are heated to 3 DEG C/min, react 40 min；By system with 5 DEG C/min
185 DEG C are heated to, are filtered after 5.5 h of reaction, washing；Filter cake is soaked in 250mL1.25mol/L watery hydrochloric acid and is boiled
35min, filtering adds 250mL1mol/L NaOH solutions and is heated to 78 DEG C to without ammonia releasing, and product centrifugation, washing is done
It is dry, obtain tetranitro nickel phthalocyanine（NiTNPc）.
（3）Tetra amino nickel phthalocyanine（NiTAPc）Preparation：The g of NiTNPc 5 are dispersed in 100 ml deionized waters, are added
Na2S·9H2The g of O 27.5, react 7 h at 50 DEG C, product is washed, and dry, and obtain 2,9,16,23- tetra amino nickel phthalocyanines
（NiTAPc）.
（4）Synthesize the functionalization graphene of nickel phthalocyanine covalence graft（rGO-p-Pc）：By the mg of functionalization rGO-pPD 10 points
Dissipate in equipped with 10 ml DMFs, ice bath 20min after ultrasonic 1h obtains rGO-pPD organic dispersions；By 10
Mg2,9,16,23- tetra amino nickel phthalocyanines are scattered in the molL of 700 μ l 1-1Watery hydrochloric acid in, be cooled to 0 DEG C, add 260 μ l
3.1×10-4mol/L NaNO2The aqueous solution, obtains NiTAPc diazonium salt solutions.The NiTAPc diazonium salt solutions that will be prepared add to
In rGO-pPD organic dispersions, the h of magnetic agitation 15, filtering, washing is dried, and obtains the function graphite of nickel phthalocyanine covalence graft
Alkene（rGO-p-Pc）18.9mg, i.e. graphene/nickel phthalocyanine electrode material for super capacitor.It is computed yield and is up to 94.5 %,
Specific capacitance is up to 521F/g under the current density of 0.2A/g, and specific capacitance also retains original 78.6% after the circle of circulation 1000.
Embodiment 4：
（1）Functionalization reduced graphene（rGO-pPD）Preparation：Weigh graphene oxide（GO）300 mg, are scattered in 300 ml
In deionized water, 300 mg p-phenylenediamine are added（pPD）, after ultrasonic 1h, it is 25 wt that 300 μ l concentration are added in the case of backflow
The concentrated ammonia liquor of %, 80 DEG C of 9 h of reaction, washs after the completion of reaction, dries, and obtains functionalization reduced graphene（rGO-pPD）.
（2）Tetranitro nickel phthalocyanine（NiTNPc）Preparation：By urea（9.3 g）, 4- nitrophthalic acids（6.4 g）、
Nickel dichloride hexahydrate（2.0 g）, ammonium chloride（0.7 g）Sequentially add into flask, catalyst ammonium molybdate is added under counterflow condition
（0.1g）And 10 ml nitro benzene solvents, 155 DEG C are heated to 3 DEG C/min, react 30 min；System is added with 5 DEG C/min
Heat is filtered, washing to 185 DEG C after 4.5 h of reaction；Filter cake is soaked in 20min, mistake are boiled in 250mL1mol/L watery hydrochloric acid
Filter, adds 250mL1mol/L NaOH solutions and is heated to 90 DEG C to without ammonia releasing, and product centrifugation, washing is dried, and obtains four nitre
Base nickel phthalocyanine（NiTNPc）.
（3）Tetra amino nickel phthalocyanine（NiTAPc）Preparation：The g of NiTNPc 5 are dispersed in 100 ml deionized waters, are added
Na2S·9H2The g of O 25, react 5 h at 50 DEG C, product is washed, and dry, and obtain 2,9,16,23- tetra amino nickel phthalocyanines
（NiTAPc）.
（4）Synthesize the functionalization graphene of nickel phthalocyanine covalence graft（rGO-p-Pc）：By functionalization rGO-pPD 30mg points
Dissipate in equipped with 30 ml DMFs, ice bath 20min after ultrasonic 1h obtains rGO-pPD organic dispersions；By 10
Mg2,9,16,23- tetra amino nickel phthalocyanines are scattered in the molL of 500 μ l 1-1Watery hydrochloric acid in, be cooled to 0 DEG C, add 250 μ l
3.1×10-4mol/L NaNO2The aqueous solution, obtains NiTAPc diazonium salt solutions.The NiTAPc diazonium salt solutions that will be prepared add to
In rGO-pPD organic dispersions, the h of magnetic agitation 8, filtering, washing is dried, and obtains the functionalization graphene of nickel phthalocyanine covalence graft
（rGO-p-Pc）38mg, i.e. graphene/nickel phthalocyanine electrode material for super capacitor.It is computed yield and is up to 95.0 %, in 0.2A/
Specific capacitance is up to 600F/g under the current density of g, and specific capacitance also retains original 82.5% after the circle of circulation 1000.
Claims (10)
1. a kind of preparation method of graphene/nickel phthalocyanine electrode material for super capacitor, it is characterised in that comprise the following steps：
（1）The preparation of functionalization reduced graphene：Graphene oxide is dispersed in water, p-phenylenediamine is added, ultrasonic disperse,
Then add concentrated ammonia liquor, 70 ~ 100 DEG C of 6 ~ 24 h of reaction to be washed after the completion of reaction, dried in the case of backflow, obtain functionalization also
Former Graphene；
（2）The preparation of tetranitro nickel phthalocyanine：Urea, 4- nitrophthalic acids, nickel salt, ammonium chloride are sequentially added to flask
In, catalyst ammonium molybdate and solvent nitrobenzene are added under counterflow condition, 20 ~ 60 min are reacted at being heated to 120 ~ 170 DEG C, then
Filtered after being warming up to 170 ~ 200 DEG C of 3 ~ 8 h of reaction, washing, then filter cake is soaked in watery hydrochloric acid boils, filtered, added
It is heated to 60 ~ 95 DEG C in NaOH solution to be released to without ammonia, product centrifugation, washing is dried, and obtains tetranitro nickel phthalocyanine；
（3）The preparation of tetra amino nickel phthalocyanine：Tetranitro nickel phthalocyanine is dispersed in water, Na is added2S·9H2O, at 40 ~ 60 DEG C
4 ~ 10 h of reaction, product is washed, and is dried, and obtains tetra amino nickel phthalocyanine；
（4）The preparation of graphene/nickel phthalocyanine electrode material for super capacitor：Functionalization reduced graphene is dispersed in N, N- diformazans
In base formamide, ice bath after ultrasound obtains rGO-pPD organic dispersions；Tetra amino nickel phthalocyanine is scattered in watery hydrochloric acid, is cooled down,
Add NaNO2The aqueous solution, obtains NiTAPc diazonium salt solutions；NiTAPc diazonium salt solutions are added to the organic dispersions of rGO-pPD
In liquid, the h of magnetic agitation 6 ~ 24, filtering, washing is dried, and obtains graphene/nickel phthalocyanine electrode material for super capacitor.
2. preparation method according to claim 1, it is characterised in that step（1）The graphene oxide and p-phenylenediamine
Mass ratio be 1:3~3:1；The graphene oxide is 5 with the mass ratio of concentrated ammonia liquor:1~3:1.
3. preparation method according to claim 2, it is characterised in that the concentration of the concentrated ammonia liquor is 25wt%.
4. preparation method according to claim 1, it is characterised in that step（2）The nickel salt be Nickel dichloride hexahydrate or
Nickel sulfate.
5. preparation method according to claim 1, it is characterised in that step（2）The urea, 4- nitro O-phthalics
Acid, nickel salt, ammonium chloride, the mass ratio of ammonium molybdate are（85~100）：（60~70）：（18~22）：（6~8）：（0.8~1.5）.
6. preparation method according to claim 1, it is characterised in that step（2）The concentration of the watery hydrochloric acid is 0.5mol/
L~2mol/L。
7. preparation method according to claim 1, it is characterised in that step（2）The time boiled be 10min ~
60min。
8. preparation method according to claim 1, it is characterised in that step（3）The tetranitro nickel phthalocyanine and Na2S·
9H2The mass ratio of O is 1:8~1:3.
9. preparation method according to claim 1, it is characterised in that step（4）The tetra amino nickel phthalocyanine and watery hydrochloric acid
Mol ratio be 1:1.5~1:5, tetra amino nickel phthalocyanine and NaNO2Mol ratio be 4:5~5:4.
10. a kind of graphene/nickel phthalocyanine electrode of super capacitor obtained in the preparation method as described in claim any one of 1-9
Material, it is characterised in that mass ratio shared by nickel phthalocyanine is 5% ~ 95% in the electrode material.
Priority Applications (1)
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| CN113058649A (en) * | 2021-03-16 | 2021-07-02 | 南方科技大学 | Graphene phthalocyanine composite material and preparation method and application thereof |
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| CN107706007A (en) * | 2017-10-13 | 2018-02-16 | 北京航空航天大学 | A kind of aquo-lithium ion ultracapacitor based on graphene and organic molecule |
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| CN110010360A (en) * | 2019-04-09 | 2019-07-12 | 西北大学 | A kind of closely spherical nickel molybdate/Asia phthalocyanine composite material and its preparation method and application |
| CN110010360B (en) * | 2019-04-09 | 2021-01-05 | 西北大学 | Near-spherical nickel molybdate/subphthalocyanine composite material and preparation method and application thereof |
| CN112117132A (en) * | 2019-06-19 | 2020-12-22 | 天津工业大学 | Preparation method of molecular-grade metal phthalocyanine (phthalocyanine)/graphene (graphene oxide) composite material |
| CN113058649A (en) * | 2021-03-16 | 2021-07-02 | 南方科技大学 | Graphene phthalocyanine composite material and preparation method and application thereof |
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