CN108675284A - Polypyrrole/Ni (OH)2The preparation method and application of/sulfonated graphene ternary composite electrode material - Google Patents

Polypyrrole/Ni (OH)2The preparation method and application of/sulfonated graphene ternary composite electrode material Download PDF

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CN108675284A
CN108675284A CN201810454396.5A CN201810454396A CN108675284A CN 108675284 A CN108675284 A CN 108675284A CN 201810454396 A CN201810454396 A CN 201810454396A CN 108675284 A CN108675284 A CN 108675284A
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polypyrrole
composite electrode
sulfonated graphene
ternary composite
sgo
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黎珺
洪健凯
黎肇英
祁宇
郝臣
王晓红
黄成相
吴静波
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Jiangsu University
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    • H01BASIC ELECTRIC ELEMENTS
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Abstract

The invention belongs to combination electrode material synthesis technical fields, are related to the preparation of ternary composite electrode material, more particularly to polypyrrole/Ni (OH)2The preparation method and application of/sulfonated graphene ternary composite electrode material.The present invention will use the graphene oxide sodium borohydride reduction for improving the synthesis of Hummer ' s methods first, and aryl diazonium salts are added and obtain sulfonated graphene, and nickel salt is then added and obtains SGO/Ni (OH) through 180~200 DEG C of 5~6h of hydro-thermal reaction2, reacted under the action of with polypyrrole in dopant, after last washed, drying to obtain the final product.The present invention is with polypyrrole, Ni (OH)2It is combined into ternary electrode material with modified sulfonated graphene, by preparing pyrroles and SGO/Ni (OH)2Different molar ratios are reacted, and are synthesized using chemical oxidative polymerization.Present invention process, equipment are simple, and raw material is readily available, and manufacturing cost is cheap, of reduced contamination, are suitable for industrialized production, and operating condition is easily controllable, and made product chemical property is superior, have very high specific capacitance, there is good commercial use.

Description

Polypyrrole/Ni (OH)2The preparation method of/sulfonated graphene ternary composite electrode material and Using
Technical field
The invention belongs to combination electrode material synthesis technical fields, are related to the preparation of ternary composite electrode material, especially relate to And polypyrrole/Ni (OH)2The preparation method and application of/sulfonated graphene ternary composite electrode material.
Background technology
Up to the present, ultracapacitor(SC)Energy stores application prospect broken conventional batteries commercialization, Breakthrough is also achieved in fields such as aviations.Either folding or mechanical strength test, all solid state SC structures and property It can keep good, show the characteristic of imaginable flexibility electrode material.
With Ni (OH)2With NiO be representative based on nickel material electrode, excellent electroactive and ion permeates strong spy Property, become interesting fake capacitance electrode.During faraday's reaction, electroactive material can be by Rapid reversible also Original reaction, stores charge between electrolyte and electrode surface.Nanoscale Ni (OH)2It is anti-that its quick redox can be improved Should be able to power, shorten ion diffusion path, to electrolyte be efficiently entering electrode cause electric double layer and fake capacitance react play it is important Effect.The capacitance of SCs depends on the quantity and its utilization rate of active material, and in other words, active material utilization is higher, electricity The capacitance of pole material is bigger.Therefore, active material bears the power density and energy density of entire SCs.
It is a kind of more effectively to improve graphene(GO)The method of irreversible accumulation is multiple with the material with fake capacitance property It closes, such as conducting polymer:Polypyrrole(PPy).The synergistic effect of GO and fake capacitance material can improve conductivity, have high than electricity Hold, energy density, power density and cycle-index.It is current studies have shown that by various active materials such as Ni (OH)2, PPy etc. It is fixed on graphene, the application of SCs can be improved.Active material with fake capacitance performance is grown in GO and forms tri compound Material has become one of hot spot of future studies.In order to avoid the defect of carbon material, at the same also enhance active material the advantages of, if Counting rational tri compound structure has maximization performance.
Invention content
The purpose of the present invention is using the sulfonated graphene of functionalization for material, with PPy, Ni (OH)2It is compound to obtain ternary The electrode material for super capacitor of electrode.
Technical scheme is as follows:
Polypyrrole/Ni (OH)2The preparation method of/sulfonated graphene ternary composite electrode material, includes the following steps:
A, using natural crystalline flake graphite as raw material, graphene oxide is synthesized with Hummer ' s methods are improved, it is spare after washing, drying;
B, graphene oxide is scattered in deionized water, it is evenly dispersed to obtain a concentration of 0.9~1 mg/ml through ultrasonic disperse Graphene oxide brown suspension, compound concentration are the sodium borohydride aqueous solution of 0.9~1.0 mg/ml, use aqueous sodium carbonate The pH value of graphene oxide suspension is adjusted to 9~10, sodium borohydride aqueous solution is added in graphene oxide suspension, body Product is than about 1:1, after whisking uniformly, 80 DEG C of water-baths are persistently stirred, and suspension from brown becomes black and along with agglomeration Generation, fully after reaction, mixed liquor is cooled to room temperature, ultrasound stripping 15min;
C, under the conditions of being stirred continuously, aryl diazonium salts are slowly dropped in sodium borohydride reduction graphene oxide products therefrom, Quality is about than 3:1, after ice-water bath fully reacts, deionized water dialysis 7d obtains sulfonated graphene after supersound process(SGO);
D, according to by every 0.282~0.941g nickel salts and 0.03 g SGO ultrasonic disperses in 10mL deionized waters, ultrasonic 30min Afterwards plus 0.2mL NH3•H2The ratio of O prepares solution, is sealed against in a kettle, 180~200 DEG C of 5~6h of hydro-thermal reaction, so Washing, alcohol are washed afterwards, and 50~60 DEG C of vacuum dryings obtain SGO/Ni (OH)2
E, p-methyl benzenesulfonic acid is measured(P-TSA)Pretreated pyrroles and SGO/Ni (OH) is added in solution2, ultrasonic disperse 10~ Ammonium persulfate is slowly added dropwise in 20min(APS)Solution stirs 8~10 h under the conditions of 0~5 DEG C of ice-water bath, is washed through washing, alcohol Afterwards in 50~60 DEG C of vacuum drying ovens dry 10~12h to get;The volume of wherein each reactant, mass ratio are:30~40 mL Containing 0.414 g p-methyl benzenesulfonic acid:The pretreated pyrroles of 0.1~0.3mL:0.1g SGO/Ni(OH)2:20 mL contain 0.1186g Ammonium persulfate solution.
In the more excellent disclosed example of the present invention, Hummer ' s methods described in step A prepare graphite oxide, including by crystalline flake graphite H is added2SO4And NaNO3Mixing, is placed in ice-water bath and is reacted, and reaction a period of time adds deionized water and H2O2, continue anti- It answers;Product is ultrasonic in deionized water, then deionized water, ethyl alcohol is used to rinse respectively, it is dried to obtain final graphene oxide. Specifically, Hummer ' s methods prepare graphite oxide:The concentrated sulfuric acid and 5 of 230 mL mass concentrations 98% is added in dry beaker G pin acid is received, cooling under ice-water bath, and when the temperature of system is less than 5 DEG C, 10 g crystalline flake graphites are added in stirring, delay after mixing Slow that 30 g potassium permanganate are added, controlling reaction temperature is 10~15 DEG C, and beaker is placed in 35 DEG C of water bath with thermostatic control after 2 h of reaction In, continuing to be stirred to react 2h, is continuously added to 460 mL of deionized water, control reacting liquid temperature continues to stir 30 min at 98 DEG C, 1.4 L deionized waters are added and terminate reaction, add the hydrogen peroxide of 25 mL mass concentrations 30%, at this moment solution becomes from brownish black Vivid yellow.It filters while hot, dilute hydrochloric acid (1 is used in combination:10 volume ratios) product is washed into filtrate without S04 2- (BaCl2 Solution detection is without precipitation), then be washed with deionized water to neutrality to get to graphite oxide.The acquired filter cake obtained is disperseed again Into water, uniform solution is formed, after ultrasound removes 15min, 5min is centrifuged, is separated off unoxidized graphite and the oxygen of multilayer Graphite, finally obtains the dilute aqueous solution of graphite oxide, and 60 DEG C of baking ovens dry 12 h to get graphene oxide.
In the more excellent disclosed example of the present invention, a concentration of 5 wt% of aqueous sodium carbonate described in step B.
In the more excellent disclosed example of the present invention, aryl diazonium salts described in step C, the ratio of reactant is according to will be per 72mg Sodium nitrite is dissolved in 40 g water, is cooled to 0 DEG C or so, is mixed with the HCl/water solution of 184 mg p-aminobenzene sulfonic acid, 2g 1M Uniformly, it is fully reacted under the conditions of ice-water bath after 30~40min to obtain the final product.
In the more excellent disclosed example of the present invention, nickel salt described in step D is Ni (NO3)2·6H2O。
In the more excellent disclosed example of the present invention, the molar ratio of SGO and nickel salt described in step D is 1:1~7.
In the more excellent disclosed example of the present invention, 200 DEG C of reaction 5h of hydro-thermal reaction described in step D.
In the more excellent disclosed example of the present invention, the pretreatment of pyrroles described in step E includes that a small amount of pyrrole monomer is poured into container In, be put into zeolite, magneton, 100 DEG C of setting oil bath pot temperature is evaporated under reduced pressure, 0.92~0.94 MPa of vacuum pump pressure it Between, during distillation, a small amount of zinc powder is added to prevent oxidizable pyrrole, has fraction to steam at 68 DEG C or so, is evaporated before removing Colourless pyrrole monomer liquid is obtained after point.
In the more excellent disclosed example of the present invention, step D, washing, alcohol described in E is washed to use deionized water, absolute ethyl alcohol to hand over respectively Three times for washing.
According to polypyrrole/Ni (OH) made from the method for the invention2/ sulfonated graphene ternary composite electrode material is made It is laid in bottom for the sulfonated graphene of substrate, it is about 1 μm that, which there are apparent accordion, length in surface,.
Another object of the present invention is to disclose the application of obtained ternary complex, that is, is used as super Capacitor electrode material.
PPy/Ni(OH)2/ SGO tri compounds electrode material for super capacitor is in 1 A g of current density-1, there is high ratio 1632.5 F g of capacitance-1, 1000 times cycle after capacity retention ratio 86%.
This experiment reagent used is all that analysis is pure, commercially available.
Advantageous effect
The present invention is with polypyrrole, Ni (OH)2Be combined into ternary electrode material with modified sulfonated graphene, by prepare pyrroles and SGO/Ni(OH)2Different molar ratios are reacted, and are synthesized using chemical oxidative polymerization.Present invention process, equipment are simple, Raw material is readily available, and manufacturing cost is cheap, of reduced contamination, is suitable for industrialized production, and operating condition is easily controllable, made product electricity Chemical property is superior, has very high specific capacitance, there is good commercial use.
Description of the drawings
The X ray diffracting spectrum of Fig. 1,2 gained sample of embodiment(XRD);
The SEM spectrum of Fig. 2,2 gained sample of embodiment.
Specific implementation mode
With reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand this hair It is bright, but the invention is not limited in following embodiments.
Embodiment 1
0.659 g nickel nitrates and 0.03 g SGO ultrasonic disperses are weighed in 10mL deionized waters, is added after ultrasonic 30min 0.2mL NH3•H2O, then be sealed against in a kettle, reaction kettle is put into sustained response 6h in 180 DEG C of baking oven, reaction knot Washed after beam, alcohol is washed, dried in 50 DEG C of vacuum drying ovens, obtain SGO/Ni (OH)2.By 30 mL, 0.414 g to toluene sulphur Acid(P-TSA)0.1mL pyrroles and 0.1g SGO/Ni (OH) is added in solution2It is ultrasonic in Ultrasound Instrument according to solution is prepared into 10min, 20 mL 0.1186g ammonium persulfates(APS)Solution is slowly added into above-mentioned solution, and in 0~5 DEG C of ice-water bath condition Under be stirred to react 8 h, washed after reaction, after alcohol is washed in 50 DEG C of vacuum drying ovens dry 10h.
Embodiment 2
0.659 g nickel nitrates and 0.03 g SGO ultrasonic disperses are weighed in 10mL deionized waters, is added after ultrasonic 30min 0.2mL NH3•H2O, then be sealed against in a kettle, reaction kettle is put into sustained response 6h in 200 DEG C of baking oven, reaction knot Washed after beam, alcohol is washed, dried in 60 DEG C of vacuum drying ovens, obtain SGO/Ni (OH)2.By 30 mL, 0.414 g to toluene sulphur Acid(P-TSA)0.2mL pyrroles and 0.1g SGO/Ni (OH) is added in solution2It is ultrasonic in Ultrasound Instrument according to solution is prepared into 10min, 20 mL 0.1186g ammonium persulfates(APS)Solution is slowly added into above-mentioned solution, and in 0~5 DEG C of ice-water bath condition Under be stirred to react 8 h, washed after reaction, after alcohol is washed in 60 DEG C of vacuum drying ovens dry 12h.
The SEM of sample such as Fig. 2, figure it is seen that the SGO as substrate is laid in bottom, there is apparent fold on surface Shape, length are about 1 μm.
The Ni (OH) prepared by hydro-thermal method2Slabbing structure, is evenly dispersed in the surfaces SGO, particle it is smaller and It is evenly distributed.
Embodiment 3
0.659 g nickel nitrates and 0.03 g SGO ultrasonic disperses are weighed in 10mL deionized waters, is added after ultrasonic 30min 0.2mL NH3•H2O, then be sealed against in a kettle, reaction kettle is put into sustained response 5h in 200 DEG C of baking oven, reaction knot Washed after beam, alcohol is washed, dried in 60 DEG C of vacuum drying ovens, obtain SGO/Ni (OH)2.By 30 mL, 0.414 g to toluene sulphur Acid(P-TSA)0.3mL pyrroles and 0.1g SGO/Ni (OH) is added in solution2It is ultrasonic in Ultrasound Instrument according to solution is prepared into 10min, 20 mL 0.1186g ammonium persulfates(APS)Solution is slowly added into above-mentioned solution, and in 0~5 DEG C of ice-water bath condition Under be stirred to react 10 h, washed after reaction, after alcohol is washed in 60 DEG C of vacuum drying ovens dry 12h.
Embodiment 4
0.282 g nickel nitrates and 0.03 g SGO ultrasonic disperses are weighed in 10mL deionized waters, is added after ultrasonic 30min 0.2mL NH3•H2O, then be sealed against in a kettle, reaction kettle is put into sustained response 5h in 180 DEG C of baking oven, reaction knot Washed after beam, alcohol is washed, dried in 60 DEG C of vacuum drying ovens, obtain SGO/Ni (OH)2.By 30 mL, 0.414 g to toluene sulphur Acid(P-TSA)0.1mL pyrroles and 0.1g SGO/Ni (OH) is added in solution2It is ultrasonic in Ultrasound Instrument according to solution is prepared into 10min, 20 mL 0.1186g ammonium persulfates(APS)Solution is slowly added into above-mentioned solution, and in 0~5 DEG C of ice-water bath condition Under be stirred to react 10 h, washed after reaction, after alcohol is washed in 60 DEG C of vacuum drying ovens dry 10h.
Embodiment 5
0.941 g nickel nitrates and 0.03 g SGO ultrasonic disperses are weighed in 10mL deionized waters, is added after ultrasonic 40min 0.2mL NH3•H2O, then be sealed against in a kettle, reaction kettle is put into sustained response 6h in 200 DEG C of baking oven, reaction knot Washed after beam, alcohol is washed, dried in 60 DEG C of vacuum drying ovens, obtain SGO/Ni (OH)2.By 40 mL, 0.414 g to toluene sulphur Acid(P-TSA)0.3mL pyrroles and 0.1g SGO/Ni (OH) is added in solution2It is ultrasonic in Ultrasound Instrument according to solution is prepared into 20min, 20 mL 0.1186g ammonium persulfates(APS)Solution is slowly added into above-mentioned solution, and in 0~5 DEG C of ice-water bath condition Under be stirred to react 10 h, washed after reaction, after alcohol is washed in 60 DEG C of vacuum drying ovens dry 12h.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields, Similarly it is included within the scope of the present invention.

Claims (10)

1. polypyrrole/Ni (OH)2The preparation method of/sulfonated graphene ternary composite electrode material, which is characterized in that including as follows Step:
A, using natural crystalline flake graphite as raw material, graphene oxide is synthesized with Hummer ' s methods are improved, it is spare after washing, drying;
B, graphene oxide is scattered in deionized water, the evenly dispersed oxidations of a concentration of 0.9~1 mg/ml is obtained through ultrasound Graphene brown suspension, compound concentration are the sodium borohydride aqueous solution of 0.9~1.0 mg/ml, are adjusted with aqueous sodium carbonate Sodium borohydride aqueous solution is added in graphene oxide suspension by the pH value of graphene oxide suspension to 9~10, volume ratio About 1:1, after whisking uniformly, 80 DEG C of water-baths are persistently stirred, and fully after reaction, mixed liquor is cooled to room temperature, ultrasound stripping 15min;
C, under the conditions of being stirred continuously, aryl diazonium salts are slowly dropped in sodium borohydride reduction graphene oxide products therefrom, Quality is about than 3:1, after ice-water bath fully reacts, deionized water dialysis 7d obtains sulfonated graphene SGO after supersound process;
D, according to by every 0.282~0.941g nickel salts and 0.03 g SGO ultrasonic disperses in 10mL deionized waters, ultrasonic 30min Afterwards plus 0.2mL NH3•H2The ratio of O prepares solution, is sealed against in a kettle, 180~200 DEG C of 5~6h of hydro-thermal reaction, so Washing, alcohol are washed afterwards, and 50~60 DEG C of vacuum dryings obtain SGO/Ni (OH)2
E, p-methyl benzenesulfonic acid solution is measured, pretreated pyrroles and SGO/Ni (OH) is added2, 10~20min of ultrasonic disperse, delay It is slow that ammonium persulfate solution is added dropwise, 8~10 h are stirred under the conditions of 0~5 DEG C of ice-water bath, it is true at 50~60 DEG C after washing, alcohol are washed In empty baking oven dry 10~12h to get;The volume of wherein each reactant, mass ratio are:30~40 mL are containing 0.414 g to first Benzene sulfonic acid:The pretreated pyrroles of 0.1~0.3mL:0.1g SGO/Ni(OH)2:20 mL ammonium persulfate solutions containing 0.1186g.
2. polypyrrole/Ni (OH) according to claim 12The preparation method of/sulfonated graphene ternary composite electrode material, It is characterized in that:A concentration of 5 wt% of aqueous sodium carbonate described in step B.
3. polypyrrole/Ni (OH) according to claim 12The preparation method of/sulfonated graphene ternary composite electrode material, It is characterized in that:Nickel salt described in step D is Ni (NO3)2·6H2O。
4. polypyrrole/Ni (OH) according to claim 12The preparation method of/sulfonated graphene ternary composite electrode material, It is characterized in that:The molar ratio of SGO and nickel salt described in step D is 1:1~7.
5. polypyrrole/Ni (OH) according to claim 12The preparation method of/sulfonated graphene ternary composite electrode material, It is characterized in that:Hydro-thermal reaction described in step D is 200 DEG C of reaction 5h.
6. polypyrrole/Ni (OH) according to claim 12The preparation method of/sulfonated graphene ternary composite electrode material, It is characterized in that:The pretreatment of pyrroles described in step E includes pouring into a small amount of pyrrole monomer in container, is put into zeolite, magneton, setting 100 DEG C of oil bath pot temperature, is evaporated under reduced pressure, and between 0.92~0.94 MPa of vacuum pump pressure, during distillation, is added Enter a small amount of zinc powder to prevent oxidizable pyrrole, there is fraction to steam at 68 DEG C or so, colourless pyrrole monomer is obtained after removing front-end volatiles Liquid.
7. polypyrrole/Ni (OH) according to claim 12The preparation method of/sulfonated graphene ternary composite electrode material, It is characterized in that:Step D, washing, alcohol described in E are washed to use deionized water, absolute ethyl alcohol alternately to wash three times respectively.
8. according to polypyrrole/Ni (OH) made from any the methods of claim 1-72/ sulfonated graphene ternary composite electrode material Material.
9. according to polypyrrole/Ni (OH) described in right 82/ sulfonated graphene ternary composite electrode material, it is characterised in that:As The sulfonated graphene of substrate is laid in bottom, and it is about 1 μm that, which there are apparent accordion, length in surface,.
10. a kind of 8 or 9 polypyrrole/Ni (OH) of claim2The application of/sulfonated graphene ternary composite electrode material, It is characterized in that:It is used as electrode material for super capacitor.
CN201810454396.5A 2018-05-14 2018-05-14 Polypyrrole/Ni (OH)2The preparation method and application of/sulfonated graphene ternary composite electrode material Pending CN108675284A (en)

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Cited By (1)

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CN109950056A (en) * 2019-04-09 2019-06-28 哈尔滨理工大学 A kind of preparation of hollow NiO@N-C nanometer tube combination electrode material

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