CN102013330B - Film for graphene/porous nickel oxide composite super capacitor and preparation method thereof - Google Patents

Film for graphene/porous nickel oxide composite super capacitor and preparation method thereof Download PDF

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CN102013330B
CN102013330B CN2010105473840A CN201010547384A CN102013330B CN 102013330 B CN102013330 B CN 102013330B CN 2010105473840 A CN2010105473840 A CN 2010105473840A CN 201010547384 A CN201010547384 A CN 201010547384A CN 102013330 B CN102013330 B CN 102013330B
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film
graphene
porous
nickel oxide
super capacitor
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CN2010105473840A
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Chinese (zh)
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CN102013330A (en
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涂江平
夏新辉
麦永津
王秀丽
谷长栋
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浙江大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention discloses a film for a graphene/porous nickel oxide composite super capacitor. The invention is characterized in that the film is of a disordered nano porous structure, the aperture range is 10 to 350nm, the thickness of the film is 1 to 5 mu m, and the weight ratio of graphene to nickel oxide is (0.5:100) to (2:100). The method for preparing the film comprises the following steps: dissolving graphite oxide sheets and magnesium nitrate into an isopropanol solution so as to form a positively-charged graphite oxide sheet sol, then carrying out electrophoretic deposition on the obtained sol so as to obtain a graphene film; and through taking the graphene film as a deposition carrier, preparing a three-dimensional porous film for the graphene/porous nickel oxide composite super capacitor by using a chemical bath film-coating method. The porous composite thin film prepared by the method has the advantages of good mechanical capacity and super-capacitance property, high-discharge specific capacitance, high-ratio charge-discharge properties, high cycle life and the like, and has wide application prospects in the fields such as electric automobiles, communication, consumer electronics, signal control and the like.

Description

Graphene/porous nickel oxide compound super capacitor film and preparation method thereof
Technical field
The present invention relates to material with carbon element and transistion metal compound compound super capacitor film and preparation method thereof, especially Graphene/porous nickel oxide compound super capacitor film and preparation method thereof.
Background technology
Ultracapacitor is high energy, the green energy-storing device of a kind of performance between battery and traditional capacitor; Advantage such as have the power density height, the speed that discharges and recharges is fast, have extended cycle life and operating temperature range is wide has broad application prospects in fields such as electric automobile, communication, E-consumer and signal controlling.Electrode material is the core component of ultracapacitor, and its performance has directly determined the quality of integral device.Along with the expansion in supercapacitor applications field and deeply, the electrode material that research and development have high specific capacitance amount, high cycle life becomes particularly urgent.
Carbon-based material is to study the earliest, and most widely used electrochemical capacitance material is mainly used in double electric layer capacitor.Carbon-based material is owing to have the specific area (2000mg of super large -1) and minimum electric double layer spacing (<10 Thereby) formation super large charge storage capacity.Carbon-based material has high cycle life characteristics (10 6Inferior), but have the lower (<200Fg of discharge capacity -1) and problem such as the high current charge-discharge capacitance fade is very fast.The transition metal oxide based capacitor has caused the great interest of people because of its high specific capacitance on the other hand.The transition metal oxide based capacitor belongs to the Faraday pseudo-capacitance device; Its Charge Storage process not only comprises the storage on the electric double layer; And through quick redox reaction storage power takes place on the electrode; Generation is far above the ratio electric capacity of carbon-based material (can reach carbon material material 3~7 times), but the cyclical stability of said material not ideal enough (<10 5Inferior), can not satisfy practical application.Therefore these two kinds of different attribute materials are carried out compoundly, utilize advantage separately possibly form electrochemical capacitance material with the high cycle life of high power capacity.
The ultracapacitor discharge process is an electrochemical reaction process, wherein relate to the dual injection/extraction of electronics and ion, so the electrochemical capacitance performance of material links to each other closely with the device surface topography.An effective way that improves material electrochemical capacitance performance is that material is carried out the porous design; The electrochemical capacitance film of preparation loose structure; Its 3 D stereo intersection loose structure not only can provide bigger reactivity area, and can good short distance diffusion admittance be provided for reactive ion.
Summary of the invention
The objective of the invention is for the discharge that improves the electrochemical capacitance material than electric capacity and cycle life, and compound electrochemical capacitance film of a kind of Graphene/porous nickel oxide that proposes and preparation method thereof.
The compound electrochemical capacitance film of Graphene/porous nickel oxide of the present invention has unordered nano-porous structure, pore diameter range 10-350nm, and film thickness 1-5 μ m, the weight ratio of Graphene and nickel oxide is 0.5: 100-2: 100.
The preparation method of Graphene/porous nickel oxide compound super capacitor film, its step is following:
(1) oxidized graphite flake and magnesium nitrate were dissolved in the positively charged graphite oxide film sol of formation in the aqueous isopropanol by weight 100: 1.
(2) with the nickel foam be work electrode, the optics platinized platinum is an auxiliary electrode, and the graphite oxide film sol for preparing with step (1) is an electrolyte, and in electrochemistry bipolar electrode system, applying voltage is 50-150V, reaction time 30s-5min.
(3) sample taking-up nature dries after 60-90 ℃ of saturated hydrazine hydrate atmosphere reduction forms graphene film.
(4) nickelous sulfate and potassium peroxydisulfate were dissolved in the deionized water by weight 6: 1; Obtain nickel sulfate solution; The graphene film bath vertically of step (3) preparation is placed nickel sulfate solution, add mass concentration 20% ammoniacal liquor then, the weight ratio of ammoniacal liquor and nickelous sulfate is 1.5: 1.
(5) behind 20-50 ℃ of following vigorous stirring reaction 1-5h, take out sample, dry the back naturally and under 300-450 ℃ of argon gas condition, calcined 1-2 hour, make Graphene/porous nickel oxide compound super capacitor film.
The thickness of Graphene/porous nickel oxide compound super capacitor film can be controlled according to the reaction time, and its pore size can be adjusted through calcining heat.The nickel oxide film of preparation has 3 D stereo crossover network structure, the pore size 10-350nm of film, film thickness 1-5 μ m.
The present invention is the deposition carrier with the graphene film, prepares three-dimensional porous Graphene/porous nickel oxide compound super capacitor film through the chemical bath coating method.Porous network helps increasing the contact area of membrane electrode and electrolyte; And bigger effectively active reaction area is provided; For electrochemical reaction provides good electron and ions diffusion passage, shorten the diffusion length raising electrochemical capacitance performance of ion simultaneously to the electrochemical capacitance film.
Graphene/porous nickel oxide compound super capacitor film the good cycling stability of the present invention's preparation, charge/discharge capacity is high, and high rate capability is excellent, and material conductivity is high, especially is fit to work under the super large charging or discharging current condition.
Description of drawings
Fig. 1 Graphene/porous nickel oxide compound super capacitor film sem photograph.
Embodiment
Embodiment 1:
Take by weighing the 5g oxidized graphite flake and add in the 1000mL aqueous isopropanol, add the 0.05g magnesium nitrate again, ultrasonic 30min forms stable faint yellow graphite oxide film sol as electrolyte.Transfer to electrolyte in the electrochemistry bipolar electrode system then, wherein nickel foam is a work electrode, and the optics platinized platinum is an auxiliary electrode.Applying voltage is 100V, and reaction 30s obtains the oxidized graphite flake film.Then the oxidized graphite flake film is positioned over reduction 12h formation graphene film in 60 ℃ of saturated hydrazine hydrate steam, film thickness is 10nm.
Take by weighing the 120g nickelous sulfate respectively and the 20g potassium peroxydisulfate places beaker, add the 1000mL deionized water then, be stirred to dissolving fully.Afterwards vertical subsides of foamed nickel supported graphene film is put on the walls of beaker, its conducting surface is towards solution, and nonconductive surface is sealed with insulating cement.The ammoniacal liquor that adds 180g mass concentration 20% then; Behind 35 ℃ of vigorous stirring reaction 1h, take out sample; Naturally dry back calcining under 350 ℃ of argon gas conditions and made Graphene/porous nickel oxide compound super capacitor film in 1 hour, the sem photograph of this film is seen Fig. 1.The pore size 20-250nm of film, film thickness 1 μ m, the weight ratio of Graphene and nickel oxide is 0.5: 100.
Embodiment 2:
Take by weighing the 20g oxidized graphite flake and add in the 2000mL aqueous isopropanol, add the 0.2g magnesium nitrate again, ultrasonic 30min forms stable faint yellow graphite oxide film sol as electrolyte.Transfer to electrolyte in the electrochemistry bipolar electrode system then, wherein nickel foam is a work electrode, and the optics platinized platinum is an auxiliary electrode.Applying voltage is 50V, and reaction 5min obtains the oxidized graphite flake film.Then the oxidized graphite flake film is positioned over reduction 12h formation graphene film in 75 ℃ of saturated hydrazine hydrate steam, film thickness is 50nm.
Take by weighing the 240g nickelous sulfate respectively and the 40g potassium peroxydisulfate places beaker, add the 2500mL deionized water then, be stirred to dissolving fully.Afterwards vertical subsides of foamed nickel supported graphene film is put on the walls of beaker, its conducting surface is towards solution, and nonconductive surface is sealed with insulating cement.The ammoniacal liquor that adds 360g mass concentration 20% then takes out sample behind 20 ℃ of vigorous stirring reaction 2h, dry back calcining under 450 ℃ of argon gas conditions naturally and made Graphene/porous nickel oxide compound super capacitor film in 1.5 hours.The pore size 30-300nm of film, film thickness 2.5 μ m, the weight ratio of Graphene and nickel oxide is 1: 100.
Embodiment 3:
Take by weighing the 40g oxidized graphite flake and add in the 2500mL aqueous isopropanol, add the 0.4g magnesium nitrate again, ultrasonic 30min forms stable faint yellow graphite oxide film sol as electrolyte.Transfer to electrolyte in the electrochemistry bipolar electrode system then, wherein nickel foam is a work electrode, and the optics platinized platinum is an auxiliary electrode.Applying voltage is 150V, and reaction 5min obtains the oxidized graphite flake film.Then the oxidized graphite flake film is positioned over reduction 12h formation graphene film in 90 ℃ of saturated hydrazine hydrate steam, film thickness is 100nm.
Take by weighing the 480g nickelous sulfate respectively and the 80g potassium peroxydisulfate places beaker, add the 4000mL deionized water then, be stirred to dissolving fully.Afterwards vertical subsides of foamed nickel supported graphene film is put on the walls of beaker, its conducting surface is towards solution, and nonconductive surface is sealed with insulating cement.The ammoniacal liquor that adds 720g mass concentration 20% then takes out sample behind 35 ℃ of vigorous stirring reaction 5h, dry back calcining under 300 ℃ of argon gas conditions naturally and made Graphene/porous nickel oxide compound super capacitor film in 2 hours.The pore size 50-350nm of film, film thickness 5 μ m, the weight ratio of Graphene and nickel oxide is 2: 100.
With the Graphene of processing/porous nickel oxide compound super capacitor film is as positive pole, nickel foam is made negative pole, and mercury/mercuric oxide electrode is a reference electrode, its electrochemical capacitance performance of test in three-electrode system.Electrolyte is 1MKOH, and charging/discharging voltage is 0-0.55V, and circulation measurement the reversible of Graphene/porous nickel oxide compound super capacitor film discharges and recharges than electric capacity, charge-discharge performance and high magnification characteristic in 25 ± 1 ℃ of environment.
Graphene of the present invention/porous nickel oxide compound super capacitor film has following characteristics:
1. charge/discharge capacity is high, good cycling stability.The Graphene of the embodiment of the invention 1, embodiment 2 and embodiment 3/porous nickel oxide compound super capacitor film 2Ag -1Discharge is respectively 400Fg than electric capacity under the condition -1, 399Fg -1And 397Fg -1, and 2000 circulation back discharges are than almost not decay of electric capacity.
2. high rate capability is good.The Graphene of the embodiment of the invention 1, embodiment 2 and embodiment 3/porous nickel oxide compound super capacitor film 20Ag -1Discharge is respectively 337FFg than electric capacity under the condition -1, 335FFg -1And 334Fg -1, 40Ag -1Discharge is respectively 324Fg than electric capacity under the condition -1, 320Fg -1And 318Fg -1, and 2000 circulation back discharges are than not obviously decay of electric capacity.This is because the one side graphene film has improved the conductivity of whole laminated film; Porous network helps increasing the contact area of membrane electrode and electrolyte on the other hand; And bigger effectively active reaction area is provided; For electrochemical reaction provides good electron and ions diffusion passage, shorten the diffusion length of ion simultaneously, improve the electrochemical capacitance performance to film.Table 1 is that electric capacity is compared in embodiment 1, embodiment 2 and the embodiment 3 Graphenes/discharge of porous nickel oxide compound super capacitor film under different discharge current densities.
Table 1
Graphene of the present invention/porous nickel oxide compound super capacitor film has high specific capacitance and high cycle life characteristics, has broad application prospects in fields such as electric automobile, communication, E-consumer and signal controlling.

Claims (1)

1. the preparation method of Graphene/porous nickel oxide compound super capacitor film; This film has unordered nano-porous structure, pore diameter range 10-350nm, film thickness 1-5 μ m; The weight ratio of Graphene and nickel oxide is 0.5: 100-2: 100, and its preparation process is following:
(1) oxidized graphite flake and magnesium nitrate were dissolved in the positively charged graphite oxide film sol of formation in the aqueous isopropanol by weight 100: 1;
(2) with the nickel foam be work electrode, the optics platinized platinum is an auxiliary electrode, and the graphite oxide film sol for preparing with step (1) is an electrolyte, and in electrochemistry bipolar electrode system, applying voltage is 50-150V, reaction time 30s-5min;
(3) dry naturally after 60-90 ℃ of saturated hydrazine hydrate atmosphere reduction forms graphene film;
(4) nickelous sulfate and potassium peroxydisulfate were dissolved in the deionized water by weight 6: 1; Obtain nickel sulfate solution; The graphene film bath vertically of step (3) preparation is placed nickel sulfate solution, add mass concentration 20% ammoniacal liquor then, the weight ratio of ammoniacal liquor and nickelous sulfate is 1.5: 1;
(5) at 20-50 ℃ of following vigorous stirring reaction 1-5h, dry the back naturally and under 300-450 ℃ of argon gas condition, calcined 1-2 hour, make Graphene/porous nickel oxide compound super capacitor film.
CN2010105473840A 2010-11-16 2010-11-16 Film for graphene/porous nickel oxide composite super capacitor and preparation method thereof CN102013330B (en)

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