CN103165866A - Nitrogen doped graphene/metal composite electrode and its preparation method - Google Patents
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- CN103165866A CN103165866A CN2011104183794A CN201110418379A CN103165866A CN 103165866 A CN103165866 A CN 103165866A CN 2011104183794 A CN2011104183794 A CN 2011104183794A CN 201110418379 A CN201110418379 A CN 201110418379A CN 103165866 A CN103165866 A CN 103165866A
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Abstract
Belonging to the field of composite electrodes, the invention discloses a nitrogen doped graphene/metal composite electrode and its preparation method. The nitrogen doped graphene/metal composite electrode comprises nickel foil electrodes, and nitrogen doped graphene enriched on the nickel foil electrode surfaces, wherein nitrogen atoms and carbon atoms in the graphene exist in a covalent bonding form. For the nitrogen doped graphene/metal composite electrode provided in the invention, generation of the nitrogen doped graphene can reduce the content of oxygen in the prepared graphene, and the stability is increased. At the same time, the conduction performance is also enhanced.
Description
Technical field
The present invention relates to the combination electrode field, relate in particular to a kind of nitrating Graphene/metal composite electrode and preparation method thereof.
Background technology
Since the strong K of the peace moral of Univ Manchester UK sea nurse (Andre K.Geim) etc. was prepared grapheme material in 2004, because being subject to people, its unique structure and photoelectric property pay attention to widely.Mono-layer graphite is due to its large specific area, good conduction, heat conductivility and low thermal coefficient of expansion and be considered to desirable material.As: 1. high strength, the Young mole, (1,100GPa), fracture strength: (125GPa); 2. high heat conductance, (5,000W/mK); 3. high conductivity, carrier transport rate, (200,000cm
2/ Vs); 4. high specific area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the structural property of large specific surface character and the nanoscale of its monolayer two dimension can be used as electrode material in ultracapacitor and lithium ion battery.Up to the present, the method for preparing Graphene has many kinds, wherein oxidation-reduction method is a kind ofly can prepare in a large number Graphene and a kind of higher method of productive rate, whole process relates to graphite oxidation is become to graphite oxide, graphite oxide peels off the graphene oxide of generation, by chemistry or thermal reduction, be Graphene again, hydro thermal method reduction-oxidation graphite wherein, the defect to Graphene under hyperbaric environment is repaired to some extent.
Yet, when graphite oxide is reduced into Graphene, general oxygen content is also in 10% left and right; Like this, Graphene is as electrode material, because the existence of oxygen content can cause its conductivity to reduce, oxygen exists on electrode with the form of functional group in addition, in the process of reality charging, oxygen-containing functional group can decompose, and causes electrode material unstable, makes its conductivity and electrochemical stability aspect that certain restriction be arranged.
Summary of the invention
One of problem to be solved by this invention is to provide the nitrating Graphene that a kind of conductivity is high, electrochemical stability is good/metal composite electrode.
A kind of nitrating Graphene/metal composite electrode, the nitrating Graphene that comprises metal electrode and be enriched in described surface of metal electrode, and the carbon atom in nitrogen-atoms and Graphene exists with the covalent bonding form; Wherein, described metal electrode is nickel foil, Copper Foil or foil electrode.
Another problem to be solved by this invention is to provide the preparation method of above-mentioned nitrating Graphene/metal composite electrode, and it comprises the steps:
S1, graphite oxide is added in alcoholic solvent, ultrasonic agitation 0.5～2h, obtain finely dispersed graphene oxide alcoholic solution;
S2, add metal salt solution in step S1, ultrasonic agitation 15～60 minutes, the mixed solution that obtains mixing; Wherein, described slaine is Mg (NO
3)
26H
2o, Mg (SO
4)
27H
2o, Fe (NO
3)
39H
2o or Zn (NO
3)
26H
2o;
Two metal electrodes are inserted in S3, the mixed solution intermediate gap in step S3, and access the direct voltage of 40～80V on two metal electrodes, be 5～20 minutes conduction time, stop subsequently energising, negative pole upper surface enriched in oxygen functionalized graphene at described metal electrode, and extract the metal electrode of surface enrichment graphene oxide from mixed solution, and, after drying processes, obtain graphene oxide/metal composite electrode; Wherein, described metal electrode is nickel foil, Copper Foil or foil electrode;
S4, the graphene oxide/metal composite electrode that step S3 is obtained are inserted one and are filled in the container of miscible fluid of ammoniacal liquor that volume ratio is 2: 1 and water, then container are inserted to 80～150 ℃ of reaction 2～4h, make described nitrating Graphene/metal composite electrode.
The preparation method of above-mentioned nitrating Graphene/metal composite electrode, in step S1, described graphite oxide is to adopt following technique to make:
Graphite powder, potassium permanganate, according to the mass ratio ratio of 1: 3, are added in 0 ℃ of concentrated sulfuric acid successively, be uniformly mixed 2h, then after room-temperature water bath stirs 24h; Then, under condition of ice bath, slowly add deionized water, then add the hydrogen peroxide that concentration is 30wt%, after the mixture color becomes glassy yellow afterwards, suction filtration, the hydrochloric acid that is 10wt% by concentration is again washed, suction filtration, then screening is carried out to vacuum drying treatment, obtains graphite oxide.
In the preparation method of above-mentioned nitrating Graphene/metal composite electrode,
Preferably, in step S1, described neat solvent is at least one in ethanol, isopropyl alcohol and propyl alcohol;
Preferably, in step S2, Mg (NO
3)
26H
2the concentration of O solution is 0.2～0.5mg/ml;
Preferably, in step S3, metal electrode is selected the circular nickel foil electrode that diameter is 5～10cm
Preferably, in step S3, the drying of the metal electrode of effects on surface enriched in oxygen functionalized graphene is processed and is comprised: at first the metal electrode of surface enrichment graphene oxide is placed in to atmosphere and naturally dries, then vacuum bakeout 1～3h.
Preferably, in step S4, described container is hydrothermal reaction kettle; The spacing distance of two metal electrodes is 0.5～1cm.
Nitrating Graphene of the present invention/metal composite electrode, generate the Graphene that nitrogen adulterates, and can reduce the content of oxygen in prepared Graphene, improved its stability; Also obtained enhancing simultaneously aspect conductivity.
The preparation method of nitrating Graphene of the present invention/metal composite electrode, use ammoniacal liquor to carry out hydrothermal reduction to graphene oxide, avoids using virose hydrazine hydrate to reduce to Graphene, and will reduce and complete with nitrating one step; Simultaneously, this preparation method also has following advantage:
1. the Graphene of N doping, not only can improve the stability of the Graphene after reduction, also obtained enhancing aspect conductivity;
2. use the hydro thermal method redox graphene, the defect to Graphene under hyperbaric environment is repaired to some extent;
3. by the method for electro-deposition, the electrode material Direct precipitation, on electrode slice, can save complicated coating process, and technique is simple and the time is short;
4. the electrode material Direct precipitation, on electrode slice, can reduce the equivalent series resistance (ESR) of electrode, thus the power density of more effective raising ultracapacitor.
The accompanying drawing explanation
The SEM figure that Fig. 1 is nitrating Graphene of the present invention/metal composite electrode;
Preparation technology's flow chart that Fig. 2 is nitrating Graphene of the present invention/metal composite electrode.
Embodiment
As shown in Figure 1, the nitrating of present embodiment Graphene/metal composite electrode, the nitrating Graphene that comprises metal electrode and be enriched in described surface of metal electrode, and the carbon atom in nitrogen-atoms and Graphene exists with the covalent bonding form; Wherein, described metal electrode is nickel foil, Copper Foil or foil electrode.
The preparation method of above-mentioned nitrating Graphene/metal composite electrode, as shown in Figure 2, its technological process is as follows:
S1, prepare graphite oxide: by graphite powder (the order number is 100～500 orders) add 0 ℃ the concentrated sulfuric acid (wherein, the addition of sulfuric acid is: the graphite powder that adds 1mg in the sulfuric acid of every 23ml), add again potassium permanganate (mass ratio of graphite powder and potassium permanganate is 1: 3), fully mix, stir 2h, temperature remains on below 10 ℃; Then after room-temperature water bath stirs 24h, slowly add deionized water (addition is about 17 times of sulfuric acid volume) under condition of ice bath; After 15 minutes, then add the hydrogen peroxide that 2.5mL, concentration are 30wt%, the mixture color becomes glassy yellow afterwards, the suction filtration sulfuric acid mixture, then the hydrochloric acid that is 10% by concentration is washed, suction filtration; Screening, at 60 ℃ of vacuumize 48h, obtains graphite oxide;
S2, prepare graphene oxide: graphite oxide is added in alcohols solvent (as, ethanol, isopropyl alcohol, propyl alcohol), ultrasonic agitation 0.5～2h, obtain homodisperse graphene oxide solution;
S3, prepare graphene oxide/metal composite electrode: to adding metal salt solution in the graphene oxide solution of step S2, (its concentration is 0.2～0.5mg/ml, and described slaine is Mg (NO
3)
26H
2o, Mg (SO
4)
27H
2o, Fe (NO
3)
39H
2o or Zn (NO
3)
26H
2o), ultrasonic agitation 15～60 minutes, obtain mixed solution; Using mixed solution as electrolyte, the metal that the diameter of take is 5～10cm (as, nickel foil, Copper Foil or aluminium foil) as electrode, two metal electrode Parallel Symmetrics are placed in electrolyte, and the spacing of the two poles of the earth metal electrode is 0.5～1cm, and add the direct voltage of 40～80V, electrophoresis 5～20 minutes at the two ends of two metal electrodes; Stop subsequently energising, negative pole upper surface enriched in oxygen functionalized graphene at described metal electrode, and extract the metal electrode of surface enrichment graphene oxide from mixed solution, and, through naturally drying, after 60～80 ℃ of dry processing such as vacuum bakeout 1-3 hour, obtain graphene oxide/metal composite electrode;
S4, prepare nitrating Graphene/metal composite electrode: the graphene oxide that step S3 is made/metal composite electrode is put in hydrothermal reaction kettle, the mixture (volume ratio of water and ammoniacal liquor is 2: 1) that adds ammoniacal liquor and water, then hydrothermal reaction kettle is inserted to 80～150 ℃ of reaction 2～4h, after naturally cooling to room temperature, take out, washing and drying, make nitrating Graphene/metal composite electrode.
Nitrating Graphene of the present invention/metal composite electrode, the Graphene of nitrogen doping, reduce the content of oxygen in Graphene, introduce on nitrogen-atoms and belong to the N-shaped doping, improved the concentration of Graphene charge carrier, and then improve the conductivity of electrode, simultaneously, also can improve the stability of electrode, and also obtained enhancing aspect conductivity, as shown in table 1; From the data of elementary analysis, can find out, oxygen content has substantial degradation.
Table 1
| C | H | N | O | |
| GO | 48.59 | 2.28 | 47.08 | |
| Graphene | 87.45 | 1.33 | 11.22 | |
| Nitrogen-doped graphene | 88.43 | 1.23 | 5.21 | 5.13 |
The preparation method of nitrating Graphene of the present invention/metal composite electrode, use ammoniacal liquor to carry out hydrothermal reduction to graphene oxide, avoids using virose hydrazine hydrate to reduce to Graphene, and will reduce and complete with nitrating one step; Simultaneously, this preparation method also has following advantage:
1. the Graphene of N doping, not only can improve the stability of the Graphene after reduction, also obtained enhancing aspect conductivity;
2. use the hydro thermal method redox graphene, the defect to Graphene under hyperbaric environment is repaired to some extent;
3. by the method for electro-deposition, the electrode material Direct precipitation, on electrode slice, can save complicated coating process, and technique is simple and the time is short;
4. the electrode material Direct precipitation, on electrode slice, can reduce the equivalent series resistance (ESR) of electrode, thus the power density of more effective raising ultracapacitor.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The nitrating graphene/nickel combination electrode preparation technology flow process of the present embodiment is as follows:
(1), prepare graphite oxide: 0.5g, 500 order graphite powders are added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃ again, stirs 2h, then after room-temperature water bath stirs 24h, slowly add the 46mL deionized water under condition of ice bath; After 15 minutes, then add 140mL deionized water (wherein, containing the hydrogen peroxide that 2.5mL concentration is 30%), the mixture color becomes glassy yellow afterwards, suction filtration, then the hydrochloric acid that is 10% by 250ml concentration is washed, suction filtration, at 60 ℃ of vacuumize 48h, obtain graphite oxide;
(2), prepare graphene oxide: graphene oxide is added in ethanol, and ultrasonic 0.5h, obtain homodisperse graphene oxide solution;
(3), prepare graphene oxide/nickel combination electrode: in the graphene oxide solution of (2) gained, add Mg (NO
3)
26H
2o (concentration is 0.2mg/ml), ultrasonic 15 minutes, to obtain uniform mixed solution, and using this mixed solution as electrolyte, using the nickel foil of 5cm diameter as electrode, two nickel foil electrode Parallel Symmetrics are placed in electrolyte, the direct current that adds 40V at the two ends of two nickel foil electrodes, two die openings are 0.5cm, electrophoresis 5 minutes, stop subsequently energising, negative pole upper surface enriched in oxygen functionalized graphene at described nickel foil electrode, and extract the nickel foil electrode of surface enrichment graphene oxide from mixed solution, and through naturally drying, after 80 ℃ of vacuum bakeouts wait dry the processing in 1 hour, just can obtain graphene oxide/nickel combination electrode,
(4), prepare nitrating graphene/nickel combination electrode: the graphene oxide of (3) gained/nickel combination electrode is put in the hydrothermal reaction kettle of 100ml, add 20ml ammoniacal liquor and 40ml deionized water, at 80 ℃ of reaction 4h, naturally cool to after room temperature take out, washing and drying, just can obtain nitrating graphene/nickel combination electrode.
Embodiment 2
The nitrating Graphene of the present embodiment/copper combination electrode preparation technology flow process is as follows:
(1), prepare graphite oxide: 1g, 100 order graphite powders are added in 0 ℃, the concentrated sulfuric acid of 23mL, add 3g potassium permanganate, the temperature of mixture remains on below 10 ℃ again, stirs 2h, then after room-temperature water bath stirs 24h, slowly add the 92mL deionized water under condition of ice bath; After 15 minutes, then add 300mL deionized water (wherein, containing the hydrogen peroxide that 2.5mL concentration is 30%), the mixture color becomes glassy yellow afterwards, suction filtration, then the hydrochloric acid that is 10% by 250ml concentration is washed, suction filtration, at 60 ℃ of vacuumize 48h, obtain graphite oxide;
(2), prepare graphene oxide: graphene oxide is added in isopropyl alcohol, and ultrasonic 2h, obtain homodisperse graphene oxide solution;
(3), prepare graphene oxide/copper combination electrode: in the graphene oxide solution of (2) gained, add Mg (SO
4)
27H
2o (concentration is 0.5mg/ml), ultrasonic 45 minutes, to obtain uniform mixed solution, and using this mixed solution as electrolyte, using the nickel foil of 10cm diameter as electrode, two copper foil electrode Parallel Symmetrics are placed in electrolyte, the direct current that adds 80V at the two ends of two copper foil electrodes, two die openings are 0.6cm, electrophoresis 20 minutes, stop subsequently energising, negative pole upper surface enriched in oxygen functionalized graphene at described copper foil electrode, and extract the copper foil electrode of surface enrichment graphene oxide from mixed solution, and through naturally drying, after 60 ℃ of vacuum bakeouts wait dry the processing in 3 hours, just can obtain graphene oxide/copper combination electrode,
(4), prepare nitrating Graphene/copper combination electrode: the graphene oxide of (3) gained/copper combination electrode is put in the hydrothermal reaction kettle of 100ml, add 20ml ammoniacal liquor and 40ml deionized water, at 150 ℃ of reaction 2h, naturally cool to after room temperature take out, washing and drying, just can obtain nitrating Graphene/copper combination electrode.
Embodiment 3
The nitrating graphene/aluminum combination electrode preparation technology flow process of the present embodiment is as follows:
(1), prepare graphite oxide: 0.5g, 200 order graphite powders are added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃ again, stirs 2h, then after room-temperature water bath stirs 24h, slowly add the 46mL deionized water under condition of ice bath; After 15 minutes, then add 140mL deionized water (wherein, containing the hydrogen peroxide that 2.5mL concentration is 30%), the mixture color becomes glassy yellow afterwards, suction filtration, then the hydrochloric acid that is 10% by 250ml concentration is washed, suction filtration, at 60 ℃ of vacuumize 48h, obtain graphite oxide;
(2), prepare graphene oxide: graphene oxide is added in propyl alcohol, and ultrasonic 1h, obtain homodisperse graphene oxide solution;
(3), prepare graphene oxide/aluminium combination electrode: in the graphene oxide solution of (2) gained, add Fe (NO
3)
39H
2o, (concentration is 0.3mg/ml), ultrasonic 60 minutes, to obtain uniform mixed solution, and using this mixed solution as electrolyte, using the aluminium foil of 5cm diameter as electrode, two foil electrode Parallel Symmetrics are placed in electrolyte, the direct current that adds 60V at the two ends of two foil electrodes, two die openings are 0.8cm, electrophoresis 15 minutes, stop subsequently energising, negative pole upper surface enriched in oxygen functionalized graphene at described foil electrode, and extract the foil electrode of surface enrichment graphene oxide from mixed solution, and through naturally drying, after 70 ℃ of vacuum bakeouts wait dry the processing in 2 hours, just can obtain graphene oxide/aluminium combination electrode,
(4), prepare nitrating graphene/aluminum combination electrode: the graphene oxide of (3) gained/aluminium combination electrode is put in the hydrothermal reaction kettle of 100ml, add 20ml ammoniacal liquor and 40ml deionized water, at 120 ℃ of reaction 3h, naturally cool to after room temperature take out, washing and drying, just can obtain nitrating graphene/aluminum combination electrode.
Embodiment 4
The nitrating graphene/nickel combination electrode preparation technology flow process of the present embodiment is as follows:
(1), prepare graphite oxide: 0.5g, 350 order graphite powders are added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃ again, stirs 2h, then after room-temperature water bath stirs 24h, slowly add the 46mL deionized water under condition of ice bath; After 15 minutes, then add 140mL deionized water (wherein, containing the hydrogen peroxide that 2.5mL concentration is 30%), the mixture color becomes glassy yellow afterwards, suction filtration, then the hydrochloric acid that is 10% by 250ml concentration is washed, suction filtration, at 60 ℃ of vacuumize 48h, obtain graphite oxide;
(2), prepare graphene oxide: graphene oxide is added in ethanol, and ultrasonic 1.5h, obtain homodisperse graphene oxide solution;
(3), prepare graphene oxide/nickel combination electrode: in the graphene oxide solution of (2) gained, add Zn (NO
3)
26H
2o (concentration is 0.4mg/ml), ultrasonic 30 minutes, to obtain uniform mixed solution, and using this mixed solution as electrolyte, using the nickel foil of 5cm diameter as electrode, two nickel foil electrode Parallel Symmetrics are placed in electrolyte, the direct current that adds 70V at the two ends of two nickel foil electrodes, two die openings are 1cm, electrophoresis 10 minutes, stop subsequently energising, negative pole upper surface enriched in oxygen functionalized graphene at described nickel foil electrode, and extract the nickel foil electrode of surface enrichment graphene oxide from mixed solution, and through naturally drying, after 70 ℃ of vacuum bakeouts wait dry the processing in 1.5 hours, just can obtain graphene oxide/nickel combination electrode,
(4), prepare nitrating graphene/nickel combination electrode: the graphene oxide of (3) gained/nickel combination electrode is put in the hydrothermal reaction kettle of 100ml, add 20ml ammoniacal liquor and 40ml deionized water, at 100 ℃ of reaction 2.5h, naturally cool to after room temperature take out, washing and drying, just can obtain nitrating graphene/nickel combination electrode.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. the preparation method of nitrating Graphene/metal composite electrode, is characterized in that, comprises the steps:
S1, graphite oxide is added in alcoholic solvent, ultrasonic agitation 0.5～2h, obtain finely dispersed graphene oxide alcoholic solution;
S2, add metal salt solution in step S1, ultrasonic agitation 15～60 minutes, the mixed solution that obtains mixing; Wherein, described slaine is Mg (NO
3)
26H
2o, Mg (SO
4)
27H
2o, Fe (NO
3)
39H
2o or Zn (NO
3)
26H
2o;
Two metal electrodes are inserted in S3, the mixed solution intermediate gap in step S3, and access the direct voltage of 40～80V on two metal electrodes, be 5～20 minutes conduction time, stop subsequently energising, negative pole upper surface enriched in oxygen functionalized graphene at described metal electrode, and extract the metal electrode of surface enrichment graphene oxide from mixed solution, and, after drying processes, obtain graphene oxide/metal composite electrode; Wherein, described metal electrode is nickel foil, Copper Foil or foil electrode;
S4, the graphene oxide/metal composite electrode that step S3 is obtained are inserted one and are filled in the container of miscible fluid of ammoniacal liquor that volume ratio is 2: 1 and water, then container are inserted to 80～150 ℃ of reaction 2～4h, make described nitrating Graphene/metal composite electrode.
2. the preparation method of nitrating Graphene according to claim 1/metal composite electrode, is characterized in that, in step S1, described graphite oxide is to adopt following technique to make:
Graphite powder, potassium permanganate, according to the mass ratio ratio of 1: 3, are added in 0 ℃ of concentrated sulfuric acid successively, be uniformly mixed 2h, then after room-temperature water bath stirs 24h; Then, under condition of ice bath, slowly add deionized water, then add the hydrogen peroxide that concentration is 30wt%, after the mixture color becomes glassy yellow afterwards, suction filtration, the hydrochloric acid that is 10wt% by concentration is again washed, suction filtration, then screening is carried out to vacuum drying treatment, obtains graphite oxide.
3. the preparation method of nitrating Graphene according to claim 2/metal composite electrode, is characterized in that, in step S11, it is 100～500 purpose graphite powders that described graphite powder is selected from the order number.
4. the preparation method of nitrating Graphene according to claim 1/metal composite electrode, is characterized in that, in step S1, described neat solvent is at least one in ethanol, isopropyl alcohol and propyl alcohol.
5. the preparation method of nitrating Graphene according to claim 1/metal composite electrode, is characterized in that, in step S2, the concentration of described metal salt solution is 0.2～0.5mg/ml.
6. the preparation method of nitrating Graphene according to claim 1/metal composite electrode, is characterized in that, in step S3, metal electrode is selected the circular nickel foil electrode that diameter is 5～10cm.
7. the preparation method of nitrating Graphene according to claim 1/metal composite electrode, it is characterized in that, in step S3, the drying of the nickel foil electrode of effects on surface enriched in oxygen functionalized graphene is processed and is comprised: at first the nickel foil electrode of surface enrichment graphene oxide is placed in to atmosphere and naturally dries, then vacuum bakeout 1～3h.
8. the preparation method of nitrating Graphene according to claim 1/metal composite electrode, is characterized in that, in step S4, described container is hydrothermal reaction kettle.
9. the preparation method of nitrating Graphene according to claim 1/metal composite electrode, is characterized in that, in step S4, the spacing distance of two metal electrodes is 0.5～1cm.
10. nitrating Graphene as claimed in claim 1/metal composite electrode, is characterized in that, the nitrating Graphene that comprises metal electrode and be enriched in described surface of metal electrode, and the carbon atom in nitrogen-atoms and Graphene exists with the covalent bonding form.
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