CN102610793B - Nitride substituted graphene oxide electrode and preparation method thereof - Google Patents
Nitride substituted graphene oxide electrode and preparation method thereof Download PDFInfo
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- CN102610793B CN102610793B CN201110026210.4A CN201110026210A CN102610793B CN 102610793 B CN102610793 B CN 102610793B CN 201110026210 A CN201110026210 A CN 201110026210A CN 102610793 B CN102610793 B CN 102610793B
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Abstract
The invention belongs to the field of electrochemistry energy sources, and discloses a nitride substituted graphene oxide electrode and a preparation method thereof. The preparation method of the electrode comprises the following steps: adding graphene oxide into a container which is filled with water and the bottom of which is provided with a metal concentrate body, stirring, then standing and carrying out deposition treatment, then taking out the metal concentrate body of the concentrate graphene oxide and drying, thereby obtaining the graphene oxide electrode; and placing the graphene oxide electrode in a reactor, and then introducing the mixed gas of ammonia and argon to the reactor for substitution reaction, thereby obtaining the nitride substituted graphene oxide electrode. The preparation method of the nitride substituted graphene oxide electrode provided by the invention is simple in preparation process, and parameters can be controlled; the application cost is low, and the using is wide; and meanwhile, the normally used coating technology used in the prior art is omitted, fluorination is realized by one step in the process of preparing the electrode sheet, and multiple complex flows in the material fluorination process are omitted.
Description
Technical field
The present invention relates to electrochemical energy source domain, relate in particular to a kind of nitrogen for graphene oxide electrode and preparation method thereof.
Background technology
The strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, because its unique structure and photoelectric property have been subject to people, 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, Young mole, (1,100GPa), fracture strength: (125GPa); 2, high heat conductance, (5,000W/mK); 3, high conductivity, carrier transport rate, (200,000cm
2/ V*s); 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.
Yet, due to grapheme material with and derivative easily reunite, cause the reduction of its specific area, thereby when making it as electrode material for super capacitor, the reduction of specific capacity, finally causes the reduction of prepared ultracapacitor and performance of lithium ion battery
Summary of the invention
Based on the problems referred to above, the invention provides a kind of nitrogen for graphene oxide electrode and preparation method thereof,
Nitrogen provided by the invention, for graphene oxide electrode, comprises metal concentrate, and is enriched in nitrogen on metal concentrate for graphene oxide.
Above-mentioned nitrogen, for the preparation technology of graphene oxide electrode, comprises the steps:
1, according to Hummers method (selecting from JACS, 1958,80,1339), by graphite, as graphite flake carries out oxidation reaction, make graphite oxide, then graphite oxide is added to the water, after ultrasonic dispersion, form with the homodisperse graphene oxide of monolithic layer, filtration, oven dry obtain graphene oxide;
2, graphene oxide is added to and fill water or 1-METHYLPYRROLIDONE (NMP, lower with) and bottom be placed with metal concentrate, in the container of collector aluminium foil or nickel foam, and stir, then standing, deposition processes 12～48h, the metal concentrate that takes out subsequently enriched in oxygen functionalized graphene is dried, and makes graphene oxide electrode;
3, above-mentioned graphene oxide electrode is put into reactor, with passing into the gaseous mixture of argon gas and ammonia in backward this reactor, carry out substitution reaction, make nitrogen for graphene oxide electrode; Wherein, ammonia accounts for 5～30% (volume ratios), and preferably ammonia accounts for 10% (volume ratio).
In the described substitution reaction of above-mentioned preparation method's step 3, also comprise the steps:
1., in reactor, pass into ammonia 0.5～4h;
2., pass into argon gas, and at 300～1000 ℃, carry out substitution reaction 0.5～24h; Preferred substitution reaction 1h at 700 ℃.
Preferably, in above-mentioned preparation method, after step 3 completes, also comprise the steps:
4, by making nitrogen in step 3, for graphene oxide electrode, carry out successively vacuum drying treatment, Passivation Treatment, what then dry, be pressed into different size makes nitrogen for graphene oxide electrode; Wherein, described Passivation Treatment comprises: described nitrogen is soaked in to 1-48h in the nmp solvent of Kynoar (PVDF) for graphene oxide electrode.
Nitrogen provided by the invention is for graphene oxide electrode preparation method, and technology is simple, and parameter is controlled; Implementation cost is cheap, uses extensively; Meanwhile, save conventional coating process of present stage, fluoridized a step in making electrode slice process and realize, saved the many Complicated Flows in material fluorination process.
Accompanying drawing explanation
Fig. 1 is that nitrogen of the present invention is for preparation technology's flow chart of graphene oxide electrode;
Fig. 2 is that nitrogen of the present invention is made into the charge-discharge test figure after battery electrode for graphene oxide electrode; Wherein, transverse axis: time (time), unit second (S); The longitudinal axis: voltage (Voltage), unit volt (V), wherein voltage range is 0～2.5 volt, electric current is 1A/g electrode; Equipment is the blue electric CT-2001A8 in the Wuhan battery test system of filling enamel, and glove box is German Braun glove box.
Embodiment
A kind of nitrogen provided by the invention, for graphene oxide electrode, comprises metal concentrate, as collector aluminium foil or nickel foam, and is enriched in nitrogen on metal concentrate for graphene oxide.
Above-mentioned nitrogen is as follows for preparation technology's flow process of graphene oxide electrode:
The nitrogen that graphite → graphite oxide → graphene oxide → graphene oxide electrode → nitrogen is crossed for graphene oxide electrode → Passivation Treatment is for graphene oxide electrode.
As shown in Figure 1, nitrogen is as follows for the step of preparation process of graphene oxide electrode:
The preparation of step 1, graphite oxide: utilize graphite flake, as, the natural flake graphite that purity is 99.5%, by Hummers method (selecting from JACS, 1958,80,1339), prepares graphite oxide;
The preparation of step 2, graphene oxide: by the graphite oxide the preparing ultrasonic dispersion that is added to the water, form with the homodisperse graphene oxide solution of monolithic layer, filter, dry, obtain graphene oxide;
The preparation of step 3, graphene oxide electrode: graphene oxide is added to and fills water or NMP (1-METHYLPYRROLIDONE) and bottom and be placed with metal concentrate, in the container of collector aluminium foil or nickel foam, and stir, then standing, deposition processes 12～48h, the metal concentrate that takes out subsequently enriched in oxygen functionalized graphene is dried, and makes graphene oxide electrode;
Step 4, nitrogen are for the preparation of graphene oxide electrode: above-mentioned graphene oxide electrode is put into reactor, with passing into the gaseous mixture of argon gas and ammonia in backward this reactor, carry out substitution reaction, make nitrogen for graphene oxide electrode; Wherein, ammonia accounts for 5～30% (volume ratios), and preferably ammonia accounts for 10% (volume ratio);
Step 5, nitrogen are for the Passivation Treatment of graphene oxide electrode: by making nitrogen in step 4, for graphene oxide electrode, carry out successively vacuum drying treatment, Passivation Treatment, what then dry, be pressed into different size makes nitrogen for graphene oxide electrode; Wherein, described Passivation Treatment comprises: described nitrogen is soaked in to 1-48h in NMP (1-METHYLPYRROLIDONE) solvent of PVDF (Kynoar) for graphene oxide electrode.
Wherein, in the described substitution reaction of above-mentioned preparation method's step 4, also comprise the steps:
1., in reactor, pass into ammonia 0.5～4h;
2., pass into argon gas, and at 300～1000 ℃, carry out substitution reaction 0.5～24h; Preferred substitution reaction 1h at 700 ℃.
Nitrogen provided by the invention, for graphene oxide electrode preparation method, has following technique effect:
1, technology is simple, and parameter is controlled: liquid deposition, regulates and controls the thickness of electrode slice according to the concentration of liquid-phase system and sedimentation time;
2, implementation cost is cheap: do not want expensive coating apparatus; In the process of preparation, do not need extra other activating agents such as interpolation binding agent; Solvent can recycle;
3, applied widely to material: anyly can in specific solvent, to form suspension, can use the method to obtain electrode slice.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
In the present invention, nitrogen is as follows for preparation technology's flow process of graphene oxide electrode:
Graphite → graphene oxide → graphene oxide electrode → nitriding and oxidizing Graphene electrodes
(1) graphite: purity 99.5%;
(2) graphene oxide: utilize the graphite of purity 99.5%, make graphene oxide by improved Hummers method (selecting from JACS, 1958,80,1339);
(3) be distributed in water the graphene oxide preparing is ultrasonic, in the bottom of container, place collector aluminium foil, static, deposition processes 12 hours, takes out pole piece, dries, and makes graphene oxide electrode;
(4) nitriding and oxidizing Graphene electrodes: by gained graphene oxide electrode in (3) by with N
2reaction obtains nitriding and oxidizing Graphene electrodes; Dried graphene oxide electrode is packed in reactor and passes into dry ammonia 0.5h, then pass into argon gas and at 700 ℃, react 1h with graphene oxide, can obtain nitriding and oxidizing Graphene; To the gas that continues to pass in reactor, it is the gaseous mixture of argon gas and ammonia; Wherein, in reactor, ammonia accounts for 10% (volume ratio) of mist, and argon gas is as the diluent gas of ammonia;
(5) nitriding and oxidizing Graphene electrodes: vacuumize, Passivation Treatment, is soaked in the nmp solvent of PVDF, dries.
Embodiment 2
In the present invention, nitrogen is as follows for preparation technology's flow process of graphene oxide electrode:
Graphite → graphene oxide → graphene oxide electrode → nitriding and oxidizing Graphene electrodes
(1) graphite: purity 99.5%;
(2) graphene oxide: with embodiment 1;
(3) graphene oxide electrode: be distributed in water the graphene oxide preparing is ultrasonic, place collector aluminium foil in the bottom of container, static, deposition processes 48 hours, takes out pole piece, dries;
(4) nitriding and oxidizing Graphene electrodes: dried graphene oxide electrode is packed in reactor and passes into dry ammonia 0.5h, then pass into argon gas and react 6h with graphene oxide at 300 ℃, can obtain nitriding and oxidizing Graphene; To the gas that continues to pass in reactor, it is the gaseous mixture of argon gas and ammonia; Wherein, in reactor, ammonia accounts for 5% (volume ratio) of mist, and argon gas is as the diluent gas of ammonia;
(5) nitriding and oxidizing Graphene electrodes: vacuumize, Passivation Treatment, is soaked in the nmp solvent of PVDF, dries.
Embodiment 3
In the present invention, nitrogen is as follows for preparation technology's flow process of graphene oxide electrode:
Graphite → graphene oxide → graphene oxide electrode → nitriding and oxidizing Graphene electrodes
(1) graphite: purity 99.5%;
(2) graphene oxide: with embodiment 1;
(3) graphene oxide electrode: by the ultrasonic NMP of being distributed to of the graphene oxide preparing (1-METHYLPYRROLIDONE), place nickel foam in the bottom of container, static, deposition processes 24 hours, takes out pole piece, dries;
(4) nitriding and oxidizing Graphene electrodes: dried graphene oxide electrode is packed in reactor and passes into dry ammonia 0.5h, then pass into argon gas and react 0.5h with graphene oxide at 1000 ℃, can obtain nitriding and oxidizing Graphene; To the gas that continues to pass in reactor, it is the gaseous mixture of argon gas and ammonia; Wherein, in reactor, ammonia accounts for 30% (volume ratio) of mist, and argon gas is as the diluent gas of ammonia
(5) nitriding and oxidizing Graphene electrodes: vacuumize, Passivation Treatment, is soaked in the nmp solvent of PVDF, dries.
Embodiment 4
In the present invention, nitrogen is as follows for preparation technology's flow process of graphene oxide electrode:
Graphite → graphene oxide → graphene oxide electrode → nitriding and oxidizing Graphene electrodes
(1) graphite: purity 99.5%;
(2) graphene oxide: with embodiment 1;
(3) graphene oxide electrode: by the ultrasonic NMP of being distributed to of the graphene oxide preparing (1-METHYLPYRROLIDONE), place nickel foam in the bottom of container, static, deposition processes 12 hours, takes out pole piece, dries;
(4) nitriding and oxidizing Graphene electrodes: dried graphene oxide electrode is packed in reactor and passes into dry ammonia 0.5h, then pass into argon gas and react 3.5h with graphene oxide at 600 ℃, can obtain nitriding and oxidizing Graphene; To the gas that continues to pass in reactor, it is the gaseous mixture of argon gas and ammonia; Wherein, in reactor, ammonia accounts for 8% (volume ratio) of mist, and argon gas is as the diluent gas of ammonia;
(5) nitriding and oxidizing Graphene electrodes: vacuumize, Passivation Treatment, is soaked in the nmp solvent of PVDF, dries.
In order to test the conductive capability of nitriding and oxidizing Graphene electrodes, the present invention is made into battery or electrode for capacitors by test nitriding and oxidizing Graphene electrodes, carries out charge-discharge test.It is as follows,
Nitriding and oxidizing Graphene electrodes is rolled into sheet, and breaks into card punch the circular electrode that diameter is 15mm, accurately weigh;
In glove box, by this electrode, barrier film and electrolyte are assembled into ultracapacitor according to ultracapacitor manufacture craft, and its septation is celgard2000 (U.S. Nader company product), the Et that electrolyte is 1mol/L
4nBF
4/ AN solution or Et
4nBF
4/ PC solution.
Ultracapacitor constant current charge-discharge curve chart, as shown in Figure 2, transverse axis: time (time), unit second (S); The longitudinal axis: voltage (Voltage), unit volt (V), wherein voltage range is 0～2.5 volt, electric current is 1A/g electrode; Equipment is the blue electric CT-2001A8 in the Wuhan battery test system of filling enamel, and glove box is German Braun glove box.
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 (4)
1. nitrogen, for a preparation method for graphene oxide electrode, is characterized in that, comprises the steps:
Graphene oxide is added to and filled in the container that water or 1-METHYLPYRROLIDONE and bottom is placed with metal concentrate, and stir, then standing, deposition processes, the metal concentrate that takes out subsequently enriched in oxygen functionalized graphene is dried, and makes graphene oxide electrode;
Above-mentioned graphene oxide electrode is put into reactor, with passing into the gaseous mixture of argon gas and ammonia in backward this reactor, carry out substitution reaction, make nitrogen for graphene oxide electrode;
The above-mentioned nitrogen that makes is dried to processing, Passivation Treatment successively for graphene oxide electrode, and what then dry, be pressed into different size makes nitrogen for graphene oxide electrode; Described standing, deposition processes time is 12～48h;
In described substitution reaction, also comprise the steps:
First, in reactor, pass into ammonia 0.5～4h;
Then, pass into argon gas, and carry out substitution reaction 0.5～24h at 300～1100 ℃;
Described Passivation Treatment comprises: described nitrogen is soaked in to 1-48h in the 1-METHYLPYRROLIDONE solvent of Kynoar for graphene oxide electrode.
2. preparation method according to claim 1, is characterized in that, described metal concentrate is collector aluminium foil or nickel foam.
3. preparation method according to claim 1, is characterized in that, the temperature of described substitution reaction is 700 ℃, and the substitution reaction time is 1h.
4. preparation method according to claim 1, is characterized in that, in described gaseous mixture, ammonia accounts for 5～30% (volume ratios).
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| CN103633333A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Nitrogen-doped or boron-doped graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor |
| CN103633334A (en) * | 2012-08-24 | 2014-03-12 | 海洋王照明科技股份有限公司 | Graphene/aluminum foil composite current collector, preparation method thereof, electrochemical electrode and electrochemical cell or capacitor |
| CN103680974A (en) * | 2012-09-14 | 2014-03-26 | 海洋王照明科技股份有限公司 | Graphene/nickel composite material, preparation method thereof, electrode plate and capacitor |
| CN104638276A (en) * | 2014-12-03 | 2015-05-20 | 南京大学 | Photoelectrochemical battery and preparation method thereof |
| CN105044179B (en) * | 2015-06-17 | 2016-03-30 | 青岛大学 | A kind of three-dimensional grapheme modified electrode detecting tumor markers and preparation method thereof |
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| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
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| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| N-Doping of Graphene Through Electrothermal Reactions with Ammonia;Xinran Wang et al;《Science》;20090508;第324卷(第5928期);摘要 * |
| Xinran Wang et al.N-Doping of Graphene Through Electrothermal Reactions with Ammonia.《Science》.2009,第324卷(第5928期), |
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