CN102610793A - 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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- CN102610793A CN102610793A CN2011100262104A CN201110026210A CN102610793A CN 102610793 A CN102610793 A CN 102610793A CN 2011100262104 A CN2011100262104 A CN 2011100262104A CN 201110026210 A CN201110026210 A CN 201110026210A CN 102610793 A CN102610793 A CN 102610793A
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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 the 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 nurses of the peace moral of Univ Manchester UK (Andre K.Geim) etc. were prepared grapheme material in 2004, pay attention to widely because its particular structure and photoelectric property have received people.Mono-layer graphite is because its big 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/ V*s); 4, high specific area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the structural property of the big specific surface character and the nanoscale of its monolayer two dimension can be used as electrode material in ultracapacitor and lithium ion battery.
Yet, since grapheme material with and derivative reunite easily, 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 lithium ion battery performance
Summary of the invention
Based on the problems referred to above, the present invention provides a kind of nitrogen for graphene oxide electrode and preparation method thereof,
Nitrogen provided by the invention comprises metal concentrate for the graphene oxide electrode, and is enriched in nitrogen on the metal concentrate for graphene oxide.
Above-mentioned nitrogen comprises the steps: for the preparation technology of graphene oxide electrode
1, according to Hummers method (selecting from JACS, 1958,80,1339); With graphite, carry out oxidation reaction like graphite flake, make graphite oxide, then graphite oxide is added in the entry; After the ultrasonic dispersion, form with the homodisperse graphene oxide of monolithic layer, filtration, oven dry obtain graphene oxide;
2, graphene oxide is added to fill water or N-methyl pyrrolidone (NMP; Down with) and the bottom be placed with metal concentrate; In the container like collector aluminium foil or nickel foam, and stir, then leave standstill, deposition processes 12～48h; Take out the metal concentrate oven dry of enrichment graphene oxide subsequently, make the graphene oxide electrode;
3, above-mentioned graphene oxide electrode is put into reactor, in this reactor, feed the gaseous mixture of argon gas and ammonia subsequently, carry out substitution reaction, make nitrogen for the graphene oxide electrode; Wherein, ammonia accounts for 5～30% (volume ratios), and preferred ammonia accounts for 10% (volume ratio).
In the said substitution reaction of above-mentioned preparation method's step 3, also comprise the steps:
1., in reactor, feed ammonia 0.5～4h;
2., feed argon gas, and under 300～1000 ℃, carry out substitution reaction 0.5～24h; Preferred 700 ℃ of following substitution reaction 1h.
Preferably, among the above-mentioned preparation method, step 3 also comprises the steps: after accomplishing
4, carry out vacuum drying treatment, Passivation Treatment with making nitrogen in the step 3 successively for the graphene oxide electrode, what dry, be pressed into different size then makes nitrogen for the graphene oxide electrode; Wherein, said Passivation Treatment comprises: said nitrogen is soaked in 1-48h in the nmp solvent of Kynoar (PVDF) for the graphene oxide electrode.
Nitrogen provided by the invention is for the graphene oxide electrode preparation method, and technology is simple, controllable parameters; Implementation cost is cheap, uses extensively; Simultaneously, save present stage coating process commonly used, fluoridized step realization in making the electrode slice process, saved the many complicated flow process in the material fluorination process.
Description of drawings
Fig. 1 is the preparation technology flow chart of nitrogen of the present invention for the graphene oxide electrode;
To be nitrogen of the present invention be made into the charge-discharge test figure behind the battery electrode for the graphene oxide electrode to Fig. 2; 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 the 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 comprises metal concentrate for the graphene oxide electrode, like collector aluminium foil or nickel foam, and is enriched in nitrogen on the metal concentrate for graphene oxide.
Above-mentioned nitrogen is following 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 the graphene oxide electrode.
As shown in Figure 1, nitrogen is following for the step of preparation process of graphene oxide electrode:
The preparation of step 1, graphite oxide: utilize graphite flake, as, purity is 99.5% natural flake graphite, through Hummers method (selecting from JACS, 1958,80,1339), and the preparation graphite oxide;
The preparation of step 2, graphene oxide: with the graphite oxide that the prepares ultrasonic dispersion that is added to the water, form, filter, oven dry, obtain graphene oxide with the homodisperse graphene oxide solution of monolithic layer;
The preparation of step 3, graphene oxide electrode: graphene oxide added to filling water or NMP (N-methyl pyrrolidone) and bottom and be placed with metal concentrate; In the container like collector aluminium foil or nickel foam; And stir; Then leave standstill, deposition processes 12～48h, the metal concentrate oven dry of taking out the enrichment graphene oxide subsequently makes the graphene oxide electrode;
Wherein, in the said substitution reaction of above-mentioned preparation method's step 4, also comprise the steps:
1., in reactor, feed ammonia 0.5～4h;
2., feed argon gas, and under 300～1000 ℃, carry out substitution reaction 0.5～24h; Preferred 700 ℃ of following substitution reaction 1h.
Nitrogen provided by the invention has following technique effect for the graphene oxide electrode preparation method:
1, technology is simple, controllable parameters: liquid deposition, the thickness of regulating and control electrode slice according to the concentration and the sedimentation time of liquid-phase system;
2, implementation cost is cheap: not expensive coating apparatus; In the process of preparation, do not need extra other activating agents such as interpolation binding agent; Solvent can recycle;
3, extensive to the material scope of application: as anyly can in specific solvent, to form suspension, can use this method to obtain electrode slice.
Below in conjunction with accompanying drawing, further explain is done in preferred embodiment of the present invention.
Embodiment 1
Nitrogen is following for preparation technology's flow process of graphene oxide electrode among the present invention:
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 through improved Hummers method (selecting from JACS, 1958,80,1339);
(3) be distributed in the water the graphene oxide for preparing is ultrasonic, place the collector aluminium foil in the bottom of container, static, deposition processes 12 hours is taken out pole piece, and oven dry makes the graphene oxide electrode;
(4) nitriding and oxidizing Graphene electrodes: with gained graphene oxide electrode in (3) through with N
2Reaction obtains the nitriding and oxidizing Graphene electrodes; The graphene oxide electrode that drying has been got well is packed into and is fed dry ammonia 0.5h in the reactor, feeds argon gas and graphene oxide then and reacts 1h down at 700 ℃, promptly can obtain the nitriding and oxidizing Graphene; The gas that in reactor, continues to feed is the gaseous mixture of argon gas and ammonia; Wherein, ammonia accounts for 10% (volume ratio) of mist in the reactor, 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, oven dry.
Nitrogen is following for preparation technology's flow process of graphene oxide electrode among the present invention:
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 the water the graphene oxide for preparing is ultrasonic, place the collector aluminium foil in the bottom of container, static, deposition processes 48 hours is taken out pole piece, oven dry;
(4) nitriding and oxidizing Graphene electrodes: the graphene oxide electrode that drying has been got well is packed into and is fed dry ammonia 0.5h in the reactor, feeds argon gas and graphene oxide then and reacts 6h down at 300 ℃, promptly can obtain the nitriding and oxidizing Graphene; The gas that in reactor, continues to feed is the gaseous mixture of argon gas and ammonia; Wherein, ammonia accounts for 5% (volume ratio) of mist in the reactor, 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, oven dry.
Nitrogen is following for preparation technology's flow process of graphene oxide electrode among the present invention:
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: in the ultrasonic NMP of being distributed to of the graphene oxide for preparing (N-methyl pyrrolidone), place nickel foam in the bottom of container, static, deposition processes 24 hours is taken out pole piece, oven dry;
(4) nitriding and oxidizing Graphene electrodes: the graphene oxide electrode that drying has been got well is packed into and is fed dry ammonia 0.5h in the reactor, feeds argon gas and graphene oxide then and reacts 0.5h down at 1000 ℃, promptly can obtain the nitriding and oxidizing Graphene; The gas that in reactor, continues to feed is the gaseous mixture of argon gas and ammonia; Wherein, ammonia accounts for 30% (volume ratio) of mist in the reactor, 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, oven dry.
Nitrogen is following for preparation technology's flow process of graphene oxide electrode among the present invention:
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: in the ultrasonic NMP of being distributed to of the graphene oxide for preparing (N-methyl pyrrolidone), place nickel foam in the bottom of container, static, deposition processes 12 hours is taken out pole piece, oven dry;
(4) nitriding and oxidizing Graphene electrodes: the graphene oxide electrode that drying has been got well is packed into and is fed dry ammonia 0.5h in the reactor, feeds argon gas and graphene oxide then and reacts 3.5h down at 600 ℃, promptly can obtain the nitriding and oxidizing Graphene; The gas that in reactor, continues to feed is the gaseous mixture of argon gas and ammonia; Wherein, ammonia accounts for 8% (volume ratio) of mist in the reactor, 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, oven dry.
In order to test the conductive capability of nitriding and oxidizing Graphene electrodes, the present invention will test the nitriding and oxidizing Graphene electrodes and be made into battery or electrode for capacitors, carry out charge-discharge test.It is as follows,
The nitriding and oxidizing Graphene electrodes is rolled into sheet, and uses card punch to break into the circular electrode of diameter, accurately weigh as 15mm;
With this electrode, barrier film and electrolyte are assembled into ultracapacitor according to the ultracapacitor manufacture craft in glove box, and its septation is celgard2000 (U.S. Nader Company products), and electrolyte is the Et of 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 the 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 above-mentioned statement to preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. a nitrogen is characterized in that for the preparation method of graphene oxide electrode, comprises the steps:
Graphene oxide added to filling water or N-methyl pyrrolidone and bottom and be placed with in the container of metal concentrate, and stir, then leave standstill, deposition processes, the metal concentrate oven dry of taking out the enrichment graphene oxide subsequently makes the graphene oxide electrode;
Above-mentioned graphene oxide electrode is put into reactor, in this reactor, feed the gaseous mixture of argon gas and ammonia subsequently, carry out substitution reaction, make nitrogen for the graphene oxide electrode.
2. preparation method according to claim 1 is characterized in that, said metal concentrate is collector aluminium foil or nickel foam.
3. preparation method according to claim 1 is characterized in that, saidly leaves standstill, the deposition processes time is 12～48h.
4. preparation method according to claim 1 is characterized in that, in the said substitution reaction, also comprises the steps:
At first, in reactor, feed ammonia 0.5～4h;
Then, feed argon gas, and under 300～1000 ℃, carry out substitution reaction 0.5～24h.
5. preparation method according to claim 4 is characterized in that, the temperature of said substitution reaction is 700 ℃, and the substitution reaction time is 1h.
6. preparation method according to claim 1 is characterized in that, in the said gaseous mixture, ammonia accounts for 5～30% (volume ratios).
7. according to the arbitrary described preparation method of claim 1 to 7, it is characterized in that this preparation method also comprises the steps:
The above-mentioned nitrogen that makes is carried out dried, Passivation Treatment successively for the graphene oxide electrode, and what dry, be pressed into different size then makes nitrogen for the graphene oxide electrode.
8. preparation method according to claim 8 is characterized in that, said Passivation Treatment comprises: said nitrogen is soaked in 1-48h in the N-crassitude ketone solvent of Kynoar for the graphene oxide electrode.
9. a nitrogen is characterized in that for the graphene oxide electrode, and this electrode comprises metal concentrate, and is enriched in nitrogen on the metal concentrate for graphene oxide.
10. nitrogen according to claim 9 is characterized in that for the graphene oxide electrode said metal concentrate is collector aluminium foil or nickel foam.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105044179A (en) * | 2015-06-17 | 2015-11-11 | 青岛大学 | Three-dimensional graphene-modified electrode used for detecting tumor markers and preparation method of three-dimensional graphene-modified electrode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2011-01-25 CN CN201110026210.4A patent/CN102610793B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (1)
| Title |
|---|
| XINRAN WANG ET AL: "N-Doping of Graphene Through Electrothermal Reactions with Ammonia", 《SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105044179A (en) * | 2015-06-17 | 2015-11-11 | 青岛大学 | Three-dimensional graphene-modified electrode used for detecting tumor markers and preparation method of three-dimensional graphene-modified electrode |
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