CN102956864A - Preparation method of nitrogen-doped graphene electrode - Google Patents
Preparation method of nitrogen-doped graphene electrode Download PDFInfo
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- CN102956864A CN102956864A CN2011102511629A CN201110251162A CN102956864A CN 102956864 A CN102956864 A CN 102956864A CN 2011102511629 A CN2011102511629 A CN 2011102511629A CN 201110251162 A CN201110251162 A CN 201110251162A CN 102956864 A CN102956864 A CN 102956864A
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Abstract
The invention provides a preparation method of a nitrogen-doped graphene electrode, which comprises the following steps: acquiring a graphene oxide suspension; mixing the graphene oxide suspension with a metal salt solution to obtain an electrolyte; putting at least one pair of electrode pieces connected with direct current into the electrolyte, switching on the direct current to carry out electrophoresis so as to obtain electrode pieces with graphene oxide deposited on the surface, and drying under vacuum conditions; reacting the graphene oxide deposited on the surface of the dried electrode pieces with ammonia gas to carry out nitrogen doping reaction, thereby obtaining a nitrogen-doped graphene electrode precursor; and in a hydrogen protective atmosphere, carrying out reduction reaction on the nitrogen-doped graphene electrode precursor and hydrogen to obtain the low-oxygen-content graphene-doped graphene electrode. The preparation method provided by the invention has the advantages of simple technique, high efficiency and low cost; and the nitrogen-doped graphene electrode prepared by the method has the advantages of low equivalent series resistance, high electric conductivity and low oxygen content in the nitrogen-doped graphene in the nitrogen-doped graphene electrode.
Description
Technical field
The invention belongs to the electrode technology field, specifically a kind of preparation method of nitrating Graphene electrodes.
Background technology
Prepared grapheme material since the strong K of the peace moral of Univ Manchester UK sea nurse (Andre K.Geim) etc. in 2004, pay attention to widely because its unique structure and photoelectric property have been subject to people.Single-layer graphene is because 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.
At present, the technique of tradition preparation electrode slice (comprising the Graphene electrodes sheet) is comparatively complicated, and adds certain binding agent, has increased the equivalent series resistance of electrode slice, affects the power density of ultracapacitor.And, when graphite oxide is reduced into Graphene, general oxygen content also about 10%, like this, with it during as electrode material, so that there is certain restriction its conductivity and electrochemical stability aspect.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of technique simple, efficient is high, the preparation method of the nitrating Graphene electrodes that cost is low, the nitrating Graphene electrodes equivalent series resistance of the method preparation is low, conductivity is high, and the nitrating Graphene oxygen content in the nitrating Graphene electrodes is low.
In order to realize the foregoing invention purpose, the technical scheme of the embodiment of the invention is as follows:
A kind of preparation method of nitrating Graphene electrodes comprises the steps:
Obtain graphene oxide suspension;
Described graphene oxide suspension is mixed with metal salt solution, be mixed with electrolyte;
At least one pair of electrode slice that will be connected with direct current is put into described electrolyte, connects direct current and carries out electrophoresis, obtains the electrode slice that surface deposition has graphene oxide, and dry under vacuum condition;
Graphene oxide and the ammonia of dried described electrode slice surface deposition are carried out the nitrogen doping reaction, obtain nitrating Graphene electrodes precursor;
Under hydrogen shield, described nitrating Graphene electrodes precursor and hydrogen are carried out reduction reaction, obtain described nitrating Graphene electrodes.
The preparation method of above-mentioned nitrating Graphene electrodes has the following advantages at least:
1. adopt the method for electro-deposition, so that contain graphene oxide material Direct precipitation on electrode slice, graphene oxide obtains the nitrating Graphene electrodes after nitrogen mixes, reduces, the method has been avoided the binding agent use, thereby effectively reduce the equivalent series resistance (ESR) of this nitrating Graphene electrodes, when with the nitrating Graphene electrodes during for the preparation of ultracapacitor, power density that can more effective raising ultracapacitor;
With the graphene oxide Direct precipitation on electrode slice, carry out again nitrating and reduction and obtain the nitrating Graphene electrodes, thereby simplified the preparation technology of this nitrating Graphene electrodes, improved production efficiency and business efficiency, effectively overcome the deficiency of traditional preparation electrode process complexity;
With the graphene oxide Direct precipitation on electrode slice, carry out again nitrating and reduction and obtain the nitrating Graphene electrodes, thereby significantly improved this nitrating Graphene electrodes electrical conductance, also strengthened simultaneously the stability of this nitrating Graphene electrodes;
4. the nitrating Graphene on the nitrating Graphene electrodes is that graphene oxide is reduced by ammonia doping first, prepare by hydrogen reducing again, greatly reduce the content of oxygen in the nitrating Graphene by the reduction of 2 footworks, so that the nitrating graphene-structured that generates is more stable, conductivity is high;
Description of drawings
Fig. 1 is embodiment of the invention nitrating Graphene electrodes preparation method's process flow diagram;
Fig. 2 is the scanning of scanning electron microscope figure of the nitrating Graphene electrodes of the embodiment of the invention 1 preparation.
Fig. 3 is that the button cell of application example of the present invention preparation is constant current charge-discharge lab diagram under the 1A/g at electric current.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the invention provides a kind of technique simple, and efficient is high, the preparation method of the nitrating Graphene electrodes that cost is low.This nitrating Graphene electrodes preparation method's technological process specifically comprises the steps: as shown in Figure 1
S1: obtain graphene oxide suspension;
S2: described graphene oxide suspension is mixed with metal salt solution, be mixed with electrolyte;
S3: at least one pair of electrode slice that will be connected with direct current is put into described electrolyte, connects direct current and carries out electrophoresis, obtains the electrode slice that surface deposition has graphene oxide, and dry under vacuum condition;
S4: graphene oxide and the ammonia of dried described electrode slice surface deposition are carried out the nitrogen doping reaction, obtain nitrating Graphene electrodes precursor;
S5: under hydrogen shield, described nitrating Graphene electrodes precursor and hydrogen are carried out reduction reaction, obtain the nitrating Graphene electrodes of low oxygen content.
Particularly, among the above-mentioned steps S1, graphene oxide suspension preferably obtains as follows: will prepare in advance graphite oxide and the dispersant obtained, and under hyperacoustic effect, obtain described graphene oxide suspension.Wherein, this dispersant is preferably alcohol, such as ethanol, propyl alcohol etc., can certainly be other organic solvents such as benzene, oxolane; The time of this hyperacoustic effect is preferably 30～60 minutes.
In the method for above-mentioned graphene oxide suspension preparation, the preparation method of graphite oxide can obtain graphite oxide according to improved hummers method, and is concrete referring to the step S11 among the embodiment 1.Before this graphite oxide and dispersant, also the graphite oxide that obtains can be preferably 5～30 seconds at vacuum condition and 500～800 ℃ of lower heat treated times in advance.Like this heat treatment energy so that graphite oxide under the effect of heat, discharge portion gas, so that between layers spacing increase of graphite oxide, be easier to peel off into monolithic, thereby can shorten the time that ultrasonic wave is processed, further energy efficient is boosted productivity and production cost, simultaneously so that the area of graphene oxide lamella keeps larger.In addition, the concentration of this graphene oxide suspension can be allocated flexibly according to actual conditions, and the present invention is not particularly limited and requires.
Further preferably, further comprising carbon nano-tube in the above-mentioned graphene oxide suspension, the mass ratio of this carbon nano-tube and graphene oxide is preferably 1: 2～and 1, more preferably 1: 1.This compound method that contains the graphene oxide suspension of carbon nano-tube is: take by weighing each component by both preferred proportions first, mix again to add or join in the dispersant respectively and mix, under hyperacoustic effect, obtain containing the graphene oxide suspension of carbon nano-tube.
Further preferably, carbon nano-tube is the acidifying nanotube, and this acidifying carbon nano-tube refers to the carbon nano-tube after peracid treatment, and the acid treatment step of this nanotube is:
Carbon nano-tube is added in the acid solution, under 60 ℃ of-90 ℃ of conditions, added hot reflux 1 hour～3 hours.Filter washing and drying.This acid is restriction not, for example, and watery hydrochloric acid, dilute sulfuric acid, rare nitric acid etc.; By carbon nano-tube being used the acid solution immersion treatment, so that carbon nano tube surface functional group (such as OH, COOH) quantity increases greatly.
Particularly, among the above-mentioned steps S2, in electrolyte, the mass ratio of graphene oxide and slaine is 1: 1～2.Wherein, the slaine in this metal salt solution is Mg (NO
3)
26H
2O, Mg (SO
4)
27H
2O, Fe (NO
3)
39H
2O, Zn (NO
3)
26H
2At least a among the O; The concentration of this metal salt solution can be prepared flexibly according to needs of production, but should preferably guarantee both content described above in electrolyte, and the concentration of metal salt solution is 0.2mg/ml～0.5mg/ml.
Further, in above-mentioned steps S2, with after metal salt solution mixes, also the preferred ultrasonic wave that adopts is processed 15min～60min to this mixed liquor with graphene oxide suspension.Like this, be conducive to improve dispersion more even of graphene oxide and slaine.
Perhaps further, when containing the carbon nano-tube of the content described in above-mentioned step S1 in the graphene oxide suspension, the graphene oxide suspension that will contain carbon nano-tube is with after metal salt solution mixes, and also the preferred ultrasonic wave that adopts is processed 15min～60min to this mixed liquor.
Particularly, among the above-mentioned steps S3, the preferred 40V～80V of direct voltage that is electrically connected on these two paired electrode slices, and the preferred 0.5cm～1cm of spacing between the two paired electrode slices, 0.5cm more preferably, the preferred 5min～20min of electrophoresis time.Spacing between this preferred electrophoretic voltage and paired two electrode slices can better improve electrophoresis efficient, has improved the speed of graphene oxide at the electrode slice surface deposition.This preferred electrophoresis time is so that the thickness of the graphene oxide layer of electrode slice surface deposition is suitable, thereby when guaranteeing nitrating Graphene electrodes performance, reduces production costs.This electrode slice can be selected nickel foil electrode slice, foil electrode sheet, corrosive aluminum foil electrode slice or copper foil electrode sheet, and the diameter of this electrode slice is 5cm～10cm.Certainly, can also be according to the concrete needs of producing, to the shape of electrode, size and kind are made suitable replacement or change flexibly.
In this step S3, after electrophoresis was complete, the reply electrode slice carried out drying, in order to guarantee stable at the dry run performance of electrode slice behind this electrophoresis, should carry out drying at vacuum condition, the dry volatile material of removing simultaneously on the electrode slice that sticks to surface deposition and have graphene oxide.Dry mode preferably but not only for after naturally drying first, toasted 1～3 hour again.Baking gets final product according to this area temperature commonly used.
Further preferably, when the electrolyte among the above-mentioned steps S2 is when containing the graphene oxide of carbon nano-tube, in electrophoresis process, carbon nano-tube is carried out electrophoresis in company with graphene oxide, with graphene oxide at the electrode slice surface deposition.
Particularly, among the above-mentioned steps S4, the flow of the ammonia of gaseous state is preferably 50ml/min～80ml/min.The temperature that graphene oxide and ammonia carry out the nitrogen doping reaction is preferably 500 ℃～800 ℃, and the reaction time is preferably 2～4 hours.This preferred ammonia usage, can so that in the nitrating Graphene that generates the content of nitrogen element at the content range an of the best, thereby further improve the electrochemical stability performance of this nitrating Graphene, simultaneously so that the graphene oxide of electrode slice surface deposition and ammonia fully react, improve the utilance of reactant, thereby further reduce production costs.The preferred time that this graphene oxide electrode and ammonia react can guarantee that both fully react, so that the graphene oxide nitrating in the graphene oxide electrode is an amount of.
Further preferably, when depositing graphene oxide and carbon nano-tube mixed layer on the electrode slice surface of above-mentioned steps S3 preparation, occur under these 500 ℃～800 ℃ conditions in the nitrogen doping reaction process, carbon nano-tube can effectively be inserted between graphene layer; Perhaps the functional group on the carbon nano-tube and the functional group on the Graphene react mutually, make carbon nano-tube be grafted on the Graphene surface, so that Graphene is separated from each other out between layers, increase the Graphene specific area to reach, effectively avoid Graphene to reunite and the generation of lamination, and then increased the purpose of the ratio electric capacity of the product that contains this nitrating Graphene electrodes such as ultracapacitor.
This be because, the inventor finds in the process of research, when the nitrating Graphene electrodes of step S5 preparation is carried out in the dry process, the two-dimensional structure of Graphene is easy to occur to reunite in drying loses the water process of interlayer and is stacked, curling or the height fold, finally cause the utilance of its specific area to reduce, thereby affected at last the product that contains this nitrating Graphene electrodes such as the ratio electric capacity of ultracapacitor.The inventor further studies discovery, when mixing carbon nano-tube in the graphene oxide of the electrode slice surface deposition that step S3 prepares, can effectively solve this difficult problem, this carbon nano-tube can effectively be avoided the generation of Graphene reunion and lamination, effectively improves the Graphene specific area.Further research is found, when the mass ratio of carbon nano-tube and graphene oxide be preferably 1: 2～1 the time, Graphene is reunited relative larger with the minimum Graphene specific area of probability of lamination phenomenon generation.
Particularly, among the above-mentioned steps S5, the temperature of reduction reaction is preferably 500 ℃～800 ℃, and the time of reaction is preferably 1～2 hour.This preferred reducing condition is guaranteeing that energy efficient further reduces production costs, and simultaneously, has improved the efficient of reduction reaction under the prerequisite that the nitrating graphene oxide fully reduces.
Therefore, the preparation method of above-mentioned nitrating Graphene electrodes adopts the method for electro-deposition, so that contain graphene oxide material Direct precipitation on electrode slice, graphene oxide obtains the nitrating Graphene electrodes after nitrogen mixes, reduces, the method has been avoided the binding agent use, thereby effectively reduce the equivalent series resistance (ESR) of this nitrating Graphene electrodes, when with the nitrating Graphene electrodes during for the preparation of ultracapacitor, power density that can more effective raising ultracapacitor; With the graphene oxide Direct precipitation on electrode slice, carry out again nitrating and reduction and obtain the nitrating Graphene electrodes, thereby simplified the preparation technology of this nitrating Graphene electrodes, production efficiency and business efficiency have been improved, effectively overcome the deficiency of traditional preparation electrode process complexity, also significantly improve simultaneously this nitrating Graphene electrodes electrical conductance, strengthened the stability of this nitrating Graphene electrodes; Nitrating Graphene on the nitrating Graphene electrodes is that graphene oxide is reduced by ammonia doping first, prepare by hydrogen reducing again, greatly reduce the content of oxygen in the nitrating Graphene by the reduction of 2 footworks, so that the nitrating graphene-structured that generates is more stable, conductivity is high.
Now take concrete nitrating Graphene electrodes preparation method as example, the present invention is further elaborated.
Embodiment 1
A kind of preparation method of nitrating Graphene electrodes comprises following processing step:
S11: the preparation of graphite oxide: be that 100 purpose natural flake graphite powder join 0 ℃ with the 0.5g particle diameter, 11.5mL the concentrated sulfuric acid in, add again 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃, stir 2h, then after room-temperature water bath stirs 24h, under condition of ice bath, slowly add the 46mL deionized water, behind the 15min, then add 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), after thing color to be mixed becomes glassy yellow, carrying out suction filtration, is that 10% hydrochloric acid washs with 250ml concentration at last, behind the suction filtration, namely obtain graphite oxide at 60 ℃ of vacuumize 48h.
S12: the preparation of graphene oxide suspension: the graphite oxide among the step S11 is added in the ethanol, and ultrasonic dispersion can obtain graphene oxide suspension in 30 minutes.
S13: surface deposition has the nickel electrode preparation of graphene oxide: add Mg (NO first in the graphene oxide suspension of S12 gained
3)
26H
2O solution (concentration is 0.2mg/ml), ultrasonic 15min, obtaining even electrolyte, and so that in this electrolyte, graphene oxide and Mg (NO
3)
26H
2The mass ratio of O is 1: 1, nickel foil electrode Parallel Symmetric with a pair of 5cm diameter is placed in the electrolyte again, the direct current that between two nickel foil electrodes, adds 40V, the spacing of two nickel foil electrodes is 0.5cm, electrophoresis 5min, obtaining surface deposition has the nickel electrode of graphene oxide, after then this electrode being dried naturally, in 60 ℃ of lower vacuum bakeouts 1 hour.
S14: the preparation of nitrating Graphene electrodes precursor: have the nickel electrode of graphene oxide to be put into the centre of heating furnace pipe the surface deposition of drying and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, the flow of control ammonia is at 80ml/min, passed into ammonia 5 minutes, then the Bas Discharged with in the tube furnace heats stove, the rate of heat addition with 10 ℃/min is warming up to 500 ℃ of reaction temperatures, keep 2h, react complete after, cool to room temperature in ammonia atmosphere.
S15: the preparation of nitrating Graphene electrodes: pass into hydrogen in tube furnace, then deaeration heats stove, the rate of heat addition with 10 ℃/min is warming up to 500 ℃ of reaction temperatures, keeps 1h, then cooling, stop to pass into hydrogen, obtain the nitrating Graphene electrodes of low oxygen content.
The nitrating Graphene electrodes of the present embodiment 1 preparation is carried out the electron scanning micrograph analysis, and its profile picture as shown in Figure 2.As shown in Figure 2, the nitrating Graphene of the present embodiment 1 preparation has covered electrode slice fully, well is deposited on the electrode slice.
The nitrating Graphene that deposits on the nitrating Graphene electrodes with the present embodiment 1 preparation carries out elementary analysis, and analysis result is: the C constituent content is that 94.6%, N constituent content is that 2.5%, O constituent content is 2.3%, other elements 0.6%.Compare with the amount of oxidation (about 10%) of the Graphene for preparing according to reduction such as existing general hydrazine hydrates, the nitrating Graphene oxygen content of the present embodiment preparation is low.
Embodiment 2
A kind of preparation method of nitrating Graphene electrodes comprises following processing step:
S21: the preparation of graphite oxide: be that 500 purpose natural flake graphite powder join 0 ℃ with the 0.5g particle diameter, 11.5mL the concentrated sulfuric acid in, add again 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃, stir 2h, then after room-temperature water bath stirs 24h, under condition of ice bath, slowly add the 46mL deionized water, behind the 15min, then add 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), after thing color to be mixed becomes glassy yellow, carrying out suction filtration, is that 10% hydrochloric acid washs with 250ml concentration at last, behind the suction filtration, namely obtain graphite oxide at 60 ℃ of vacuumize 48h.
S22: the preparation of graphene oxide suspension: the graphite oxide among the step S21 is added in the isopropyl alcohol, and ultrasonic dispersion can obtain graphene oxide suspension in 30 minutes.
S23: surface deposition has the nickel electrode preparation of graphene oxide: add Mg (NO first in the graphene oxide suspension of S22 gained
3)
26H
2O solution (concentration is 0.2mg/ml), ultrasonic 15min, obtaining even electrolyte, and so that in this electrolyte, graphene oxide and Mg (SO
4)
27H
2The mass ratio of O is 1: 2, nickel foil electrode slice Parallel Symmetric with two pairs of parallel connections is placed in the electrolyte again, the direct current that between the paired electrode sheet, adds respectively 40V, the spacing of two paired electrode slices is 0.5cm, electrophoresis 5min, obtaining surface deposition has the nickel electrode of graphene oxide, after then this nickel electrode being dried naturally, in 60 ℃ of lower vacuum bakeouts 3 hours.
S24: the preparation of nitrating Graphene electrodes precursor: have the nickel electrode of graphene oxide to be put into the centre of heating furnace pipe the surface deposition of drying and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, the flow of control ammonia is at 80ml/min, passed into ammonia 10 minutes, then the Bas Discharged with in the tube furnace heats stove, the rate of heat addition with 10 ℃/min is warming up to 500 ℃ of reaction temperatures, keep 4h, react complete after, cool to room temperature in ammonia atmosphere.
S25: the preparation of nitrating Graphene electrodes: pass into hydrogen in tube furnace, then deaeration heats stove, the rate of heat addition with 10 ℃/min is warming up to 500 ℃ of reaction temperatures, keeps 1h, then cooling, stop to pass into hydrogen, obtain the nitrating Graphene electrodes.
Embodiment 3
A kind of preparation method of Graphene electrodes comprises following processing step:
S31: the preparation of graphite oxide: referring to the step S11 of embodiment 1.
S32: the preparation of graphene oxide suspension: the graphite oxide among the step S31 is added in the oxolane, and ultrasonic dispersion 2 hours is to graphene oxide suspension.
S33: surface deposition has the nickel electrode preparation of graphene oxide: add Mg (NO first in the graphene oxide suspension of S32 gained
3)
26H
2O solution (concentration is 0.5mg/ml), ultrasonic 60min, obtaining even electrolyte, and so that in this electrolyte, graphene oxide and Fe (NO
3)
39H
2The mass ratio of O is 1: 1, nickel foil electrode Parallel Symmetric with a pair of 10cm diameter is placed in the electrolyte again, the direct current that between a pair of nickel foil electrode, adds 80V, the spacing between electrodes of a pair of nickel foil electrode is 0.5cm, electrophoresis 20min, obtaining surface deposition has the nickel electrode of graphene oxide, after then this nickel electrode being dried naturally, in 60 ℃ of lower vacuum bakeouts 3 hours.
S34: the preparation of nitrating Graphene electrodes precursor: have the nickel electrode of graphene oxide to be put into the centre of heating furnace pipe the surface deposition of drying and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, the flow of control ammonia is at 80ml/min, passed into ammonia 10 minutes, then the Bas Discharged with in the tube furnace heats stove, the rate of heat addition with 10 ℃/min is warming up to 800 ℃ of reaction temperatures, keep 2h, react complete after, cool to room temperature in ammonia atmosphere.
S35: the preparation of nitrating Graphene electrodes: pass into hydrogen in tube furnace, then deaeration heats stove, the rate of heat addition with 10 ℃/min is warming up to 800 ℃ of reaction temperatures, keeps 2h, then cooling, stop to pass into hydrogen, obtain the nitrating Graphene electrodes.
Embodiment 4
A kind of preparation method of Graphene electrodes comprises following processing step:
S41: the preparation of graphite oxide: referring to the step S21 among the embodiment 2.
S42: the preparation of graphene oxide suspension: the graphite oxide powder among the step S41 is added in the propyl alcohol, and ultrasonic dispersion can obtain graphene oxide suspension in 30 minutes.
S43: surface deposition has the corrosive aluminum foil electrode preparation of graphene oxide: add Zn (NO first in the graphene oxide suspension of S42 gained
3)
26H
2O solution (concentration is 0.5mg/ml), ultrasonic 30min, obtaining even electrolyte, and so that in this electrolyte, graphene oxide and Zn (NO
3)
26H
2The mass ratio of O is 1: 2, corrosive aluminum foil electrode Parallel Symmetric with the 7cm diameter of three pairs of parallel connections is placed in the electrolyte again, the direct current that between two paired corrosive aluminum foil electrodes, adds 60V, the spacing of two paired corrosive aluminum foil electrodes is 0.5cm, electrophoresis 12min, obtaining surface deposition has the corrosive aluminum foil electrode of graphene oxide, after then this corrosive aluminum foil electrode being dried naturally, in 60 ℃ of lower vacuum bakeouts 3 hours.
S44: the preparation of nitrating Graphene electrodes precursor: have the corrosive aluminum foil electrode of graphene oxide to be put into the centre of heating furnace pipe the surface deposition of drying and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, the flow of control ammonia is at 80ml/min, passed into ammonia 10 minutes, with the Bas Discharged in the tube furnace, then stove is heated, the rate of heat addition with 10 ℃/min is warming up to 650 ℃ of reaction temperatures, keep 2h, react complete after, cool to room temperature in ammonia atmosphere.
S45: the preparation of low oxygen content nitrating Graphene electrodes: pass into hydrogen in tube furnace, then deaeration heats stove, the rate of heat addition with 10 ℃/min is warming up to 650 ℃ of reaction temperatures, keeps 1h, then cooling, stop to pass into hydrogen, obtain nitrating Graphene corrosive aluminum foil electrode.
Embodiment 5
A kind of preparation method of Graphene electrodes comprises following processing step:
S51: the preparation of graphite oxide: referring to the step S21 among the embodiment 2.
S52: contain the preparation of the graphene oxide suspension of carbon nano-tube: with the carbon nano-tube after the graphene oxide among the step S51 and the acidified processing by weight 1: 1 ratio add in the ethanol, ultrasonic dispersion can obtain containing the graphene oxide suspension of carbon nano-tube in 30 minutes, the step of the carbon nano-tube after the acidified processing is, carbon nano-tube is added in the dilute hydrochloric acid solution, under 90 ℃ of conditions, added hot reflux 3 hours.
S53: surface deposition contains the copper foil electrode preparation of the graphene oxide of carbon nano-tube: add Mg (NO first in the graphene oxide suspension that contains carbon nano-tube of S42 gained
3)
26H
2O solution (concentration is 0.5mg/ml), ultrasonic 15min, obtaining even electrolyte, and so that in this electrolyte, graphene oxide and carbon nano-tube and Mg (NO
3)
26H
2The mass ratio of O is 1: 1, copper foil electrode Parallel Symmetric with the 5cm diameter of three pairs of parallel connections is placed in the electrolyte again, the direct current that between two paired copper foil electrodes, adds 40V, the spacing of two paired copper foil electrodes is 0.5cm, electrophoresis 5min, obtain the copper foil electrode that surface deposition contains the graphene oxide of carbon nano-tube, after then this copper foil electrode being dried naturally, in 60 ℃ of lower vacuum bakeouts 3 hours.
S54: nitrating contains the preparation of the Graphene electrodes precursor of carbon nano-tube: have the graphene oxide copper foil electrode that contains carbon nano-tube to be put into the centre of heating furnace pipe the surface deposition of drying and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, the flow of control ammonia is at 80ml/min, passed into ammonia 10 minutes, with the Bas Discharged in the tube furnace, then stove is heated, the rate of heat addition with 10 ℃/min is warming up to 500 ℃ of reaction temperatures, keep 2h, react complete after, cool to room temperature in ammonia atmosphere.
S55: the low oxygen content nitrating contains the preparation of the Graphene electrodes of carbon nano-tube: pass into hydrogen in tube furnace, deaeration, then stove is heated, the rate of heat addition with 10 ℃/min is warming up to 500 ℃ of reaction temperatures, keep 1h, then cooling stops to pass into hydrogen, obtains the Graphene electrodes that nitrating contains carbon nano-tube.
Embodiment 6
A kind of preparation method who contains the Graphene electrodes of carbon nano-tube, the preparation process that contains the Graphene electrodes of carbon nano-tube referring to embodiment 5, difference is, contain in the process for preparation of graphene oxide suspension of carbon nano-tube, the carbon nano-tube after graphite oxide powder and the acidified processing by weight 2: 1 ratio adds in the isopropyl alcohol.
Application example
With the application of Graphene electrodes in button cell of above-described embodiment 5 preparations, this button cell prepares as follows:
The pole piece of above-described embodiment 5 preparation is carried out roll extrusion with roller mill, the pole piece of roll-in is broken into the circular pole piece that diameter is 10mm with card punch, accurately weigh.
The assembling of battery: in glove box with pole piece, barrier film and electrolyte assemble according to cell making process, its septation is celgard 2000, electrolyte is the 1-ethyl-3-methylimidazole tetrafluoro boric acid salting liquid of 0.5mol/L, leave standstill after assembling is finished and carry out the constant current charge-discharge test after one day, wherein voltage range is 0-1.85V, and electric current is that 1A/g carries out constant current charge-discharge.
This charging and discharging curve as shown in Figure 3, as shown in Figure 3, each complete circulation is symmetrical, and efficiency for charge-discharge can reach 98%, power density formula by ultracapacitor calculates as can be known, and the power density of this ultracapacitor has obtained significant raising.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a nitrating Graphene electrodes comprises the steps:
Obtain graphene oxide suspension;
Described graphene oxide suspension is mixed with metal salt solution, be mixed with electrolyte;
At least one pair of electrode slice that will be connected with direct current is put into described electrolyte, connects direct current and carries out electrophoresis, obtains the electrode slice that surface deposition has graphene oxide, and dry under vacuum condition;
Graphene oxide and the ammonia of dried described electrode slice surface deposition are carried out the nitrogen doping reaction, obtain nitrating Graphene electrodes precursor;
Under hydrogen shield, described nitrating Graphene electrodes precursor and hydrogen are carried out reduction reaction, obtain described nitrating Graphene electrodes.
2. the preparation method of nitrating Graphene electrodes according to claim 1, it is characterized in that: further comprise carbon nano-tube in the described graphene oxide suspension, the mass ratio of described carbon nano-tube and graphene oxide is 1: 2～1.
3. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, it is characterized in that: in described electrolyte, the mass ratio of graphene oxide and slaine is 1: 1～2.
4. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, it is characterized in that: the slaine in the described metal salt solution is Mg (NO
3)
26H
2O, Mg (SO
4)
27H
2O, Fe (NO
3)
39H
2O, Zn (NO
3)
26H
2At least a among the O.
5. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, it is characterized in that: in the described electrolyte, the concentration of slaine is 0.2mg/ml～0.5mg/ml.
6. the preparation method of nitrating Graphene electrodes according to claim 1 is characterized in that: the direct voltage that described two paired electrode slices connect is 40V～80V, and the spacing of described paired two electrode slices is 0.5cm～1cm; The time of described electrophoresis is 5min～20min.
7. according to claim 1 or the preparation method of 6 described nitrating Graphene electrodes, it is characterized in that: described electrode slice is nickel foil, aluminium foil, corrosive aluminum foil or the Copper Foil of 5cm～10cm diameter.
8. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, it is characterized in that: described graphene oxide and ammonia carry out in the process of nitrogen doping reaction, and the flow of ammonia is 50ml/min～80ml/min.
9. the preparation method of nitrating Graphene electrodes according to claim 8, it is characterized in that: the temperature that described graphene oxide and ammonia carry out the nitrogen doping reaction is 500 ℃～800 ℃, and the reaction time is 2～4 hours.
10. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, it is characterized in that: the temperature of described reduction reaction is 500 ℃～800 ℃, and the time of reaction is 1～2 hour.
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